ГОДИШЕН ОТЧЕТ № 212015

ИНСТИТУТ ПО МИНЕРАЛОГИЯ И КРИСТАЛОГРАФИЯ „АКАД. ИВАН КОСТОВ“

БЪЛГАРСКА АКАДЕМИЯ НА НАУКИТЕ

Годишен отчет № 21, 2015Институт по минералогия и кристалография „Акад. Иван Костов“Българска академия на науките

Редакционна колегия:Проф. д-р Росица НиколоваДоц. д-р Владислав Костов-Китин Доц. д-р Росица ТиторенковаДоц. д-р Михаил ТарасовПроф. д-р Борис ШивачевДоц. д-р Желязко ДамяновПроф. д-р Огнян ПетровД-р Яна Цветанова

Адрес:София 1113, ул. „Акад. Г. Бончев“, бл. № 107Факс: (+359 2) 9797056Тел: (+359 2) 9797055E-mail: mincryst@clmc.bas.bg

Web site: http://www.imc.bas.bg

© Институт по минералогия и кристалография „Акад. Иван Костов“, 2015

III

Съдържание

Въведение ........................................................................................................V1. Проблематика на ИМК ................................................................................VI

1.1. Преглед на изпълнението на целите (стратегически и опе ративни), оценка и анализ на постигнатите резултати и на перспективите на ИМК в съответствие с мисията и приоритетите, съобразени с утвърдените научни тематики .................................................................................VI

1.2. Изпълнение на Националната стратегия за развитие на науч ните изследвания 2020. Извършвани дейности и постигнати ре зултати по конкретните приоритети ....................VIII

1.3. Полза за обществото от извършваните дейности .......................XI1.4. Взаимоотношения с институции .................................................. XIV1.5. Общонационални и оперативни дейности, обслужващи

държавата .......................................................................................... XV1.5.1. Практически дейности, свързани с индустрията,

енергетиката, околната среда, селското стопанство, национални културни институции и др. (относими към получаваната субсидия) .......................................................... XV

1.5.2. Проекти, финансирани от национални институции (без ФНИ) ................................................................................ XVII

2. Резултати от научната дейност през 2015 г. ..................................... XVIII2.1. Най-важно научно постижение ................................................... XVIII2.2. Най-значимо научно-приложно постижение ............................... XX

3. Международно научно сътрудничество ............................................... XX4. Участие на ИМК в подготовката на специалисти през 2015 г. ......... XXII5. Експертна дейност................................................................................. XXIII6. Иновационна и стопанска дейност и анализ на нейната

ефективност ...........................................................................................XXIV7. Кратък анализ на финансовото състояние на ИМК през 2014 г. ...XXIV8. Издателска и информационна дейност през 2015 г..........................XXV9. Информация за Научния съвет на звеното ......................................XXVI10. Заключение ..........................................................................................XXVII

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V

Въведение

В съответствие със своята мисия и предмет на дейност Институтът по минералогия и кристалография „Акад. Иван Костов“ (ИМК) и през 2015 г. продължи да допринася за устойчивото развитие на обществото и обогатя-ването на човешките познания в областта на минералогията и кристалогра-фията чрез задълбочени мултидисциплинарни изследвания на природни, техногенни и експериментално моделирани минерални системи и нови ма-териали.

Институтът продължава убедително да защитава пред научната общ-ност и пред обществото извоюваната висока оценка (А/А/А) за дейността си и да доказва своята международна конкурентоспособност в сферата на научните си приоритети и области на компетентност.

В съответствие с основната идея на Националната стратегия за раз-витие на научните изследвания 2020, че образованието, научните из-следвания, технологичното развитие и иновациите са основата за постигане на динамичен и устойчив икономически растеж, през измина-лата година учените от ИМК работиха за реализацията на научно-изследо-вателски проекти, публикуваха резултатите от своите изследвания, участ-ваха в научни конференции, обучаваха млади специалисти, провеждаха специализирани курсове, организираха и бяха лектори в международни летни училища.

Поради нарастване на средната възраст на изследователите и пенсио-ниране на висококвалифицирани специалисти през последните няколко го-дини обучението на докторанти и млади изследователи е засилено целена-сочено. В резултат на това четирима от отчислените през 2015 г. с право на защита докторанти бяха назначени на работа в института.

И през тази година ИМК беше търсен партньор при решаването на на-учно-приложни и технологични задачи, свързани с добива и ефективното използване на минерални ресурси, характеризиране на нови материали и различни продукти на рудодобивната, фармацевтичната, хранително-вкусо-вата промишленост и тази за строителни материали.

Използвайки взаимно допълващи се аналитични апаратури, високо квалифицираните експерти в института осъществяват детайлна характе-ристика на кристалната структура, структурните особености (дефекти, фа-зови преходи, нееднородности и др.), фазов и химичен състав на практичес-ки всички видове материали. Създаденият в ИМК апаратурен комплекс е уникален за България, не само със своята ефективност, но и с това, че част от апаратурата е единствена в страната.

За поредна година поддръжката на апаратурния комплекс, об-служващ голям брой институти от БАН, е отговорност само на ИМК и всичко, което е постигнато от учените в института е с це-ната на много усилия, крайни икономии и лишения.

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1. Проблематика на ИМК

ИМК притежава доказан мултидисциплинарен научен капацитет, мо-дерна изследователска инфраструктура, способна да обезпечи конкуренто-способни изследвания в много широк спектър на природните науки, и добре развито проектно, институционално и кадрово сътрудничество с български и чуждестранни научни организации от различни области.

Институтът е сред първите в БАН и страната интердисциплинарни зве-на, чийто тематичен обхват преминава отвъд границите на няколко фунда-ментални области на научното познание (минералогия и минерални ресур-си, кристалография, химия и физика), обединени от идеята за комплексно изучаване на природни, техногенни и синтетичните материали, което е предпоставка за тяхното целенасочено и ефективно използване.

Предметът на дейност и основна мисия на ИМК са фундаментални и приложни научни изследвания, консултантска, експертна, обслужваща и аналитична дейност; приложение на научните резултати и подготовка на висококвалифицирани специалисти в областта на минералогията и кристалографията, изследване и моделиране на природни и техногенни минерални системи. Основните приоритети, по които се работи в инсти-тута са:

• Изследване на минерали и минерални системи с цел определяне на техния състав, структура и свойства. Разработване на генетични модели за търсене и проучване на находища на минерални суровини;

• Израстване, синтез и характеризиране на моно- и поликристални материали. Модифициране на минерали и материали c цел подобряване на техните сорбционни, каталитични и йонообменни свойства;

• Изучаване на важни за опазването и екологосъобразното използва-не на околната среда природни и техногенни минерални системи.

1.1. Преглед на изпълнението на целите (стратегически и опе­ративни), оценка и анализ на постигнатите резултати и на перспективите на ИМК в съответствие с мисията и приорите-тите, съобразени с утвърдените научни тематики

Постигането на основните стратегически цели на ИМК е свързано с осъществяване на научноизследователския план на института, поддържане на екип от висококвалифицирани експерти, обучение на млади специалис-ти, подкрепа на междуинституционалното и международното сътрудничест-во и поддръжка и обновяване на лабораторния комплекс.

Научната дейност на института през 2015 г. беше изцяло подчинена на изпълнението на научния план на звеното (http://imc.bas.bg/bg1/index.php/2012-14). Научноизследователските задачи са част от три проекта, съ-ответстващи на основните приоритети, свързани с изучаване на Земята,

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нови материали и технологии и опазване на околната среда. Част от задачи-те са финансирани от външни за БАН източници по договори с Фонд „Науч-ни изследвания“, Програмата за европейско териториално сътрудничество „Гърция-България 2007–2013“ и ОП „Развитие на човешките ресурси“.

Резултатите от научноизследователската дейност на института са отразени общо в 67 научни публикации. От тях в списания с импакт-фак-тор са общо 38, като 32 са отпечатани, а 6 – под печат, 54 от общия брой публикации са в реферирани и индексирани списания и сборници, а 13 – в нереферирани. Учените от института са представили 58 доклада на 28 международни научни форума. През изминалата година 224 публикации на учените от института са цитирани общо 875 пъти. С отчитане на условията и възможностите за научна дейност в БАН и страната като цяло, получените резултати са много добри, особено за малък институт като ИМК с двадесет и девет души изследователски състав през 2015 г.

Следвайки съвременните тенденции на мултидисциплинарно развитие на науката в света, понастоящем ИМК разполага с екип от висококвалифи-цирани специалисти в областта на минералогията, минералните суровини, кристалографията, физиката и химията, които са в състояние да осигурят комплексно мултидисциплинарно изучаване и решаване на най-съвремен-но ниво на сложни проблеми на природни, техногенни и експериментално моделирани минерални системи и новосинтезирани материали. Академич-ният състав включва 29 учени: 5 професори, 14 доценти, 3 главни асис-тенти, 5 асистенти и 2 специалисти с докторска степен. От тях един учен е доктор на науките, а 21 са доктори. През 2015 година, освен дейностите по задачи от научноизследователските проекти, хабилитираните учени от ИМК изпълняваха и ангажиментите си по подготовка на висококвалифицирани млади специалисти чрез ръководство на докторанти, провеждане на спе-циализирани курсове, участие в организирането и провеждането на между-народни училища.

През изминалата година в института се обучаваха докторанти по акре-дитираната докторска програма „Минералогия и кристалография“ (акреди-тация от НАОА до 2019 г. с много висока обща оценка 9.79), която предлага съвременна интердисциплинарна подготовка в съответствие с най-новите тенденции в развитието на минералогията и кристалографията в света. Об-щият брой на докторантите беше 9, 7 от които – на редовна докторантура, 1 на самостоятелна подготовка и 1 задочен. През 2015 един от докторантите защити докторска дисертация, а петима са отчислени с право на защита, като четирима от тях са назначени на длъжност асистент в института.

Наред с научните изследвания и подготовката на специалисти учените от ИМК с цената на много лишения и икономии успяха да поддържат в работ-но състояние лабораторния комплекс. Институтът разполага с 8 съвременни собствени лаборатории и дялово участие в други 3 външни. През 2015 г. със средства по проект CheRRIE бе закупен рентгеново флуоресцентен спек-

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трометър за елементен анализ (WDXRF) SUPERMINI 200 с придружаващо оборудване: Автоматична машина за пробоподготовка на стопилкови табле-ти, както и Система за мониторинг на гама фона MIRA Gamma Dose Rate Monitoring System. Допълвайки лабораторния комплекс на ИМК се разширя-ват и възможностите за решаване на различни научно-приложни проблеми в сферата на материалознанието.

В момента ИМК е най-комплексно и модерно оборудваната и с най-висококвалифициран научен състав и обслужващ персонал организация в България в областта на детайлното изследване на структурата, състава, свойствата, поведението и взаимодействията на твърдата материя (незави-симо от произхода и размерите) и системите, които тя формира.

Въпреки назначените четирима нови асистенти средната възраст на учените от академичния състав все още е висока (около 51 години). Поради ниското заплащане на труда на научните работници, младите специалисти, обучавани в института, след като получат знания и умения на добро ниво се реализират като учени извън страната. Това безспорно е основен проблем в цялата академия на науките и ако не се вземат спешни мерки за обръщане на тенденциите ние ще продължим да бъдем нископлатени обучители на високоплатени специалисти.

1.2. Изпълнение на Националната стратегия за развитие на науч­ните изследвания 2020. Извършвани дейности и постигнати ре­зултати по конкретните приоритети

Научноизследователския план на ИМК, актуализиран през 2014 г. е в съответствие с Националната стратегия за научни изследвания 2020, На-ционалната програма за развитие: България 2020, и Рамковата програма на ЕС за научни изследвания и иновации „Хоризонт 2020“. През изминала-та година в института се работеше по трите планови проекта, включващи 32 задачи, като изследванията бяха фокусирани върху приоритетите на на-ционалните и европейските програми. По основните приоритети на НСРНИ 2020 през годината са осъществени следните дейности:

Приоритет 1: Енергия, енергийна ефективност и транспорт: раз-витие на зелени и екотехнологии

По този приоритет са задачите, включени в плановия проект „Техноген-ни минерални системи и минерални суровини: характеристика, находища, ефективни и екологосъобразни приложения“.

Дейностите през годината са свързани с минералого-техноложка оценка на минералните суровини от находище Кремиковци; фазово-мине-раложка и химична характеристика на въглища и биомаса, както и твърдите продукти от тяхното изгаряне, пиролиза и газификация; ефективно използ-ване на твърди отпадъци за получаване на екологични продукти.

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Резултатите са представени в 7 публикации.Една от тези публикации е в TOP-25 ARTICLES IN THE SUBJECT AREA

(the most read publications – counted by article downloads on SciVerse and ScienceDirect): Vassilev, S., Vassileva, C., Vassilev, V., 2015. Advantages and disadvantages of composition and properties of biomass in comparison with coal: An overview. Fuel, 158: 330–350.

No 2 in FUEL for 07­09.2015No 13 in FUEL for 04­06.2015No 24 in Environmental Science Subject Area for all (168) journals for

07­09.2015No 25 in Energy Subject Area for all (82) journals for 07–09.2015Резултатите в това приоритетно направление могат да бъдат обобще-

ни по следния начин:Систематизирани са предимствата и недостатъците на биомасата,

като възобновяем източник на енергия в сравнение с тези на въглищата като традиционно гориво

Дефинирани са технологичните и екологични предимства и недоста-тъци, свързани с устойчивото оползотворяване на биомасата и пепелите от биомаса.

Показано е, че пепели от мазут и шлака от мазут, отделени като отпад-ни продукти от ТЕЦ биха били потенциален ресурс за извличане на ценни елементи (V, Ni, Mo, Zn, Ag, Cd, Cr, Cu, Pb, Fe, др.) след подходящи физични сепарации и/или химични третирания.

Завършен е първият етап от изследването по заявка на „Барит Май-нинг“ ЕООД.

Показано е, че интензивното смилане на био-отпадък „черупки от яйца“ води до промяна на свойствата на био-отпадъка и повишава реакционност-та му способност. В резултат този био-отпадък може да намери приложение като сорбент при дехлорирането на устойчиви органични замърсители, в качеството на подобрител на почвите, за модифициране свойствата на кал-циево-силикатни системи и др.

Приоритет 2: Здраве и качество на живота, биотехнологии и еколо-гично чисти храни

В този приоритет се включват задачи и от трите планови проекта, свър-зани с подобряване качеството на живот. Продължи работата по задачите финансирани от Програмата за Европейско териториално сътрудничество „Гърция – България 2007–2013“, по проект CheRRIE „Химичен и радиологи-чен риск в затворена среда“. Проектът завърши успешно през ноември 2015 г.

Дейностите са свързани с измерване на радиационния фон и химич-ните замърсявания в сградния фонд от традиционни (бетон, тухли, дървени подови настилки, мебели и др.) и съвременни (гипсовите плочи, гранито-грес, винилови настилки и др.) строителни материали.

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Резултат от дейностите е база данни за радиационния фон и химич-ните замърсявания на сградния фонд в трансграничния регион България–Гърция, която да подпомага работата на строители и архитекти при избор на материали и планиране на ремонтни дейности.

През годината учени от института работиха и по задачи, свързани с опазване на околната среда в частта, касаеща разработване на нови мате-риали със сорбционни и йонно обменни характеристики, за пречистване на подземни и питейни води.

Една от задачите, по които се работи, е финансово подкрепена от Фонд „Научни изследвания“, проект „Структурна биология и специфика на ДНК Г-квадруплекси лиганд взаимодействия“ с цел кристализация и определяне на структурата на биологични макромолекули (ДНК). Осъществен е първият етап от изследването, оптимизирани са условията за кристализация и са определени кристалните структури на два от образците.

Темата на докторската дисертация на зачисления редовен докторант през 2015 г. „Структурни характеристики на биологичен апатит изследвани с вибрационна (микро-ИЧ и Раманова) спектроскопия“ съответства на приори-тет 2 на НСРНИ 2020, както и другите изследвания върху структурните харак-теристики и изменения на апатит, изграждащ зъбните структури.

Приоритет 3: Нови материали и технологииГоляма част от задачите и по трите планови проекта, по които работят

учените в ИМК, са свързани с този приоритет. Получаването и изследването на нови материали с предварително зададени свойства има пряка връзка и с всички останали приоритети на стратегията, затова част от дейностите и резултатите са посочени в другите три приоритета на НСРНИ 2020.

Дейностите включват израстване на нови материали (оптични крис-тали, неорганични съединения, метал-органични съединения, малки ор-ганични молекули, зеолити, зеолитоподобни материали, слоисти двойни хидроксиди, и др.), модифициране на природни материали c оглед подобря-ване на техните сорбционни, каталитични и други свойства.

Резултатите са свързани с посочване областите за евентуално при-ложение на новополучените материали на база определяне фазов състав, кристална структура, структурни нееднородности и различни параметри и свойства. Потенциал представлява направлението за синтез на нови ми-нерални фази и материали въз основа на отпадни продукти, вече детайлно характеризирани в ИМК.

Приоритет 4: Културно-историческо наследствоКъм това направление са задачите, свързани с изследванията на архео-

ложки обекти.Дейностите включват изследване на локални нееднородности и

археометрични параметри на благороднометални минерализации от ме-

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тасоматити и разсипи в Източни Родопи; фазов и химичен състав на архео-ложки артефакти за целите на реставрация, консервация и опазване на културното историческо наследство; както и отделни аналитични изслед-вания на мазилки и пигменти от тракийски гробници, съвместно с екипи от археолози.

Резултатите са: Изяснен е съставът (минерали, неорганични и органични добавки) на

пигменти и мазилки от археоложки обекти с национална значимост.Определени са предполагаемите райони, които са източник на суро-

вините за производство на изследваните археоложки обекти (пигменти, ма-зилки, керамики и др.) въз основа на състава на материалите и геоложкия строеж на разглежданите райони, наличието на рудни находища и рудопро-явления, древния добив и металургична дейност.

Въпреки че, в посочените в НСРНИ 2020 приоритети няма таки-ва, свързани с геология и полезни изкопаеми, убеждението на учени-те в института е, че това са изследвания, които трябва да продъл-жат, защото са особено важни за изучаването на моделни системи на дълготрайни процеси в геоложки времеви период (милиони годи-ни) и имат пряко отношение към решаването на различни екологич-ни проблеми.

Дейности: Изследване на минерали и минерални тела, формиращи литосферата, с оглед дефиниране на техния фазов състав, структурни вза-имоотношения, процеси на образуване и изменение, закономерности.

Резултати: Разработки на геолого-генетични модели и критерии за прогнозиране, търсене и проучване на находища на минерални суровини.

Заслужават внимание описаните нови за България минерали: мелилит, есенеитов тип клинопироксен, политипът воластонит-2М и богат на титан андрадит, като част от дисертация, защитена в института през 2015 г.

Продължава надграждането на библиографската картотека, (над 3300 записа), посветена на изучаването на минералното разнообразие на Бълга-рия – перспективна база данни за изграждане на продукт от типа – Енцикло-педия на Минералите в България.

1.3. Полза за обществото от извършваните дейности

Ползата за общество е пряко свързана с осъществените през годината изследователски, образователни и експертни дейности и постигнатите ре-зултати от тях.

Въпреки че в института няма реализиран на пазара готов продукт, съ-ществуват перспективи някои от разработките да достигнат до такава фаза при наличие на интерес и подходяща форма на финансиране. Перспективи съществуват в следните приоритетни направления:

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Приоритет 1: Енергия, енергийна ефективност и транспорт: раз-витие на зелени и екотехнологии

Резултатите от проекта „Минералогия, геохимия и екологосъобразно приложение на твърди горива и техните отпадни продукти от термична пре-работка“, изпълняван в ИМК-БАН, представляват научна основа за устано-вяване, прогнозиране, ограничаване, елиминиране и решаване на редица проблеми, свързани с: (1) подобряване качеството на твърдите горива; (2) избор на подходящ технологичен и екологосъобразен процес за тре-тиране на съответния тип гориво; (3) търсене на решения за комплексно, ефективно, безотпадно и екологосъобразно оползотворяване на твърди от-падъци от изгаряне, (4) ограничаване на вредното за околната среда въз-действие на използваните горива.

Изясняването на предимствата и недостатъците на биомасата в срав-нение с тези на въглищата е от полза за създаването на нови или модифи-цирането на вече съществуващите технологии за производство на енергия от твърди горива.

Получените резултати ясно посочват необходимостта от дискусия за оценка на устойчивите ресурси от биомаса за производството на биогорива и биохимикали във връзка с глобалните климатични промени и екологични въздействия.

Изследванията на пепели и шлаки от изгаряне на мазут в ТЕЦ, пред-ставя тези отпадъчни продукти като потенциална суровина за: (1) извличане на ценни елементи (V, Ni, Mo, Zn, Ag, Cd, Cr, Cu, Pb, Fe, и др.); (2) добавки при производството на строителни материали, стабилизатори на почви и др.; (3) производство на активирани въглеродни материали или като гориво за повторно изгаряне в ТЕЦ.

Приоритет 2: Здраве и качество на живота, биотехнологии и еколо-гично чисти храни

Данните, получени по проект CheRRIE, са предоставени на Национа-лен център по радиобиология и радиационна защита и ще намерят отра-жение в Националната програма за намаляване въздействието на радон в сгради върху здравето на българското население 2013–2017 г., чиято инсти-туционална рамка и изпълнители включват различни държавни институции, Камарата на архитектите и Камарата на инженерите в инвестиционното проектиране.

Приложение на български природни зеолити за пречистване на води с високо и ниско съдържание на елементите цезий и стронций, класифицира-ни като „опасни елементи“ (“hazardous elements”).

Въз основа на детайлните изследванията върху структурното състоя-ние и изменение на денталния апатит при различни въздействия може да се прецизира работата на денталните лекари за по-качествено и безопас-но лечение.

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За института особено важно е стартирането на ново за страната на-правление в областта на кристалографията (биологична кристалография), свързано с определяне структурата на големи молекули (белтъци, ДНК).

Приоритет 3: Нови материали и технологииЕкологичен синтез на материали с полезни свойства за опазване на

околната среда. Получаването на зеолит Х от летлива пепел на ТЕЦ, по-казващ висок адсорбционен капацитет по отношение на въглеродния ди-оксид, би имало двоен екологичен ефект: от една страна, утилизация на летлива пепел от ТЕЦ, а от друга – използване на получения продукт за улавяне на СО2.

Оптимизиране на условията за получаване на порести и слоисти мате-риали с подобрени сорбционни, йонообменни и каталитични свойства.

Приоритет 4: Културно-историческо наследствоОт национално значение са проведените археоминераложки изслед-

вания, които подпомагат изучаването, съхраняването и популяризиране-то на културно-историческите ценности на страната. Например в резултат на установеното от колектив на НАИМ и ИМК, че Ада тепе (Крумовград) е най-старият рудник в Европа за добив на злато от коренни скали, той се превръща в международен феномен. По този повод са създадени няколко документални филма, включително и от Nat. Geog. Channel и предстои из-граждането на музей на открито в района на Крумовград.

Продължава надграждането на библиографската картотека, (над 3300 записа), посветена на изучаването на минералното разнообразие на Бълга-рия – перспективна база данни за изграждане на продукт от типа – Енцикло-педия на Минералите в България.

Резултатите, получени през 2015 г. по тематиките, свързани с изучава-не на минералното разнообразие, ще помогнат за установяване на нови за страната минерали, индикативни за специфични условия на минералообра-зувателни процеси и по-ефективно търсене и проучване на находища на ниско сулфидни руди на златото, среброто и др.

Педагогическата и образователна дейност, осъществявана в ИМК е в съответствие с основната идея на Национална стратегия за раз-витие на научните изследвания 2020, че образованието, научните изслед-вания, технологичното развитие и иновациите са основата за постигане на динамичен и устойчив икономически растеж. През изминалата година уче-ните от института обучаваха млади специалисти от различни звена на БАН и българските университети, провеждаха специализирани курсове, органи-зираха и бяха лектори в международни летни училища. Поради нарастване на средната възраст на изследователите и пенсиониране на висококвали-фицирани специалисти през последните няколко години обучението на док-торанти и млади изследователи беше засилено целенасочено. В резултат

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на това през 2015 година двама от отчислените с право на защита докто-ранти бяха назначени на работа в ИМК, а други двама в началото на 2016 г. Тематиките и на двамата редовни докторанта в института съответстват на приоритетни направления от НСРНИ2020.

Експертната дейност, осъществена от служителите в ИМК за нуж-дите на държавните органи (Митница), ВУЗ и българския бизнес (Асарел Медет АД, Дънди Прешъс Металс, Барит Майнинг ЕООД и др.) несъмнено допринася за ефективното решаване, както на теоретични, така и на чисто практически задачи и технологични проблеми.

1.4. Взаимоотношения с институции

Научната и научно-приложната дейност на ИМК се извършва в сътруд-ничество с редица български фирми, научни институти от БАН, Универси-тети, както и с някои държавни институции. В института се обучават док-торанти и от други институти или университети (курсове по Инфрачервена спектроскопия, вибрационна спектроскопия, рентгено-дифракционни мето-ди, термични методи и т.н.). Традиционно е научното ни сътрудничество, от-разено в публикациите на ИМК, с колеги от други институти на БАН – Инсти-тута по обща и неорганична химия, Институт по органична химия с център по фитохимия, Института по катализ, Института по полимери, Института по молекулярна биология, Института по физикохимия, Институт по физиология на растенията и генетика, Геологически Институт и т.н., както и с повечето български Университети: Минно-геоложки Университет, СУ „Св. Климент Ох-ридски“ – Факултет по химия и фармация, Физически факултет; МУ – София Факултет по фармация, Факултет по дентална медицина, Университет по хранителни технологии Пловдив и други.

За времето на провеждането си, обхващащо почти цялата 2015 г., стра-тегическият проект CheRRIE допринесе за създаване на нови партньорски взаимоотношения и връзки с международни и български обществени орга-низации, някои от които обещават активно сътрудничество в бъдеще. Сред тях са: Университетът Аристотел в Солун (Гърция), катедра „Инженер-на химия“; Технологичен институт ATEI в Солун (Гърция); Камара на архитектите в България и др. В хода на провежданите изследвания по проекта бяха установени тесни връзки с две звена на Министерство на здравеопазването, а именно: Национален център за обществено здра-ве и анализи и Национален център по радиобиология и радиационна защита (НЦРРЗ). Сътрудничеството с последното звено и по-конкретно из-ползването на техни консумативи (датчици), техника, инструкции и методика за пасивно замерване на газ радон в затворени помещения, както и пълното предоставяне на получените резултати превърнаха част от дейността по проект CheRRIE в пилотен проект по Националната програма за намаля-ване въздействието на радон в сгради върху здравето на българско-

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то население 2013–2017 г., чиято институционална рамка и изпълнители включват: Национален координационен съвет (НКС), създаден от министъ-ра на здравеопазването: МЗ, МОСВ, МРР, МИП, МТСП, МФ, МОН, АЯР, Ка-мара на архитектите, Камарата на инженерите в инвестиционното про-ектиране. За мащабите на проект CheRRIE говорят и установените връзки между изследователските екипи и представителите на местните власти в Южна България и по конкретно с кметствата и общините в редица насе-лени места от Областите, прилежащи до границата ни с Гърция, а именно: Област Благоевград (Благоевград, Симитли, Сандански, Мелник, Гоце Дел-чев, Банско, Елешница, м. Предела); Област Хасково (Хасково, Минерални бани), Област Кърджали (Кърджали); Област Смолян (Златоград). От стра-на на местните власти бе ползвана логистика за обектите на изследване, а обратно им бяха предоставени резултати, касаещи възможни рискове за здравето на населението, инструкции за безопасност и друга информация по темата на проекта. В хода на реализация на заплануваните дейности по проект CheRRIE, взаимодействие, подкрепа и съдействие бяха получени от редица бизнес-ориентирани организации, компании и т.н., като: РОФА Лабораторис енд Проусес Аналайзърс, Корнойбург, Австрия, „Це Це ЕС България“ ООД, „Аква Тера Консулт“ ЕООД, „Ай Ти Стаф“ ЕООД, Балкански научно-образователен център по екология и опазване на околната среда – София (БНОЦЕООС-София), Интер Травел Партнерс ЕООД, „Национална оценителска компания“ ЕООД, „Bright VD“ ЕООД, (B3.13.03/28.02.2014 CheRRIE Chemical and Radiological Risk in the Indoor Environment).

Изследването на хибридни неорганично-полимерни материали на ос-новата на зеолит-полиимидни вещества се извършва съвместно с Институт по макромолекулна химия, Яш, Румънска Академия на науките (Зеолит-полиимидни хибридни материали със зададени свойства).

