Katalitikus éééés sug áááárkrrkkrk éééémiai elj áááárrrrááások a ...aekimhp/EK/hirek/KOTEB_13_02... · 2013. 2. 28. · MTA Energiatudom áááányi Kutat óóóókkkköööözpont

MTA EnergiatudomMTA EnergiatudomMTA EnergiatudomMTA EnergiatudomMTA EnergiatudomMTA EnergiatudomMTA EnergiatudomMTA Energiatudomaacuteaacuteaacuteaacuteaacuteaacuteaacuteaacutenyi Kutatnyi Kutatnyi Kutatnyi Kutatnyi Kutatnyi Kutatnyi Kutatnyi Kutatoacuteoacuteoacuteoacuteoacuteoacuteoacuteoacutekkkkkkkkoumloumloumloumloumloumloumloumlzpontzpontzpontzpontzpontzpontzpontzpont

Katalitikus Katalitikus Katalitikus Katalitikus Katalitikus Katalitikus Katalitikus Katalitikus eacuteeacuteeacuteeacuteeacuteeacuteeacuteeacutes sugs sugs sugs sugs sugs sugs sugs sugaacuteaacuteaacuteaacuteaacuteaacuteaacuteaacuterkrkrkrkrkrkrkrkeacuteeacuteeacuteeacuteeacuteeacuteeacuteeacutemiai eljmiai eljmiai eljmiai eljmiai eljmiai eljmiai eljmiai eljaacuteaacuteaacuteaacuteaacuteaacuteaacuteaacuterrrrrrrraacuteaacuteaacuteaacuteaacuteaacuteaacuteaacutesok sok sok sok sok sok sok sok

a ka ka ka ka ka ka ka koumloumloumloumloumloumloumloumlrnyezetvrnyezetvrnyezetvrnyezetvrnyezetvrnyezetvrnyezetvrnyezetveacuteeacuteeacuteeacuteeacuteeacuteeacuteeacutedelembendelembendelembendelembendelembendelembendelembendelemben

TakTakTakTakTakTakTakTakaacuteaacuteaacuteaacuteaacuteaacuteaacuteaacutecs Erzscs Erzscs Erzscs Erzscs Erzscs Erzscs Erzscs Erzseacuteeacuteeacuteeacuteeacuteeacuteeacuteeacutebetbetbetbetbetbetbetbet

MTA 2013 februMTA 2013 februMTA 2013 februMTA 2013 februMTA 2013 februMTA 2013 februMTA 2013 februMTA 2013 februaacuteaacuteaacuteaacuteaacuteaacuteaacuteaacuter 27r 27r 27r 27r 27r 27r 27r 27

Az elfogyasztott gyoacutegyszerek jelentős

haacutenyada nem sziacutevoacutedik fel hanem

kivaacutelasztoacutedik eacutes a vizelettel szennyviacutezbe majd

a szennyviacutez tisztiacutetoacutekba jut

Az erősen toxikus szennyezők mint a

gyoacutegyszer molekulaacutek nehezen bonthatoacuteak a

szennyviacuteztisztiacutetaacutesra hagyomaacutenyosan

alkalmazott moacutedszerekkel

Szerves szennyezSzerves szennyezőők gyk gyoacuteoacutegyszer molekulgyszer molekulaacuteaacutek k az az eacuteeacutellőővizekbenvizekben

Pharmaceuticals detected in environment(Data collected from 132 publications between 1997 and 2009)

Lucia HMLM Santos AN Araujo Adriano Fachini A Pena C Delerue-Matos MCBSM Montenegro Journal of Hazardous Materials 175 (2010) 45ndash95

Max konc ngl Orszaacuteg

Lipid szabaacutelyozoacutek

Bezafibrate 27 Neacutemeto

Cofibric acid

165 Neacutemeto

270 Neacutemeto

170 Neacutemeto

53 Olaszo

Gemfibrozil 70 Kanada

Laacutez- eacutes

faacutejdalomcsillapiacutetoacutek

Diclofenac 6 Neacutemeto

Ibuprofen 3 Neacutemeto

Phenazone250 Neacutemeto

400 Neacutemeto

Propylphenazone80 Neacutemeto

120 Neacutemeto

Antibiotikum Tylosin 17 Olaszo

Antiepilektikum Carbamazepine24 Kanada

258 USA

Citosztatikum Bleomycin 13 Anglia

Antipszichosztatikumok Diazepam10 Anglia

235 Olaszo

Gyoacutegyszervegyuumlletek koncentraacutecioacuteja az ivoacuteviacutezben

bullbullOHOH

bull Advanced Oxidation Processes (AOPs) ndashnagyhateacutekonysaacuteguacuteoxidaacutecioacutes eljaacuteraacutesok OH gyoumlk segiacutetseacutegeacutevel bontjaacutek le a toxikus vegyuumlleteket

Ezen eljaacuteraacutesok keacutemiai fotokeacutemiai fotokatalitikus eacutes elektrokeacutemiai moacutedszerek melyek koumlzoumls jellemzőkeacutent a rendkiacutevuumll reaktiacutev hidroxilgyoumlk (OH) keacutepzeacuteseacuten alapszanak Iacutegeacuteretes koumlrnyzetbaraacutet technoloacutegiaacutek melyek alkalmasak kis mennyiseacutegben toxikus eacutes bioloacutegiai kezeleacutessel nem eliminaacutelhatoacute vegyuumlleteket tartalmazoacute szennyviacutezek kezeleacuteseacutere

A hidroxilgyoumlkoumlk keacutemiai koumlteacuteseket szakiacutetanak fel

bullbullbullbullbullbullbullbullbullbullbullbullOHOHOH

bullbull KatalKataliacuteiacuteziszis

bullbull Nedves oxidNedves oxidaacuteaacutecicioacuteoacute katalitikus nedves oxid katalitikus nedves oxidaacuteaacutecicioacuteoacute

bullbull EEB (ionizB (ionizaacuteaacutelloacuteoacute sugsugaacuteaacuterzrzaacuteaacutes)s)

bullbull KombinKombinaacuteaacutelt mlt moacuteoacutedszerekdszerek a fenti ma fenti moacuteoacutedszerek dszerek

kombinkombinaacuteaacutellaacuteaacutesasa

IntInteacuteeacutezetzetuumluumlnkben folynkben folyoacuteoacute kutatkutataacuteaacutesok a sok a gygyoacuteoacutegyszerek lebontgyszerek lebontaacuteaacutessaacuteaacutera vizes oldatbanra vizes oldatban