Работата по синтез и характеристика на функционални материали с тетраедрично-октаедрични структурни скелети се осъществява съвместно с Институт по неорганична химия на Чешка академия на науките, а из-следванията по проект „Получаване на органо-минерални подобрители за почви“ съвместно с Естонска Академия на науките.

1.5. Общонационални и оперативни дейности, обслужващи дър-жавата

1.5.1. Практически дейности, свързани с индустрията, енергетика-та, околната среда, селското стопанство, национални културни ин-ституции и др. (относими към получаваната субсидия)

Потребители на научни продукти, експертен капацитет и аналитични изследвания на ИМК през 2015 г. бяха повече от двадесет държавни ин-

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ституции, наши и чуждестранни индустриални предприятия и организации. Общата стойност на реализираните продукти възлиза на 15 245 лв. ИМК участва и в организацията и управлението на редица дейности с национал-на значимост:

ИМК е седалище на Българско Кристалографско Дружество (БКД), http://www.bgcryst.com/. Налице е продуктивно и ползотворно взаимодейст-вие между институти на Българска академия на науките и юридическо лице с нестопанска цел. От 10 до 15 учени-изследователи от звеното поддържат редовно или периодично членството си в Дружеството, а останалите члено-ве са колеги от други институти в БАН, български и чужди университети и научни институции. БКД редовно организира научни форуми (симпозиуми, семинари, срещи, школи и пр.), които дават отлична възможност за изява и популяризиране дейността на учените в България. През 2015 г. в резултат на усилията на учените от БАН и в частност от ИМК се проведе първата за България и Югоизточна Европа Международна школа по метод на Ритвелд (метод за решаване на различни кристалохимични и микроструктурни за-дачи, свързани с изучаване на кристалното вещество въз основа на данни, получени за него от прахова рентгенова дифракция) http://www.bgcryst.com/RS2015/. Събитието предизвика интерес и активност на 61 регистрирани участници от 16 страни. Инициативата, беше припозната и подкрепена и от Министерството на образованието и науката, Европейската криста-лографска асоциация и Международния кристалографски съюз, които отразиха събитието и в своите месечни бюлетини.

През годината се проведе и втората балканска школа по фундаментал-на кристалография през месец юли в Истанбул, Турция http://www.cryst.ehu.es/crystr2015/ Съорганизатор на училището е и БКД, а двама от учените в ИМК, бяха поканени лектори. Проведеният научен форум следва хроноло-гично първото за Балканите подобно училище, организирано от БКД и про-ведено в Гюлечица, България през 2012 година. Участието на голям брой млади учени от България в тези обучения по кристалография нееднозначно показва, че усилията на учените от БКД (основно от институти на БАН) за предаване на знанията и уменията в областта на кристалографията са нуж-ни и оценени от нашите млади колеги.

Много от учените в ИМК са съпричастни към дейността на Българското геологическо дружество (БГД). Редовни членове на БГД са 24 учени и слу-жители от звеното. В проведената Юбилейна национална конференция с международно участие „Геонауки 2015“ от ИМК участваха 12 учени, които изнесоха 10 научни доклада със свои резултати, постигнати в областта на минералогията.

ИМК е научно средище на българската минераложка общност, обеди-нена в Българското минералогическо дружество, чиято Интернет страница (http://www.clmc.bas.bg/Minsoc/) е част от нашия уебсайт. В института се про-веждат регулярните сбирки на дружеството, където наши и чужди учени док-

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ладват и дискутират актуални резултати от научни изследвания в областта на минералогията и минералните ресурси.

ИМК е хранител на базовата академична колекция „Минералното раз-нообразие на България“, съдържаща уникални образци от минералното богатство на страната и специализирани работни материали от изследо-вателските проекти и задачи на изследователите-минералози от института; активен участник в националните и международните форуми на издигнатата от Националния музей „Земята и хората“ Софийска инициатива „Съхра-няване на минералното разнообразие“, чиято основна цел е да опази за бъдещите поколения минералното богатство на Земята.

1.5.2. Проекти, финансирани от национални институции (без ФНИ)

През 2015 г. учените от ИМК работиха по 2 проекта, финансирани от национални институции:

„Химичен и радиологичен риск в затворена среда“ (Chemical and Radiological Risk in the Indoor Environment – CheRRIE) се осъществи с финан-совата подкрепа на Програмата за европейско териториално сътрудничест-во „Гърция-България 2007–2013“. Основната цел на проекта е разработване на ефективен механизъм за защита на общественото здраве от химични и радиологични опасности в закрити помещения в трансграничните реги-они, участващи в програмата за междурегионално сътрудничество. Осъ-ществени са измерване на радиационния фон и възможните радиационни и химични замърсявания в сградния фонд на моделните региони; оценка на опасността за здравето на населението от излагане на йонизиращо лъчение и токсични химикали от структурите със строителни материали; създаване на база данни за сградния фонд в регионите, която да бъде използвана от строители, търговци, производители на строителни материали, експерти и държавни органи с оглед предотвратяването на потенциални опасности за здравето на населението.

„Подкрепа за развитието и реализацията на докторанти, постдокто-ранти и млади учени в областта на материалознанието, минералогията и кристалографията“ (BG051PO001-3.3.06-0027), който се осъществи с фи-нансовата подкрепа на Оперативна програма „Развитие на човешките ре-сурси“, съфинансирана от Европейския социален фонд на Европейския съюз. В него партньор на ИМК е Катедра „Органична химия“ към Факултета по Химия и Фармация на Софийския Университет „Св. Климент Охридски“ (ФХФ-СУ). Основната цел на проекта е да съдейства за научното развитие на докторанти, постдокторанти и млади учени с интереси в областта на ма-териалознанието, минералогията и кристалографията, за повишаване ка-чеството на научните изследвания и подобряване на условията за тяхната професионална реализация за увеличаване на приноса на тези учени в из-граждането на икономика, основана на знанието. През 2015 г. бяха органи-зирани 5 лекционни курса по предварително уточнени тематики в сферата

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на минералогията, кристалографията и материалознанието, а целевата гру-па от млади учени и докторанти получи чудесната възможност да предста-ви резултатите от своите изследвания на международни научни форуми в страната и чужбина.

2. Резултати от научната дейност през 2015 г.

Резултатите от научноизследователската дейност на института са от-разени общо в 67 научни публикации. От тях в списания с импакт-фактор са общо 38, като 32 са отпечатаните и 6 под печат, 54 от общите публикации са в реферирани сборници, а 13 са в нереферирани и индексирани списания и сборници. Учените от института са представили 58 доклада на 28 между-народни научни форума.

През изминалата година 224 публикации на учените от института са цитирани общо 875 пъти. С отчитане на условията и възможностите за на-учната дейност в БАН и страната като цяло, получените резултати са много добри, особено за малък институт, като ИМК с двадесет и седем души ака-демичен състав.

Налице е слабо нарастване на общия брой публикации в сравнение с 2014 г. (за сравнение 60 – 2014 г., 98 – 2013 г., 71 – 2012 г., 103 – 2011 г., 99 – 2010 г., 94 – 2009 г., 100 – 2008 г., 92 – 2007 г.) и на броя публикации с импакт фактор (33 за 2014 г.).

На фона на запазената научна продуктивност за 2015 г. ясно се очерта-ва нарастването на броя на цитиранията, които за 2015 г. са 875 (за срав-нение съотношението статии/цитати е: 2014 г. 176/696; 2013 г. – 230/728; 2012 – 192/567; 2011 – 158/271). Това е един много добър атестат за качеството на нашата научна продукция и нейната продължителна актуалност и значимост в професионалните научни общности.

2.1. Най­важно научно постижение

За 2015 г. година могат да бъдат формулирани научни постижения и в двете основни научни направления, по които се работи в института, а имен-но: минералогия и кристалография.

МинералогияЗа пръв път в България са описани минералите: мелилит, есенеитов

тип клинопироксен, политипа воластонит-2М и андрадити с високо съдър-жание на титан. Находките им са индикация за високотемпературен генезис, включващ магмен и последващ постмагмен етап. Установен е също така и рядко срещания в световен мащаб Te-съдържащ канфелдит (Ag8Sn(S,Te)6) – нов минерал за България от епитермално златно-сребърно рудопроявле-ние Черешките (Ц. Родопи). Описани са нови за България разновидности на минерала монацит-(La) и монацит-(Nd), обогатени на Тh, установени в образци от Игралищенския гранитен плутон (ЮЗ България).

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Изследванията са осъществени изцяло в ИМК от научен колектив в състав: доц. д-р М. Тарасов, доц. д-р Е. Тарасова, д-р Я. Цветанова, доц. д-р Р. Титоренкова, д-р М. Кадийски, д-р Валентин Ганев, проф. д-р О. Петров и Е. Анастасова.

Основен принос: Установени и описани са пет нови за България мине-рала и минерални разновидности.

Публикации:Tzvetanova, Y., Tarassov, M., Ganev, V., Piroeva, I. 2015. Ti-rich andradites in skarns

from Zvezdel-Pcheloyad ore deposit, Eastern Rhodopes, Bulgaria. – In: Short Com-munications of „Geosciences 2015“, Jubilee National Conference with International Participation „90 Years Bulgarian Geological Society“, 41–42 (ISSN 1313-2377)

Tarassov, M., Anastasova, E., Tarassova, E. 2015. First data on monazite with а negative Ce anomaly from the Igralishte pluton, Southwestern Bulgaria. – In: Short Com-munications of „Geosciences 2015“, Jubilee National Conference with International Participation „90 Years Bulgarian Geological Society“, 35–36 (ISSN 1313-2377).

Tarassova, E., Tarassov, M. 2015. New data on Au-Ag mineralization in the Chereshkite ore occurrence, Central Rhodopes, Bulgaria. – In: Short Communications of „Ge-osciences 2015“, Jubilee National Conference with International Participation „90 Years Bulgarian Geological Society“, 37–38 (ISSN 1313-2377).

Цветанова, Я. 2015. Кристалохимични и структурни характеристики на минерали от скарните в Звезделския плутон. Дисертация за получаване на ОНС „Доктор“, БАН, София, 183 с.

КристалографияИМК подкрепя предложението на ИОХЦФХ за съвместно научно пости-

жение:Конформационното поведение на 3-метил-4-(4-метилбензоил)-1-фе-

нил-пиразол-5-он е изследвано с комбинация от монокристална рентгено-

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ва дифрактометрия, ЯМР в разтвор и в твърдо състояние и с квантово-хи-мични изчисления (DFT) в газова фаза. Съединението може да съществува в 4 различни тавтомерни форми в зависимост от кето-енолната тавтоме-рия на пиразолоновата ацилна група и на ацилния заместител в позиция 4 на пръстена. Показано е, че в разтвор са предпочетени кето-енолните тавтомери с вътрешномолекулна водородна връзка. Кристализационни-те експерименти обаче доведоха да изолиране на пет различни кристал-ни фази: три жълти и две бели. Изследванията с монокристална рентге-ноструктурна дифрактометрия и ЯМР в твърдо състояние показаха, че са получени три дезмотропа на съединението, два от които под формата на два различни конформационни полиморфа. Теоретичните пресмятания са в пълно съответствие с наблюдаваните експериментални резултати.

Разработката е резултат от съвместните усилия на експерти от четири различни специалности с ръководител доц. Ваня Куртева.

Основен принос: За първи път в научната литература се докладва за изолиране на повече от два дезмотропа на дадено съединение.

Kurteva, V., B. Shivachev, R. Nikolova, S. Simova, L. Antonov, L. Lubenov, M. Petrovac, 2015. Conformational behaviour of 3-methyl-4-(4-methylbenzoyl)-1-phenyl-pyrazol-5-one: a sudden story of three desmotrops. – RSC Adv. 2015, 5, 73859–73867.

2.2. Най­значимо научно­приложно постижение

Изследван е сорбционния процес на стронций при използване на бъл-гарски природен клиноптилолит. Установени са оптималните параметри за pH, време на контакт и концентрация на стронциеви йони по време на сорбционния процес, който протича бързо и се описва с дифузионни модели, базирани на три алгоритъма (Langmuir, Freundlich и Dubinin–Raduchkevich). Изследването дава добри възможности за евтини приложения при пречист-ване на питейна и индустриална вода (от ядрената енергетика) от радиоак-тивен стронций (89Sr).

Lihareva, N., O. Petrov, Y. Tzvetanova, M. Kadiyski, V. A. Nikashina. 2015. Evaluation of the possible use of a Bulgarian clinoptilolite for removing strontium from water media. – Clay minerals, 50, 55–64.

3. Международно научно сътрудничество

ИМК си сътрудничи с научни институции извън страната в рамките на съвместни проекти, финансирани по европейски програми, както и проек-ти по двустранни спогодби на БАН. ИМК кани и международно признати учени, като гост-лектори и консултанти по различни проблеми, свързани с осъществяване на научноизследователския план на института. Наши из-следователи също са канени като лектори в чужди университети.

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През годината по покана на ИМК в рамките на двустранното сътрудни-чество с Румънската академия на науките в института бяха изнесени ака-демични лекции от колеги от Института по макромолекулярна химия, Яш, Румънска академия на науките.

Поканен по проект „G-quadruplexes – Ligand Interactions“ експерт от син-хротронния център на университета в Станфорд SLAC National Accelerator Laborator, проведе софтуерно обучение за отдалечен достъп до апарати в SLAC и изнесе семинар по техники за разшифроване на структурата на макромолекули (белтъци и ДНК). В резултат на това сътрудничество в нача-лото на 2015 г. бе одобрен проект за осигуряване на апаратно време за из-мерване на образци в линейния ускорител в Станфорд (Калифорния, САЩ, Stanford Linear Accelerator Center – SLAC) (grant: 4B60).

За осъществяване на съвместни разработки в института гостува колега от Чешката академия на науките.

Учени от института бяха гост-професори във факултета „Науки за зе-мята“ към Хамбургския университет (Faculty of Earth Sciences, University of Hamburg) и Университета Миньо, Гимараеш, Португалия (Department of Physics, University of Minho, Gimaraes, Portugal) по покана на съответните университети.

Финансиран от немската служба за академичен обмен DAAD наш учен работи по съвместен проект в лабораториите на Университета Хамбург.

Изследователи от ИМК представиха резултати от изследванията си на международни научни форуми в България и чужбина. Разходите за участието на докторантите в международни и национални научни форуми се поемаха от проект по ОП „Човешки ресурси“ или в някои случаи бяха фи-нансирани от организаторите, а тези на учените по други финансово обез-печени проекти или от техни лични средства. Международната активност през 2015 г. на ИМК в този аспект може да бъде оценена като много добра.

Значим в международен план е проекта „Химичен и радиологи-чен риск в затворена среда“, (Chemical and Radiological Risk in the Indoor Environment – CheRRIE). Той се осъществява с финансовата подкрепа на Програмата за европейско териториално сътрудничество „Гърция-България 2007–2013“.

Проектът CHERRIE имаше за цел да въведе ефективен механизъм за защита на общественото здраве от химични и радиологични опасности в за-крити и застроени сгради в транс-граничните региони, участващи в програ-ма за междурегионално сътрудничество Гърция – България. ИМК е водеща организация в проекта в сътрудничество с двама български партньори и 4 партньорски организации (два университета и две браншови организации) от Гърция. Получените резултати от анализите на химични и радиоактивни замърсители, както и направените сравнителни анализи и експертни оценки за здравния риск дават възможност да бъдат формулирани следните кон-статации, изводи и препоръки:

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• Получени са данни за качеството на въздуха в различен тип сграден фонд от четири погранични области между България и Гърция;

• Установено е, че измерените концентрационни натоварвания на хи-мични и радиоактивни замърсители в изследваните помещения са по-ниски през летния период.

• По-високи концентрации от групата на алифатните замърсители (преди всичко формаладехид и ацеталдехид) са установени в наскоро ре-новирани обекти;

Работен семинар на участници в проекта с представители на заинтересованите партньори

• В районите с по-висок естествен радиационен фон са установени и по-високи стойности за съдържанието на радон в помещенията;

• За установяване на очакваното затихване на емисиите в помеще-нията с ново обзавеждане и ремонтни строителни дейности се препоръчва провеждане на последващи контролни измервания;

• Като превантивна мярка се препоръчва компетентните органи да ак-тивизират извършвания качествен аналитичен контрол върху появяващите се на пазара нови строителни материали и изделия и особено внасяните материали и изделия от страни извън границите на ЕС, като основно внима-ние се обърне на генерирането на формалдехид, ацеталалдехид и радон.

4. Участие на ИМК в подготовката на специалисти през 2015 г.

Общият брой на докторантите през 2015 г. беше 9, като 7 от тях редов-на докторантура, 1 на самостоятелна подготовка и 1 задочен. През 2015 г. един от докторантите защити докторска дисертация, а четирима са отчисле-ни с право на защита.

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В института е изградена необходимата материална база за обучение и изследователска дейност на докторантите. На всеки от тях е осигурено работно място с персонален компютър, свързан в локална мрежа и със ско-ростен интернет достъп, библиотека с богат набор от научна литература и периодика в областта на минералогията, кристалографията и минералните суровини, както и възможности за ползване на специализирани собствени и чужди бази данни. Наред с това се осигурява достъп до специализира-ните библиотеки на другите институти на БАН и на Централната библио-тека. За всички специалисти и докторанти е обезпечено ползването на лабораторната техника, както и съответните информационни и софт уерни програми за обработка на резултатите от изследователската работа. Всич-ки условия за реализация на планираните работи са налице. Центърът за обучение на БАН осигурява чрез своите специфични звена подготовката по чужди езици и по компютърни информационни технологии. ИМК пред-лага на докторантите си необходимата презентационна техника и конфе-рентна зала за периодични докладвания на резултатите от тяхната дейност. Изключително важен за реализирането на докторантските изследвания и участия в научни форуми бе приключилият през годината проект „Подкрепа за развитието и реализацията на докторанти, постдокторанти и млади уче-ни в областта на материалознанието, минералогията и кристалографията“ (BG051PO001-3.3.06-0027).

През изминалата година учени от ИМК бяха хонорувани преподаватели по няколко учебни програми за студенти в Минно-геоложки университет „Св. Иван Рилски“, Нов Български Университет, Софийски университет „Климент Охридски“.

И през 2015 г. учените от ИМК проведоха специализирани курсове към ЦО-БАН.

Участието на учените от ИМК в обучението на студенти и докторанти през 2015 г. е: 205 ч. лекции и 165 ч. упражнения. За сравнение в предход-ните години то е било, както следва: 2014 г. – 259 ч. лекции и 362 ч упраж-нения, 2013 г. – 320 ч. лекции и 228 ч. упражнения, 2012 г. – 164 ч. лекции и 68 ч. упражнения, 2011 г. – 355 ч. лекции и 110 ч. упражнения; 2010 г. – 131 ч. лекции и 44 ч. упражнения; 2009 г. – 201 ч. лекции и 99 ч. упражнения; 2008 г. – 249 ч. лекции и 292 ч. упражнения. Учените от института са търсени лектори и преподаватели, но тенденцията за общо намаляване на броя на студен-тите в университетите (особено в сферата на природните науки) и острата финансова криза са причини за непълната реализация на потенциала им в това отношение.

5. Експертна дейност

Експертната дейност на учените от ИМК през 2015 г. включваше учас-тия в организационни комитети, управителни органи на дружества и екс-пертни съвети; участие в научни журита като членове и председатели; в

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редакционни колегии на престижни международни списания и сборници от конференции; рецензии на статии към международни списания и проекто-предложения към ФНИ.

Учени от ИМК председателстват Българското кристалографско дру-жество (БКД), както и Българското геоложко дружество (БГД), а други са изборни членове, участващи в ръководството на тези дружества.

Изтъкнати специалисти от ИМК са членове на управителните органи на Международната асоциация по природни зеолити, на Техническа Група Въглища 2 (TGC 2 – “Coal preparation, conversion and upgrading”) към Изсле-дователския Фонд за въглища и стомана (RFCS) на Европейската комисия. Други учени членуват в Националния комитет по геология към Международ-ния съюз по геологически науки (IUGS) и Националния комитет по геодезия и геофизика към Международния съюз по геодезия и геофизика (IUGG), в ръководството на Хумболтовия съюз в България (НПО).

В редакционните колегии на престижните международни списания Fuel (“Elsevier”), Coal Combustion and Gasification Products (“Allen Press”), и Waste and Biomass Valorization (“Springer”), в изданията на БАН списания „Геохимия, Минералогия и Петрология“, “Geologica Balcanica”, в нацио-налното списание „Списание на БГД“ и сборника с научни съобщения от национална конференция с международно участие „Геонауки 2015“ участ-ват учени от ИМК.

6. Иновационна и стопанска дейност и анализ на нейната ефективност

Институтът не дава под наем помещения и материална база. Въпреки че ИМК не развива внедрителска и стопанска дейност в чист вид, то пора-ди високата интердисциплинарна квалификация и съвременна аналитична апаратура, институтът е търсен партньор при решаването на сложни науч-но-приложни и технологични проблеми в областта на добива и ефективното оползотворяване на минерални ресурси, характеризирането на новосинте-зирани материали и различни промишлени продукти. Доказателство за това са многобройните потребители на научни продукти и аналитични изследва-ния на ИМК през 2015 г. от индустрията, институтите на БАН и университети-те. Анализът на тези потребители показва, че индустриалните предприятия и малки частни фирми в страната не могат да се ангажират с дългосрочно сътрудничество с научни организации и търсят експертизата на нашите спе-циалисти само за неотложни анализи, в случай на временни технологични проблеми или за експертно-консултантска дейност.

7. Кратък анализ на финансовото състояние на ИМК през 2014 г.

Финансовата рестрикция на бюджета на БАН (и респективно на ИМК), започнала още през 2010 г., продължи и през изминалата 2015 г. На базата

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на въведения подход за диференцирано институционално финансиране на институтите на Академията съобразно резултатите от дейността бю-джетната субсидия на ИМК е 525 719 лв. спрямо предходната година от 536 781 лв. Около 95% от бюджетната субсидия бе изразходва-на само за заплати, стипендии и осигуровки. Единствено собствените приходи на института позволиха да се поемат най-необходимите разходи за издръжка и в крайна сметка – да се осигурят сравнително нормални усло-вия за изпълнението на изследователските проекти. Средната брутна ме-сечна работна заплата в ИМК за 2015 г. е 768.00 лв.

Цялостната финансова дейност в ИМК е обхваната от системата за финансово управление и контрол както като вътрешно институтска нор-мативна база, така и като регулярна управленска и финансово-счетоводна практика. В института са приети и се изпълняват пълен набор от документи, регламентиращи счетоводната политика, документооборота, правилата за финансовата дейност и нейния контрол, системата за оценка на риска и т.н.

8. Издателска и информационна дейност през 2015 г.

От 1995 г. ИМК издава ежегодно годишен отчет на английски език, в който във вид на резюмета са представени основните резултати от изследо-вателската дейност през съответната година, пълен библиографски списък на публикуваните статии и изнесените доклади на различни прояви у нас и в чужбина, участието на учените в обучението на докторанти и подготовката

Статистически данни за посещаемостта на страницата на института

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на студенти, международното сътрудничество, структурата, апаратурното обезпечение, кадровото развитие на учените и др.

ИМК разполага с постоянен високоскоростен достъп до интернет, вътрешноинститутска мрежа и собствен уебсайт (www.imc.bas.bg). Обнове-ният през 2013 г. дизайн на уебстраницата на института, се актуализира регулярно и предоставя за публично ползване обширна информация за ор-ганизацията, структурата, персонала, публикационната активност, научните планове, финансираните проекти, предоставяните услуги, актуалните съби-тия, геоколекциите, провежданите обществени поръчки и др., както и пълно-то електронно издание на английски език на годишните отчети на института от неговото създаване до днес. Чрез сайта се осъществяват онлайн връзки със сродни научни организации и издания в областта на минералогията и кристалографията.

През 2015 г. посещенията на институтския уебсайт са нараснали с око-ло 90% в сравнение с предходната година.

9. Информация за Научния съвет на звеното

На 13.10.2015 г. изтече четиригодишният мандат на НС (2011–2015).Поради това през 2015 г. в ИМК има два легитимни НС.

Списъчен състав на НС до 13.10.2015 г.

№ по ред Име и фамилия Научно звание

и степенОсновна

месторабота

1. Огнян Петров – председател проф. д-р ИМК–БАН2. Юрий Кълвачев – зам.-председател доц. д-р ИМК–БАН3. Надя Петрова – секретар доц. д-р ИМК–БАН4. Желязко Дамянов (директор на ИМК) доц. д-р ИМК–БАН5. Борис Шивачев проф. д-р ИМК–БАН6. Вилма Петкова доц. д-р НБУ, ИМК–БАН7. Михаил Тарасов доц. д-р ИМК–БАН8. Росица Николова проф. д-р ИМК–БАН9. Станислав Василев проф. дгн ИМК–БАН

10. Христина Василева проф. д-р ИМК–БАН11. Владислав Костов доц. д-р ИМК–БАН12. Диана Нихтянова доц. д-р ИМК–БАН13. Евгения Тарасова доц. д-р ИМК–БАН14. Здравко Цинцов доц. д-р ИМК–БАН15. Олег Витов доц. д-р ИМК–БАН16. Любомир Димитров доц. д-р ИМК–БАН17. Росица Титоренкова доц. д-р ИМК–БАН18. Милен Кадийски гл. ас. д-р ИМК–БАН

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На 02.12.2015 г., след назначаване на нов директор на ИМК от 01.12.2015 г. бе проведено Общо събрание на учените, което избра нов НС (Протокол № 40/02.12.2015 г.).

Списъчен състав на НС към 31.12.2015 г.

№ по ред Име и фамилия Научно звание

и степенОсновна

месторабота

1. Михаил Тарасов – председател доц. д-р ИМК–БАН2. Юрий Кълвачев – зам.-председател доц. д-р ИМК–БАН3. Ирина Маринова – секретар доц. д-р ИМК–БАН4. Росица Николова (директор на ИМК) проф. д-р ИМК–БАН5. Борис Шивачев проф. д-р ИМК–БАН6. Огнян Петров проф. д-р ИМК–БАН7. Станислав Василев проф. дгн ИМК–БАН8. Христина Василева проф. д-р ИМК–БАН9. Владислав Костов доц. д-р ИМК–БАН

10. Диана Нихтянова доц. д-р ИМК–БАН11. Евгения Тарасова доц. д-р ИМК–БАН12. Желязко Дамянов доц. д-р ИМК–БАН13. Здравко Цинцов доц. д-р ИМК–БАН14. Луиза Димова доц. д-р ИМК–БАН15. Надя Петрова доц. д-р ИМК–БАН16. Росица Титоренкова доц. д-р ИМК–БАН17. Вилма Петкова доц. д-р НБУ, ИМК–БАН

10. Заключение

Представените в настоящия отчет данни и техният кратък анализ да-ват основание научноизследователската дейност на ИМК през 2015 г. да бъде оценена като успешна, въпреки финансовите и други затруднения. В условия на хроничен недостиг на средства научната работа се развиваше изцяло в рамките на предмета на дейност и тематичните приоритети на ин-ститута, както и в съответствие с политиките и програмите за изпълнение на стратегическите цели и приоритетни направления на БАН и Националната стратегия за научни изследвания 2020.

Научната продуктивност за 2015 г. се запазва в сравнение с предишна-та година, но рязко нараства броят на цитиранията, които за 2015 г. са 875. Това е един много добър атестат за качеството на научна продук-ция на ИМК и нейната продължителна актуалност и значимост в професионалните научни общности.

Директор: проф. д-р. Р. НиколоваНаучен секретар: доц. д-р. Р. Титоренкова

ANNUAL REPORT # 212015

INSTITUTE OF MINERALOGY AND CRYSTALLOGRAPHY “ACAD. IVAN KOSTOV”

BULGARIAN ACADEMY OF SCIENCES

Annual Report # 21, 2015Institute of Mineralogy and Crystallography “Acad. Ivan Kostov”, Bulgarian Academy of Sciences

Editorial Board:Prof. Dr. Rossitsa NikolovaAssoc. Prof. Dr. Vladislav Kostov-KytinAssoc. Prof. Dr. Rossitsa TitorenkovaAssoc. Prof. Dr. Mihail TarassovProf. Dr. Boris ShivachevAssoc. Prof. Dr. Zhelyazko DamyanovProf. Dr. Ognyan PetrovDr. Yana Tzvetanova

Address:Acad. G. Bonchev St., bl. 107, 1113 Sofia, BulgariaFax: (+359 2) 9797056 Phone: (+359 2) 9797055E-mail: mincryst@clmc.bas.bg

Web site: http://www.imc.bas.bg

© Institute of Mineralogy and Crystallography “Acad. Ivan Kostov”, 2015

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Contents

Introduction ....................................................................................................... 71. Trends of activity ......................................................................................... 13

1.1. Short history ........................................................................................ 131.2. Mission, areas of activities and priorities ......................................... 131.3. Relation with the research policies and programs .......................... 141.4. Research topics and capacity ............................................................ 151.5. Research infrastructure ...................................................................... 151.6. Benefits for Science, Business and Society ..................................... 16

2. Structure and Staff ...................................................................................... 182.1. Short description of the structural units .......................................... 192.2. Staff ...................................................................................................... 21

3. Main Equipment .......................................................................................... 254. Research Topics ......................................................................................... 26

4.1. Mineral Systems and Mineral Genesis .............................................. 261. Divergent drift of Adriatic-Dinaridic and Moesian carbonate

platforms during the rifting phase witnessed by Triassic MVT Pb-Zn and SEDEX deposits (Palinkaš L., Z. Damyanov, S. Šoštarić, S. Palinkaš, I. Marinova) ................................................ 26

2. Microstructural peculiarities of migmatisation in rocks of the Serbo-Macedonian Massif (L. Macheva) .......................................... 26

3. Geochemistry and geochronology of orthogneisses in Bode Saadu area, southwestern Nigeria and their implications for the Palaeoproterozoic evolution of the area (V. Ganev, C. Okonkwo) ..................................................................................... 28

4. Plate tectonic aspects of the Triassic carbonate-hosted stratiform-stratabound base-metal deposits in the Western Balkan, NW Bulgaria (I. Marinova, Z. Damyanov) ............................ 30

5. Brief comparative characteristics of minerals of the elements of the platinum group of sediments in Bulgaria (Z. Tsintsov) ............ 30

6. Ti-rich andradites in skarns from Zvezdel-Pcheloyad ore deposit, Eastern Rhodopes, Bulgaria (Y. Tzvetanova, M. Tarassov, V. Ganev, I. Piroeva) .................................................... 32

7. New data on Au-Ag mineralization in the Chereshkite ore occurrence, Central Rhodopes, Bulgaria (E. Tarassova, M. Tarassov) ...................................................................................... 34

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8. First data on monazite with а negative Ce anomaly from the Igra lishte pluton, Southwestern Bulgaria (M. Tarassov, E. Anastasova, E. Tarassova) .......................................................... 36

9. Formation of bonanza electrum from upward flow of boiling colloidal solution. Case study from the Khan Krum low-sulfidation gold deposit, SE Bulgaria (I. Marinova) ..................... 38

10. Bladed quartz texture and its relationship with the electrum mineralization in the Eocene, low-sulfidation Kuklitsa gold deposit, Krumovgrad goldfield, SE Bulgaria. Geological implications (I. Marinova) .................................................................. 39

11. Morphology and zoning of apatite crystals as indicator for magma mixing in Petrohan pluton, Western Balkan, Bulgaria (E. Tacheva, M. Ta rassov, E. Tarassova) ............................ 41

4.2. Environmental Mineralogy and Biomineralogy .............................................................................. 42

12. Mineralogy, geochemistry and environmentally safety application of solid fuels and their combustion and pyrolysis products (S. Vassilev, C. Vassileva) .................................................. 42

13. Risk management of Koprivlen landslides (M. Kadiyski, S. Sarov, G. Frangov, V. Kostov-Kytin, S. Sarova, V. Stoyanov, L. Macheva, V. Petkova, T. Papaliangas) ..................... 45

14. Synthesis of carbon dioxide adsorbents by zeolitization of fly ash (Yu. Kalvachev, D. Zgureva, S. Boycheva, B. Barbov, N. Petrova) ...................................................................... 46

15. Mechanical testing of acid treatment mixtures of biomass and poultry excrement with sulfuric acid (Е. Serafimova, S. Milenkova, V. Stoyanov, Y. Pelovski, V. Petkova) ......................... 46

16. IR and Raman micro-spectroscopy applied for studying structural characteristics of dental apatite (R. Titorenkova, D. Vasilev, G. Jegovа, M. Rashkova) ................................................ 47

17. Preparation and characterization of pastes based on calcium phosphate powders and sodium hyaluronate (R. Ilieva, O. Petrov, E. Dyulgerova) ................................................................. 48

4.3. Modeling and Modification of Mineral Systems ............................... 49

18. Transformation of perlite in phillipsite and its possible application as ion-exchanger (L. Dimitrov, N. Lihareva, O. Petrov) ..................... 49

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19. Thermal decomposition of zinc hydroxy-sulfate-hydrate minerals (N. Petrova, Ts. Staminirova, G. Kirov) ............................... 50

20. Compositional and structural study of partially exchanged on Na+, K+, Mg2+ and Ca2+ natural heulandite (L. Dimowa, I. Piroeva, S. Atanasova-Vladimirova, B. Shivachev, S. Petrov) .......................................................................................... 52

21. Structural and thermal transformations on high energy milling of natural apatite (V. Petkova, V. Koleva, B. Kostova, S. Sarov) ........................................................................................... 53

22. Thermal and kinetic characteristics of some oil shale samples (T. Ka ljuvee, R. Kuusik, V. Petkova) ................................... 55

4.4. Synthesis, Composition, Structure, and Properties of Minerals and New Materials ........................................................... 56

23. G-quadruplex DNA structures, crystallization remarks (L. Dimowa, H. Sbirkova, L. Tsvetanova, R. Nikolova, P. Hristoff, G. Radoslavov, T. Dou kov, T. Todorova, B. Shivachev) .................................................................................... 56

24. Structural characterization of ionexchanged ETS-4 (L. Tsvetanova, R. Nikolova) ............................................................. 57

25. Structural insights into M2O–Al2O3–WO3 (M = Na, K) system by electron diffraction tomography (I. Andrusenko, Y. Krysiak, E. Mugnaioli, T. Gorelik, D. Nihtianova, U. Kolb) ............................... 59

26. Electromechanical properties of polyimide composites containing titanium dioxide nanotubes (E. Hamciuc, M. Ignat, C. Hamciuc, I. Stoica, L. Dimitrov, Yu. Kalvachev, M. Olariu) ........... 61

27. Seed-assisted synthesis of nanosized Beta zeolite (B. Barbov, Yu. Kalvachev)................................................................ 62

28. Seed-mediated approach for the size-controlled synthesis of mordenite type zeolite from organic template free initial gel (T. Todorova, Yu. Kalvachev) ....................................................... 63

29. Comparison between thermal behaviour of γ-MnC2O4.2H2O in oxidative and inert media (B. Donkova, V. Petkova) ..................... 64

30. Impact of preparation method and chemical composition on physicochemical and photocatalytic properties of nano- dimensional magnetite-type materials (Z. Cherkezova-Zheleva, K. Zaharieva, M. Tsvetkov, V. Petkova, M. Milanova, I. Mitov) .......... 65

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31. Selective synthesis of monoglycerol oleate and investigation of its anti-wear performance as a friction modifier (S. Kеrekov, N. Gospodinova, L. Dimitrov, M. Nikolov) ......................................... 66

32. Mechanical tests of composite ceramic materials (Е. Serafimova, S. Milenkova, V. Stoyanov, Y. Pelovski, V. Petkova) ........................................................................................ 67

33. From kröhnkite- to alluaudite-type of structure: easy synthesis of novel sodium manganese sulfates with electrochemical properties in alkaline ion batteries (D. Marinova, V. Kostov, R. Nikolova, R. Kukeva, E. Zhecheva, M. Sendova-Vasileva, R. Stoyanova) ....... 67

4.5. PhD Theses .......................................................................................... 68

34. Crystal-chemical and structural characteristics of minerals from skarns in Zvezdel pluton (Y. Tzvetanova).......................................... 68

5. International Cooperation ........................................................................... 706. Visiting Scientists ....................................................................................... 707. Research Topics, Announced for International Partnership

Collaboration ............................................................................................... 718. Publications and Reports at Scientific Forums ........................................ 72

8.1. Published Articles and Reports (indexed in Web of Science, IF or SJR) ............................................. 72

8.2. Published Articles and Reports (not indexed in Web of Science, IF or SJR) ...................................... 74

8.3. Publications in press (indexed in Web of Science, IF or SJR) ............................................. 77

8.4. Publications in press (not indexed in Web of Science, IF or SJR) ...................................... 77

8.5. Reports at Scientific Forums ............................................................. 788.6. PhD Theses ......................................................................................... 82

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Introduction

In connection with its mission and basic subject of activity during 2015 the Institute of Mineralogy and Crystallography “Academician Ivan Kostov” (IMC) continued to give impact to the sustainable development of society and enrich-ment of the human knowledge in the fields of mineralogy and crystallography conducting profound multidisciplinary investigations on natural, technogenic, and experimentally modeled mineral systems and new materials.

IMC continues to strongly defend in front of the scientific community and the society as a whole its high evaluation status (A/A/A) for scientific impact and to prove its international competiveness in the sphere of its scientific priorities and fields of competence.

During 2015, the scientists in IMC worked for realization of research pro-jects, publication of the scientific results, participation in scientific conferences, education of young researchers, conducting of specialized workshops, and or-ganization of international summer schools. This activity is in direct correspond-ence with the National Strategy for development of the scientific studies (2020), which considers that education, scientific investigations, technological develop-ment and innovations stay in the background for realizing dynamic and sustain-able economic growth.

Due to the increased mean age of the staff and retirement of high-quality specialists IMC paid special attention during the last years for teaching of young researchers and PhD students. As a result, four of the PhD students were given the right to defend their thesis and were appointed for assistant professors in IMC.

Again, in 2015 IMC was a preferred partner for conducting an application-re-search and technological tasks connected with mining and effective utilization of mineral resources, characterization of new materials and various products from the mining, pharmaceutical, and food industries as well as the industry for build-ing and construction materials.

Combining the available in IMC analytical apparatuses the highly qualified experts realize detailed characteristics of the crystal structure, structural pecu-liarities (defects, phase transitions, heterogeneities, etc.), phase and chemical composition of practically all kinds of materials. The created in IMC laboratory equipment is unique for Bulgaria not only for its effectiveness but also with the fact that part of the equipment is the only one in Bulgaria.

For another consecutive year the maintenance of the laboratory complex, which serves for many institutes in the Bulgarian Academy of Sciences is a re-sponsibility only of IMC. All achieved by the researchers in IMC is with the big price of many efforts, restricted funds and financial shortcoming.

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Benefits for Society from the conducted activities in IMCThe impact for Society is directly related to the realized during 2015 inves-

tigations, teaching, and expert activities and the obtained results. Although IMC has not realized products on the market there exist perspectives for some of the achievements to reach such a stage in case of interest and financing. These per-spectives are in the following directions:

Priority 1: Energy, energetic effectiveness, and transport: Development of green ecotechnologies.

The results from the project “Mineralogy, geochemistry and environmentally safety application of solid fuels and their combustion and pyrolysis products”, conducted in IMC-BAS, represent a scientific background for establishment, prognosis, restriction, elimination, and solving of many problems connected with: (1) improvement of the quality of the solid fuels; (2)selection of suitable techno-logical and ecological process for treatment of the corresponding type of fuel; (3) selection of decisions for complex, effective, safety, end environmentally friendly utilization of solid waste after combustion; (4) restriction of the harmful impact of the used fuels for environment.

The studies on ashes and slag from burning of mazut in TEPs characterize these waste products as a potential raw material for: (1) extraction of valuable elements (V, Ni, Mo, Zn, Ag, Cd, Cr, Cu, Pb, Fe, etc.); (2) additions in construction materials, stabilizers for soil, etc.; (3) production of active hydrocarbon materials or used as fuel for secondary burning in TEPs.

Priority 2: Health and quality of life, biotechnologies and ecologically pure foodThe data, obtained in the frame of the project CheRRIE were officially de-

posited with the National Center of Radiation Prevention and will find place in the National Program for lowering the influence of radon in buildings on the health of the Bulgarian population 2013–2017. The institutional frame of this Program includes different state institutions, the Chamber of Architects and the Chamber of Engineers and Investment planning.

Utilization of Bulgarian natural zeolites for purification of water with high and low concentrations of the ions of cesium and strontium, which are classified as “dangerous elements” (“hazardous elements”).

Based on detailed studies on the structural state and changes in dental apatite caused by different factors there can be offered a more precise operation of the dental specialists for more qualitative and safety curing.

For IMC of special importance is the starting of a new for the country direc-tion in the field of crystallography – biological crystallography. This will be based on refinement of the crystal structure of giant molecules – proteins and DNA.

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Priority 3: New materials and technologiesEcological synthesis of materials with useful properties for preservation of

the environmentThe synthesis of zeolite X from fly ash from TEPS, displaying high sorption

capacity for carbon dioxide is with potential for double effect: from one side the utilization of fly ash and from another side the use of the obtained product for capture of CO2.

Optimization of the conditions for synthesis of porous and layered materials with improved sorption, ion exchange, and catalytic properties.

Priority 4: Cultural-historical heritageThe conducted archaeo-mineralogical studies have national significance

and the results support the study, preservation and popularization of the cultural-historical values of Bulgaria. For example, as a result of the found by the re-searchers of IMC that mine Ada Tepe (Krumovgrad) is the oldest mine in Europe for mining of gold from parent rocks this mine attains the character of internation-al phenomenon. Based on this, documentary movies were produced including Nat. Geog. Channel as well. Under construction is an open museum in the region of Krumovgrad town.

Continues the creation of a bibliographic file (above 3300 entries) devoted to the investigation of the mineral diversity of Bulgaria – perspective data base for creation of a product of the type – Encyclopedia of the Minerals in Bulgaria.

The results obtained in 2015 in the frame of themes connected with inves-tigation of the mineral diversity will help for establishment of new minerals for Bulgaria, which are indicative for specific conditions in the mineral-forming pro-cesses as well as for more effective prospecting of deposits of low-sulfide ores of gold, silver, etc.

Educational activityThe teaching activity in IMC is in correspondence with the main idea of

the National strategy for development of the scientific investigations 2020, which emphasizes on education, scientific studies, technological develop-ment and innovations to be the background for achieving dynamic and sus-tainable economical growth. During 2015 the scientists of IMC have educated young scientists from different units of BAS and Bulgarian Universities; have conducted specialized courses; have organized and have been lectors at In-ternational Summer Schools. As a result, in 2015 two of the PhD students al-lowed defending their PhD theses have been appointed assistant professors in IMC. Their research projects correspond to the priorities of the National Strategy 2020.

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Expert activityThe colleagues from IMC conducted expertise for governmental institutions,

Customs, Universities, business companies (Assarel Medet AD, Dundy Precious Metals, Barite Mining EOOD, etc.), which gives impact to effective decisions of theoretical and practical tasks and technological problems.

Results from the scientific activity during 2015The obtained scientific results have been published in 67 scientific papers.

Those with impact factor are 38. The researchers from IMC have participated in 28 international scientific forums with 58 reports. During 2015 the citations of 225 papers of researchers in IMC reached the number 875.

Counting for the conditions of work and the existing possibilities in BAS and the country as a whole the obtained results are good enough, especially for a small institute like IMC, having 27 academic researchers.

A tendency is noticed for a slight increase of the publications compared to 2014 (60 in 2014, 98 in 2013, 71 in 2012, 103 in 2011, 99 in 2010, 100 in 2008, 92 in 2007).

Important fact is the increase of the number of citations for 2015 being 875. For comparison the ratio papers/citations is: 2014 – 179/696, 2013 – 230/728, 2012 – 192/567, 2011 – 158/271. This is a very good attestation for our scientific production and its continuing actuality and significance in the professional scien-tific fields.

Most important scientific achievementFor 2015 there can be formulated scientific achievements in the two main

scientific directions of IMC, namely mineralogy and crystallography.

MineralogyThe following minerals are described for the first time for Bulgaria: melilite,

esseneite type clinopyroxene, wollastonite-2M polytype and Ti-rich andradites with high content of schorlomite component. These finds are indication for a high-temperature genesis, including magmatic stage of the skarn processes followed by post-magmatic one. Also proved is the rarely met worldwide Te-bearing can-fieldite (Ag8Sn(S,Te)6) – a new mineral found in Bulgaria in the epithermal gold-silver ore formation Chereshkite (Central Rhodopes). Also, described are two new for Bulgaria varieties of the mineral monazite – monazite-(La) and monazite-(Nd), which are enriched in Th. These minerals are found in samples from the Igralishte pluton (SW Bulgaria).

The above mineralogical studies were conducted entirely in IMC by the sci-entific group: Assoc. Prof. M. Tarassov, Assoc. Prof. E. Tarassova, Dr. Y. Tzve-

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tanova, Assoc. Prof. R. Titorenkova, Dr. M. Kadiyski, Dr. V. Ganev, Prof. Dr. O. Petrov, and E. Anastasova.

Main achievement: Found and described are five new for Bulgaria miner-als and mineral varieties

Publications:Tzvetanova, Y., Tarassov, M., Ganev, V., Piroeva, I. 2015. Ti-rich andradites in skarns

from Zvezdel-Pcheloyad ore deposit, Eastern Rhodopes, Bulgaria. – In: Short Com-munications of “Geosciences 2015”, Jubilee National Conference with International Participation “90 Years Bulgarian Geological Society”, 41–42 (ISSN 1313-2377).

Tarassov, M., Anastasova, E., Tarassova, E. 2015. First data on monazite with а negative Ce anomaly from the Igralishte pluton, Southwestern Bulgaria. – In: Short Com-munications of “Geosciences 2015”, Jubilee National Conference with International Participation “90 Years Bulgarian Geological Society”, 35–36 (ISSN 1313-2377).

Tarassova, E., Tarassov, M. 2015. New data on Au-Ag mineralization in the Chereshkite ore occurrence, Central Rhodopes, Bulgaria. – In: Short Communications of “Ge-osciences 2015”, Jubilee National Conference with International Participation “90 Years Bulgarian Geological Society”, 37–38 (ISSN 1313-2377).

Tzvetanova, Y. 2015. Crystal-chemical and structural characteristics of minerals from skarns in Zvezdel pluton. PhD Thesis, BAS, Sofia, 183 p.

CrystallographyIMC supports the proposal of the Institute of Organic Chemistry with Centre

of Phytochemistry (IOCCP – Bulgarian Academy of Sciences) for mutual scien-tific achievement:

The conformational behaviour of 3-methyl-4-(4-methylbenzoyl)-1-phenyl-pyrazol-5-one was studied with a combination of single crystal XRD, NMR in solution and in solid state and with quantum-chemical calculations (DFT) in gas phase. The compound can adopt four different tautomers, determined by the

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combination of the keto–enol tautomerism of pyrazolone and the attached 4-acyl carbonyl group. Potential energy surface simulations in gas phase show that each of the tautomeric forms has stable conformers, defined by energy minima, which could potentially be obtained in solid state. NMR analyses indicate that the keto–enol conformations with intramolecular H-bonding are preferred in solu-tions. Crystallization trials produced five different crystal phases, three yellow and two colorless. The single crystal XRD and solid state NMR structural analyses revealed that three desmotropes are obtained, two of them as two different con-formational polymorphs. The theoretical calculations are in full agreement with the experimental data.

This study is a result of the combined efforts of experts from four different disciplines coordinated by Assoc. Prof. Vanya Kurteva

Main achievement: This is the first report about isolation of more than two desmotropes of a given compound.

V. Kurteva, B. Shivachev, R. Nikolova, S. Simova, L. Antonov, L. Lubenov, M. Petrovac, 2015. Conformational behaviour of 3-methyl-4-(4-methylbenzoyl)-1-phenyl-pyrazol-5-one: a sudden story of three desmotrops. RSC Adv. 2015, 5, 73859–73867.

Most important scientific and applied achievementThe sorption process of strontium ions on Bulgarian natural zeolite (clinop-

tilolite) is investigated. Established are the optimal parameters of pH, time of contact, and concentration of strontium ions during sorption. The process pro-ceeds fast and is well described by diffusion models based on three algorithms (Langmuir, Freundlich и Dubinin–Raduchkevich). The study proposes good pos-sibilities for cheap utilizations in purification of drinking water and industrial waste waters (from nuclear power plants) from radioactive 89Sr.

Lihareva, N., O. Petrov, Y. Tzvetanova, M. Kadiyski, V. A. Nikashina. 2015. Evaluation of the possible use of a Bulgarian clinoptilolite for removing strontium from water media. – Clay minerals, 50, 55–64.

Director: (Prof. Dr. R. Nikolova)

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1. Trends of activity

1.1. Short history

The Institute was established in 1984 under the name Institute of Applied Mineralogy of the Bulgarian Academy of Sciences. In 1995 it was transformed into Central Laboratory of Mineralogy and Crystallography (CLMC) which inher-ited the best specialists, the equipment and the most vital scientific themes from the former academic institute. Since 2005 the CLMC was named after the famous Bulgarian mineralogist and crystallographer Academician Ivan Kostov.

From July 1, 2010 the CLMC was renamed to Academician Ivan Kostov In-stitute of Mineralogy and Crystallography after the high overall score (A/A/A) for the five-year (2004–2008) achievements and activities based on the evaluation procedure from the International Science Review Committee.

1.2. Mission, areas of activities and priorities

The IMC mission is to contribute to the sustainable development of socie-ty and enlarging human knowledge in the fields of Mineralogy, Crystallography and Mineral Resources by comprehensive multidisciplinary research of natu-ral, technogenic and experimentally modeled mineral systems and synthesized new materials.

The main areas of activities of IMC include basic studies and applied research, consulting, expertise, service and analytic activities, practical appli-cation of scientific results and training of high qualified specialists in the fields of mineralogy and crystallography, investigation and modeling of natural and technogenic mineral systems.

Based on the outlined areas of activities, the main scientific priorities of IMC are:

Understanding the earth

– Investigation of minerals and mineral systems aiming at determination of their composition, structure, properties, relationships, processes of formation and alteration, and modes of distribution.

– Development of genetic models and criteria for prognosis, prospecting and exploration of mineral deposits.

new Materials and technologies

– Growing, synthesis and characterization of single and polycrystalline ma-terials (optical and laser-grade single crystals, micro- and mesoporous phases, glasses, etc.).

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– Modification of minerals and materials aiming at improving their sorption, catalytic and ion-exchange properties as well as searching for possibilities for their optimal application.

environMental Protection

– Investigation of important for environmental protection and ecologically friendly utilization natural and technogenic mineral systems accentuating at coals, ores, and waste products of their processing.

natUre and natUral resoUrces of BUlgaria

– Investigation, analysis, and prognosis of mineral resources of Bulgaria aiming at their effective and environmentally friendly utilization.

– Studying, preservation and collecting of the mineral diversity, geological and landscape natural heritage of Bulgaria through supporting “National Minera-logical Database”, “Heavy Minerals Map of Bulgaria”, and a basic academic col-lection “Mineral Diversity of Bulgaria”.

training and edUcation

– National Program Accreditation for education and training of PhD students in “Mineralogy and Crystallography”.

– Educational programs and training courses for students and specialists from Bulgarian and foreign universities and institutes.

1.3. Relation with the research policies and programs

The IMC Research Plan 2014–2016 was focused in line with the main objectives of the National Strategy of Scientific Research – 2020, the National Development Programme: Bulgaria 2020, and the EU Framework Programme for Research & Innovation – Horizon 2020. The available human, material, financial and information resources were directed to the implementation of the BAS strategic policies “Science as the main driving force in the develop-ment of knowledge-based national society and economy”, “Scientific potential and research infrastructure as a part of the European Research Area” and “National identity and cultural diversity in Europe and in the world”. The IMC participates in the realization of the following basic programs:

– Sustainable development, rational and efficient use of natural resources – Competitiveness of the Bulgarian economy and capacity for scientific

innovation – Informational, expert and operative services to the Bulgarian state and

society – High-quality competitive education

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– The history of Bulgaria, Bulgarian lands and Bulgarian people

1.4. Research topics and capacity

Fundamental scientific knowledge on the structure, composition, properties and formation conditions of minerals and materials that mineralogy and crystal-lography give by their powerful methodology and set of most advanced analytical methods, now has an extremely wide range of applications: both in all fields of the Natural Sciences (Earth Science, Materials Science, Life Science, Environmental Science) and in the industry (mining and geology, mineral resources and prod-ucts, environmental protection, pharmaceutical and biomedical industry, etc.)

Following the modern trend of multidisciplinary scientific development world-wide, the Institute currently has a team of high-qualified specialists in the fields of mineralogy, crystallography, mineral resources, physics and chemistry working in leading in Bulgaria and well-recognized abroad Research Groups in:

– Mineralogy, Geochemistry and Utilization of Coal and Coal Products – Characterization and Evaluation of Mineral Raw Materials – Mineral Deposits Modeling, Mapping and Prognosis – Archaeomineralogy and Technological Mineralogy – Ecology and Utilization of Waste Products – Crystal Structure, Composition and Properties of Minerals and Materials – Structural and Chemical Transformations of Minerals and Materials – Natural Zeolites and Microporous Analogs – Synthesis of New Functional and Nanosized Materials – Crystal Growth of Optical Crystals

The productivity and competitiveness of the main research topics, devel-oped in IMC, are internationally proven. During the last years they are gradually adapted to the national and European scientific priorities with emphasis on the efficient utilization of mineral resources, raw materials and wastes, materials sci-ence and nanotechnology, ecology and cultural and historical heritage.

1.5. Research infrastructure

With its own 8 analytical and experimental laboratories (Electron Microsco-py, X-Ray Powder and Single Crystal Diffraction Analysis, Spectroscopy, Ther-mochemistry, Experimental Mineralogy and Crystal Growth, Chemistry, Optical Microscopy, Samples and Preparations) and shares in other 3 external ones (Ra-man, Mossbauer, LA-ICP-MS), IMC is currently the best equipped and with most highly qualified research staff organization in Bulgaria in the field of detail study

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of structure, composition, properties, behavior and interactions of solid matter (regardless of its origin and size) and systems it forms.

During the last few years, IMC, as a principal institution, organized consor-tia with leading BAS institutes, Sofia University and University of Chemical Tech-nology and Metallurgy for purchasing modern research infrastructure by budg-et and project financing: new scanning electron microscope SEM EVO 25LS – CARL Zeiss SMT, new thermochemical equipment SETSYS Evolution 24 TGA-DTA/DSC with mass spectrometer OmniStar of Setaram Instrumentation, new infrared microscope Hyperion 2000 of Bruker, new X-ray powder diffrac-tometer D2 Phaser Bruker AXS, new X-ray single crystal diffractometer Oxford Diffraction Supernova A with two X-ray sources and Oxford Cryosystems Co-bra temperature attachment, etc.

Currently IMC has a powerful set of analytical equipment which is capable of ensuring practically the whole research range in the field of materials science.

1.6. Benefits for Science, Business and Society

As a result from the fulfillment of the topics in the research plan for 2015, there have been obtained a series of important for science and national indus-try results, namely: new knowledge about the composition, structure, properties, modes of formation, behavior during technological processing and effective uti-lization of minerals, new materials, mineral resources, natural and technogenic mineral systems from the Bulgarian geo-space; synthesis of a number of new materials with predicted structure and properties and modification of known phas-es for application as ion-exchangers, sorbents, catalysts, membranes, dyes, soil amenders, electronic components, medical and optical products; development of technologies for production of nanosized zeolites; growing of crystals possessing conical refraction suitable for design of lasers with high brightness; upgrade and actualization of national data bases for minerals, mineral resources and newly synthesized crystal phases.

Being a leading public scientific institution in the sphere of mineralogy, mineral resources, crystallography, and materials science, the Institute offers a wide range of research, expert, consulting, and analytical services for business, government administration, and scientific-innovation sector. For many years partners and cli-ents of the expert-consulting services offered by our scientists are tens of compa-nies from various industrial sectors (survey, prospecting, mining and processing of mineral raw materials; new materials, pharmaceutics; environmental protection, etc.), scientific research organizations, universities, and museums.

IMC is engaged in the organization and management of a range of activi-ties of particular national importance for the science and society:

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– IMC is a scientific center of the Bulgarian mineralogical community united in the Bulgarian Mineralogical Society (http://www.clmc.bas.bg/Minsoc/) the web-page of which is maintained by the Institute. The regular monthly sessions of the Society are held in IMC where Bulgarian and foreign scientists report and discuss new results from their research in the fields of mineralogy and mineral resources.

– IMC is the seat of the Bulgarian Crystallographic Society (http://www.bgcryst.com) with Chairman Prof. Dr. R. Nikolova – Director of the IMC, the organization and core staff of which is dominated by our scientists working in the field of crystallogra-phy and mineralogy. The webpage of the Crystallographic Society is also maintained by the IMC. From September 28 to October 3, 2015 in Sofia was held the Interna-tional School on Introduction in the Rietveld structure refinement.

– IMC by its scientists is a vigorous member in the organizing and publishing activities of the Bulgarian Geological Society and Bulgarian Crystallographic Society.