NemesfNemesfeacuteeacutemoxidTi hmoxidTi haacuteaacutelloacuteoacutekatalizkatalizaacuteaacutetoroktorok

Kereskedelmi

Ru-Ir oxid bevonatuacute Ti haacuteloacute katalizaacutetor

(Magneto BV Hollandia)

Sajaacutet keacutesziacuteteacutesű

Ru oxid

Pd oxid

Ru-Ir oxid (keacutemiailag tisztiacutetott Ti haacuteloacutera felvitt)

Ru-Ir oxid

Ir-Ta oxid (mechanikusan homokfuacutevaacutessal tisztiacutetott Ti haacuteloacutera felvitt)

Hungarian patent application P 08 00677

Kereskedelmi RuKereskedelmi Ru--Ir oxidTi hIr oxidTi haacuteaacutelloacuteoacute felfeluumluumlletelete

Kereskedelmi RuKereskedelmi Ru--Ir oxidTi hIr oxidTi haacuteaacutelloacuteoacute felfeluumluumllete lete kb 200 kb 200 oacuteoacutera hasznra hasznaacuteaacutelat utlat utaacuteaacutenn

RuRu--Ir oxidTi hIr oxidTi haacuteaacutelloacuteoacute (k(keacuteeacutemiai tisztmiai tisztiacuteiacutettaacuteaacutes) fels) feluumluumlletelete

RuRu--Ir oxidTi hIr oxidTi haacuteaacutelloacuteoacute (mechanikusan (mechanikusan tiszttisztiacuteiacutetott) feltott) feluumluumlletelete

A Ti haacuteloacute katalizaacutetorok oumlsszehasonliacutetaacutesa

TOC ndashtotal organic carbon content

TOC csoumlkkeneacutes egy ipari szennyviacutez (7) (a)

eacutes fenolaacutet oldat oxidaacutecioacutejaacuteban (b) kuumlloumlnboumlző monolit katalizaacutetorokkal

a) 230 oC 50 bar b ) 200 oC 50 bar

IONIZIONIZAacuteAacuteLLOacuteOacute SUGSUGAacuteAacuteRZRZAacuteAacuteSS

Forraacutesok eacutes moacutedszerek a degradaacutecioacute eacutes koumlveteacuteseacutere

Gammaforraacutes Analiacutezis UV-VIS HPLC

KOI BOI TOC Microtox toxicitaacutes (Vibrio fischeri)

EB ndash elektron gyorsiacutetoacute

Impulzusradioliacutezis meacuterőegyuumlttes

Hiacuteg vizes oldatokban a sugaacuterzaacutes elsődleges hataacutesa a viacutez radioliacutezise

H2O rarr

bullH eaq

minus bullOH H+ OHminus H2O

2 H

2

G (bullH) = 006 microm J-1 G(bullOH) = 028 microm J-1 G(eaqminus) = 028 microm J-1

Radioliacutezis vizes oldatban

oxigoxigeacuteeacuten jelenln jelenleacuteeacutetteacuteeacutebenben

Szuperoxid gyoumlkanion (O2minusbull) eacutes perhidroxil gyoumlk (HO2

bull)

eaqminus +O2 rarr O2

minusbull k = 12 times 1010 molndash1 dm3 sndash1

Hbull + O2 rarr HO2bull k = 19 times 1010 molndash1 dm3 sndash1

OH

NaO

CH3

OH

CH3

OH

CH3

OH

Cl

OH

Cl

OH

Cl

OH

OH

O

O

ClCl

O

CH3O

OHO

CH3

OH

O

O

O

CH3

NHOH

Na

O

O

O

S

Na

OO

O

S

N

N

NH2

OH

NH2

OH

NH2

OH

CH3

ONH

OH

Cl

Cl

NH

OH

O

Cl Cl

NH2 CH3

O

O CH3

OH

OH

OH

OH

O

OH

O

OH

O

OH

O

OH

O

OH

0

500 000

1 000 000

1 500 000

2 000 000

2 500 000

Ibuprofen

Num

ber

of

boxes s

old

2001

2005

Ibuprofen (IBP)

bull nem-szteroid gyulladaacutesgaacutetloacute

(NSAID)

bull faacutejdalom csillapiacutetoacute

bull Advil Algoflex Nurofen

Rhinathiol Ibustar

(RS)-2-[4-(2-metilpropil)fenil]propaacutensav

M Farreacute D Barceloacute Toxicity testing of wastewater and sewage sludge by biosensors bioassays and chemical analysis Trends in Analytical Chemistry Vol 22 No 5 (2003)

Applications of radiation chemistry to understand the fate and transport of emerging pollutants of

concern in coastal waters by Kimberly Greenwood Jones 2007

OH

O

Illeacutes E Takaacutecs E Dombi A Gajda-Schrantz

K Raacutecz G Gonter K Wojnaacuterovits L

Hydroxyl radical induced degradation of

ibuprofen Science of the Total Environment

447 286ndash292 (2013)

200 250 300 350 400 45000

05

10

15

20

Abs

orba

nce

Wavelength nm

0 kGy

025 kGy05 kGy

075 kGy15 kGy

1 kGy

00 05 10 1500

02

04

06

08

10

Rel

co

ncen

trat

ion

Dose kGy

UV spektrumok N2O-dal teliacutetett 1 times 10minus4 mol dmminus3 IBP oldatban (bullOH

reakcioacute) pH sim44 Inset IBP koncentraacutecioacute vaacuteltozaacutesa a doacutezissal (HPLC

elvaacutelasztaacutes utaacuten dioacutedasoros detektaacutelaacutessal meacutert kromatograacutefaacutes csuacutecsok

integraacutelja)