– IMC is a custodian of the basic academic collection “Mineral Diversity of Bulgaria” including unique samples of the Bulgarian mineral wealth as well as specialized working materials concerned with the scientific projects and problems of the IMC mineralogists.

– IMC is an active member in the national and international conferences of the Sofia initiative “Preservation of Mineral Diversity”, organized by the National Museum “Earth and Man” and devoted on the preservation of the mineral wealth of Earth for the future generations.

Due to the specificity of its scientific capacity the collaboration of the scien-tists from IMC with the national and regional institutions in Bulgaria and Europe is connected, most of all, with the realization of a great number of research projects with external financing as well as with our potentialities for competent expert opinions on problems concerned for example with the effective utilization of natu-ral resources, environmental protection, effect of various natural products on hu-man health, qualification of drug products of the pharmaceutical industry, etc.

Many of our scientists are participants in different forms of the scientific life on a national and international level – chairmen and members of governing councils of scientific societies, members of editorial boards of international and national journals, reviewers of scientific papers, participants in scientific juries in competitions for academic positions, etc.

With its active and multi-component international engagements the IMC de-fends its prestige as a competitive scientific organization and continues to suc-cessfully integrate in the developing European Research Area.

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2. Structure and Staff

The whole range of operative activities of IMC is organized in 3 research departments (Mineralogy and Mineral Raw Materials, Experimental Mineralogy and Crystallography, and Structural Crystallography and Materials Science) in-cluding 8 analytical and experimental laboratories as well as in a small group of administrative and support staff.

IMC – Organization chart

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2.1. Short description of the structural units

Department “Mineralogy and Mineral Raw Materials”Research Topics– Mineral Systems– Technogenic SystemsResearch Activity– Studying mineral objects formed in natural gradient systems aiming at the

development of genetic models and their practical applications– Studying the phase composition, qualitative characteristics and distribu-

tion of components in technogenic systems formed in using mineral raw materials as well as their impact on the environment

– Creation and actualization of mineralogical data basesMain Research Objects: magmatic and metamorphic rocks; fluorite and bar-

ite deposits; sedimentary exhalative polymetallic deposits; metalliferous sediments from ocean rift zones; coals and products of their combustion; waste products from power engineering, metallurgy and ore dressing; agates; platinum-group minerals; accessory minerals; heavy minerals concentrates; archaeological artifacts.

Department “Experimental Mineralogy and Crystallography”Research Topics– Synthesis and Crystallization of Minerals and Materials– Modeling of Natural Processes and SystemsResearch Activity– Synthesis and crystallization of minerals and materials in model systems– Investigation of products and processes of their formation– Experimental modeling of natural processes in gradient fieldsMain Research Objects: microporous materials, natural zeolites, tungsten

minerals, bentonites, phosphorites, sorbents based on clays and zeolites, ti-tanium and zirconium silicates, basaltic glasses, catalysts, laser optics grade single crystals.

Department “Structural Crystallography and Materials Science”Research Topics– Crystal Chemistry– Physics of MineralsResearch Activity– Determining of the crystal structure, phase and chemical composition and

properties of minerals, single crystals, crystalline and polycrystalline materials

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– Synthesizing of new chemical compounds with particular structures and properties

– Completing crystallographic and spectroscopic databases for minerals and materials

Main Research Objects: optical crystals and glasses, new crystalline materi-als, zeolite type materials and thin films.

Analytical and Experimental Laboratories– Laboratory of Electron Microscopy: (i) local investigations of the morpholo-

gy, preferred orientation, phase and chemical composition, textural relationships, structural defects and structure of inorganic natural and synthetic phases, nano-sized materials and thin films using various techniques of transmission electron microscopy; (ii) quantitative and qualitative characterization (morphology, micro-structure, chemical composition, phase and chemical inhomogeneities) of mas-sive, dispersed, polished and non-polished minerals, rocks, synthesized phases, thin films and other materials including biological tissues using scanning electron microscopy and electron microprobe analysis.

– Laboratory of X-Ray Diffraction Analysis: (i) determining unit-cell param-eters, space group symmetry and atom positions in the structure of crystalline phases by X-ray single crystal diffraction analysis; (ii) X-ray powder diffraction analysis with possibilities for: qualitative phase analysis, unit cell parameters re-finement, profile analysis of peaks, structural analysis of polycrystalline phases by the Rietveld method, quantitative analysis of natural and synthetic materials.

– Laboratory of Spectroscopy: measuring spectra of optical absorption in the mid-, near-infrared, visible and ultraviolet regions.

– Laboratory of Thermochemistry: determining phase transition tempera-tures, chemistry of thermal reactions, kinetic and thermodynamic parameters of reactions and phase transitions in TG, DTG, DTA, and DSC regimes.

– Laboratory of Experimental Mineralogy and Crystal Growth: (i) low tem-perature (up to 200 °C) hydrothermal synthesis of microporous and layered mate-rials; (ii) crystal growth by the Flux method; (iii) high temperature electrochemical experiments in melts; (iv) crystal growth (up to 1660 °C) by the Bridgman Stock-barger method (Crystallox); (v) synthesis of ceramic and polycrystalline compos-ites through hot pressing (Crystallox) (up to 1500 °C and to 100 MPa pressure).

– Chemical Laboratory: analyses of rocks, ores, waste waters and techno-genic products by standard analytical methods and atomic absorption analysis.

– Laboratory of Optical Microscopy: study of rocks, ores, minerals and tech-nogenic products in reflected and transmitted light with possibilities for obtaining

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digital images by polarizing microscopes Leitz Orthoplan and Jenapol, micro-hardness tester PMT-3 and binocular lenses.

– Laboratory of Samples and Preparations: crushing, milling, sieving analysis, separation, preparation of polished plates and samples, thin and polished sections.

2.2. Staff

The academic staff of IMC comprises 28 scientists: 5 Full Professors, 14 As-sociate Professors, 6 Assistant Professors and 3 Researchers with a PhD degree, including 1 D.Sc. and 25 PhD holders. In 2015 Y. Tzvetanova successfully defend-ed a PhD thesis entitled “Crystal-chemical and structural characteristics of miner-als from skarns in Zvezdel pluton” (May 21, 2015), and B. Barbov was appointed Assistant Professor in Mineralogy and Crystallography.

The average age of scientists from the academic staff is about 51 years. They are highly qualified specialists in the fields of mineralogy, mineral deposits, crystallography, physics, and chemistry that provides a complex multidisciplinary investigation of the problems concerned with natural, technogenic, and experimen-tally modeled mineral systems and newly synthesized materials. The majority of scientists have specialized in leading scientific institutions in Belgium, Germany (4 fellows of the “Alexander von Humboldt” Foundation), Spain, Russia, USA, Swit-zerland, Japan, etc. In 2015, scientists from the Institute conducted various training programs and specialized courses for undergraduate and PhD students from the University of Hamburg, PhD School of the Bulgarian Academy of Sciences, Sofia University “St. Kliment Ohridski”, University of Mining and Geology “St. Ivan Rilski” and New Bulgarian University.

In addition to the academic staff, 7 Researchers with university degrees work also in the Institute most of which engaged with service and maintenance activities in the 8 analytic and experimental laboratories but part of them have their own re-search topics and areas of specialization within the framework of the main scientific projects. They are encouraged to perform active investigations with potential to be developed further into PhD theses.

IMC has also a small team of high-qualified specialists in the field of admin-istrative, organization, legal, personnel and financial-accounting activities with rich experience in the organization, supply, financial planning, spending and reporting of cash flows as well as experienced supporting, technical and subsidiary staff.

Nine PhD students were trained in the Institute in 2015. It should be noted the clear trend in recent years of increased interest in training offered by our PhD

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program “Mineralogy and Crystallography”. The main reasons for this are highly interdisciplinary nature of the training, using modern analytical and experimental equipment and highly qualified team of tutors and lecturers of specialized courses.

2.2.1. Board

– Director: Dr. Zhelyazko Damyanov – till 30.11.2015– Director: Dr. Rossitsa Nikolova – since 01.12.2015– Deputy Director: Dr. Ognyan Petrov – till 30.11.2015– Deputy Director: Dr. Vladislav Kostov-Kytin – since 01.12.2015– Scientific Secretary: Dr. Rossitsa Titorenkova

Department “Mineralogy and Mineral Raw Materials”– Head: Dr. Mihail Tarassov– Staff – 12

Department “Experimental Mineralogy and Crystallography”– Head: Dr. Vladislav Kostov-Kytin– Staff – 9

Department “Structural Crystallography and Materials Science”– Head: Dr. Boris Shivachev– Staff – 12

Administration:– Chief: Valeri Genov, MSc.– Chief Accountant: Krasimira Gavrilova– Staff – 6

Support Staff – 5

2.2.2. Scientific Council

Dr. Mihail Tarassov – ChairmanDr. Yuri Kalvachev – Vice ChairmanDr. Irina Marinova – SecretaryDr. Rossitsa Nikolova – Director of IMCDr. Boris ShivachevDr. Ognyan Petrov D.Sc. Stanislav VassilevDr. Christina VassilevaDr. Vladislav Kostov-Kytin

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Dr. Diana NihtianovaDr. Eugenia TarassovaDr. Zhelyazko DamyanovDr. Zdravko TsintsovDr. Louisa Dimowa – since 02.12.2015Dr. Nadia PetrovaDr. Rossitsa TitorenkovaDr. Vilma PetkovaDr. Lubomir Dimitrov – till 02.12.2015Dr. Oleg Vitov – till 02.12.2015Dr. Milen Kadiyski – till 02.12.2015

2.2.3. Research Staff

Professors

DSc., Dr. Stanislav VassilevDr. Ognyan PetrovDr. Boris Shivachev – since 17.09.2015Dr. Christina Vassileva – since 17.09.2015Dr. Rossitsa Nikolova – since 17.09.2015

Associate Professors

Dr. Boryana MihailovaDr. Diana NihtianovaDr. Eugenia TarassovaDr. Irina MarinovaDr. Louisa Dimova – since 17.09.2015Dr. Lubomir DimitrovDr. Mihail TarassovDr. Nadia PetrovaDr. Oleg Vitov – retired 10.11.2015Dr. Rossitsa TitorenkovaDr. Vilma PetkovaDr. Vladislav Kostov-KytinDr. Yuri KalvachevDr. Zdravko TsintsovDr. Zhelyazko Damyanov

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Assistant ProfessorsDr. Elena Tacheva Dr. Milen KadiyskiDr. Valentin GanevMSc. Krasimir Kossev (self-training PhD student)MSc. Svilen Gechev – till 01.12.2015MSc. Lilia TsvetanovaMSc. Borislav Barbov – since 01.10.2015

ResearchersDr. Nadejda LiharevaDr. Stanislav FerdovMSc. Lachezar PetrovMSc. Lubomira MachevaMSc. Petya IvanovaMSc. Svetlana AngelovaMSc. Valeri GenovDr. Yana Tzvetanova – defended a thesis on 21.05.2015

PhD studentsMSc. Borislav BarbovMSc. Christina SbirkovaMSc. Eva AnastasovaMSc. Lilia TsvetanovaMSc. Krasimir Kossev (self-training PhD student)MSc. Mariana Eneva-DimitrovaMSc. Totka TodorovaMSc. Vencislav DulgerovMSc. Dimitar Vasilev

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3. Main Equipment

Laboratory of Electron Microscopy– CARL ZEISS SMT SEM EVO LS25 with EDAX Trident system– Philips EM 420T (120kV) with EDAX 9100/70– Philips SEM 515 with WEDAX-3A– Philips SEM 515– various subsidiary and peripheral devices

Laboratory of X-Ray Diffraction Analysis – Oxford Diffraction Supernova A X-ray single crystal diffractometer

with two X-ray sources and Oxford Cryosystems Cobra temperature attachment

– Enraf Nonius 586 CAD 4 X-ray single crystal diffractometer – Bruker AXS - D2 Phaser X-ray powder diffractometer – DRON 3M X-ray powder diffractometer with PC-based system for

phase identification – specialized data processing software, full ICDD database and struc-

ture databases ICSD, CSD, and PDB

Laboratory of Spectroscopy – Bruker FT-IR spectrometer Tensor 37 with HYPERION 2000 FT-IR

microscope – Varian UV-VIS spectrophotometer CARY-100 Scan

Laboratory of Thermochemistry – SETARAM SETSYS 2400 TGA-DTA/DSC system with PFEIFFER

OmniStar mass spectrometer/gas analyzer – Stanton Redcroft differential scanning calorimeter DSC 1500 – Stanton Redcroft differential thermal analyzers STA 781 and DTA 675 – Stanton Redcroft thermomechanical analyzer TMA 790

Laboratory of Experimental Mineralogy and Crystal Growth – Low temperature (up to 150°C), low pressure (up to 5 MPa) hydro-

thermal crystallization – Melt growth by the Bridgman-Stockbarger method (Crystalox) – Flux growth – Hot-pressing (up to 1500°C, up to 100 MPa) (Crystallox) – Furnaces of different type up to 1600°C

Laboratory of X-ray fluorescence spectrometry (XRF)

– SUPERMINI 200 system – wavelength dispersive X-ray fluorescence (WDXRF) spectrometer for elemental analysis

– MIRA Gamma Dose Rate Monitoring System

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4. Research Topics4.1. Mineral Systems and Mineral Genesis

1. Divergent drift of Adriatic­Dinaridic and Moesian carbonate plat-forms during the rifting phase witnessed by Triassic MVT Pb­Zn and SEDEX deposits (Palinkaš L., Z. Damyanov, S. Šoštarić, S. Palinkaš, I. Marinova)

Early-intracontinental rifting of Pangea was a result of thermal doming in Uppermost Permian time giving rise to the formation of horst-graben structures, followed by slow subsidence, marine transgression and evaporite deposition. The consequences of incipient magmatism and a high heat flow are numerous geo-thermal fields and subterrestrial hydrothermal siderite-barite-polysulfide deposits. Advanced rifting magmatism as a successive stage in the Middle Triassic brought intensive submarine volcanism, accompanied by coeval sedimentation of chert and siliciclastics, building up volcanogenic-sedimentary formations. Volcanic ac-tivity with explosive phases and the generation of large volumes of pyroclastic rocks in the rifts produced concomitant mineralization with numerous sedimenta-ry exhalative (SEDEX) deposits of Fe-Mn-Ba-polysulfides. The passive continen-tal margin of northern Gondwanaland is flanked by the AdriaDinaridic carbonate platform, while the Moesian carbonate platform is a counterpart on the European passive continental margin. They were divergently drifted in the course of the ad-vanced rifting. A fast growing carbonate platform, developing gradually, covered evidence of the earlier intracontinental rifting and their ore formations. However, the carbonate platforms themselves host specific Pb-Zn deposits, well known as a Mississippi valley type, (MVT) or Bleiberg-Mežica type according the traditional European terminology. Triassic MVT and SEDEX deposits are symmetrically situ-ated on the both sides of the divergent passive margins in this early history of the Tethyan ocean. The paper gives a brief description of the MVT and SEDEX de-posits, in the two carbonate platforms and rifts in between, formed synchronously and in a similar manner on opposing sides of the diverging continental margin.

2. Microstructural peculiarities of migmatisation in rocks of the Serbo­Macedonian Massif (L. Macheva)

This investigation is focused on the high grade metamorphic rocks cropping out in Ograzhden and Belassitsa Mountains – metagranitoids, plagiogneisses, Pl-bearing schists, Al-rich schists and amphibolites. Previous work was referred

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to establish the nature of protoliths of the rocks, whereas the focus of this study was placed on the detailed microstructural peculiarities of migmatization.

Our research shows that only granitic orthogneisses and plagiogneisses display evidence for melting. The migmatization completely destroys the texture of the parent rocks and change dramatically the microstructural characteristics including grain size, grain shape and grain boundary geometry.

Based on the reaction textures as well as on appearance of some minerals and disappearance of others we can make some inferences about melt-producing and melt-consuming metamorphic reactions. We suppose that the initial stage of melting starts with a muscovite dehydratation reaction both in orthogneisses and plagiogneisses which consumes muscovite and produces potassium feldspar:

Ms + Qtz → Kfs + Als (Sil) + H2OThe implementation of this reaction is supported by the expected formation

of fibrolite needles in destabilized muscovite grains as in the neighbouring quartz grains. At pH2O = 5 kbar this reaction realizes at 680 °C.

As we observe consumption of plagioclase by potassium feldspar, we sup-pose that also the following reaction is possible:

Ms + Pl + Qtz → Kfs + Als (Sil) + MeltAccording to Spear (1989) the temperature of this reaction is ~650–700 °C

and pressure 5–6 kbar in the sillimanite stability field. In some cases we have observed formation of garnet together with the disappearance of biotite. We can suppose the following reaction to be responsible for the consumption of the biotite:

Pl + Bt + Als (Sil) + Qtz → Kfs + Grt + MeltThe realization of this reaction according Spear (1989) needs increase of

the temperature above 700 °C.The microstructures are extremely informative for the mechanism of migmatite

formation. There are many structures and microstructures in granitic orthogneisses and plagiogneisses which evidenced the formation of leucosomes and neosomes of these rocks by anatexis. These are: cuspate outlines of potassium feldspar filling pores between plagioclase and quartz grains; symplectitic replacement aggregates of feldspar and quartz after destabilized muscovite that are explained by reactions between peritectic grains and cooling melt; microgranophyric intergrowths of quartz and alkali feldspar in patches between primary grains; filling of cracks or shears in plagioclase by potassium feldspar or quartz; veinlets of inferred former melt (now pseudomorphs) consisting of quartz, K-feldspar, or sodic plagioclase along inferred former intragranular fractures; euhedral form of minerals that crystallize from the melt; corrosion of plagioclase grains at the contact with a melt.

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Microstructural peculiarities give some inferences for the metamorphic con-ditions. The presence of antiperthites in orthogneisses and plagiogneisses points to metamorphic conditions in the upper part of amphibolite or granulite facies. Combined basal and prismatic sliding in quartz, characteristic for gneisses caus-ing formation of chessboard textures appears at temperatures ~600 °C, as well as its recrystallisation via grain boundary migration.

An attempt was made to evaluate the role of the heterogeneous nature of deformation on micro- and macro scale on the location of leucosome and the extent of migmatization. In this connection it has been established enrichment of leucosome in the apical parts of the folds and along shear zones.

3. Geochemistry and geochronology of orthogneisses in Bode Saadu area, southwestern Nigeria and their implications for the Palaeoprote-rozoic evolution of the area (V. Ganev, C. Okonkwo)

Bode Saadu area, southwestern Nigeria is underlain by metasedimentary and metaigneous rocks including orthogneisses which have been intruded by largely undeformed granitic rocks of probable Pan-African (ca. 600 Ma) age. The metamorphic rocks have been subjected to several phases of both ductile and brittle deformation. Three suites of orthogneisses of granodioritic composition have been identified in the area, locally they contain xenoliths of metasediments. Geochemical analyses show that they are calc-alkaline, magnesian, metalumi-nous and possess the characteristics of granitoids emplaced in magmatic arcs. The in-situ LA-ICP-MS U-Pb dating of zircons (Fig. 1) in these orthogneisses

Fig. 1. CL and BSE images of the zircons from the Bode Saadu Granodioritic Gneiss.

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has yielded upper Concordia intercept (Fig. 2) Palaeoproterozoic ages of 2236 ± 29 Ma, 2228 ± 32 Ma and 2179 ± 28 Ma. These indicate the times of crystal-lization of these rocks and attest to a long period of magmatism associated with the Eburnean orogeny in this part of Nigeria. The gneisses bear the imprints of several deformation events in the form of foliations, folds and shear zones. The geochronological data enable constraints to be placed on the timing of the devel-opment of some of these structures and also indicate that some of the metasedi-mentary units are at least of Palaeoproterozoic age. Similar Palaeoproterozoic orthogneisses have been documented in some other parts of southwestern Nige-ria, in Central Hoggar area of the Tuareg Shield and in the Borborema Province of Brazil and support their correlation as part of West Gondwana. Obtained geo-chemical and geochronological data from the orthogneisses of Bode Saadu area indicate an important period of crust formation associated with orogenic activity during the Palaeoproterozoic and that the Eburnean orogeny affected this part of the Nigerian basement complex.

This investigation [23] is collaborative work between Department of Applied Geology, Federal University of Technology, Akure, Nigeria and Institute of Miner-alogy and Crystallography, Bulgarian Academy of Sciences, Sofia, Bulgaria.

Fig. 2. Wetherill Concordia plot of the Bode Saadu Granodioritic Gneiss.

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4. Plate tectonic aspects of the Triassic carbonate­hosted stratiform­stratabound base­metal deposits in the Western Balkan, NW Bulgaria (I. Marinova, Z. Damyanov)

The Triassic carbonate-hosted stratiform-stratabound base-metal deposits in the Western Balkan, NW Bulgaria, have well defined regional geological and tectonic settings, styles of mineralization, mineralogical, geochemical and iso-topic data. Their genesis, however, remains controversial in the framework of plate tectonic models, and is not supported by comparative analysis of possible counterpart candidates within the NW Tethyan domain. Besides, the crucial miss-ing information is the geochronology of the ore mineralization relative to the Trias-sic carbonate host rocks. The article stresses the ambiguities due to the lack of mineralization age dating, and emphasizes the necessity for building a convinc-ing plate tectonic model based on the relevant geodynamic setting. A prospective direction of research is the critical comparison with equivalent sediment-hosted base-metal deposits within the continental margin environments such as those in the Alps and Dinarides as well as others in the Alpine-Himalayan orogen and worldwide [64].

5. Brief comparative characteristics of minerals of the elements of the platinum group of sediments in Bulgaria (Z. Tsintsov)

Clarifying the characteristics of platinum-group minerals (PGM) in the sed-iments of Bulgaria creates prerequisites for better insight into the conditions of mineral forming processes associated with ultrabasite events in the regions, moreover, as an important raw material source these minerals need to have preliminary assessment of their industrial value. Their indicator features can be used to guide search works in the areas of both the placers and the host min-eralization of the of platinum-group elements (PGE). According to the develop-ment of the ultrabasite events in Bulgaria, PGM are established in placers from the southern part of the country. According to unpublished data of the author these mineralizations are proven in the sediments dredged from the river bed of Danube river from the Bulgarian coast, but they have not been studied in this work are not subject to discussion. Manifestations of this group of minerals can be conditionally divided into two major regions of the country – one, covering the east-southeast (conventionally denoted as area I) parts of Bulgaria and the other, located in the south-southwestern (conditionally designated as an area II) parts of the country (Fig. 1).

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In the recent 30 years the sediments of the area I have been the subject of strong interest from a number of Bulgarian researchers, who established PGE-mineralization in the sediments around the villages of Konstantinovo (Novoseltsi), Varshilo, Zidarovo, Goren Chiflik and Straldja town.

The present summary describes samples from Pt-Fe alloy from the vicinity of Kipilovo village. The minerals from the region include native elements and al-loys: native platinum, Pt-Fe; isoferroplatinum, Pt3Fe; rutheniridosmine, Os-Ir-Ru; ruthenium, Ru; iridium, Ir; osmium, Os; palladium, Pd. The sulphides and re-lated compounds are cooperite, PtS; braggite, (Pt,Pd,Ni)S; visotskite, (Pd, Ni)S; laurite, RuS2; erlichmanite, OsS2; malanite, (Cu,Pt,Ir)S2; hollingworthite, RhAsS; vasilite, (Pd,Cu)16(S,Te)7; telluropalladinite, Pd9Te4.

The PGE mineralization from sediments of region II, located in the depos-its of Struma, Mesta, Palakaria, Varbitsa, Uyneshtitsa, includes native platinum, Pt-Fe; isoferroplatinum, Pt3Fe; iridium, Ir; osmium Os; ruthenium, Ru; rutheniri-dosmine, Os-Ir-Ru. Also, sulphides and related compounds are proved: coop-

Fig. 1. Schematic map of the distribution of PGM in sediments of Bulgaria (card acording to Dabovski 2008, with the addition of the author).

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erite, PtS; mertieite II, Pd8(Sb,As)3; braggite, (Pt,Pd,Ni)S; bowieite, (Rh, Ir)2S3; kashinite (Ir,Rh)2S3; rustenburgite, Pt3S; cuprorhodsite, CuRh2S4; sperrylite, PtAs2; laurite, RuS2; erlichmanite, OsS2; irarsite, IrAsS; hollingworthite, RhAsS. Furthermore, the author of this communication has unpublished materials for the presence of PGM in the sediments of the rivers Jerman, Dragovishtitsa, Iskar, Eleshnitsa, and Arda.

PGM from both regions show some similarity in the degree of mechanical processing and the values of their morphometric parameters. An essential dif-ference, however, is registered in the particle size – these from region I are sig-nificantly coarser and have a high concentration in the deposit. In the sediments around Varshilo village, their concentration is up to 60 mg/m3, while the content in region II is below 1 mg/m3. The species composition of the discussed group minerals from both areas is dominated by Pt-containing phases – in area I these are Pt-Fe alloys, while in region II it is sperrylite. In both cases, the content of the dominant phase is over 98–99% of the total amount of PGM.

The predominant content of Pt-containing minerals in the sediments from the two regions is likely due to the similarity in the relative amounts of PGE in the primary magmas as a result of which there are formed similar PGM.

Later, secondary processes have influenced in varying degrees of the ul-trabasite bodies in region II and have caused decomposition of the Pt-Fe alloys and created crystallization environment for formation of sperrylite as a dominant PGM. In this way, the initial geochemical specialization of the ultrabasites from region II was preserved, but the species nature of the minerals-carriers of PGE in them was significantly changed. This immediately reflected in the composition of PGM in the relevant placers [54, 118].

6. Ti­rich andradites in skarns from Zvezdel­Pcheloyad ore deposit, Eastern Rhodopes, Bulgaria (Y. Tzvetanova, M. Tarassov, V. Ganev, I. Piroeva)

The composition of Ti-rich garnets and their paragenetic relationships are known to be indicative of activity of SiO2 and O2 in magmas and hydrothermal flu-ids, mobility of Ti during metamorphism, origin of metasomatic fluids, and magma differentiation processes.

Ti-rich garnets have been found in skarn xenoliths in mine gallery No 68 in the Zvezdel-Pcheloyad Pb-Zn ore deposit. These xenoliths, without any relation with carbonate-bearing protolith, are entirely hosted by monzonitic rocks of the second intrusive phase of the Zvezdel pluton. The mineral assemblage includes

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garnets of the grossular-andradite series (Adr96.61–3.10), fassaitic clinopyroxene (Al2O3 – up to 17.75 wt%), clinopyroxene of the diopside-hedenbergite series (Di91.17–27.12), wollastonite-2M, plagioclase (Ab100–3.30), with subordinate calcite, quartz, epidote, prehnite, melilite, chlorite, thaumasite and zeolites. Titanite, apa-tite and magnetite occur as accessory minerals.

Ti-rich garnets occur in varying amounts in all skarn zones studied. Under polarized light microscope, they appear as brown to red-brown isotropic crys-tals with strongly corroded margins testifying to instability conditions (Fig. 1a, b). These garnets crystallize during the earlier postmagmatic stage of the skarn pro-cess. Anisotropic garnets of the later generations commonly overgrow the earlier garnets preserving sharp contacts between them (Fig. 1c).

Electron probe microanalysis (EPMA) reveals only slight variation in the chemical composition of the studied garnet grains. Fe2O3(t) ranges from 18.39 to 24.80 wt%, TiO2 from 4.18 to 13.10 wt%, Al2O3 from 2.48 to 7.30 wt%, and MgO from <0.05 to 0,84 wt%. The compositions are characterized by significant deficiency of SiO2 – 28.56–30.92 wt% (Si <2.60 in the standard formula). In pre-vailing part of analyses the content of TiO2 is higher than 8 wt% corresponding to schorlomite composition according to the classification criteria of some authors.

Fig. 1: a–b, photomicrographs of Ti-rich garnets in plane-polarized transmitted light; c, BSE-images show-ing a sharp contact between Ti-andradites and grossu-lare of later generation; d, ternary diagram of the Y-site of the garnet structure with plotted points of the studied Ti-rich andradites; e, chondrite-normalized REE pat-

terns for Ti-rich garnets

b

a c d

e

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Compositions of garnets with TiO2 >8 wt% are plotted on a ternary diagram of the Y-site contents of the generalized end-members {Ca3}[R2

3+](Si3)O12, {Ca3}[R24+]

(SiR23+)O12 and {Ca3}[R

4+R2+](Si3)O12, for R4+ = Ti, R3+ = Fe3+, and R2+ = Fe2+. These end-members correspond to andradite, schorlomite and morimotoite, re-spectively. As is seen in Fig. 1d, almost all our compositions fall in the field of andradite (defined as Ti-rich andradites or melanites), two – in the field of schorlo-mite and one – on the boundary between the fields of morimotoite and andradite.