HPLC-diode array detection

H3C

OH

CH3

O

CH3

CH3

O

CH3

O

OHO

CH3

CH3

CH3

CH3

CH3

CH3 OH

CH3

O O

OHO

OH

CH3

CH3

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OHOH

(1) mz 133 (2) mz 149 (3) mz 175 (4) mz 177

(6) mz 177 (8) mz 221(7) mz 221(5) mz 177

(9) mz 237

H3C

OH

CH3

O

CH3

1timestimestimestimes10-4 mol dm-3 ibuprofen solution

A degradaacutecioacutes termeacutekek azonosiacutetaacutesa


Toxicity measured by Microtox (inhibition of Vibrio

fischeri)110-4 mol dm-3 air saturated ibuprofen solution gamma-radiolysis

0 1 2 3 40

5

10

15

20

25

30

35

40IBP 1 x 10-4 mol dm-3

Dose kGy

Inh

ibit

ion

00

05

10

cc

0

00 05 10 15 200

20

40

60

80

100

120

140

160

180 1633

1839

2303

2533

8997

Ab

so

rban

ce

Dose kGy

Changes of fluorescence inhibition in Vibrio fisheri toxicity test and the relative concentration of unaltered IBP molecules as a function of dose measured in 1x10-4 mol dmminus3 air saturated IBP solution (bullOH + O2

minusbullHO2bull reaction)

HPLC-diode array

detection

TOTAL COLIFORM AND FECAL COLIFORM VALUES MEASURED WITH

SAMPLES FROM A MUNICIPAL WASTEWATER TREATMENT PLANT AFTER

BIOLOGICAL TREATMENT BEFORE STERILIZATION AND AFTER

STERILIZATION BY CHLORINE TREATMENT OR IRRADIATION

SampleFree Cl

mg dm-3

Total Cl

mg dm-3

Dose

kGy

Total

Coli

Fecal

Coli

Fec C

Total C

I01 - - - 730 75 102

IICl1 007 009 - 560 52 93

Irad1

- - 05 1 0 -

- - 1 1 0 -

- - 20 0 0 -

I02 - - - 900 90 99

IICl2 lt005 006 - 700 80 114

Irad2

- - 05 0 0 -

- - 1 0 0 -

- - 20 0 0 -

COMPARISON OF CODK AND BOD5 VALUES MEASURED WITH SAMPLES

FROM A MUNICIPAL WASTEWATER TREATMENT PLANT AFTER BIOLOGICAL

TREATMENT BEFORE DISINFECTIONAND AFTER DISINFECTION BY

CHLORINE TREATMENT OR IRRADIATION

Sample TreatmentCODk

mg dm-3

BOD5

mg dm-3

BOD5CODk

I01 - 46 16 35

IICl1 Cl 62 16 26

Irad1

05 kGy 36 lt10 (6) lt17

1 kGy 32 lt10 (8) lt25

20 kGy 36 lt10 (5) lt14

I02 - 53 17 32

IICl2 Cl 58 15 26

Irad2

05 kGy 31 lt10 (7) lt23

1 kGy 39 lt10 (7) lt18

20 kGy lt30 (28) lt10 (5) lt18

25

Nedves oxidaacutecioacute eacutes sugaacuterzaacutes (20 bar oxigeacuten)

Gyoacutegyszergyaacuteri szennyviacutez kezeleacutese

Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

Erősen toxikus szennyviacutez

Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2


Az ionizaacuteloacute sugaacuterzaacutest alkalmazoacute viacutez eacutes szennyviacutez kezeleacutesi technoloacutegiaacutek előnyei

oEnergia takareacutekos eacutes koumlrnyezet kiacutemeacutelő

o Nincs szuumlkseacuteg adaleacutekra koumlnnyű automatizaacutelni

o Elsziacutenteleniacuteti a szennyvizet bontja a konjugaacutelt

rendszereket sziacutencentrumokat

o Sugaacuterkeacutemiai uacuteton szagtalaniacutet

oFertőtleniacutet a mikroorganizmusok DNA-jat roncsolja

oA kezelt szennyviacutez hasznaacutelhatoacute pl oumlntoumlzeacutesre

Wastewater TreatmentFlue gas Purification Sludge Disinfection

Az ionizaacuteloacute sugaacuterzaacutes koumlrnyezetveacutedelmi alkalmazaacutesai

A teacutemaacutehoz kapcsoloacutedoacute neacutehaacuteny uacutejabb koumlzlemeacuteny

bullWojnaacuterovits L Takaacutecs E Irradiation treatment of azo-dye containing wastewater an overview Radiat Phys Chem 77 225-244 (2008) bullMelo R Leal J P Takaacutecs E Wojnaacuterovits L Radiolytic degradation of gallic acid and its derivatives in aqueous solution J Hazard Mater 172 1185-1192 (2009)bullHomlok R Takaacutecs E Wojnaacuterovits L Elimination of diclofenac from wastewater using irradiation technology Chemosphere 85 603-608 (2011)bullCsay T Raacutecz G Takaacutecs E Wojnaacuterovits L Radiation degradation of pharmaceutical residues in water chloramphenicol Radiat Phys Chem81 1489-1494 (2012) bullIlleacutes E Takaacutecs E Dombi A Gajda-Schrantz K Gonter K Wojnaacuterovits L Radiation induced degradation of ketoprofen in dilute aqueous solution Radiat Phys Chem 81 1479-1483 (2012) bullChamam M Foumlldvaacutery CM Hosseini AM Tungler A Takaacutecs E Wojnaacuterovits L Mineralization of aqueous phenolate solutions a combination of irradiation treatment and wet oxidation Radiat Phys Chem 81 1484-1488 (2012)

bullSzaboacute L Toacuteth T Homlok R Takaacutecs E Wojnaacuterovits L Radiolysis of paracetamol in dilute aqueous solution Radiat Phys Chem 81 1503-1507 (2012) bullHomlok R Takaacutecs E Wojnaacuterovits L Ionizing radiation induced reactions of 26-dichloroaniline in dilute aqueous solution Radiat Phys Chem 81 1499-1502 (2012) bullHomlok R Takaacutecs E Wojnaacuterovits L Degradation of organic molecules in advanced oxidation processes Relation between chemical structure and degradability Chemosphere DOI 101016jchemosphere201211073bullIlleacutes E Takaacutecs E Dombi A Gajda-Schrantz K Raacutecz G Gonter K Wojnaacuterovits L Hydroxyl radical induced degradation of ibuprofen Science of the Total Environment 447 286ndash292 (2013)


KKoumloumlszszoumloumlnetnet

Wojnaacuterovits LaacuteszloacuteTungler AntalCsay TamaacutesIlleacutes Erzseacutebet

Nemzetkoumlzi Atomenergia UumlgynoumlkseacutegOTKA 60096 80154 the Swiss-Hungarian project SH214

Salvatore Silvano Emmi (Bologna)Rita Paiva Melo (Lisszabon)Bumsoo Han (Daejon Korea)Sunil Sabharwal (IAEA Beacutecs)

Homlok RenaacutetaRaacutecz GergelySzaboacute LaacuteszloacuteSaacutegi Gyuri

Dombi Andraacutes Szegedi EgyetemMakoacute Magdolna FCsMToacuteth Tuumlnde BME VBK

Homonnay Zoltaacuten ELTE KI

Az elfogyasztott gyoacutegyszerek jelentős

haacutenyada nem sziacutevoacutedik fel hanem

kivaacutelasztoacutedik eacutes a vizelettel szennyviacutezbe majd

a szennyviacutez tisztiacutetoacutekba jut

Az erősen toxikus szennyezők mint a

gyoacutegyszer molekulaacutek nehezen bonthatoacuteak a

szennyviacuteztisztiacutetaacutesra hagyomaacutenyosan

alkalmazott moacutedszerekkel

Szerves szennyezSzerves szennyezőők gyk gyoacuteoacutegyszer molekulgyszer molekulaacuteaacutek k az az eacuteeacutellőővizekbenvizekben






Cofibric acid

165 Neacutemeto

270 Neacutemeto

170 Neacutemeto

53 Olaszo


Laacutez- eacutes





400 Neacutemeto


120 Neacutemeto



258 USA



235 Olaszo


bullbullOHOH












Kereskedelmi




Ru oxid

Pd oxid


Ru-Ir oxid











a) 230 oC 50 bar b ) 200 oC 50 bar








H2O rarr

bullH eaq


2 H

2





bull)




OH

NaO

CH3

OH

CH3

OH

CH3

OH

Cl

OH

Cl

OH

Cl

OH

OH

O

O

ClCl

O

CH3O

OHO

CH3

OH

O

O

O

CH3

NHOH

Na

O

O

O

S

Na

OO

O

S

N

N

NH2

OH

NH2

OH

NH2

OH

CH3

ONH

OH

Cl

Cl

NH

OH

O

Cl Cl

NH2 CH3

O

O CH3

OH

OH

OH

OH

O

OH

O

OH

O

OH

O

OH

O

OH

0

500 000

1 000 000

1 500 000

2 000 000

2 500 000

Ibuprofen

Num

ber

of

boxes s

old

2001

2005

Ibuprofen (IBP)


(NSAID)



Rhinathiol Ibustar





OH

O





447 286ndash292 (2013)

200 250 300 350 400 45000

05

10

15

20

Abs

orba

nce

Wavelength nm

0 kGy

025 kGy05 kGy

075 kGy15 kGy

1 kGy

00 05 10 1500

02

04

06

08

10

Rel

co

ncen

trat

ion

Dose kGy




integraacutelja)


H3C

OH

CH3

O

CH3

CH3

O

CH3

O

OHO

CH3

CH3

CH3

CH3

CH3

CH3 OH

CH3

O O

OHO

OH

CH3

CH3

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OHOH

(1) mz 133 (2) mz 149 (3) mz 175 (4) mz 177

(6) mz 177 (8) mz 221(7) mz 221(5) mz 177

(9) mz 237

H3C

OH

CH3

O

CH3






0 1 2 3 40

5

10

15

20

25

30

35

40IBP 1 x 10-4 mol dm-3

Dose kGy

Inh

ibit

ion

00

05

10

cc

0

00 05 10 15 200

20

40

60

80

100

120

140

160

180 1633

1839

2303

2533

8997

Ab

so

rban

ce

Dose kGy



HPLC-diode array

detection





SampleFree Cl

mg dm-3

Total Cl

mg dm-3

Dose

kGy

Total

Coli

Fecal

Coli

Fec C

Total C

I01 - - - 730 75 102

IICl1 007 009 - 560 52 93

Irad1

- - 05 1 0 -

- - 1 1 0 -

- - 20 0 0 -

I02 - - - 900 90 99

IICl2 lt005 006 - 700 80 114

Irad2

- - 05 0 0 -

- - 1 0 0 -

- - 20 0 0 -






mg dm-3

BOD5

mg dm-3

BOD5CODk

I01 - 46 16 35

IICl1 Cl 62 16 26

Irad1

05 kGy 36 lt10 (6) lt17

1 kGy 32 lt10 (8) lt25

20 kGy 36 lt10 (5) lt14

I02 - 53 17 32

IICl2 Cl 58 15 26

Irad2

05 kGy 31 lt10 (7) lt23

1 kGy 39 lt10 (7) lt18

20 kGy lt30 (28) lt10 (5) lt18

25



Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486


Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2




























Cofibric acid

165 Neacutemeto

270 Neacutemeto

170 Neacutemeto

53 Olaszo


Laacutez- eacutes





400 Neacutemeto


120 Neacutemeto



258 USA



235 Olaszo


bullbullOHOH












Kereskedelmi




Ru oxid

Pd oxid


Ru-Ir oxid











a) 230 oC 50 bar b ) 200 oC 50 bar








H2O rarr

bullH eaq


2 H

2





bull)




OH

NaO

CH3

OH

CH3

OH

CH3

OH

Cl

OH

Cl

OH

Cl

OH

OH

O

O

ClCl

O

CH3O

OHO

CH3

OH

O

O

O

CH3

NHOH

Na

O

O

O

S

Na

OO

O

S

N

N

NH2

OH

NH2

OH

NH2

OH

CH3

ONH

OH

Cl

Cl

NH

OH

O

Cl Cl

NH2 CH3

O

O CH3

OH

OH

OH

OH

O

OH

O

OH

O

OH

O

OH

O

OH

0

500 000

1 000 000

1 500 000

2 000 000

2 500 000

Ibuprofen

Num

ber

of

boxes s

old

2001

2005

Ibuprofen (IBP)