According to LA-ICP-MS analyses, the Ti-rich andradites are enriched in V (890–1535 ppm), Zr (1400–1814 ppm), Y (236–399 ppm), Sc (4–170 ppm), Nb (28–62 ppm), Th (45–89 ppm), Ga (15–24 ppm), Co (3–10 ppm), Ta (2–7 ppm), U (5–27 ppm), Sn (8–16 ppm), and Hf (36–43 ppm). All studied garnets are extremely depleted in LIL elements (Cs, Rb and Ba). Only Sr varies from 10 to 17 ppm. The ΣREE content in the Ti-rich garnets (264.8–929.2 ppm) is distinctly higher than that in the skarn rocks (62.66–100.3 ppm) and the monzonite (185.4– 190.5 ppm). Chondrite-normalized REE patterns of Ti-rich garnets display weak or pronounced negative Eu anomalies (Eu/Eu* = 0.39–0.85), generally flat to slightly decreasing HREE shapes, and LaN/YbN = 0.15–1.74 (Fig. 1e). The (La/Sm)N ratio is <1.0, whereas (Gd/Lu)N >1.0.

The obtained data suggest significant mobility of Ti, V, Zr, Y, and REE during the earliest stage of the postmagmatic skarn process and relatively low activity of SiO2 and O2 in the hydrothermal fluids [55, 120].

7. New data on Au­Ag mineralization in the Chereshkite ore occur-rence, Central Rhodopes, Bulgaria (E. Tarassova, M. Tarassov)

The Chereshkite deposit is located between two small villages Dolno Che-resh kite and Gorno Chereshkite, in the Central Rhodopes, near the Greek bor-der. The Au-Ag mineralization is hosted by small granitoid bodies and partially by gneisses. The ore forming process in the deposit is accompanied by inten-sive silicification and sericitization of the wallrock. During the examination of a series of Au-Ag ore samples from the deposit, a new mineral for Bulgaria and for the deposit – Te-bearing canfieldite (Ag8Sn(S,Te)6) and two new minerals for the deposit – Te-bearing polybasite (Cu(Ag,Cu)6Ag9Sb2(S,Te)11) and Se-bearing acanthite (Ag2(S,Se)) were found and studied by us. Description of these miner-als, including their occurrence, chemical composition and genesis is given in the present report [52, 115].

Polished sections and polished thin sections prepared from 10 ore samples from the deposit are firstly examined on an optical microscope Leitz Orthoplan Pol.

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Then, the massive polished samples were coated with carbon for backscattered electron (BSE) imaging and chemical composition examination of the phases at 20 kV on a scanning electron microscope ZEISS SEM EVO 25LS equipped with an EDAX Trident analytical system.

Pyrite occurring as euhedral crystals grouped in aggregates with size of 1–3 mm, is most abundant mineral in the deposit (to 30 vol.%). The pyrite is presented by homogeneous (1) and zonal (2) varieties. In reflected light optical microscope, the zonal pyrite shows alternation of prevailing light-yellow zones and thin zones with pink hue. The latter zones are characterized by increased contents of As (up to 10 wt.%) corresponding to arsenian pyrite, and contain inclusions of galena, silver-bearing tennantite, arsenopyrite, chalcopyrite and bismuthinite. In homogeneous pyrite there are emulsion-like disseminated in-clusions of canfieldite, acanthite, polybasite, sphalerite and galena (Fig. 1a). The pyrite is partially replaced by gersdorffite and siegenite. Native silver, elec-trum (Ag 33.4 wt.%) and marcasite are found in quartz aggregates. During the earlier research of the deposit were also described andorite, stromeyerite and krennerite.

Fig. 1. (a) Pyrite aggregate with emulsion-like disseminated inclusions; (b) Emulsion-like inclusions of Te-bearing canfieldite, Ag-bearing galena and fine intergrowths of Te-bearing canfieldite and (Ag,Fe,Sn,Te,S) containing phase in pyrite; (c) Euhedral and emulsion-like inclusions of Te-bearing

polybasite and aggregate of acanthite and Ag-bearing galena in pyrite.

Canfieldite appears as solitary nonuniformly distributed in the pyrite еmulsion-like inclusions with size 2–15 µm and even outlines without any signs of corrosion (Fig. 1а). More rarely canfieldite forms aggregates with silver-bearing galena (Ag up to 1.1 wt.%) or fine intergrowths with a (Ag, Fe, Sn, Te, S)-con-taining mineral not identified by us because of its very small size (Fig. 1b). The studied canfieldite characterized by high contents of tellurium 11.6–15.2 wt.% which defines the minerals as Te-bearing canfieldite. Beside tellurium the miner-als contains also Fe 1.8–3.9 wt.%. Te-bearing canfieldite Ag8Sn(S,Te)6 is rarely

36

occurred silver-tin sulfide. For the first time, this variety of canfieldite with Te content of 8.69 wt.% was described for lead-zinc-silver ores from Revelstoke, British Columbia, Canada. Te-bearing canfieldite is found in several localities of the world – in Japan (Tsumo Au-Cu-Pb-Zn hydrothermal postskarn deposit), Ar-gentina (several Ag-Sn deposits), Switzerland (Ag-Sn mineralizations in Lengen-bach Quarry) and some others.

Аcanthite occurs as individual emulsion-like inclusions or aggregates with galena (Fig. 1с). The studied acanthite contains up to 5.1 wt.% of Se which is common isomorphic element in the mineral. Based on its chemical composition the mineral can be specified as Se-bearing acanthite.

Polybasite occurs as emulsion-like inclusions and euhedral crystals in pyrite (Fig. 1с). In some inclusions the mineral is found together with galena or sphal-erite. The chemical composition of the mineral (contents of Te 5.45–5.97 wt.%,) classifies it as Te-bearing polybasite.

In the present study of the Au-Ag mineralization of the Chereshkite de-posit, a new mineral for Bulgaria and for the deposit – Te-bearing canfieldite (Ag8Sn(S,Te)6), two new minerals for the deposit – Te-bearing polybasite (Cu(Ag,Cu)6Ag9Sb2(S,Te)11) and Se-bearing acanthite (Ag2(S,Se)) as well as ar-senian pyrite are described giving new genetic facts for the deposit and being a good guide of epithermal precious-metal deposits. The authors assume that the described emulsion-like disseminated Ag, Te and Se-containing minerals in the pyrite are result of decomposition of a higher-temperature (FeS2 dominated) solid solution.

8. First data on monazite with а negative Ce anomaly from the Igra­lishte pluton, Southwestern Bulgaria (M. Tarassov, E. Anastasova, E. Tarassova)

Recently, during a systematic investigation of REE-Th-U minerals in the Ig-ralishte granite pluton (243 Ma), Southwestern Bulgaria, we found unusual Ce-depleted forms of monazite (LREEPO4). First data on the occurrence and chemi-cal composition of the mineral, its relationships with other minerals and possible genesis are discussed in our work [51, 114]. The Ce-depleted monazite is dis-tinguished from the magmatic accessory monazite only in BSE images in SEM with strongly enhanced contrast. The mineral is found only as microcrystals sized between 0.3 to 3.0 mm (some aggregates of its crystals are with size to 7 mm). The Ce-depleted monazite occurs as (i) fine veinlets crosscutting the magmatic accessory monazite-(Ce) (the most common case) and other minerals as plagio-

37

clase (more rare case); (ii) aggregate replacing the peripheral parts of the primary monazite-(Ce) crystals; (iii) outer zone of a complex texture of replacement of the magmatic monazite consisting of the central relic monazite surrounded by apatite zone and then by zone of secondary monazite; (iv) individual crystals or their ag-gregates replacing apatite crystals.

Chemical composition of the neoformed secondary monazite is character-ized by the following features:

– very low content of Ce 1.5–6.0 wt.% especially in comparison with the content of Ce in the unaltered magmatic monazite-(Ce) 22–27 wt.%;

– chondrite normalized LREE patterns (Fig. 1) of the secondary monazite show strong Ce anomaly; the distribution of other LREE (La, Pr, Nd, Sm) is close to that of the unaltered monazite although slight fractionation of the elements – decrease in the content of La (from 12–13 to 10–12 wt.% in unaltered and sec-ondary monazites, respectively) and increase in the content of Nd (from 8–9 to 9–11 wt.%) and Sm (from 1.3–1.4 to 1.2–2.3 wt.%) can be seen in Fig. 1;

Fig. 1. Chondrite-normalized LREE patterns of monazite-(Ce) and secondary Ce-depleted monazite.

– Ce-depletion in the composition of secondary monazite is accompa-nied by essential increase in the content of Th (to 16 wt.%), U (to 2 wt.%), Y (to 3 wt.%), Ca (to 4%), Si (to 2 wt.%), as compared with the composition of unal-tered monazite (Th – to 7 wt.%, U – to 1 wt.%, Y – to 2.0 wt.%, Ca – to 0.6 wt.%, Si – to 0.7 wt.%);

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– according to the current nomenclature of monazite solid solutions, the neoformed Ce-depleted monazite can be classified as monazite-(La) or mon-azite-(Nd) (the contents of La and Nd are very close) enriched by cheralite (CaTh(PO4)2) component.

Cerium occurs in nature as Ce3+ like the majority of lanthanides, or as Ce4+ in oxidizing conditions. It is generally accepted that Ce anomalies (positive or negative) in minerals, rocks and waters is indication for oxidizing comparatively low-temperature conditions. Negative Ce anomalies in REE minerals from meta-morphic rocks can serve as evidence for a later metamorphic event developed in highly oxidized and fluid-rich environments.

The chemical alteration of the magmatic monazite into Ce-depleted mona-zite in the Igralishte pluton could be connected with the tectonic and hydrothermal overprint (to 300±50°C) at 36.36±0.56 Ma according to Rb-Sr analysis of whole rock and biotite. This thermal overprint can be related to the Paleogene volcanism in the region and well corresponds to our recent data on the alteration of zircon.

9. Formation of bonanza electrum from upward flow of boiling colloi-dal solution. Case study from the Khan Krum low­sulfidation gold de-posit, SE Bulgaria (I. Marinova)

Revision of bonanza electrum micro-textures along sinusoidal-walled vein-lets from the Khan Krum low-sulfidation gold deposit led to revealing of some new textural features of higher order in addition to the reported already. The new data resulted also in refinement of the conceptual model for formation of bonanza electrum in steep sinusoidal-walled veinlets already presented (Ann. Rep. No. 20, 2014). For reliable explanation of the observed mineral textures the author used an approach of integration of the microscopic observations with results of experiments and simulations of colloidal solution flow along natural or artificial micro-cracks/micro-channels. This approach allowed the author to take together into consideration the specific electrum distribution along sinu-soidal-walled veinlets, the joint geometry and the experimentally obtained flow patterns in joints/channels of similar geometry. As a result of this study, the author concluded that the electrum colloidal particles flowing along saturated sinusoidal-walled micro-joints experience (i) physical retention in relatively thick portions of the joints, and in micro-joints perpendicular to the former; (ii) lateral inertial focusing into equilibrium bands; and (iii) vapor-liquid interface capturing [42, 90]. It was also infered that in steep sinusoidal-walled joints the largest electrum agglomerations form in turbulent flow of auriferous colloidal solution

39

in portions of abrupt joint thickness expansion (Fig. 1, inset b3), followed by weaker electrum enrichment resulted from re-circulation of laminar flow in por-tions of gradual thickness increase (Fig. 1, inset b2), while the barren narrow portions form in a laminar flow (Fig. 1, inset b1) [43, 91].

10. Bladed quartz texture and its relationship with the electrum min-eralization in the Eocene, low­sulfidation Kuklitsa gold deposit, Kru-movgrad goldfield, SE Bulgaria. Geological implications (I. Marinova)

In the Kuklitsa gold deposit bladed quartz is observed (i) in veinlets cross-cutting low-angle layer-like massive silicification just above the Tokachka detach-ment fault and (ii) in steep veins of sharp tectonic contacts and starting at the level of approximately 100 m above the detachment fault. Both styles of epith-ermal mineralization are constrained to the hanging wall of the detachment fault and are developed in clastic sediments: breccias, breccia-conglomerates and sandstones. Outcrops of both types of bladed quartz have similar heights a.s.l. but are separated in space (Fig. 1).

Fig. 1. Conceptual model for formation of bonanza electrum along sinusoidal-walled joints from upward flow of boiling colloidal solution: a – drawing of segment of the studied veinlet (to scale); b – scheme of upward flow of boiling auriferous silicate colloidal solution. In insets – expected

flow patterns.

40

In the first style, bladed quartz is accompanied by 10–20 vol.% of adularia; scarce pyrite; and electrum segregations of the highest grade ever has been ob-served in this deposit. All these minerals are very fine-grained – up to 10–20 µm in size. The former platy calcite there was deposited along cracks cross-cutting massive quartz of low electrum grade.

In the second style, bladed quartz associates with adularia (1–2 vol.%), both to about 10–20 µm in size and scarce electrum and pyrite grains also of similar size.

These observations integrated with recent findings (Ann. Report No 20, 2014) allowed the author to conclude that the bladed quartz of the first type (vein-lets of bladed quartz associated with increased adularia abundance) marks the first boiling level of more pronounced degree of boiling and hence – more effec-tive precipitation of electrum being just above the Tokachka detachment fault. The second type (the vein bladed quartz) marks a level of low-degree boiling, and of respective lower electrum grade. It is modeled as resulted from later boiling episodes in synthetic faults of the detachment fault.

Fig. 1. Geological map of the Kuklitsa deposit (courtesy of BMM) and author’s cross section along I-II line: 1–2 – Eo-cene: 1 – Coal-bearing-sandstone forma-tion (massive sandstones and siltstones), 2 – polymictic breccias; 3 – Maastrichtian-Paleocene: Krumovgrad group (coarse polymictic breccias, breccia-conglomerates and sandstones); 4–5 – pre-Paleogene basement: 4 – Rupchos group (layered am-phibolites, amphibole and biotite gneisses), 5 – Arda group (equigranular and porphy-roblastic gneissic granites); 6 – lithologic contact; 7 – bedding/foliation; 8 – fault: a – traced, b – inferred; 9 – Tokachka detach-ment fault; 10 – cracking; 11 – silica sinter; 12 – intense silicification; 13 – moderate silicification; 14 – argillization; 15 – quartz veins; 16 – strike and dip of fault/quartz vein; 17 – outcrops of bladed quartz, this study; 18 – inferred fault, this study; 19 –

site of sampling.

41

The second style of bladed quartz outcrops in the central part of the deposit in two areas of elongated shapes with elongation in NW-SE direction. Both areas are almost parallel. On the cross-section it is seen that the two areas appear offset by a steep right normal-slip fault of vertical and horizontal displacements ~ 50 m and ~ 100 m, respectively (Fig. 1). It is supposed that the fault is in the central portion of the deposit and of north-south strike, and is hidden below thick diluvial sediments which cover the right slope of small incised valley [41, 89].

11. Morphology and zoning of apatite crystals as indicator for magma mixing in Petrohan pluton, Western Balkan, Bulgaria (E. Tacheva, M. Ta­rassov, E. Tarassova)

Effects of magma mixing on morphology and zoning of accessory apatite from the rocks (granodiorite, diorite and gabbro) of the Petrohan pluton (Western Balkan) are discussed in the work [50, 113].

Short prismatic, long prismatic and needle-like apatite crystals are found in the studied rocks. It is shown that the presence of elongated (needle-like and a part of long prismatic) crystals of the mineral is caused by the rapid cooling of the crystallization media containing fluids and is unequivocal evidence of the magma mixing – mixing of the mafic magma and the more cold and partially solidified granodiotic one.

Normal growth zoning of apatite is typical for short and long prismatic crystals (Fig. 1a). This type of zoning is well visible in BSE images in SEM with strongly enhanced contrast, and correlates with the variation in REE and Y con-tent. A part of the long prismatic crystals shows zones with clear signs of growth

Fig. 1. BSE images of long prismatic apatite crystals with normal growth zoning (a) and zoning with clear signs of growth break and dissolution (b).

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break and dissolution (Fig. 1b). These interruptions mark a stage of significant change in the chemical composition of the crystallization media associated with the emplacement of the mafic melt into incompletely crystallized granodiorites.

4.2. Environmental Mineralogy and Biomineralogy

12. Mineralogy, geochemistry and environmentally safety application of solid fuels and their combustion and pyrolysis products (S. Vassi-lev, C. Vassileva)

An extended overview of the advantages and disadvantages of biomass composition and properties for biofuel application was conducted based on refer-ence peer-reviewed data plus own investigations [31]. Initially, some general con-siderations and comparisons about composition and properties of biomass and coal as the most popular solid fuel are addressed. Then, some of the major advan-tages related to the composition and properties of biomass and/or biomass ash (BA) are discussed. They include: (1) high values of volatile matter, H, structural organic components, extractives and reactivity of biomass, water-soluble nutrient elements and alkaline-earth elements in biomass and BA, and pH of BA; and (2) low values of C, fixed C, ash, N, S, Si and initial ignition and combustion tem-peratures of biomass, and low contents of many trace elements including haz-ardous ones in biomass and BA. Further, some of the major disadvantages con-nected with the composition and properties of biomass and/or BA are described. They comprise: (1) high values of moisture and O in biomass, water-soluble frac-tion, alkaline and halogen elements, and some hazardous trace elements in bio-mass and BA; (2) low values of energy density (bulk density and calorific value), pH and ash-fusion temperatures of biomass, and bulk density and size of BA; (3) highly variable composition and properties of biomass and BA; and (4) in-definite availability of sustainable biomass resources for production of biofuels. It was found that the disadvantages of biomass for biofuel and biochemical applica-tions prevail over the advantages; however, the major environmental, economic and social benefits appear to compensate the technological and other barriers caused by the unfavourable composition and properties of biomass. Finally, a discussion about the availability of sustainable biomass resources for production of biofuels and biochemicals is given. It was emphasized that the conversion of biomass sources from natural ecosystems into energy resources may lead to serious environmental problems. The native ecosystems should be avoided, to a maximum extent, as resources for biofuel production. The potential favourable

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resources for that purpose should be focused preferably on: (1) non-edible agri-cultural, forest, feed and food residues; (2) semi-biomass (contaminated biomass and industrial biomass wastes); (3) short-rotation energy crops such as specifi-cally cultivated forest, grass and algae plantations, but grown only on existing low productive, degraded or contaminated non-arable land and in wastewater or contaminated ponds; and (4) animal and human wastes. The potential bio-mass resources for biofuel and biochemical production should always be divided initially into sustainable and unsustainable management resources under strictly specified environmental criteria [31].

The performance of a commercial multielement standardless/precalibrated XRF method for elemental analysis of raw biomass with limited prior sample preparation was studied [22]. Quick and reliable inorganic elemental chemical analysis of biomass (including solid biofuels) is of importance in the increasing utilization and trade of biomass. In particular, it is important for the exploitation of contaminated/dirty biomass/biomass waste, and potentially also as a tool in ascertaining the type/origin of biomass. X-ray fluorescence (XRF) spectrometry performed directly on the raw biomass with limited prior sample preparation is an attractive method for performing such inorganic elemental analysis. Therefore, the performance of a commercial multielement standardless XRF method pur-chased with a 4 kW wavelength dispersive (WD) XRF spectrometer was carefully investigated by analyzing five common biomass types (switchgrass, corn stover, eucalyptus, beech, and pine wood). Sample preparation involves milling the raw biomass using cutter and rotor mills (avoiding ball-milling) and coldpressing the powdered samples into pellets using wax binder. The accuracy (trueness and pre-cision) is determined by comparing the XRF data with the elemental composition obtained by standard elemental analysis (ICP-OES and ion-chromatography). The elements positively detected by the XRF are Na, Mg, Al, Si, P, S, Cl, K, Ca, Mn, Fe, Co, Ni, Cu, Zn, Sr, and maybe Mo. For elements above 25 ppm, the XRF data show a relative systematic error (bias, trueness) typically better than ±15% independent of the concentration. Quantifying elements below 25 ppm (Co, Ni, Cu, Zn, Sr, Mo) is possible in some cases, but it requires a more detailed study for each specific element. Quantification of silicon (Si) by XRF works well for concentrations >100 ppm. The XRF method can further be used to estimate the ash yield from biomass combustion with a relative bias better than ±10%. XRF method generally produces reliable results (keeping in mind the limitations and needed bias corrections) with errors comparable to the standard reference meth-ods. This suggests that typical standardless/precalibrated XRF methods work

44

well in elemental analysis of raw biomass (keeping in mind the limitations) and therefore could be considered for general usage in, for example, industrial ana-lytical laboratories requiring fast elemental analysis of biomass [22].

The major scientific and applied achievements of the long-term project “Min-eralogy, geochemistry and sustainable application of solid fuels (coal, biomass, municipal solid waste and coke) and their waste products (fly ash, bottom ash and slag) from thermal conversion” carried out at the Institute of Mineralogy and Crystallography – BAS were systematized [58]. The work is based on 89 publi-cations, most of them in international peer-reviewed journals, as well as on 27 international conferences’ reports and posters. The phase-mineral and chemi-cal composition of coals from various deposits worldwide and their solid waste products from power plants was identified and characterized for their advanced utilization. New combined chemical and mineral classifications of inorganic mat-ter in coal and coal ash were also created. The phase-mineral and chemical composition of coke products derived from the pyrolysis of municipal solid wastes was identified and characterized. As a result, some technological approaches for immobilization of toxic heavy metals during coke combustion were proposed. Low-cost catalytic sorbents for reduction of industrial NOx gases were produced and characterized. They are based on coal coke impregnated with transition met-als recovered from petroleum waste. Detailed data of biomass and biomass ash were used for systematization of: chemical and phase-mineral composition and properties of biomass and biomass ash; behavior of biomass during combustion; ash-fusion and ash-formation mechanisms of biomass; combined chemical and mineral classifications of biomass and biomass ash; and technological and en-vironmental advantages and challenges related to sustainable utilization of bio-mass and biomass ash [58].

The chemical and phase-mineral composition, as well as thermal behavior of mazut fly ash (MFA) and slag (MS) generated from a Syrian power plant were studied [32]. The data show that these waste combustion products could be po-tentially used for recovery and extraction of a number of valuable elements (V, Ni, Mo, Zn, Ag, Cd, Cr, Cu, Pb, Fe, and others) after appropriate physical separations and/or chemical treatment. Recovery and leaching of the valuable components should be followed by additional studies of MFA and MS residues for their suit-ability as building materials (cement and concrete), for road construction, soil sta-bilizer and other applications. Due to the high contents of transition metals in MFA and MS, these products may also be directly used as catalysts in production of different active sorbents for NOx reduction in stack emissions. The high content

45

of unburned organic components in MFA (67%) emphasizes possible options for char separation and subsequent producing of activated carbon materials, or as fuel for re-burning in the power plant. On the other hand, the present study also emphasizes that a number of toxic and potentially toxic elements (Ag, Cd, Co, Cr, Mo, Ni, Pb, S, V and Zn) have high concentrations in MFA and MS and they could potentially contaminate soils, waters, air and plants during transport, stor-age, processing and/or utilization of MFA and MS. The water-soluble phases (like sulphates) of the above elements could be particularly dangerous because they are highly mobile and could penetrate in animal and human digesting chains via contaminated waters, soils or vegetation [32].

13. Risk management of Koprivlen landslides (M. Kadiyski, S. Sarov, G. Frangov, V. Kostov­Kytin, S. Sarova, V. Stoyanov, L. Macheva, V. Pet-kova, T. Papaliangas)

The present paper provides detailed results from the implementation of pro-ject RISKLIDES in the framework of European Territorial Cooperation Programme “Greece-Bulgaria 2007–2013”. The study shows the geological and hydrogeo-logical features, as well as the risk mitigation strategy, and risk management of two landslides, developed in Miocene-Pliocene sediments next to Koprivlen village, Gotse Delchev municipality, Blagoevgrad region, SW Bulgaria. A detailed characteristic of the area has been made, including data for the seismic situation, water table, and seasonal rain values. Fieldwork included sample collecting, low-scale geological mapping, and core boring. Laboratory analyses were performed on the collected samples for mineralogical phase identification as well as for rock

Fig. 1. 3D model of landslide Koprivlen-1, scale in meters

Fig. 2. 3D model of landslide Kopriv-len-2, scale in meters

46

and soil strength. As a result, detailed low-scale 3D GIS maps of the landslides were produced (Figs. 1, 2) . A landslide risk management and mitigation strategy is provided for the prevention of the development of Koprivlen landslides [37].

14. Synthesis of carbon dioxide adsorbents by zeolitization of fly ash (Yu. Kalvachev, D. Zgureva, S. Boycheva, B. Barbov, N. Petrova)

Coal-combusting power plants are simultaneously among the main emit-ters of carbon dioxide and the main generator of solid by-products, such as fly ash . In our works [5, 63] an attempt to find a common solution for these envi-ronmental problems is reported. This study describes a synthesis procedure for zeolite X by interaction of fly ash, originating from Bulgarian lignite coals with sodium hydroxide (NaOH), followed by hydrothermal treatment. Ash residues, containing 52.66 mass% of SiO2 and 23.37 mass% of Al2O3, were subjected to a dual-stage fusionhydrothermal conversion. Coal ash and NaOH mixture at a ratio of 1:2 was sintered at 550 °C, and after dilution with water under continu-ous stirring, the reaction mixture was charged into an autoclave for hydrothermal reaction occurring for 2 h at 90 °C [5]. The obtained zeolite X was characterized by scanning electron microscopy and X-ray diffraction, and it was subjected to thermogravimetric analysis before and after exposure to carbon dioxide flow. The sorption capacity of the so-obtained zeolite with respect to carbon dioxide is estimated by using the thermogravimetric method. Determination of its adsorption capacity toward CO2 was carried out at 22 °C, it was measured to be 60 mg g–1 at this temperature, and the adsorption–desorption equilibrium was reached after 1 h under flow conditions (30 mL min–1). The sorption capacity of fly ash-based zeolite was compared to that of a reference zeolite X, synthesized from pure starting materials [63].

15. Mechanical testing of acid treatment mixtures of biomass and poultry excrement with sulfuric acid (Е. Serafimova, S. Milenkova, V. Stoyanov, Y. Pelovski, V. Petkova)

Various great quantities of solid wastes are generated from different indus-tries. During last 100 years generated solid wastes are more than those from the previous period of human civilization. The global objective is to minimize wastes but mostly of wastes are deposited, creating long term negative effects for human health. One promising direction for solving the problem is to create compositions containing poultry excrement and ash from the biomass, which is acid -treated with sulfuric acid.

47

To study these compositions several samples were produced at a specific homogenization then left to rest for several days. The process of production/granulation changes the physical properties of the mixture and to study it the static strength of the granules are examined. The obtained results show that the static strength of the granules in different mixtures varies, but exceeds the requirements of the standard, i.e. the tablets were prepared with good adhesion, pelletizing ability and excellent strength characteristics. The data analysis shows that the sufficient compression strength of the tablet may be achieved at wide range of initial moisture content, which indicates that it is possible to create com-positions with different ratio of components [48].

16. IR and Raman micro­spectroscopy applied for studying structural characteristics of dental apatite (R. Titorenkova, D. Vasilev, G. Jegovа, M. Rashkova)

Different vibrational spectroscopic techniques were applied to probe the structural state of dental apatite.

The IR reflection spectra (Fig. 1a) collected along the profile from the sur-face tooth enamel in depth to dentine-enamel junction (DEJ) reveal a gradual decrease of the intensity and change of the intensity ratio between the two most intensive peaks at 1050 and 1095 cm–1, resulting from antisymmetric stretching vibrations of phosphate group (ν3 PO4). These peaks are slightly shifted in the spectrum of dentine. Such spectral variations may be associated with increase of structural disorder and decrease of the size of crystallites toward DEJ. The main reason for increase of structural defects in biological hydroxyapatite is the isomorphic substitution of carbonate for phosphate group, known as B-type, and

Fig. 1. a, IR reflection spectra collected along the profile a (see Fig. 1c) from the surficial enamel (1) to dentine (5); b, ATR IR spectra collected from the profile b (see Fig. 1c) from the surficial enamel (1) to dentine (4–5); c, BEC image of cross section of tooth with indicated profiles, along which the

measurements were taken

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carbonate for hydroxyl group, known as A-type carbonate substitution. The pres-ence of B-type carbonate substitution is evidenced by the peaks at 874, 1450 and 1470 cm–1 caused by ν2 (CO3) bending and antisymetric ν3 (CO3) stretching of carbonate group, respectively (Fig. 1a, b). It has been shown, that antisym-metric stretching of phosphate group in apatite is most sensitive to the degree of carbonate substitution, thus the change of the intensity ratio of the two char-acteristic peaks at 1050 and 1095 cm–1 (ν3 PO4) is most probably related to de-gree of B-type carbonate substitution. Raman spectroscopy was applied to check this assumption, because according to the selection rules, symmetric stretching modes should be better resolved. An increase of the peak at 1071 cm–1 (ν1 B-type CO3) with decrease of that at 1048 cm–1 (ν3 PO4) confirmed that carbonate for phosphate group substitution in the enamel apatite gradually increases from the surficial layer to dentine.