(NSAID)



Rhinathiol Ibustar





OH

O





447 286ndash292 (2013)

200 250 300 350 400 45000

05

10

15

20

Abs

orba

nce

Wavelength nm

0 kGy

025 kGy05 kGy

075 kGy15 kGy

1 kGy

00 05 10 1500

02

04

06

08

10

Rel

co

ncen

trat

ion

Dose kGy




integraacutelja)


H3C

OH

CH3

O

CH3

CH3

O

CH3

O

OHO

CH3

CH3

CH3

CH3

CH3

CH3 OH

CH3

O O

OHO

OH

CH3

CH3

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OHOH

(1) mz 133 (2) mz 149 (3) mz 175 (4) mz 177

(6) mz 177 (8) mz 221(7) mz 221(5) mz 177

(9) mz 237

H3C

OH

CH3

O

CH3






0 1 2 3 40

5

10

15

20

25

30

35

40IBP 1 x 10-4 mol dm-3

Dose kGy

Inh

ibit

ion

00

05

10

cc

0

00 05 10 15 200

20

40

60

80

100

120

140

160

180 1633

1839

2303

2533

8997

Ab

so

rban

ce

Dose kGy



HPLC-diode array

detection





SampleFree Cl

mg dm-3

Total Cl

mg dm-3

Dose

kGy

Total

Coli

Fecal

Coli

Fec C

Total C

I01 - - - 730 75 102

IICl1 007 009 - 560 52 93

Irad1

- - 05 1 0 -

- - 1 1 0 -

- - 20 0 0 -

I02 - - - 900 90 99

IICl2 lt005 006 - 700 80 114

Irad2

- - 05 0 0 -

- - 1 0 0 -

- - 20 0 0 -






mg dm-3

BOD5

mg dm-3

BOD5CODk

I01 - 46 16 35

IICl1 Cl 62 16 26

Irad1

05 kGy 36 lt10 (6) lt17

1 kGy 32 lt10 (8) lt25

20 kGy 36 lt10 (5) lt14

I02 - 53 17 32

IICl2 Cl 58 15 26

Irad2

05 kGy 31 lt10 (7) lt23

1 kGy 39 lt10 (7) lt18

20 kGy lt30 (28) lt10 (5) lt18

25



Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486


Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2


























Cofibric acid

165 Neacutemeto

270 Neacutemeto

170 Neacutemeto

53 Olaszo


Laacutez- eacutes





400 Neacutemeto


120 Neacutemeto



258 USA



235 Olaszo


bullbullOHOH












Kereskedelmi




Ru oxid

Pd oxid


Ru-Ir oxid











a) 230 oC 50 bar b ) 200 oC 50 bar








H2O rarr

bullH eaq


2 H

2





bull)




OH

NaO

CH3

OH

CH3

OH

CH3

OH

Cl

OH

Cl

OH

Cl

OH

OH

O

O

ClCl

O

CH3O

OHO

CH3

OH

O

O

O

CH3

NHOH

Na

O

O

O

S

Na

OO

O

S

N

N

NH2

OH

NH2

OH

NH2

OH

CH3

ONH

OH

Cl

Cl

NH

OH

O

Cl Cl

NH2 CH3

O

O CH3

OH

OH

OH

OH

O

OH

O

OH

O

OH

O

OH

O

OH

0

500 000

1 000 000

1 500 000

2 000 000

2 500 000

Ibuprofen

Num

ber

of

boxes s

old

2001

2005

Ibuprofen (IBP)


(NSAID)



Rhinathiol Ibustar





OH

O





447 286ndash292 (2013)

200 250 300 350 400 45000

05

10

15

20

Abs

orba

nce

Wavelength nm

0 kGy

025 kGy05 kGy

075 kGy15 kGy

1 kGy

00 05 10 1500

02

04

06

08

10

Rel

co

ncen

trat

ion

Dose kGy




integraacutelja)


H3C

OH

CH3

O

CH3

CH3

O

CH3

O

OHO

CH3

CH3

CH3

CH3

CH3

CH3 OH

CH3

O O

OHO

OH

CH3

CH3

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OHOH

(1) mz 133 (2) mz 149 (3) mz 175 (4) mz 177

(6) mz 177 (8) mz 221(7) mz 221(5) mz 177

(9) mz 237

H3C

OH

CH3

O

CH3






0 1 2 3 40

5

10

15

20

25

30

35

40IBP 1 x 10-4 mol dm-3

Dose kGy

Inh

ibit

ion

00

05

10

cc

0

00 05 10 15 200

20

40

60

80

100

120

140

160

180 1633

1839

2303

2533

8997

Ab

so

rban

ce

Dose kGy



HPLC-diode array

detection





SampleFree Cl

mg dm-3

Total Cl

mg dm-3

Dose

kGy

Total

Coli

Fecal

Coli

Fec C

Total C

I01 - - - 730 75 102

IICl1 007 009 - 560 52 93

Irad1

- - 05 1 0 -

- - 1 1 0 -

- - 20 0 0 -

I02 - - - 900 90 99

IICl2 lt005 006 - 700 80 114

Irad2

- - 05 0 0 -

- - 1 0 0 -

- - 20 0 0 -






mg dm-3

BOD5

mg dm-3

BOD5CODk

I01 - 46 16 35

IICl1 Cl 62 16 26

Irad1

05 kGy 36 lt10 (6) lt17

1 kGy 32 lt10 (8) lt25

20 kGy 36 lt10 (5) lt14

I02 - 53 17 32

IICl2 Cl 58 15 26

Irad2

05 kGy 31 lt10 (7) lt23

1 kGy 39 lt10 (7) lt18

20 kGy lt30 (28) lt10 (5) lt18

25



Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486


Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2























bullbullOHOH












Kereskedelmi




Ru oxid

Pd oxid


Ru-Ir oxid











a) 230 oC 50 bar b ) 200 oC 50 bar








H2O rarr

bullH eaq


2 H

2





bull)




OH

NaO

CH3

OH

CH3

OH

CH3

OH

Cl

OH

Cl

OH

Cl

OH

OH

O

O

ClCl

O

CH3O

OHO

CH3

OH

O

O

O

CH3

NHOH

Na

O

O

O

S

Na

OO

O

S

N

N

NH2

OH

NH2

OH

NH2

OH

CH3

ONH

OH

Cl

Cl

NH

OH

O

Cl Cl

NH2 CH3

O

O CH3

OH

OH

OH

OH

O

OH

O

OH

O

OH

O

OH

O

OH

0

500 000

1 000 000

1 500 000

2 000 000

2 500 000

Ibuprofen

Num

ber

of

boxes s

old

2001

2005

Ibuprofen (IBP)


(NSAID)



Rhinathiol Ibustar





OH

O





447 286ndash292 (2013)

200 250 300 350 400 45000

05

10

15

20

Abs

orba

nce

Wavelength nm

0 kGy

025 kGy05 kGy

075 kGy15 kGy

1 kGy

00 05 10 1500

02

04

06

08

10

Rel

co

ncen

trat

ion

Dose kGy




integraacutelja)


H3C

OH

CH3

O

CH3

CH3

O

CH3

O

OHO

CH3

CH3

CH3

CH3

CH3

CH3 OH

CH3

O O

OHO

OH

CH3

CH3

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OHOH

(1) mz 133 (2) mz 149 (3) mz 175 (4) mz 177

(6) mz 177 (8) mz 221(7) mz 221(5) mz 177

(9) mz 237

H3C

OH

CH3

O

CH3






0 1 2 3 40

5

10

15

20

25

30

35

40IBP 1 x 10-4 mol dm-3

Dose kGy

Inh

ibit

ion

00

05

10

cc

0

00 05 10 15 200

20

40

60

80

100

120

140

160

180 1633

1839

2303

2533

8997

Ab

so

rban

ce

Dose kGy



HPLC-diode array

detection





SampleFree Cl

mg dm-3

Total Cl

mg dm-3

Dose

kGy

Total

Coli

Fecal

Coli

Fec C

Total C

I01 - - - 730 75 102

IICl1 007 009 - 560 52 93

Irad1

- - 05 1 0 -

- - 1 1 0 -

- - 20 0 0 -

I02 - - - 900 90 99

IICl2 lt005 006 - 700 80 114

Irad2

- - 05 0 0 -

- - 1 0 0 -

- - 20 0 0 -






mg dm-3

BOD5

mg dm-3

BOD5CODk

I01 - 46 16 35

IICl1 Cl 62 16 26

Irad1

05 kGy 36 lt10 (6) lt17

1 kGy 32 lt10 (8) lt25

20 kGy 36 lt10 (5) lt14

I02 - 53 17 32

IICl2 Cl 58 15 26

Irad2

05 kGy 31 lt10 (7) lt23

1 kGy 39 lt10 (7) lt18

20 kGy lt30 (28) lt10 (5) lt18

25



Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486


Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2






























Kereskedelmi




Ru oxid

Pd oxid


Ru-Ir oxid











a) 230 oC 50 bar b ) 200 oC 50 bar








H2O rarr

bullH eaq


2 H

2





bull)




OH

NaO

CH3

OH

CH3

OH

CH3

OH

Cl

OH

Cl

OH

Cl

OH

OH

O

O

ClCl

O

CH3O

OHO

CH3

OH

O

O

O

CH3

NHOH

Na

O

O

O

S

Na

OO

O

S

N

N

NH2

OH

NH2

OH

NH2

OH

CH3

ONH

OH

Cl

Cl

NH

OH

O

Cl Cl

NH2 CH3

O

O CH3

OH

OH

OH

OH

O

OH

O

OH

O

OH

O

OH

O

OH

0

500 000

1 000 000

1 500 000

2 000 000

2 500 000

Ibuprofen

Num

ber

of

boxes s

old

2001

2005

Ibuprofen (IBP)


(NSAID)



Rhinathiol Ibustar





OH

O





447 286ndash292 (2013)

200 250 300 350 400 45000

05

10

15

20

Abs

orba

nce

Wavelength nm

0 kGy

025 kGy05 kGy

075 kGy15 kGy

1 kGy

00 05 10 1500

02

04

06

08

10

Rel

co

ncen

trat

ion

Dose kGy




integraacutelja)


H3C

OH

CH3

O

CH3

CH3

O

CH3

O

OHO

CH3

CH3

CH3

CH3

CH3

CH3 OH

CH3

O O

OHO

OH

CH3

CH3

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OHOH

(1) mz 133 (2) mz 149 (3) mz 175 (4) mz 177

(6) mz 177 (8) mz 221(7) mz 221(5) mz 177

(9) mz 237

H3C

OH

CH3

O

CH3






0 1 2 3 40

5

10

15

20

25

30

35

40IBP 1 x 10-4 mol dm-3

Dose kGy

Inh

ibit

ion

00

05

10

cc

0

00 05 10 15 200

20

40

60

80

100

120

140

160

180 1633

1839

2303

2533

8997

Ab

so

rban

ce

Dose kGy



HPLC-diode array

detection





SampleFree Cl

mg dm-3

Total Cl

mg dm-3

Dose

kGy

Total

Coli

Fecal

Coli

Fec C

Total C

I01 - - - 730 75 102

IICl1 007 009 - 560 52 93

Irad1

- - 05 1 0 -

- - 1 1 0 -

- - 20 0 0 -

I02 - - - 900 90 99

IICl2 lt005 006 - 700 80 114

Irad2

- - 05 0 0 -

- - 1 0 0 -

- - 20 0 0 -






mg dm-3

BOD5

mg dm-3

BOD5CODk

I01 - 46 16 35

IICl1 Cl 62 16 26

Irad1

05 kGy 36 lt10 (6) lt17

1 kGy 32 lt10 (8) lt25

20 kGy 36 lt10 (5) lt14

I02 - 53 17 32

IICl2 Cl 58 15 26

Irad2

05 kGy 31 lt10 (7) lt23

1 kGy 39 lt10 (7) lt18

20 kGy lt30 (28) lt10 (5) lt18

25



Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486


Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2
























Kereskedelmi




Ru oxid

Pd oxid


Ru-Ir oxid











a) 230 oC 50 bar b ) 200 oC 50 bar








H2O rarr

bullH eaq


2 H

2





bull)