ATR spectra of dentine are more intensive due to better contact of Ge ATR crystal and better penetration depth in softer material compared to enamel. The peaks of amides at 1665, 1552 and 1240 cm–1 reveal varying amount of organic compound in dentine (Fig. 1b).

It is shown that IR reflection and Raman spectroscopy (633 nm excitation wavelengths) are more appropriate techniques for studying enamel, while for dentine better results are obtained using ATR IR micro-spectroscopy. Due to the gradual change of the enamel apatite we should consider the whole profile from the surface to the dentine-enamel junction when studying the effect of various dental treatments [56, 57, 122, 123, 124].

17. Preparation and characterization of pastes based on calcium phos-phate powders and sodium hyaluronate (R. Ilieva, O. Petrov, E. Dyulgerova)

Series of paste-like materials were prepared on the basis of mono- or bi-phase calcium phosphate powders and sodium hyaluronate. Three procedures for preparation of CaP powders were applied and, as a result samples with differ-ent chemical, phase and morphological characteristics were obtained. The influ-ence of the latest as well as of the composition of the liquid phase and the solid to liquid ratio on the formation features and mechanical strength of the materials were investigated. It was found that high energy milling stimulates the binding capacity of the hydroxyapatite but not of β-TCP. In the cases of sodium hyaluro-nate solution the initial setting time is more than 20 min and the final about 1h. The included citric acid significantly reduces the settings time (3 min initial setting time) but decreases the pH of the SBF and distilled water below 4.

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It is of interest to underline that this study was inspired by the idea to pre-pare smart material for endodontics as root canal sealers, which is bio-inductive and promotes regeneration processes in the apical region [36]. This is a new challenge in 21st century endodontics studies related with the clinical application of new materials that can adopt to ever-changing microenvironment of the canal system. Having in mind this, we are hopeful for future investigation and results in this new disputable fields and to assist dentists in providing more predictable and reliable endodontic treatments.

4.3. Modeling and Modification of Mineral Systems

18. Transformation of perlite in phillipsite and its possible application as ion­exchanger (L. Dimitrov, N. Lihareva, O. Petrov)

Naturally occurring rhyolitic glass (perlite) was used as a starting material. The used perilite was in the form of natural rock, which was additionally crushed and milled in agate mortar to a fraction with less than 0.250 mm.

A supplementary method was elaborated to nano-sized zeolite EMT prepa-ration, which utilizes the waste mother waters from this synthesis for transforma-tion of natural perlite into phillipsite.

0 10 20 30 40 5002468

101214

Cs 13.28 meq/L Sr 9,05 meq/L K 4.58 meq/L

Con

cent

ratio

n, m

eq/L

Time, h

Fig. 1. Extent of Cs+, Sr2+ and K+ removal with time, from single cations solutions. In the legend there are presented the initial concentrations of the ions from which the ion-exchange is performed.

The obtained phillipsite sample was tested as ion-exchanger with solutions containing K+, Cs+ and Sr2+ for simulated radioactive fixation of these ions (Fig. 1). Cation-exchange effectiveness was also tested for Cs+ and Sr2+ solutions, con-taminated with nonionic surfactant Pluronic 123.

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The obtained distributions coefficients for K+, Cs+ and Sr2+ ions for the phil-lipsite sample, prepared from perlite are comparable or better than the ones, reported in the literature for synthetic titanium octahedral molecular sieve.

19. Thermal decomposition of zinc hydroxy­sulfate­hydrate minerals (N. Petrova, Ts. Staminirova, G. Kirov)

The thermal decomposition of three structurally and chemically close com-pounds: Zn4(OH)6SO4.4H2O, NaZn4(OH)6SO4Cl.6H2O and CaZn8(OH)12(SO4)2Cl2.9H2O, known as namuwite, gordaite and “Ca-gordaite” was comparatively studied. The thermal effects, the released volatiles and solid residues were studied in the range of 20 to 1000 °C using TG-DTA-MS and PXRD analyses.

The aforementioned minerals are found in natural conditions as alteration products of zinc ores and slag. Namuwite and gordaite compose the protective corrosion layer (zinc rust), which secures the excellent resistance of zinc and zinc-plated steel in urban, industrial and marine conditions. The interest towards the processes and the products of thermal decomposition of the zinc hydroxy sulfate Zn4(OH)6SO4.4H2O is provoked at first from their significance for the hy-drometallurgy of the zinc and the lead and in the latest years – as a precursor for production of micro- and nano-sized ZnO for various applications.

Fig. 1. Gordaite thermal decomposition: a) DTA-TG-MS data; b) Powder XRD patterns of initial and thermal treated samples.

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The thermal decomposition process of all three compounds includes release of water during successive dehydration and dehydroxylation and evolving of the other volatile components (Cl and SO2). The first stage of dehydration occurs in the low temperature region by the retention of the layered structure with an un-disturbed hydroxide layer and a shrunk interlayer. The release of last interlayer water molecules induces the dehydroxylation of the hydroxide layer. As a result, ZnO and a series of secondary hydroxides and hydroxy-salts: Zn3(OH)2(SO4)2 (in the decomposition of the three compounds), b-ZnOHCl (in the case of both gordaites) and Ca(OH)2 (for Ca-gordaite) were formed. The existence and forma-tion of Zn3(OH)2(SO4)2 for the first time were proved by powder XRD data. The destruction of all secondary hydroxyl-containing compounds during the second stage of the dehydroxylation leads to formation of Zn3O2(SO4)2, ZnCl2 and CaSO4

Fig. 2. Type, thermal stability and transformation of phases obtained during thermal decomposition of namuwite (bleak); gordaite (grey) and Ca-gordaite (white). The phases obtained at the expense

of: a) interlayer dehydration; b) dehydroxylation and destruction of hydroxide layers; c) the presence of Cl anion; d) the presence of interlayers Na or Ca cations.

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at middle temperature region. In the high temperature region the evolving of SO2, O2 and HCl was occurred due to the decomposition of the SO4-groups and ZnCl2 hydration, respectively. At temperatures up to 1000 °C, ZnO was found to be the main final product of the thermal decomposition of the three minerals. In the case of gordaites an anhydrite and a Na-Zn-SO4 X-ray amorphous phase were also presented. DTA-TG-MS data and powder XRD patterns of initial and thermal treated gordaite are presented on Fig. 1, while the type, thermal stability and transformation of phases obtained during thermal decomposition of namuwite; gordaite and Ca-gordaite on Fig. 2.

20. Compositional and structural study of partially exchanged on Na+, K+, Mg2+ and Ca2+ natural heulandite (L. Dimowa, I. Piroeva, S. Atanaso-va-Vladimirova, B. Shivachev, S. Petrov)

Single crystals of natural heulandite (HEU) from Iskra deposit (Bulgaria) are the initial material for this study. Four parts of this material were select-ed and were subject to partial ion-exchange on Na+, K+, Mg2+ and Ca2+ ions. The chemical composition of the natural and the exchanged samples was ob-tained by EDS analysis and the derived crystal chemical formula for this HEU is (Na1.05K1.20Ca1.90Sr1.18)Al8.35Si27.65O72.nH2O. Weight losses associated with zeo-litic H2O in the channels were obtained by TG. The single crystal X-ray structural

Fig. 1. Cation and H2O positions in natural heulandite end exchanged forms. A) natural-HEU, B) Ca-HEU, C) K-HEU and D) Na-HEU.

53

refinement revealed the topology of the Si/Al framework and located the posi-tions and site occupancies of the exchanging cations and water molecules in the channels A and B running along [010] and channel C along [001]. Initial (natural) heulandite crystals contain predominantly Ca2+ as framework counter ion and some amounts of Na+, K+ and Sr2+. Sodium and strontium ions are positioned Sr and Na/Sr positions in channel A. It was found out that in this early stage of Ca exchange that Ca2+ replaces Na+ from their mixed Na/Sr position. The K+-exchange leads to surplus of the positive charge, which removes indirectly Na+ without affecting Sr2+. In the Na+-exchanged form the sodium content increases in the mixed Na/Sr and Na position and small amount of Na+ is detected in the calcium position in channel B. The data obtained from EDS and structural refine-ment show that for the employed procedure Mg2+ ion exchange is not observed and its position at the center of the large channel A remains empty.

This study [8] aimed to bring some light on the effect of partial cation ex-change of natural non-modified heulandite. The single crystal structural refine-ment of the Na- K- and Ca-exchanged HEU forms shows that at the early stage of ion-exchange (up to seven (7) days) only cations located in the large channel A are affected except the Sr2+ one. The amounts of Ca2+ in channel B remain almost unchanged.

21. Structural and thermal transformations on high energy milling of natural apatite (V. Petkova, V. Koleva, B. Kostova, S. Sarov)

In this work we are investigated the isomorphic substitution and thermal decomposition of sedimentary fluorine apatite (FAp) (with Ca/P ratio >1.67) from Tunisia after high-energy- milling (HEM) activation at different time from 10 to 600 min. The chemical composition of the material includes: 29.6% Р2О5

total and

Table 1. Occupancy of the cation positions as displayed on Fig. 1

Channel Positions

Cation positions(Fig. 1)

Occupancy of the cation positions

Nat HEU Ca-HEU Na-HEU K-HEU

A~M1 Na/Sr, Ca/Sr, Na 0.29/0.3 0.18/0.32 0.4 0.09/0.36A~M1 Na 0.18A~M1 Sr 0.05 0.32B M2 Ca2 0.47 0.47 0.45 0.45B M2 Na 0.06C~M3 K 0.36 0.32 0.1 0.54

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46.5% CaO (main components) and 3.5% F; 0.55% R2O3 (R = Al, Fe); 1.1% SO3; 1.9% SiO2 (a low content in comparison with other natural apatites from North Africa or Asia); 0.35% MgO; 0.05% Cl; 6,6% CO2 as the impurities. HEM is a well-known approach for pre-paring various solid materials and for increasing their reactivity. The solid-state transformation of the initial and HEM activated apatite samples was examined by chem-ical analysis, BET, powder XRD, FTIR spectroscopy and thermal analysis. The structure of natural apatite allows isomorphic substi-tutions of carbonate, hydroxyl and metal ions by PO4

3–, Ca2+ and F–. The obtained powder XRD data indicate an increased defective-ness of the apatite structure in the course of the HEM. The solid state transformations of the initial and HEM activated apatite are examined by TG-DTA analyses. It is found that the thermal stability of the activated samples decreas-es as compared to the initial sam-

ple. This is related with the increased defectivity of the apatite structure during the high energy milling shown by the XRD data. The thermal analysis allows the differentiation of the structurally bonded A, B and A-B types carbonate ions from these originating from the calcite and dolomite admixtures.

The results obtained demonstrate that the mechanical distortion and the structural changes related with the migration of the carbonate ions from B type to A type channel positions are the main factors responsible for the enhanced solubility of the high energy activated FAp [24].

Fig. 1. TG curves of apatite in respect to the milling time 10–600 min

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22. Thermal and kinetic characteristics of some oil shale samples (T. Ka-ljuvee, R. Kuusik, V. Petkova)

The thermal behaviour of different oil shale samples (Estonia, Jordan, Isra-el, Morocco) was studied using a Setaram Setsys 1750 thermoanalyzers coupled to a Nicolet 380 FTIR Spectrometer. The experiments were carried out under non-isothermal heating conditions up to 1000 °C at different heating rates in an oxidizing atmosphere. A model-free kinetic analysis approach based on the dif-ferential isoconversional method of Friedman was used to calculate the kinetic parameters [38].

The thermooxidative decomposition of oil shale samples proceeded in three steps. Firstly, thermooxidation of volatile organic compounds occurred – depend-ing on the heating rate, up to 460 °C. Secondly, thermooxidation of heavier part of organic matter (kerogen) and fixed carbon as well as thermooxidation of pyrite proceeded up to 580 °C. Finally, carbonates contained in oil shale samples de-composed up to 870 °C.

Fig. 1. TG curves of samples at a heating rate of 1 °C min–1 (a) and 20 °C min–1 (b)

a) b)

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The combined TG-FTIR study of thermooxidative decomposition of samples made it possible to identify in addition to CO2 and H2O as major gases evolved a number of gaseous species like CO, SO2, COS, methane, ethylene, etc. formed and evolved at that. The value of activation energy E in the low-temperature oxi-dation region was for Estonian and Jordanian oil shale samples lower than that in the high-temperature region which was contrary for Israeli and Moroccan oil shale samples.

Therefore, the results obtained indicated the complex multi-step character of the thermooxidative decomposition of the oil shale samples studied.

4.4. Synthesis, Composition, Structure, and Properties of Minerals and New Materials

23. G­quadruplex DNA structures, crystallization remarks (L. Dimowa, H. Sbirkova, L. Tsvetanova, R. Nikolova, P. Hristoff, G. Radoslavov, T. Dou-kov, T. Todorova, B. Shivachev)

Possible human DNA sequences that can form G-quadruplex motif (G4) have been already identified. Using a new PCR procedure for the rapid iden-tification of G4 motif, we have further narrowed the choice DNA sequences to some 200 ones. In order to prove and fine tune the PCR procedure some of the sequences (Scheme 1) were selected for crystallization trial while other were subject to ligand binding by thermophoresis and ITC studies.

Scheme 1. Selected DNA sequences

A search for G-quadruplexes motifs in the PDB and NDB databases showed some 190 structures (100 NMR and 90 from X-ray experiments). Some of the G4 DNA have been used for DNA-ligand interaction with several ligands. Thus, the “exact” number of G4 sequences is limited to around 58 (from X-ray). Fortunately most of the reported structures featured the crystallization conditions (though not all of the conditions were properly described, e.g. the while the reagent conditions were listed their concentration were lacking in the databases).

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Thus, a suggested crystallization screen should be based on:PEG 400, KCl, Na/K cacodylate, Spermine tetrachloride, MPD, H2O, vapor

diffusion method, hanging drop, RT (293 K), pH 6.0–8.0, water must be ~50%v/v, DNA 1.0 to 1.4 mM.

Unfortunately, the crystal nucleation and growth is basically performed in a relatively constrained area of conditions and undoubtedly the use of such a re-stricted “crystallization set” may bias the real G4 structural features.

Table 1. Repetitions of crystallization reagents in the G4 crystallization conditions

Reagent Count PEG (various, 400 dominates) 21MPD, 2-methyl-2,4-pentanediol 24K cacodylate / potassium 27/ 29Na cacodylate /sodium chloride 27/18Spermine 19Ammonium/ammonium acetate 11/2Ca 3pH 7.0 to 8.0 / 6.5 to 7.0 34/24Total number of conditions/structures 58

Undeniably the conclusion is that the presence of K+ in the crystallization conditions stabilizes the G4 motif and in order to use the G4 in vivo one should investigate G4 formation in close relation with mechanisms of K uptake and release [70, 112].

24. Structural characterization of ionexchanged ETS­4 (L. Tsvetanova, R. Nikolova)

Single crystal X-ray diffraction (XRD) studies were performed on the crystal structure of Na-K-ETS-4 ant its ion-exchanged forms with mono- and divalent ions (Ag+, Cs+, Mg2+, Ba2+, Mn2+, Ni2+, Cu2+ and Zn2+).

Single crystal XRD experiments were carried out at room –290K (RT) and low temperature –150K (LT). For additional characterization of the materials the following methods were used: SEM (EDS); DTA-TG-DTG; powder XRD.

The data from single crystal XRD and EDS studies show that complete ion exchange is realized in the case of Ag- and Ba- forms of ETS-4. The ion ex-change causes deformation of the structure framework, realized by reducing of the unit cell volume. The degree of deformation decreases in the following order:

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Ba-> Zn-> Cu->Mn-ETS-4 (Table 1). The highest values are found for the Ba-ETS-4 and Zn-ETS-4 forms.

The charge compensation in structure is achieved by both metal ions and hydrogen atoms. The Ag- and Cs-ETS-4 samples show highest ion exchange capacity (Table 2).

Table 1. Framework deformation at room temperature and 150K, present in percentage

Ion exchanged forms of ETS-4

Volume of the unit cell, RT(Å)

Volume of the unit cell, LT(Å)

Percentage deformation of the volume of unit cell after ion exchange

Percentage deformation of the volume of

unit cell after ion exchange (RT)

and LT

Na-K 1165.7 1161.93 0 0.33Ag 1165.6 1157.4 0 0.71Cs 1169.6 1156.1 0.33 increase 1.16Mg 1165.5 1157.0 0 0.73Ba 1105.5 1105.5 5.17 0Mn 1143.4 1145.8 1.92 0.20 increaseNi 1155.8 1160.1 0.85 0.37 increaseCu 1139.1 1140.7 2.29 0.14 increaseZn 1116.8 – 4.2 –

Table 2. Calculated a theoretical CEC (cation exchanged capacity) on measured Mr (relative molecular mass) and equivalents by single crystal XRD

Na-K-ETS-4 CEC Ag-ETS-4 CEC Cs-ETS-4 CECRT LT RT LT RT LT

4.24 meq/g 4.23 meq/g 2.83 meq/g 2.86 meq/g 2.73 meq/g 2.73 meq/g

Mg-ETS-4 CEC Ba-ETS-4 CEC Mn-ETS-4 CECRT LT RT LT RT LT

2.24 meq/g 2.55 meq/g 2.30 meq/g 2.34 meq/g 2.25 meq/g 2.18 meq/g

Ni-ETS-4 CEC Cu-ETS-4 CEC Zn-ETS-4 RT CECRT LT RT LT

2.07 meq/g1.29 meq/g 1.49 meq/g 1.59 meq/g 1.70 meq/g

According to the thermal analyses Mg- and Mn- forms of ETS-4 are ones with highest water amount, which is expected due to the high hygroscopicity of these ions.

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25. Structural insights into M2O–Al2O3–WO3 (M = Na, K) system by electron diffraction tomography (I. Andrusenko, Y. Krysiak, E. Mugnaioli, T. Gorelik, D. Nihtianova, U. Kolb)

For transmission electron microscopy (TEM), electron dispersive X-ray spectroscopy (EDX) and automated diffraction tomography (ADT) investiga-tions, powdered samples were dispersed in ethanol using an ultrasonic bath and

Fig. 1. STEM images and the corresponding EDX spectra of (a)–(b) K5Al(W3O11)2, (c)–(d) NaAl(WO4)2 (phase II) and (e)–(f) Na2W2O7 (phase I).

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Fig. 2. Reconstructed three-dimensional diffraction volumes obtained by ADT data. K5Al(W3O11)2 reconstructed diffraction volume projected down c*(a) and b* (b), where reflections 7k0 are marked with a circle; Na2W2O7 (phase I) diffraction volume projected down c* (c) and a* (d); NaAl(WO4)2 (phase II) diffraction volume projected down c* (e) and a* (f). Cells are sketched close to the diffraction center. The three possible C-centered orthorhombic cells able to describe the diffraction volume of Na2W2O7 and NaAl(WO4)2 are shown in the upper-right corner of (c). Extinctions due to glide planes are marked by arrows. Note that the panel shows projections of three-dimensional diffraction volumes and not two-dimensional in-zone patterns. Therefore, what may be misunderstood to be a single

reflection is in fact the projection of a column of reflections.

sprayed on carbon-coated copper and gold grids using a sonifier. TEM, EDX and ADT measurements were carried out with a FEI TECNAI F30 S – TWIN trans-mission electron microscope equipped with a field emission gun and working at 300 kV. TEM images and nanoelectron diffraction (NED) patterns were taken with a CCD camera (14-bit GATAN 794MSC, 1024×1024 pixels) and acquired by

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Gatan Digital Micrograph software. Scanning transmission electron microscopy (STEM) images were collected by a FISCHIONE high-angular annular dark field (HAADF) detector and acquired by Emispec ES Vision software. EDX spectra were acquired using an Oxford EDAX EDX spectrometer, equipped with a Si/Li detector and an ultrathin window. Gold grids were used for the quantification of sodium, because in EDX spectra K-lines of sodium partially overlap with L-lines of conventional copper grids.

Three-dimensional electron diffraction data were collected using an auto-mated acquisition module developed for FEI microscopes. For high tilt experi-ments all acquisitions were performed with a FISCHIONE tomography holder. A condenser aperture of 10 μm and mild illumination settings were used in order to produce a semi-parallel beam of 50 nm in diameter on the sample. Crystal position tracking was performed in microprobe STEM mode and NED patterns were acquired sequentially in steps of 1°. Tilt series were collected within a total tilt range up to 120°, occasionally limited by overlapping of surrounding crystals or grid edges.

ADT data were collected both with and without electron beam precession (precession electron diffraction, PED). PED was used in order to improve reflec-tion intensity integration quality, while data sets without precession were used for accurate cell parameter determination. PED was performed using a Digistar unit developed by NanoMEGAS Company. The precession angle was kept at 1.2°. The ADT3D software package was used for three-dimensional electron diffrac-tion data processing.

The main strength of electron diffraction is the possibility of collecting data from single nanoscopic crystallites, even inside polyphasic mixtures.

In this paper [1] we describe the structure analysis of nanocrystalline K5Al(W3O11)2 and NaAl(WO4)2 based on electron diffraction tomography data ac-quired using the ADT method.

26. Electromechanical properties of polyimide composites containing titanium dioxide nanotubes (E. Hamciuc, M. Ignat, C. Hamciuc, I. Stoica, L. Dimitrov, Yu. Kalvachev, M. Olariu)

Polyimide composite films were prepared by casting solutions resulting from direct mixing of a poly(amic acid) and titanium dioxide (TiO2) nanotubes (TNTs) onto glass plates, followed by thermal imidization. TNTs with inner diameter of 4–5 nm, outer diameters of approximately 10–12 nm and length of several hun-dreds of nanometers were synthesized by the hydrothermal method and their

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surface was modified by treating with 3-aminopropyltriethoxysilane. A series of polyimide composite films with various contents of TNTs were easily prepared by a solution mixing technique. The morphology of the nanotubes was investi-gated by using high-resolution transmission electron microscopy. The influence of TNTs content on structural, thermal, and electromechanical properties of pure polyimide and composite films was studied. The scanning electron microscopy and atomic force microscopy showed good compatibility between TNTs filler and polyimide matrix. The value of average roughness of film surface increases with increasing the content of TNTs. The films were flexible, tough, and exhibited high thermal stability. The films exhibited electrostrictive properties with the strains proportional to the square of electric field. The actuation for each sample in-creased with the increase of the voltage. Thus, nanometric displacements in the range of 250–800 nm were obtained when an electric voltage of 500 V was ap-plied on the film surface [13].

Dynamic mechanical analysis and broadband dielectric spectroscopy were used to evidence relaxation processes into the films. The electrical properties were evaluated on the basis of dielectric constant and dielectric loss, and their variation with frequency and temperature. At lower temperature the films showed a secondary β relaxation correlated with local movements. The introduction of TNTs led to strong decrease of activation energy of β relaxation, as well as the appearance of an additional β1 process. At higher temperature a α relaxation and a conductivity process were evidenced. The dielectric constant of the films was in the range of 3.40–5.34, at 100 °C and 1 kHz while the dielectric loss, in the same conditions, was in the range of 0.015–0.110. By increasing the TNTs content, an increase of the dielectric constant values was observed. The maxi-mum of σ relaxation peak shifted to higher temperature. The additional heating of the film containing 20% TNTs, at 400 °C for 3 h, results in strong decreasing of the β relaxation and shifting of the α relaxation to higher temperature range. The properties of these polyimide/TNTs composites make them attractive materi-als for advanced applications where good thermal characteristics and improved dielectric constant are required [66].

27. Seed­assisted synthesis of nanosized Beta zeolite (B. Barbov, Yu. Kalvachev)

The high industrial interest to zeolite Beta originates from the broad Si/Al range in zeolite Beta (5 – ∞) and its particular structure, being an intergrowth of different polymorphs and therefore being disordered in one dimension. The com-

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bination of three-dimensional pore architecture composed of intersecting 12-ring channels with strong acid sites makes this zeolite useful catalyst in a number of processes – such as catalytic cracking, hydroisomerisation, alkylation of aromat-ics, and esterification reactions, etc. In order to obtain nanosized crystals of zeo-lite Beta hydrothermal seed-induced synthesis is performed. Nanosized zeolites are important in catalytic and adsorptive applications. Smaller crystals of zeolites have larger surface areas and less diffusion limitations compared to zeolites with micrometer-sized crystals. Zeolite Beta with high crystallinity is obtained from the system with the following molar ratio: 9TEAOH: xAl2O3: 100SiO2: 420H2O where x= 1.66, 1.0 and 0.5, when the Si/Al ratio is between 30 and 100. Samples syn-thesized with a ratio Si/Al <25 have amorphous structure. Attempts to synthesize zeolite Beta are successful also with a ratio Si/Al = 100, but then the yield is very small. Synthesis of zeolite Beta without the use of Al (Si/Al = ∞) were unsuccess-ful despite the long crystallization time of more than 200 hours.

In the experiments for the synthesis of zeolite Beta in the presence of both types of seeds – crystal seeds and suspension of mother liquor, were obtained crystalline products from initial gel having a ratio Si/Al = 25, 50, 100 and ∞, while attempts for the synthesis of zeolite Beta with a ratio Si/Al = 12,5 are fail despite the use of 5 wt% seeds and crystallization time of 168 hours. Samples with high crystallinity are obtained during the synthesis of zeolite Beta with both types of seeds. The yield of zeolite Beta in the presence of suspension of mother liquor is higher than that of zeolite Beta synthesized in the presence of a crystal seeds. The crystalline samples of zeolite Beta synthesized in the presence of both types of seeds with different ratio (Si / Al = 25, 50, 100, and ∞) are nanosized. The size of the crystallites varies between 100 and 400 nm [3].

28. Seed­mediated approach for the size­controlled synthesis of mor-denite type zeolite from organic template free initial gel (T. Todorova, Yu. Kalvachev)

Due to extensive channel system in combination with high thermal and acidic stability mordenite is widely used as a catalyst in reactions of hydrocrack-ing, isomerization, hydroisomerization, alkylation, reforming, and the production of dimethylamine. Hydrothermal synthesis of mordenite without using of organic SDA’s in the system 18 SiO2 : Al2O3 : 1.24 K2O : 1.21Na2O : xH2O (x=600, 280 and 22.5) is performed.

The resulting product has uniform particles with high crystallinity. Two syn-thesis approaches are applied. In the first one a standard initial gel is subjected

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to hydrothermal crystallization for period ranging between 2 and 7 days. The second approach includes the use of seeds as the same initial gel composition is employed. The crystal growth kinetics of mordenite at different seed content was studied. The seed amount was adjusted to be 1, 2 and 5 wt% from the total silica amount in the gel. The initial gel was aged for 24 hours at room temperature, and then the synthesis is carried out in 160 °C and 180 °C for period between 6 and 168 hours. The seeds are synthesized from starting gel having molar composi-tion: 18 SiO2 : Al2О3 : 1.24K2O : 1.21Na2O : 280H2O. The crystallization of seeds was performed under static conditions for a period of 120 hours at 180 °C. By using of seed-assisted process, we were able to synthesize mordenite crystals of submicrometric range. Water content in the initial gel and the amount of added seed are the parameters, which strongly influence on the particle size of resulting products. By changing of these parameters the size of zeolite particles can be controlled. It was found that seed concentration and water content in the initial gel are the key factors influencing the crystallization time and the physicochemical properties of crystalline products. Six hours is the shortest time in which zeolite mordenite with high crystallinity is obtained [29].

29. Comparison between thermal behaviour of γ­MnC2O4.2H2O in oxi-dative and inert media (B. Donkova, V. Petkova)

Sparingly soluble manganese oxalate is an appropriate precursor for prepa-ration of various nano-sized manganese oxides which explains the growing inter-est to its utilization and investigation of its thermolysis.

Recently, three crystal forms of manganese oxalate are known – monoclinic α-MnC2O4.2H2O (SG C2/c), orthorhombic γ-MnC2O4.2H2O (P212121) and or-thorhombic trihydrate MnC2O4.3H2O (Pcca). While the mechanism and products of thermal decomposition of monoclinic dihydrate have been extensively studied by various methods, the literature data for the trihydrate and orthorhombic dihy-drate are quite scarce.

The aim of the present study is to investigate and compare the decom-position mechanism of the slightly known γ-MnC2O4.2H2O in oxidative and in-ert media under non-isothermal conditions with analysis of the evolved gases. Pure phase of pinkish orthorhombic dihydrate was obtained and characterized by X-ray diffraction and scanning electron microscopy. Le Bail whole pattern fit-ting analysis was performed in addition. The non-isothermal investigation was carried out in a static Air and Ar atmosphere (60 ml.min–1) at a heating rate of 5 °C.min–1 in the range of 25–800 °C, using a coupling system TG-MS – instru-

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ment SETSYS2400 combined with a mass-spectrometer. According to TG-DTA-DTG curves, dehydration proceeds in the interval 140–187 °C in Ar and 140– 182 °C in air. The corresponding intervals of decomposition are 335–434 °C in Ar and 230–361 °C in air. In inert Ar atmosphere, CO and CO2 are liberated simul-taneously and MnO is obtained as a final product. In oxidative air atmosphere the evolved CO participate in additional oxy-reduction reactions and only CO2 is detected. The decomposition is accompanied by oxidation of Mn(II) thus leading to formation of manganese oxides in higher and most probably mixed oxidation states. The investigations at other heating rates and calculation of the reaction enthalpy and activation energy of the processes under different atmospheres are in progress [9].

30. Impact of preparation method and chemical composition on phys-icochemical and photocatalytic properties of nano­dimensional mag-netite­type materials (Z. Cherkezova-Zheleva, K. Zaharieva, M. Tsvetkov, V. Petkova, M. Milanova, I. Mitov)

Nickel ferrites with different Ni content, Ni, 0 ≤ x ≤ 1, are technologically important materials for microwave, electronic, and magnetic storage devices. They are members of solid-solution series of spinel-type materials (Fe3O4–NiFe2xOFe43–xO4) having specific magnetic properties and different degree of electron delocalization. They demonstrate good gas sensing properties and cata-lytic activity in various catalytic processes, such as complete oxidation of waste gases, oxidative dehydrogenation of hydrocarbons, decomposition of alcohols, etc. The preparation of such materials is still an actual problem due to several difficulties in their synthesis and the use of special techniques.

Fig. 1. DTA and TG curves of γ-MnC2O4.2H2O decomposition in air (a) and Ar (b).

a) b)

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A series of nickel-containing ferrite materials NixFe3–xO (x = 0.25, 0.5, 1) were prepared by precipitation method using FeCl.3H2O, FeCl2.4H2O, and NiCl4.6H2O as precursors. The performed analyses show the dependence of the rate of formation of the spinel phase on the chemical composition. To obtain the exact conditions for a single-phase spinel material preparation several investi-gations have been performed: thermal analysis (thermogravimetry, differential thermogravimetry, and differential thermal analysis) and various studies of the intermediates by powder X-ray diffraction, Mössbauer spectroscopy (at room and liquid nitrogen temperature), BET method, and SEM. As a result, the appropriate conditions of obtaining monophase nanomaterials of doped magnetite are found. The synthesis involves a precipitation process combined with a low-temperature heat treatment of materials (at 300 °C and in argon atmosphere) or mechano-chemical processing.

Application of the second procedure leads to two interesting results: (1) syn-thesis of the target compounds under soft and clean conditions without heating, which is important for industrial technology and environmental protection and (2) the prepared samples have better characteristics (higher dispersion degree, better magnetic properties, and higher activity in photocatalytic purification of wastewater from the textile industry) [6].

31. Selective synthesis of monoglycerol oleate and investigation of its anti­wear performance as a friction modifier (S. Kеrekov, N. Gospodi-nova, L. Dimitrov, M. Nikolov)

Esterification of oleic acid with glycerol to monoglycerol oleate (MGO) was performed applying zeolite type FAU in the alumina matrix catalyst and immobi-

Fig. 1. TG, DTG, and DTA curves of synthesized nickel-containing

ferrite sample A.

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lized zinc succinate complex on silica-alumina. A crude glycerol, which is a side product from bio-diesel plant, was used. The heterogeneous catalyst applied for esterification could be easily separated from the product after the reaction [40].

Anti-wear properties of obtained MGO applied as additives to tree types of lubricating oils were investigated. It was found that addition of 2% MGO to SN 500 base, SAE 30 and SAE 5W 40 engine oils, was optimal, leading to 10–13% improvement of the anti-wear properties of the abovementioned oils.

32. Mechanical tests of composite ceramic materials (Е. Serafimova, S. Milenkova, V. Stoyanov, Y. Pelovski, V. Petkova)

Reuse of waste is one way to maintain the high quality of the environ-ment and to achieve the implementation of some of the principles of sustainable development. Studies provide new evidence in mechanical tests and strength characteristics and behaviour of new composite ceramic materials, which are suitable for use in the construction industry. The proposed compositions may be used directly in existing technology and equipment. This will contribute to the sustainability of economic production and better efficiency in the production of bricks [47, 99].

33. From kröhnkite­ to alluaudite­type of structure: easy synthesis of novel sodium manganese sulfates with electrochemical properties in alkaline ion batteries (D. Marinova, V. Kostov, R. Nikolova, R. Kukeva, E. Zhecheva, M. Sendova-Vasileva, R. Stoyanova)

The alluaudite-type of structure is of huge research interest as an open matrix ensuring fast alkaline ion mobility, a property that could contribute to the development of novel electrode materials for rechargeable alkaline ion batteries. In this communication, we provide new data on the formation of well-crystallized sodium manganese sulfates Na2+dMn2-d/2(SO4)3 with an alluaudite-type of struc-ture by simple dehydratation of the corresponding dihydrate Na2Mn(SO4)3·2H2O with a kröhnkite-type of structure. The structure of Na2+dMn2-d/2(SO4)3 is deter-mined on the basis of Rietveld refinement of powder XRD patterns, infrared (IR) and Raman spectroscopy and electron paramagnetic resonance at X- and Q-band frequencies (EPR). From a structural point of view, the release of two H2O molecule from the kröhnkite phase takes place by a transformation of the infinite [Mn(SO4)2(H2O)2] chains into Mn2O10 dimers bounded by distorted Na(1)O-polyhedra. The anhydrous sulfates are able to participate in the elec-trochemical reaction delivering reversible capacity of 135 mAh/g, when they are

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used as cathode materials in lithium ion cells. The stability of the alluaudite phase Na2+dMn2-d/2(SO4)3 in the lithium electrolyte solution and the mechanism of the electrochemical reaction are discussed on the basis of ex-situ EPR, IR and Ra-man spectroscopy. This is a first report on electrochemical activity of manganese-based sulfate with an alluaudite-type of structure [20].

4.5. PhD Theses

34. Crystal­chemical and structural characteristics of minerals from skarns in Zvezdel pluton (Y. Tzvetanova)

Skarn xenoliths hosted by monzonitic rocks of the second intrusive phase of the Zvezdel pluton are the focus of this study. Field observations and quan-titative determination of mineral phases using Rietveld-based XRD method are integrated with petrography, chemical and structural features of minerals, whole-rock lithogeochemistry and REE and trace elements distribution in order to: (i) delineate the skarn zones, (ii) calculate the gain-loss chemical mass balance during the skarn formation, (iii) to determine the different stages and facies dur-ing the subsequent alteration and evolution of the metasomatic processes [126].

Fig. 1. General view of the alluaudite-type structure

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The skarn nodules consist of coarse grained clinopyroxene-garnet- or gar-net-rich domains in a quartz-calcitic matrix, surrounded by wollastonite-bearing zones, which exhibit massive, spotted or banded fabrics. The following zones are determined from the contact with the monzonite rock towards the proximal parts of the nodules: monzonite → plagioclase-clinopyroxene (endoskarn) → pla-gioclase-clinopyroxene-wollastonite+epidote (endoskarn) → plagioclase-clino-pyroxene-wollastonite (endoskarn) → plagioclase-clinopyroxene-wollastonite-garnet (contact zone between endo- and exoskarns) → clinopyroxene-garnet (exoskarn) → garnet (exoskarn).

Mineral assemblages in the skarns include garnets of the grossular-andra-dite series (Adr96.61–3.13) and melanites with TiO2 content of 8.04–13.10 wt.%, fassaitic clinopyroxene (with Al2O3 – 10.17–17.75 wt.%. and Fe3+ – 0.165– 0.487 apfu), clinopyroxene of the diopside-hedenbergite series, wollastonite-2M (determined by single-crystal XRD structure refinement), plagioclase (An96.7–0.0), and calcite with subordinate quartz, epidote, prehnite and chlorite. Titanite, apa-tite and magnetite are present as accessories in all zones. Melilite occurs mainly as short prismatic crystals up to ~80 μm in length enclosed in garnet crystals from clinopyroxene-garnet zone and is composed mostly of a binary solid solution be-tween gehlenite and åkermanite with gehlenite: åkermanite ratio 60:40.

The monzonite-normalised trace elements patterns of skarn rocks reveal enrichment in V, Sc, Be, Co, Ag, Sr Zn and depletion in Ba, Cs, Rb, U, Th, W, Pb, Zr, Hf, Nb, Ta, Y, Cr, and ΣREE. The mineralogical control of REE and trace ele-ments distribution was discussed.

According to mineral assemblages two main stages have been distinguished – magmatic and postmagmatic one. The products of the magmatic stage: meli-lite, fassaitic clinopyroxene and wollastonite-I (above 800 °C) are overprinted by metasomatic anhydrous mineral assemblages of the postmagmatic stage: gar-nets, clinopyroxene of the diopside-hedenbergite series, wollastonite-II and pla-gioclase. Infiltration of late-stage fluids at lower temperature results in formation of epidote, prehnite, chlorites, thaumasite, gypsum, zeolites, quartz, and calcite.

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5. International Cooperation

• “Chemical and Radiological Risk in the Indoor Environment” (CheRRIE) – a joint research project between IMC and the Aristotle Uni-versity of Thessaloniki, Alexander Technological Education Institutes of Thessaloniki, Technical Chamber of Greece and Hellenic Association of Chemical Engineers, financially supported by the Program for Euro-pean Territorial Co-operation “Operational Programme Greece–Bulgaria 2007–-2013”, co-financed by the European Union through the European Fund for Regional Development

• “Structural studies of nanosized porous and layered materials” – a joint research project between IMC and the Institute of Inorganic Chem-istry, Czech Academy of Sciences, under the bilateral academic agree-ment with equivalent non-currency exchange.

• “Research on the kinetics of ion exchange sorption of clinoptilo-lite tuffs from Russia and Bulgaria by metal contaminants (Cs, Sr, heavy metals) in natural waters” – a joint research project between IMC and the Vernadsky Institute of Geochemistry and Analytical Chem-istry, Russian Academy of Sciences, under the bilateral academic agree-ment with equivalent non-currency exchange.

• “Minerals of rare elements in granites of S- and A-types on the ex-ample of peraluminous granites of Bulgaria and alkaline granites of the Kola Peninsula, Russia” – a joint research project between IMC and the Geological Institute of the Kola Science Centre, Russian Acade-my of Sciences, under the bilateral academic agreement with equivalent non-currency exchange.

• “Zeolite-polymer hybrid materials with tailored properties” – a joint research project between IMC and the Institute of Macromolecular Chemistry, Romanian Academy of Sciences, under the bilateral academ-ic agreement with equivalent non-currency exchange.

6. Visiting Scientists

Dr. Boriana Mihailova – Visitor-professor on “Spectroscopy of Miner-als” and “Crystal Physics” at the Faculty of Earth Sciences, University of Hamburg, GermanyDr. Stanislav Ferdov – Researcher in the Department of Physics, Univer-sity of Minho, Guimaraes, Portugal

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7. Research Topics, Announced for International Partnership Collaboration

Advanced multicomponent utilization of fly ashes from European coal-fired power stations

One of the environmental problems in Europe is the utilization of fly ashes (FAs) from coal-fired thermoelectric power stations (TPSs). This potential investi-gation will include characterization of various products recovered from FAs at Eu-ropean TPSs in an attempt for multicomponent FA utilization (MFAU). The MFAU is a necessary and unavoidable process due to the complex, heterogeneous and unique polycomponent composition of FA. The purpose will be: (i) to demon-strate how a low-cost waste can be transformed into useful, high-grade and valu-able materials, which may find various applications; (ii) to provide a basis for the advanced, multicomponent, wasteless and environmentally friendly utilization of various FAs. The knowledge about the composition of FAs is sufficient to start an advanced and effective MFAU.

Structure and properties of new multifunctional materials

Synthesis and investigation of new materials of practical importance (nano-sized zeolite-type natural and synthetic materials and thin films; ferric iron oxide materials; catalysts based on micro- and mesoporous carriers for removal of soot and nitrogen oxides from exhausted gasses; titanosilicate porous materials for ion-exchange, sorbents, and catalytic systems; materials for optical and mag-netic storage and processing of information; preparation and investigation of coal char based sorbents and catalysts). Characterization methods: X-ray diffraction, electron microscopy, Raman scattering and infrared absorption spectroscopies, optical measurements and chemical analysis. Education: M.Sc. and PhD in Min-eralogy, Crystallography and Materials Science.

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8. Publications and Reports at Scientific Forums

8.1. Published Articles and Reports (indexed in Web of Science, IF or SJR)

1. Andrusenko, I., Krysiak, Y., Mugnaioli, E., Gorelik, T.E., Nihtianova, D., Kolb, U. 2015. Structural insights into M2O-Al2O3-WO3 (M = Na, K) system by electron dif-fraction tomography. – Acta Crystallographica Section B: Structural Science, Crys-tal Engineering and Materials, 71, IUCr Journals, ISSN:2052-5206, 2052-5192, DOI:doi:10.1107/S2052520615007994, 349–357. SJR:0.75, ISI IF:2.184.

2. Antonov, L., Deneva, V., Simeonov, S., Kurteva, V., Crochet, A., Fromm, K. M., Shi-vachev, B., Nikolova, R., Savarese, M., Adamo, C. 2015. Controlled Tautomeric Switching in Azonaphthols Tuned by Substituents on the Phenyl Ring. – Chem. Phys. Chem., 16, 3, Wiley, ISSN:1439-7641, DOI:10.1002/cphc.201402691, 649–657. ISI IF:3.419.

3. Barbov, B., Kalvachev, Yu. 2015. Seed-assisted synthesis of nanosized Beta zeo-lite. – Compt. rend. Acad. bulg. Sci., 68, 8, ISSN:13101331, 983–990. SJR:0.21, ISI IF:0.307.

4. Boyadzhieva, T., Koleva, V., Zhecheva, E., Nihtianova, D., Mihaylov, L., Stoyano-va, R. 2015. Competitive lithium and sodium intercalation into sodium manganese phospho-olivine NaMnPO4 covered with carbon black. – RSC Advances, 5, 106, Royal Society of Chemistry, ISSN:2046-2069, DOI:DOI: 10.1039/C5RA17299C, 87694–87705. SJR:1.03, ISI IF:3.84.

5. Boycheva, S., Zgureva, D., Barbov, B., Kalvachev, Yu. 2015. Synthetic micro- and nanocrystalline zeolites for environmental protection systems. – Nanoscience Ad-vances in CBRN Agents Detection, NATO Science for Peace and Security Series A: Chemistry and Biology, Springer, ISBN:ISBN 978-94-017-9697, 8, 443–450. SJR:0.105.

6. Cherkezova-Zheleva, Z., Zaharieva, K.L., Tsvetkov, M.P., Petkova, V., Milanova, M.M., Mitov, I.G. 2015. Impact of preparation method and chemical composition on physicochemical and photocatalytic properties of nano-dimensional magnet-ite-type materials. – American Mineralogist, 100, Mineralogical Society of Amer-ica, ISSN:ISSN: 0003-004X, DOI:http://dx.doi.org/10.2138/am-2015-5152, 1257–1264. ISI IF:1.964.

7. Dimowa, L.T., Petrov, O.E., Djourelov, N.I., Shivachev, B.L. 2015. Structural study of Zn-exchanged natural clinoptilolite using powder XRD and positron anni-hilation data. – Clay Minerals, 50, 1, Mineralogical Society of Great Britain and Ire-land, ISSN:0009-8558, DOI:10.1180/claymin.2015.050.1.05, 41–54. SJR:0.643, ISI IF:0.969.

8. Dimowa, L.T., Piroeva, I., Atanasova-Vladimirova, S., Petrov, S., Shivachev, B. 2015. Compositional and structural study of partially exchanged on Na+, K+, Mg2+ and Ca2+ natural heulandite. – Bulg. Chem. Commun., 47, 360–367, ISSN:0324-1130, ISI IF:0.349.

9. Donkova, B., Petkova, V. 2015. Comparison between thermal behaviour of γ-MnC2O4.2H2O in oxidative and inert media. – Bulg. Chem. Commun., 47, 1, 185–189, ISSN:ISSN: 0324-1130, SJR:0.201.

10. Dyulgerov, V. M., Dimowa, L. T., Kossev, K., Nikolova, R. P., Shivachev, B.L. 2015. Solvothermal synthesis of theophylline and N,N’-(ethane-1,2-diyl)diformamide co-crystals from DMF decomposition and N-formylation trough catalytic effect of 3-carboxyphenylboronic acid and cadmium acetate. – Bulg. Chem. Commun., 47, 1, 311–316, ISSN:0324-1130, SJR:0.156, ISI IF:0.349.

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11. Gancheva, M., Naydenov, A., Iordanova, R., Nihtianova, D., Stefanov, P. 2015. Mechanochemically assisted solid state synthesis, characterization, and cata-lytic properties of MgWO4. – Journal of Materials Science, 50, 9, Springer US, ISSN:0022-2461, 1573–4803, DOI:DOI: 10.1007/s10853-015-8904-5, 3447–3456. SJR:0.93, ISI IF:2.371.

12. Gonzalez, J.R., Zhecheva, E., Stoyanova, R., Nihtianova, D., Markov, P., Chapuis, R.R., Alcantara, R., Tirado, J.L., Ortiz, G.F. 2015. A fractal-like electrode based on double-wall nanotubes of anatase exhibiting improved electrochemical behaviour in both lithium and sodium batteries. – Physical Chemistry Chemical Physics, 17, 6, Royal Society of Chemistry, ISSN:1463-9084, 1463–9076, DOI:DOI: 10.1039/C4CP04572F, 4687–4695. SJR:1.61, ISI IF:4.493.

13. Hamciuc, E., Ignat, M., Hamciuc, C., Stoika, I., Dimitrov, L., Kalvachev, Yu., Olariu, M. 2015. Electromechanical properties of polyimide composites – containing tita-nium dioxide nanotubes. – High performance polymers, 27, 5, ISSN:1361-6412, DOI:doi: 10.1177/0954008315584185, 590–598, SJR:0.385, ISI IF:1.286.

14. Hristov, P., Teofanova, D., Neov, B., Shivachev, B., Radoslavov, G. 2015. Mitochon-drial diversity in autochthonous cattle breeds from the Balkan Peninsula. – Czech Journal of Animal Science, 60, Czech Academy of Agricultural Sciences, ISSN:1212-1819, DOI:10.17221/8277-CJAS, 311–318. SJR:0.513, ISI IF:1.183.

15. Kalapsazova, M., Ortiz, G.F., Tirado, J.L., Dolotko, O., Zhecheva, E., Nihtianova, D., Mihaylov, L., Stoyanova, R. 2015. P3-type layered sodium-deficient nickel-manganese oxides: A flexible structural matrix for reversible sodium and lithium in-tercalation. – ChemPlusChem., 80, 11, WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim, ISSN:2192-6506, DOI:10.1002/cplu.201500215, 1642–1656. SJR:0.77, ISI IF:3.026.

16. Kurteva, V.B., Lubenov, L.A., Nedeltcheva, D.V., Nikolova, R.P., Shivachev B.L. 2015. Fast and efficient direct conversion of 2-aminopyridine into 2,3-disubstituted imidazo[1,2-a]pyridines. – Arkivoc, 8, ISSN:1551-7012, 282–294. ISI IF:1.165.

17. Kurteva, V.B., Shivachev, B.L., Nikolova, R.P., Simova, S.D., Antonov, L.M., Lubenov, L.A., Petrova, M.A. 2015. Conformational behaviour of 3-methyl-4-(4-methylbenzoyl)-1-phenyl-pyrazol-5-one: a sudden story of three desmotropes. – RSC Advances, 5, 60, RSC, ISSN:2046-2069, DOI:10.1039/C5RA11858A, 73859–73867. ISI IF:3.84.

18. Lihareva, N., Petrov, O., Tzvetanova, Y., Kadiyski, M., Nikashina, V. 2015. Evalua-tion of the possible use of a Bulgarian clinoptilolite for removing strontium from water media. – Clay minerals, 50, 1, Mineralogical Society, ISSN:0009-8558, DOI:DOI: 10.1180/claymin.2015.050.1.06, 55–64. SJR:0.42.

19. Machev, P., Ganev, V., Klain, L. 2015. New LA-ICP-MS U-Pb zircon dating for Strandja granitoids (SE Bulgaria): evidence for two-stage late Variscan magmatism in the internal Balkanides. – Turkish Journal of Earth Sciences, 24, ISSN:1300-0985, DOI:10.3906/yer-1407-21, 230–248, ISI IF:1.179.

20. Marinova, D., Kostov, V., Nikolova, R., Kukeva, R., Zhecheva, E., Sendova-Vasileva, M., Stoyanova R. 2015. From krohnkite- to alluaudite-type of structure: novel method of synthesis of sodium manganese sulfates with electrochemical properties in alka-limetal ion batteries. – Journal of Materials Chemistry A, 3, 44, Royal Society of Chem-istry, ISSN:2050-7488, DOI:10.1039/C5TA07204B, 22287–22299, ISI IF:7.443.

21. Mihaylov, L., Lyubenova, L., Gerdjikov, T., Nihtianova, D., Spassov, T. 2015. Selec-tive dissolution of amorphous Zr-Cu-Ni-Al alloys. – Corrosion Science, 94, Elsevier Ltd., ISSN:0010-938X, 1879-0496, DOI:doi:10.1016/j.corsci.2015.02.031, 350–358, SJR:1.77, ISI IF:4.422.

22. Morgan, T.G., George, A., Boulamanti, A.K., Alvarez, P., Adanouj, I., Dean, C., Vas-silev, S.V., Baxter, D., Andersen, L.K. 2015. Quantitative X-ray fluorescence analy-

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sis of biomass (switchgrass, corn stover, eucalyptus, beech, and pine wood) with a typical commercial multi-element method on a WD-XRF spectrometer. – Energy and Fuels, 29, 3, ACS Publications, ISSN:0887-0624, DOI:10.1021/ef502380x, 1669–1685, ISI IF:2.79.

23. Okonkwo, C., Ganev, V. 2015. Geochemistry and geochronology of orthogneisses in Bode Saadu area, southwestern Nigeria and their implications for the Palaeopro-terozoic evolution of the area. – Journal of African Earth Sciences, 109, Elsevier, ISSN:464-343X, DOI:10.1016/j.jafrearsci.2015.05.012, 131–142, ISI IF:1.403.

24. Petkova, V., Koleva, V., Kostova, B., Sarov, S. 2015. Structural and thermal transfor-mations on high energy milling of natural apatite. – J. Therm. Anal. Calorim., 121, 1, Springer, ISSN:ISSN 1388-6150, DOI:DOI 10.1007/s10973-014-4205-5, 217–225, ISI IF:2.042.

25. Petrova, A.A., Angelova, S.M., Nikolchina, I.A., Russev, R.I., Kurteva, V.B., Shi-vachev, B.L., Nikolova, R.P. 2015. Novel 13-membered cyclic dioxatetraaza scaf-folds – synthesis, solution and solid state characterization. – Bulg. Chem. Commun., 47, 1, UCB, ISSN:0324-1130, 208–220, ISI IF:0.349.

26. Philipova, I., Stavrakov, G., Vassilev, N., Nikolova, R., Shivachev, B., Dimitrov, V. 2015. Cytisine as a scaffold for ortho-diphenylphosphinobenzenecarboxamide li-gands for Pd-catalyzed asymmetric allylic alkylation. – Journal of Organometallic Chemistry, 778, Elsevier, ISSN:0022-328X, DOI:10.1016/j.jorganchem.2014.12.001, 10–20, ISI IF:2.173.

27. Shalaby, A., Nihtianova, D., Markov, P., Staneva, A.D., Iordanova, R.S., Dimitriev, Y.B. 2015. Structural analysis of reduced graphene oxide by transmission electron microscopy. – Bulg. Chem. Commun., 47, 1, Bulgarian Academy of Sciences, Union of Chemists in Bulgaria, ISSN:0324-1130, 291–295, SJR:0.16, ISI IF:0.201.

28. Stambolova, I., Blaskov, Vl., Stoyanova, D., Dimitrov, L., Milenova, K., Eliyas, Al. 2015. Hydrothermally prepared ZnO powder-form materials for photocatalytic ap-plications. – Compt. rend. Acad. bulg. Sci., 68, 4, BAN, ISSN:ISSN1310-1331, 463–468, ISI IF:0.284.

29. Todorova, T, Kalvachev, Yu. 2015. Seed-mediated approach to size-controlled synthesis of a mordenite type zeolite from organic template free initial gel. – Bulg. Chem. Commun., 47, 1, ISSN:ISSN: 0324-1130, 409–416, ISI IF:0.201

30. Tsvetanova, L.V., Petrova, N., Ferdov, S., Kostov-Kytin, V., Nikolova, R. 2015. Crys-tal structure of Ag+ exchanged ETS-4 at room temperature and 150 K. – Bulg. Chem. Commun., 47, 1, ISSN:0324-1130, 201–201, ISI IF:0.349.

31. Vassilev, S.V., Vassileva, C.G., Vassilev, V.S. 2015. Advantages and disad-vantages of composition and properties of biomass in comparison with coal: An overview. – Fuel, 158, Elsevier, ISSN:0016-2361, DOI:http://dx.doi.org/10.1016/j.fuel.2015.05.050, 330–350, SJR:1.568, ISI IF:4.091.

32. Vassileva, C.G., Daher, D.F., Vassilev, S.V. 2015. Chemical and phase-miner-al composition of mazut fly ash and slag generated from a Syrian power plant. – Compt. rend. Acad. bulg. Sci., 68, 10, Marin Drinov–BAS, 2015, ISSN:1310-1331 (Print) ISSN:2367-5535 (Online), 1277–1286, ISI IF:0.284.

8.2. Published Articles and Reports (not indexed in Web of Science, IF or SJR)

33. Gechev, S.M. 2015. Mechanical defects and impurities in laser crystals grown from natural fluorspar. – In: Short Communications of “Geosciences 2015”, Jubilee Na-tional Conference with International Participation “90 Years Bulgarian Geological Society”, Bulgarian Geological Society, ISSN:1313-2377, 19–20.

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34. Gechev, S.M., Iliev, H., Ganev, V., Mouhovski, J. 2015. Yb,Na:CaSrF2 – A promising laser crystal medium in UV-VIS-Near-IR domain. – In: Proceedings of International Conference on Transparent Optical Networks (ICTON), 17, IEEE, ISBN:978-1-4673-7880-2, DOI:10.1109/ICTON.2015.7193577, 1–4.

35. Gechev, S.M., Mouhovski, J.T., Tzvetkov, P. 2015. Fluoride crystals fabrication and processing ‒ applicability and opto-mechanical characteristics. – Materials, Methods & Technologies, 9, International Scientific Publications, ISSN:1314-7269 (online), 326–340.

36. Ilieva, R., Petrov, O., Dyulgerova, E. 2015. Preparation and characterization of pastes based on calcium phosphate powders and sodium hyaluronate. – Jour-nal of International Scientific Publications, Materials, Methods & Technologies, 9, ISSN:1314-7269, 395–403.

37. Kadiyski, M., Sarov S., Frangov, G., Kostov-Kytin, V., Sarova, S., Stoyanov, V., Macheva, L., Petkova, V., Papaliangas, T. 2015. Risk Management of Koprivlen Landslides. – Proceedings of the 10th Anniversary Scientific Conference SPACE, ECOLOGY, SAFETY, 12–14 November 2014, Sofia, Bulgaria, ISSN:1313–3888, 363–373.

38. Kaljuvee, T., Kuusik, R., Petkova, V. 2015. Thermal and kinetic characteristics of some oil shale samples. – Advanced Materials Research, 1126, Trans Tech Pub-lications, 2015, ISSN:1662-8985, DOI:10.4028/www.scientific.net/AMR.1126.67, 67–74.

39. Kalvachev, Yu., Barbov, B., Todorova, T., Dimitrov, L. 2015. Synthesis of nano-sized zeolites. – Journal of the Bulgarian Academy of Sciences, 4, ISSN:0007-3989, 23–30.