OH

NaO

CH3

OH

CH3

OH

CH3

OH

Cl

OH

Cl

OH

Cl

OH

OH

O

O

ClCl

O

CH3O

OHO

CH3

OH

O

O

O

CH3

NHOH

Na

O

O

O

S

Na

OO

O

S

N

N

NH2

OH

NH2

OH

NH2

OH

CH3

ONH

OH

Cl

Cl

NH

OH

O

Cl Cl

NH2 CH3

O

O CH3

OH

OH

OH

OH

O

OH

O

OH

O

OH

O

OH

O

OH

0

500 000

1 000 000

1 500 000

2 000 000

2 500 000

Ibuprofen

Num

ber

of

boxes s

old

2001

2005

Ibuprofen (IBP)


(NSAID)



Rhinathiol Ibustar





OH

O





447 286ndash292 (2013)

200 250 300 350 400 45000

05

10

15

20

Abs

orba

nce

Wavelength nm

0 kGy

025 kGy05 kGy

075 kGy15 kGy

1 kGy

00 05 10 1500

02

04

06

08

10

Rel

co

ncen

trat

ion

Dose kGy




integraacutelja)


H3C

OH

CH3

O

CH3

CH3

O

CH3

O

OHO

CH3

CH3

CH3

CH3

CH3

CH3 OH

CH3

O O

OHO

OH

CH3

CH3

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OHOH

(1) mz 133 (2) mz 149 (3) mz 175 (4) mz 177

(6) mz 177 (8) mz 221(7) mz 221(5) mz 177

(9) mz 237

H3C

OH

CH3

O

CH3






0 1 2 3 40

5

10

15

20

25

30

35

40IBP 1 x 10-4 mol dm-3

Dose kGy

Inh

ibit

ion

00

05

10

cc

0

00 05 10 15 200

20

40

60

80

100

120

140

160

180 1633

1839

2303

2533

8997

Ab

so

rban

ce

Dose kGy



HPLC-diode array

detection





SampleFree Cl

mg dm-3

Total Cl

mg dm-3

Dose

kGy

Total

Coli

Fecal

Coli

Fec C

Total C

I01 - - - 730 75 102

IICl1 007 009 - 560 52 93

Irad1

- - 05 1 0 -

- - 1 1 0 -

- - 20 0 0 -

I02 - - - 900 90 99

IICl2 lt005 006 - 700 80 114

Irad2

- - 05 0 0 -

- - 1 0 0 -

- - 20 0 0 -






mg dm-3

BOD5

mg dm-3

BOD5CODk

I01 - 46 16 35

IICl1 Cl 62 16 26

Irad1

05 kGy 36 lt10 (6) lt17

1 kGy 32 lt10 (8) lt25

20 kGy 36 lt10 (5) lt14

I02 - 53 17 32

IICl2 Cl 58 15 26

Irad2

05 kGy 31 lt10 (7) lt23

1 kGy 39 lt10 (7) lt18

20 kGy lt30 (28) lt10 (5) lt18

25



Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486


Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2































a) 230 oC 50 bar b ) 200 oC 50 bar








H2O rarr

bullH eaq


2 H

2





bull)




OH

NaO

CH3

OH

CH3

OH

CH3

OH

Cl

OH

Cl

OH

Cl

OH

OH

O

O

ClCl

O

CH3O

OHO

CH3

OH

O

O

O

CH3

NHOH

Na

O

O

O

S

Na

OO

O

S

N

N

NH2

OH

NH2

OH

NH2

OH

CH3

ONH

OH

Cl

Cl

NH

OH

O

Cl Cl

NH2 CH3

O

O CH3

OH

OH

OH

OH

O

OH

O

OH

O

OH

O

OH

O

OH

0

500 000

1 000 000

1 500 000

2 000 000

2 500 000

Ibuprofen

Num

ber

of

boxes s

old

2001

2005

Ibuprofen (IBP)


(NSAID)



Rhinathiol Ibustar





OH

O





447 286ndash292 (2013)

200 250 300 350 400 45000

05

10

15

20

Abs

orba

nce

Wavelength nm

0 kGy

025 kGy05 kGy

075 kGy15 kGy

1 kGy

00 05 10 1500

02

04

06

08

10

Rel

co

ncen

trat

ion

Dose kGy




integraacutelja)


H3C

OH

CH3

O

CH3

CH3

O

CH3

O

OHO

CH3

CH3

CH3

CH3

CH3

CH3 OH

CH3

O O

OHO

OH

CH3

CH3

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OHOH

(1) mz 133 (2) mz 149 (3) mz 175 (4) mz 177

(6) mz 177 (8) mz 221(7) mz 221(5) mz 177

(9) mz 237

H3C

OH

CH3

O

CH3






0 1 2 3 40

5

10

15

20

25

30

35

40IBP 1 x 10-4 mol dm-3

Dose kGy

Inh

ibit

ion

00

05

10

cc

0

00 05 10 15 200

20

40

60

80

100

120

140

160

180 1633

1839

2303

2533

8997

Ab

so

rban

ce

Dose kGy



HPLC-diode array

detection





SampleFree Cl

mg dm-3

Total Cl

mg dm-3

Dose

kGy

Total

Coli

Fecal

Coli

Fec C

Total C

I01 - - - 730 75 102

IICl1 007 009 - 560 52 93

Irad1

- - 05 1 0 -

- - 1 1 0 -

- - 20 0 0 -

I02 - - - 900 90 99

IICl2 lt005 006 - 700 80 114

Irad2

- - 05 0 0 -

- - 1 0 0 -

- - 20 0 0 -






mg dm-3

BOD5

mg dm-3

BOD5CODk

I01 - 46 16 35

IICl1 Cl 62 16 26

Irad1

05 kGy 36 lt10 (6) lt17

1 kGy 32 lt10 (8) lt25

20 kGy 36 lt10 (5) lt14

I02 - 53 17 32

IICl2 Cl 58 15 26

Irad2

05 kGy 31 lt10 (7) lt23

1 kGy 39 lt10 (7) lt18

20 kGy lt30 (28) lt10 (5) lt18

25



Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486


Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2






























a) 230 oC 50 bar b ) 200 oC 50 bar








H2O rarr

bullH eaq


2 H

2





bull)