40. Kerekov, S., Gospodinova, N., Dimitrov, L., Nikolov, M. 2015. Selective synthesis of monoglycerol oleate and investigation of its anti-wear performance as a friction modifier. – Journal of the Balkan Tribological Association, 21, 2, ISSN:1310-4772.

41. Marinova, I. 2015. Bladed quartz texture and its relationship with the electrum min-eralization in the Eocene, low-sulfidation Kuklitsa gold deposit, SE Bulgaria. – VIII International Symposium “Mineral Diversity. Research and preservation”, Abstracts, Earth and Man National Museum, 25–25.

42. Marinova, I. 2015. Colloidal and physical transport textures of electrum in a sinu-soidal-walled veinlet from the Khan Krum gold deposit, Eastern Rhodopes Moun-tain, Bulgaria. – In: Short Communications of “Geosciences 2015”, Jubilee National Conference with International Participation “90 Years Bulgarian Geological Society”, Bulgarian Geological Society, ISSN:1313-2377, 25–26.

43. Marinova, I. 2015. Refinement of the conceptual model for formation of bonanza electrum in steep sinusoidal-walled veinlets. Case study from the Khan Krum gold deposit. – In: Short Communications of “Geosciences 2015”, Jubilee National Con-ference with International Participation “90 Years Bulgarian Geological Society”, Bul-garian Geological Society, ISSN:1313-2377, 27–28.

44. Milenova, K., Zaharieva, K., Eliyas, Al., Stambolova, I., Blaskov, V., Dimitrov, O., Dimitrov, L. 2015. Alumina based photocatalysts for degradation of reactive black 5 textile dye aqueous solution activated Ag/ZnO in the decomposition of reactive black 5 and malachite green dyes. – Tribological Journal BULTRIB, 5, Society of Bulgarian Tribologists, ISSN:1313-9878, 232–238.

45. Petkova, V., Sarova, S., Kadiyski, M., Kostov, V., Stoyanov, V., Sarov, S., Gy-urova, R., Papaliangas, T. 2015. Spatial GIS layers of areas at risk of landslides for project “RISK management of natural and anthropogenic landsLIDES in the greek-bulgarian cross-border area” (RISKLIDES). – In: Proceedings of Tenth Anniversary Scientific Conference with International Participation SPACE, ECOLOGY, SAFETY, ISSN:1313-3888, 374–389.

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46. Rabadjieva, D., Gyurov, S., Kovacheva, D., Kostova, Y., Petkova, V., Petrova, N. 2015. Copper slag oxidation under isothermal and non-isothermal conditions. – Ma-terials, Methods & Technologies, 9, International Scientific Publications, ISSN:1314-7269, 358–367.

47. Serafimova, E., Milenkova, S., Stoyanov, V., Pelovski, Y., Petkova, V. 2015. Me-chanical tests of composite ceramic materials. – In: Proc. of 15th International Scien-tific Conference VSU’2015, Editors: V. Stoyanov and D. Partov, 2, VSU L. Karavelov, Sofia, ISSN:1314-071X, 456–461.

48. Serafimova, E., Stoyanov, V., Pelovski, Y., Petkova, V. 2015. Mechanical testing of acid treatment mixtures of biomass and poultry excrement with sulfuric acid. – In: Proc. of 15th International Scientific Conference VSU’2015, Editors: V. Stoyanov and D. Partov, 2, VSU L. Karavelov, Sofia, ISSN:1314-071X, 462–468.

49. Shipochka, M., Milenova, K., Dimitrov, L., Blaskov, V., Stambolova I. 2015. Hydro-thermal treatment of polymer-assisted precipitate for preparation of photocatalytic active zinc oxide powder applications. – Nanoscience & Nanotechnology, 15, 2, ISSN:1313-8995, 7–10.

50. Tacheva, E, Tarassov, M, Tarassova, E. 2015. Morphology and zoning of apatite crystals as indicator for magma mixing in Petrohan pluton, Western Balkan, Bulgar-ia. – In: Short Communications of “Geosciences 2015”, Jubilee National Conference with International Participation “90 Years Bulgarian Geological Society”, Bulgarian Geological Society, ISSN:1313-2377, 33–34.

51. Tarassov, M., Anastasova, E., Tarassova. E. 2015. First data on monazite with а negative Ce anomaly from the Igralishte pluton, Southwestern Bulgaria. – In: Short Communications of “Geosciences 2015”, Jubilee National Conference with Interna-tional Participation “90 Years Bulgarian Geological Society”, Bulgarian Geological Society, ISSN:1313-2377, 35–36.

52. Tarassova, E., Tarassov, M. 2015. New data on Au-Ag mineralization in the Chereshkite ore occurrence, Central Rhodopes, Bulgaria. – In: Short Communica-tions of “Geosciences 2015”, Jubilee National Conference with International Par-ticipation “90 Years Bulgarian Geological Society”, Bulgarian Geological Society, ISSN:1313-2377, 37–38.

53. Tasheva, А., Petkova, V., Kostova, B., Stoyanov, V. 2015. Bio-waste from poultry production (eggshells). Part 2. Organic technological applications. – In: Proc. of 15th International Scientific Conference VSU’2015, 3, ISSN:1314-071X, 235–240.

54. Tsintsov, Z. 2015. Brief comparative characteristic of minerals of the elements of the platinum group of sediments in Bulgaria. – In: Short Communications of “Geo-sciences 2015”, Jubilee National Conference with International Participation “90 Years Bulgarian Geological Society”, Bulgarian Geological Society, ISSN:1313-2377, 39– 40.

55. Tzvetanova, Y., Tarassov, M., Ganev, V., Piroeva, I. 2015. Ti-rich andradites in skarns from Zvezdel-Pcheloyad ore deposit, Eastern Rhodopes, Bulgaria. – In: Short Communications of “Geosciences 2015”, Jubilee National Conference with International Participation “90 Years Bulgarian Geological Society”, Bulgarian Geo-logical Society, ISSN:1313-2377, 41–42.

56. Vasilev, D., Jegova, G., Rashkova, M., Titorenkova, R. 2015. The effect of Er:YAG dental laser treatment with low energy on the human tooth apatite studied by Raman and IR reflection micro-spectroscopy. – Proceedings of the 8th European Confer-ence on Mineralogy and spectroscopy, 1-208, Edizioni Nuova Cultura, ISSN:0369-8963, 183–184.

57. Vasilev, D., Titorenkova, R., Jegova, G., Rashkova, M. 2015. IR and Raman micro-spectroscopy applied for studying structural characteristics of dental apatite. – In: Short Communications of “Geosciences 2015”, Jubilee National Conference with

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International Participation “90 Years Bulgarian Geological Society”, Bulgarian Geo-logical Society, ISSN:1313-2377, 43–44.

58. Vassilev, S., Vassileva, C. 2015. Mineralogy, geochemistry and environmentally safety application of solid fuels and their combustion and pyrolysis products. – Jour-nal of the Bulgarian Academy of Sciences, 4, Marin Drinov – BAS, ISSN:0007-3989, 31–38.

59. Vitov, О. 2015. Extrapolation model of the spatial distribution of gold in the Balkan Peninsula based on data from stream-sediment pan-concentrated surveys in Bul-garia. – In: Short Communications of “Geosciences 2015”, Jubilee National Confer-ence with International Participation “90 Years Bulgarian Geological Society”, Bul-garian Geological Society, ISSN:1313-2377, 47–48.

60. Yancheva, D., Cherneva, E., Quick, M., Mikhova, B., Shivachev, B., Nikolova, R., Djordjevic, A., Untergehrer, M., Jürgenliemk, G., Kraus, B., Smelcerovic, A. 2015. Synthesis, crystal structure and biological activity screening of novel N-(α-bromoacyl)-α-amino esters containing valyl moiety. Acta, 62, 3, Slovensko Kemijsko Drustvo, ISSN:1580-3155, DOI:10.17344/acsi.2015.1418, 689–699, SJR:0.206, ISI IF:0.69.

8.3. Publications in press (indexed in Web of Science, IF or SJR)

61. Adetunji, A., Olarewaju, V.O., Ocan, O.O., Ganev, V., Macheva, L. Geochemistry and U-Pb zircon geochronology of the pegmatites in Ede area, southwestern Ni-geria: A newly discovered oldest Pan African rock in southwestern Nigeria. – Jour-nal of African Earth Sciences, 115, ISSN:1464-343X, DOI:doi:10.1016/j.jafrears-ci.2015.12.006, 177–190. SJR:0.557, ISI IF:1.403.

62. Glavcheva, Z., Yancheva, D., Velcheva, B., Stamboliyska, B., Petrova N., Petkova, V., Lalev, G., Todorov, V. Analytical studies of the Alexandrovo Thracian tomb wall paintings. – Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy, 152, ISSN:1386-1425, DOI:DOI:10.1016/j.saa.2015.01.103, 622–628, ISI IF:2.35.

63. Kalvachev, Yu., Zgureva, D., Boycheva, S., Barbov, B., Petrova, N. Synthesis of carbon dioxide adsorbents by zeolitization of fly ash. – Journal Therm. Anal. Calorim-etry, first online 20 Nov, Springer, ISSN:1388-6150, DOI:10.1007/s10973-015-5148-1, 1–6, SJR:0.6, ISI IF:2.04.

64. Marinova, I., Damyanov, Z. Plate tectonic aspects of the Triassic carbonate-hosted stratiform-stratabound base-metal deposits in the Western Balkan, NW Bulgaria. – Geologica Croatica, 69, 1, ISSN:ISSN 1333-4875, SJR:0.1, ISI IF:0.702.

65. Milanova, M., Iordanova, R., Tatsumisago, M., Hayashi, A., Tzvetkov, P., Nihtian-ova, D., Markov, P., Dimitriev, Y. Structural and electrochemical characterization of LiVMoO6 obtained by soft mechanochemical synthesis. – Journal of Materials Sci-ence, 51, 7, Springer US, ISSN:0022-2461, 1573-4803, DOI:10.1007/s10853-015-9677-6, 3574–3584, SJR:0.93, ISI IF:2.371.

66. Olariu, M., Hamciuc, C., Okrasa, L., Hamciuc, E., Dimitrov, L., Kalvachev, Yu. Electrical properties of polyimide composite films containing TiO2 nanotubes. – Polymer Composites, online first 14 NOV, Wiley Online Library, ISSN:1548-0569, DOI:10.1002/pc.23851, 1–9, SJR:0.567, ISI IF:1.632.

8.4. Publications in press (not indexed in Web of Science, IF or SJR)

67. Tzanov, V., Gechev, S., Gechev, Tz. Generation of Koch N-flakes and their cor-respondence to the total and the marginal utility curves. – In: Proceedings of “The

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Application of Mathematics, Statistics and Information Technology in the Economic and Business Process Modeling”, UNWE.

8.5. Reports at Scientific Forums68. Barbov, B., Kalvachev, Yu. 2015. Seed-mediated synthesis of nanosized crys-

tals of Beta zeolites. – The 29th European Crystallographic Meeting, 23.08.2015–28.08.2015, Rovinj, Croatia.

69. Dimova, L., Dyulgerov, V.M., Petrova, N.L., Kostov-Kytin, V., Nikolova, R.P., Shivachev, B.L. 2015. New cadmium(II) three-dimensional metal-organic frame-work using terephthalic acid as ligand with intersecting 1D channels. – 6th Inter-national Symposium on Advanced Micro and Mesoporous Materials, 06.09.2015–10.09.2015, Pomorie, Bulgaria.

70. Dimowa, L., Nikolova, R.P., Sbirkova, H., Tsvetanova, L., Todorova, T., Hrist-off, P., Radoslavov, G., Doukov, Tz., Shivachev, B. 2015. G-Quadruplexes DNA structures. – XVII Meeting of Biochemists and Molecular Biologists, 10.11.2015–11.11.2015, Brno, Czech Republic.

71. Dimowa, L., Sbirkova, H., Tsvetanova, L., Todorova, T., Nikolova, R., Shivachev, B. 2015. Specific on DNA cryastallization. – XVII Meeting of Biochemists and Mo-lecular Biologists, 10.11.2015–11.11.2015, Brno, Czech Republic.

72. Gechev, S. 2015. Fluoride crystals fabrication and processing ‒ applicability and op-to-mechanical characteristics. – 17th International Conference Materials, Methods & Technologies of International Scientific Events, 07.06.2015–11.06.2015, Elenite, Bulgaria.

73. Gechev, S. 2015. Important parameters in the generation of fractals by iterated func-tion systems. – Scientific Conference on “The Application of Mathematics, Statis-tics and Information Technology in the Economic and Business Process Modeling”, 08.10.2015–08.10.2015, Sofia, Bulgaria.

74. Gechev, S. 2015. Mechanical defects and impurities in laser crystals grown from natural fluorspar. – “Geosciences 2015”, Jubilee National Conference with Interna-tional Participation “90 Years Bulgarian Geological Society”, 10.12.2015–11.12.2015, Sofia, Bulgaria.

75. Gechev, S., Iliev, H., Ganev, V., Mouhovski, J. 2015. Yb,Na:CaSrF2 – A promising laser crystal medium in UV-VIS-Near-IR domain. – 17th International Conference on Transparent Optical Networks, 05.07.2015–09.07.2015, Budapest, Hungary.

76. Hamciuc, C., Hamciuc, E., Stoica I., Olariu, M., Okrasa, L., Dimitrov, L., Kalvachev, Yu. 2015. Dielectric behaviour of polyimide films containing TiO2 nanotubes. – Ad-vances in Functional Materials, 29.06.2015–03.07.2015, Long Island, New York, USA.

77. Kadiyski, M., Sarov, S., Frangov, G., Kostov, V., Stoyanov, V., Petkova, V., Pa-paliangas, T. 2015. Risk management of Koprivlen landslides. – 18 th International Symposium on Environmental Pollution and its Impact on Life in the Mediterranean Region September, 26.08.2015–30.09.2015, Crete, Greece.

78. Kalvachev, Yu. 2015. Zeolites – crystals with unique properties: synthesis and appli-cation. – Zeolite-polymer hybrid materials, 07.05.2015–12.05.2015, Iasi, Romania.

79. Kalvachev, Yu., Todorova, T. 2015. Seed-assisted OSDA-free synthesis of mor-denite type zeolite. – Humboldt Kolleg “Beacons of Hope in the Quest for the Next Einstein in the MENA region”, 03.03.2015–07.03.2015, Fez, Morocco.

80. Kalvachev, Yu., Todorova, T. 2015. Size-controlled synthesis of a mordenite type zeolite. – The 29th European Crystallographic Meeting, 23.08.2015–28.08.2015, Rovinj, Croatia.

81. Karteva, E.G., Manchorova, N., Damyanov, Z., Karteva, T. 2015. Crystallographic analyses of coronary and root dentin: a pilot study. – 47th Meeting of the Continental

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European Division of the International Association for Dental Research, 15.10.2015–17.10.2015, Antalya, Turkey.

82. Kostova, I., Vassileva, C., Dai, S., Hower, J. 2015. Mineralogy, geochemistry and Hg content characterization of fly ashes from Maritza 3 and Varna thermoelectric power plants, Bulgaria. – 67th Annual Meeting of the International Committee for Coal and Organic Petrology, 05.09.2015–11.09.2015, Potsdam, Germany.

83. Kostov-Kytin, V. 2015. Sampling of building materials for laboratory analysis • Natu-ral materials • Artificial materials. – CheRRIE progress meeting, 27.02.2015, Thes-saloniki, Greece.

84. Kostov-Kytin, V. 2015. Sampling of building materials for laboratory analysis Chem-ical and Radiological Risk in the Indoor Environment [CheRRIE]. – CheRRIE Inter-regional stakeholders workshop, 27.02.2015, Thessaloniki, Greece.

85. Kostov-Kytin, V. 2015. System for sampling and measurement of buildings and building materials for the possible presence of sources of chemical and radiological risk. – Workshop to discuss the results of the project “Chemical and Radiological Risk in the Indoor Environment”, 29.11.2015, Sofia, Bulgaria.

86. Kostov-Kytin, V. 2015. Chemical and Radiological Risk in the Indoor Environment [CheRRIE]. – Training seminar to discuss the results of the project “Chemical and Radiological Risk in the Indoor Environment”, 29.11.2015, Sofia, Bulgaria.

87. Kreißl, S., Bolanz, R., Gottlicher, J., Steininger, R., Tarassov, M., Markl, G. 2015. The integration modes of structural bound W in hematite and goethite. – 2015 Gold-schmidt Conference, 16.08.2015–21.08.2015, Prague, Czech Republic.

88. Manchorova, N., Karteva, E., Keskinova, D., Damyanov, Z., Karteva, T. 2015. The structure of root and coronary dentin under transmitted and polarized light micros-copy: preliminary results. – XV Jubilee International Scientific Congress of Bulgarian Dental Association, 11.06.2015–14.06.2015, Burgas, Bulgaria.

89. Marinova, I. 2015. Bladed quartz texture and its relationship with the electrum min-eralization in the Eocene, low-sulfidation Kuklitsa gold deposit, SE Bulgaria. – Min-eral Diversity. Research and Preservation, 09.10.2015–12.10.2015, Sofia, Bulgaria.

90. Marinova, I. 2015. Colloidal and physical transport textures of electrum in a sinusoi-dal-walled veinlet from the Khan Krum gold deposit, Eastern Rhodopes Mountain, Bulgaria. – “Geosciences 2015”, Jubilee National Conference with International Par-ticipation “90 Years Bulgarian Geological Society”, 10.12.2015–11.12.2015, Sofia, Bulgaria.

91. Marinova, I. 2015. Refinement of the conceptual model for formation of bonanza electrum in steep sinusoidal-walled veinlets. Case study from the Khan Krum gold deposit. – “Geosciences 2015”, Jubilee National Conference with International Par-ticipation “90 Years Bulgarian Geological Society”, 10.12.2015–11.12.2015, Sofia, Bulgaria.

92. Petkova, V. 2015. In situ measurements in Southwest Bulgaria. – CheRRIE Inter-regional stakeholders workshop, 27.02.2015, Thessaloniki, Greece.

93. Petkova, V. 2015. Strategic project: Chemical and Radiological Risk in the Indoor Environment [CheRRIE]. – Workshop to discuss the results of the project “Chemical and Radiological Risk in the Indoor Environment”, 29.11.2015, Sofia, Bulgaria.

94. Petkova, V., Kostova, B., Kadiyski, M., Kaljuvee, T. 2015. Influence of SiO2 on the thermal behavior of high-energy activated natural phosphorites. – 12th Conference on calorimetry and thermal analysis of the Polish society of calorimetry and thermal analysis (PTKAT) and 5th Joint Czech – Hungarian – Polish – Slovakian thermoana-lytical conference, 06.09.2015–10.09.2015, Zakopane, Poland.

95. Petkova, V., Kostova, B., Serafimova, E., Stoyanov, V. 2015. Thermal investigation of different modified cement mortars. – 3rd Central and Eastern European Committee for Thermal Analysis and Calorimetry, 25.08.2015–28.08.2015, Ljubljana, Slovenia.

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96. Petkova, V., Kostova, B., Shopska, M., Kadinov, G., Baláž, M., Baláž, P., Kadi-yski, M. 2015. Influence of high energy milling activation on application of waste Chicken Eggshells. – 18th International Symposium on Environmental Pollution and its Impact on Life in the Mediterranean Region September, 26.08.2015–30.09.2015, Crete, Greece.

97. Petkova, V., Serafimova, E., Kostova, B. 2015. Influence of nitric-acid treated bio-mass and chicken litter mixtures on the thermal properties. – 12th Conference on calorimetry and thermal analysis of the Polish society of calorimetry and thermal analysis (PTKAT) and 5th Joint Czech – Hungarian – Polish – Slovakian thermoana-lytical conference, 06.09.2015–10.09.2015, Zakopane, Poland.

98. Petkova, V., Serafimova, E., Pelovsky, Y., Kostova, B. 2015. Spectroscopic analy-sis of nitric-acid treated mixtures on the base of biomass and chicken litter. – 18th International Symposium on Environmental Pollution and its Impact on Life in the Mediterranean Region September, 26.08.2015–30.09.2015, Crete, Greece.

99. Petkova, V., Serafimova, Е., Milenkova, S., Stoyanov, V., Pelovski, Y. 2015. Me-chanical tests of composite ceramic materials. – ХV International scientific confer-ence VSU’2015, 04.06.2015–06.06.2015, Sofia, Bulgaria.

100. Petkova, V., Serafimova, Е., Stoyanov, V., Pelovski, Y. 2015. Mechanical testing of acid treatment mixtures of biomass and poultry excrement with sulfuric acid. – ХV International scientific conference VSU’2015, 04.06.2015–06.06.2015, Sofia, Bulgaria.

101. Petkova, V., Shopska, M., Kostova, B., Kadinov, G., Baláž, M., Baláž P. 2015. Be-haviour of high energy milling activated egg-shells during thermal treatment. – 3rd Central and Eastern European Committee for Thermal Analysis and Calorimetry, 25.08.2015–28.08.2015, Ljubljana, Slovenia.

102. Petkova, V., Stoyanov, V., Kostova, B., Serafimova, E. 2015. Effects of marble on phase formation in self-compacting type decorative cement composites. – 18th International Symposium on Environmental Pollution and its Impact on Life in the Mediterranean Region September, 26.08.2015–30.09.2015, Crete, Greece.

103. Petrov, O. 2015. Rietveld quantification. – Introduction to the theoretical background of the Rietveld method and principles of crystal structure refinement from powder diffraction data, 27.09.2015–03.10.2015, Sofia, Bulgaria.

104. Petrov, О. 2015. Presentation of analytical results obtained from powder X-Ray diffraction patterns of samples from the regions of CheRRIE project in Bulgaria. – Workshop to discuss the results of the project “Chemical and Radiological Risk in the Indoor Environment”, 29.11.2015, Sofia, Bulgaria.

105. Petrov, O. 2015. Powder X-Ray diffraction of building materials from the regions of CheRRIE project in Bulgaria and Greece. – Training seminar to discuss the results of the project “Chemical and Radiological Risk in the Indoor Environment”, 29.11.2015, Sofia, Bulgaria.

106. Petrova, N. 2015. Analytical results obtained from thermal measurements of sam-ples from the regions of CheRRIE project in Bulgaria and Greece. – Workshop to discuss the results of the project “Chemical and Radiological Risk in the Indoor En-vironment”, 29.11.2015, Sofia, Bulgaria.

107. Petrova, N. 2015. DTA–TG–DTG analyses of building materials from the regions of CheRRIE project in Bulgaria and Greece. – Training seminar to discuss the results of the project “Chemical and Radiological Risk in the Indoor Environment”, 29.11.2015, Sofia, Bulgaria.

108. Serafimova, E., Petkova, V., Kostova, B. 2015. The measurement of benzen, eth-ylbenzen, toluene and xylene in indoor air in schools in Kardzhali. – XIth Scientific Conference with International Participation, “SPACE, ECOLOGY, SAFETY – SES 2014”, 04.11.2015–06.11.2015, Sofia, Bulgaria.

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109. Serafimova, E., Petkova, V., Petrov, A. 2015. Impact of greenhouse gases on cli-mate systems and forests in Bulgaria. – XIth Scientific Conference with International Participation, “SPACE, ECOLOGY, SAFETY – SES 2014”, 04.11.2015–06.11.2015, Sofia, Bulgaria.

110. Shivachev, B. 2015. Crystal structure and crystal symmetry (crystal systems, unit cell, reciprocal space, reciprocal lattice, systematic absences, Wyckoff positions). – Second Balkan School on Fundamental Crystallography and Workshop on Magnetic Symmetry, 13.07.2015–19.07.2015, Istanbul, Turkey.

111. Shivachev, B. 2015. Symmetry in reciprocal space. Diffraction symmetry: Laue classes, Friedel’s law, resonant scattering. Integral, zonal and serial reflection condi-tions and their use in the determination of the space-group symmetry. Special re-flection conditions. – Second Balkan School on Fundamental Crystallography and Workshop on Magnetic Symmetry, 13.07.2015–19.07.2015, Istanbul, Turkey.

112. Shivachev, B.L., Dimowa, L., Nikolova, R., Sbirkova, H., Tsvetanova, L., Hristoff, P., Radoslavov, G., Doukov, Tz. 2015. New G-quadruplex DNA structures. – The 29th European Crystallographic Meeting, 23.08.2015–28.08.2015, Rovinj, Croatia.

113. Tacheva, E., Tarassov, M., Tarassova, E. 2015. Morphology and zoning of apa-tite crystals as indicator for magma mixing in Petrohan pluton, Western Balkan, Bulgaria. – “Geosciences 2015”, Jubilee National Conference with International Participation “90 Years Bulgarian Geological Society”, 10.12.2015–11.12.2015, Sofia, Bulgaria.

114. Tarassov, M., Anastasova, E., Tarassova, Е. 2015. First data on monazite with а negative Ce anomaly from the Igralishte pluton, Southwestern Bulgaria. – “Geo-sciences 2015”, Jubilee National Conference with International Participation “90 Years Bulgarian Geological Society”, 10.12.2015–11.12.2015, Sofia, Bulgaria.

115. Tarassova, E., Tarassov, М. 2015. New data on Au-Ag mineralization in the Chereshkite ore occurrence, Central Rhodopes, Bulgaria. – “Geosciences 2015”, Jubilee National Conference with International Participation “90 Years Bulgarian Geological Society”, 10.12.2015–11.12.2015, Sofia, Bulgaria.

116. Tasheva, А., Petkova, V., Kostova, B., Stoyanov, V. 2015. Bio-waste from poultry production (eggshells). Part 2. Organic technological applications. – ХV International scientific conference VSU’2015, 04.06.2015–06.06.2015, Sofia, Bulgaria.

117. Todorova, T. 2015. Seeds-induced synthesis of mordenite type zeolite without or-ganic template – Zeolite-polymer hybrid materials, 07.05.2015–12.05.2015, Iasi, Romania.

118. Tsintsov, Z. 2015. Brief comparative characteristic of minerals of the elements of the platinum group of sediments in Bulgaria. – “Geosciences 2015”, Jubilee National Conference with International Participation “90 Years Bulgarian Geological Society”, 10.12.2015–11.12.2015, Sofia, Bulgaria.

119. Tsvetanova, L., Ferdov, S., Shikova, E., Todorova, T., Dimowa, L.T., Nikolova, R.P., Shivachev, B.L. 2015. Anti-tumor activity of Zn-exchanged Cinoptilolite and ETS-4. – XVII Meeting of Biochemists and Molecular Biologists, 10.11.2015–11.11.2015, Brno, Czech Republic.

120. Tzvetanova, Y., Tarassov, M., Ganev, V., Piroeva, V. 2015. Ti-rich andradites in skarns from Zvezdel-Pcheloyad ore deposit, Eastern Rhodopes, Bulgaria. – “Geo-sciences 2015”, Jubilee National Conference with International Participation “90 Years Bulgarian Geological Society”, 10.12.2015–11.12.2015, Sofia, Bulgaria.

121. Vasilev, D., Jegova, G., Rashkova, M., Titorenkova, R. 2015. Raman and IR micro-spectroscopy study of enamel treated by Er:YAG dental laser with low energy. – Introduction to the theoretical background of the Rietveld method and principles of crystal structure refinement from powder diffraction data, 27.09.2015–03.10.2015, Sofia, Bulgaria.

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122. Vasilev, D., Jegova, G., Rashkova, M., Titorenkova, R. 2015. The effect of Er:YAG dental laser treatment with low energy on the human tooth apatite studied by Raman and IR reflection micro-spectroscopy. – 8th European Conference on Mineralogy and Spectroscopy, 09.09.2015–11.09.2015, Rome, Italy.

123. Vasilev, D., Titorenkova R., Jegova, G., Rashkova, M. 2015. IR and Raman micro-spectroscopy applied for studying structural characteristics of dental apatite. – “Ge-osciences 2015”, Jubilee National Conference with International Participation “90 Years Bulgarian Geological Society”, 10.12.2015–11.12.2015, Sofia, Bulgaria.

124. Vasilev, D., Titorenkova, R. 2015. IR and Raman micro-spectroscopy applied for studying structural characteristics of dental apatite. – Second Balkan School on Fundamental Crystallography and Workshop on Magnetic Symmetry, 13.07.2015–19.07.2015, Istanbul, Turkey.

125. Zhegova, G., Titorenkova, R., Rashkova, M., Mihailova, B. 2015. Er:YAG laser-in-duced compositional changes of dental enamel – a Raman and IR reflection spectro-scopic study. – 6th Congress of International Phototherapy Association, 09.07.2015–10.07.2015, Nice, France.

8.6. PhD Theses126. Tzvetanova, Y. 2015. Crystal-chemical and structural characteristics of minerals from

skarns in Zvezdel pluton. PhD Thesis, Bulgarian Academy of Sciences, Sofia, 183 p.