OH

NaO

CH3

OH

CH3

OH

CH3

OH

Cl

OH

Cl

OH

Cl

OH

OH

O

O

ClCl

O

CH3O

OHO

CH3

OH

O

O

O

CH3

NHOH

Na

O

O

O

S

Na

OO

O

S

N

N

NH2

OH

NH2

OH

NH2

OH

CH3

ONH

OH

Cl

Cl

NH

OH

O

Cl Cl

NH2 CH3

O

O CH3

OH

OH

OH

OH

O

OH

O

OH

O

OH

O

OH

O

OH

0

500 000

1 000 000

1 500 000

2 000 000

2 500 000

Ibuprofen

Num

ber

of

boxes s

old

2001

2005

Ibuprofen (IBP)


(NSAID)



Rhinathiol Ibustar





OH

O





447 286ndash292 (2013)

200 250 300 350 400 45000

05

10

15

20

Abs

orba

nce

Wavelength nm

0 kGy

025 kGy05 kGy

075 kGy15 kGy

1 kGy

00 05 10 1500

02

04

06

08

10

Rel

co

ncen

trat

ion

Dose kGy




integraacutelja)


H3C

OH

CH3

O

CH3

CH3

O

CH3

O

OHO

CH3

CH3

CH3

CH3

CH3

CH3 OH

CH3

O O

OHO

OH

CH3

CH3

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OHOH

(1) mz 133 (2) mz 149 (3) mz 175 (4) mz 177

(6) mz 177 (8) mz 221(7) mz 221(5) mz 177

(9) mz 237

H3C

OH

CH3

O

CH3






0 1 2 3 40

5

10

15

20

25

30

35

40IBP 1 x 10-4 mol dm-3

Dose kGy

Inh

ibit

ion

00

05

10

cc

0

00 05 10 15 200

20

40

60

80

100

120

140

160

180 1633

1839

2303

2533

8997

Ab

so

rban

ce

Dose kGy



HPLC-diode array

detection





SampleFree Cl

mg dm-3

Total Cl

mg dm-3

Dose

kGy

Total

Coli

Fecal

Coli

Fec C

Total C

I01 - - - 730 75 102

IICl1 007 009 - 560 52 93

Irad1

- - 05 1 0 -

- - 1 1 0 -

- - 20 0 0 -

I02 - - - 900 90 99

IICl2 lt005 006 - 700 80 114

Irad2

- - 05 0 0 -

- - 1 0 0 -

- - 20 0 0 -






mg dm-3

BOD5

mg dm-3

BOD5CODk

I01 - 46 16 35

IICl1 Cl 62 16 26

Irad1

05 kGy 36 lt10 (6) lt17

1 kGy 32 lt10 (8) lt25

20 kGy 36 lt10 (5) lt14

I02 - 53 17 32

IICl2 Cl 58 15 26

Irad2

05 kGy 31 lt10 (7) lt23

1 kGy 39 lt10 (7) lt18

20 kGy lt30 (28) lt10 (5) lt18

25



Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486


Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2





























a) 230 oC 50 bar b ) 200 oC 50 bar








H2O rarr

bullH eaq


2 H

2





bull)




OH

NaO

CH3

OH

CH3

OH

CH3

OH

Cl

OH

Cl

OH

Cl

OH

OH

O

O

ClCl

O

CH3O

OHO

CH3

OH

O

O

O

CH3

NHOH

Na

O

O

O

S

Na

OO

O

S

N

N

NH2

OH

NH2

OH

NH2

OH

CH3

ONH

OH

Cl

Cl

NH

OH

O

Cl Cl

NH2 CH3

O

O CH3

OH

OH

OH

OH

O

OH

O

OH

O

OH

O

OH

O

OH

0

500 000

1 000 000

1 500 000

2 000 000

2 500 000

Ibuprofen

Num

ber

of

boxes s

old

2001

2005

Ibuprofen (IBP)


(NSAID)



Rhinathiol Ibustar





OH

O





447 286ndash292 (2013)

200 250 300 350 400 45000

05

10

15

20

Abs

orba

nce

Wavelength nm

0 kGy

025 kGy05 kGy

075 kGy15 kGy

1 kGy

00 05 10 1500

02

04

06

08

10

Rel

co

ncen

trat

ion

Dose kGy




integraacutelja)


H3C

OH

CH3

O

CH3

CH3

O

CH3

O

OHO

CH3

CH3

CH3

CH3

CH3

CH3 OH

CH3

O O

OHO

OH

CH3

CH3

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OHOH

(1) mz 133 (2) mz 149 (3) mz 175 (4) mz 177

(6) mz 177 (8) mz 221(7) mz 221(5) mz 177

(9) mz 237

H3C

OH

CH3

O

CH3






0 1 2 3 40

5

10

15

20

25

30

35

40IBP 1 x 10-4 mol dm-3

Dose kGy

Inh

ibit

ion

00

05

10

cc

0

00 05 10 15 200

20

40

60

80

100

120

140

160

180 1633

1839

2303

2533

8997

Ab

so

rban

ce

Dose kGy



HPLC-diode array

detection





SampleFree Cl

mg dm-3

Total Cl

mg dm-3

Dose

kGy

Total

Coli

Fecal

Coli

Fec C

Total C

I01 - - - 730 75 102

IICl1 007 009 - 560 52 93

Irad1

- - 05 1 0 -

- - 1 1 0 -

- - 20 0 0 -

I02 - - - 900 90 99

IICl2 lt005 006 - 700 80 114

Irad2

- - 05 0 0 -

- - 1 0 0 -

- - 20 0 0 -






mg dm-3

BOD5

mg dm-3

BOD5CODk

I01 - 46 16 35

IICl1 Cl 62 16 26

Irad1

05 kGy 36 lt10 (6) lt17

1 kGy 32 lt10 (8) lt25

20 kGy 36 lt10 (5) lt14

I02 - 53 17 32

IICl2 Cl 58 15 26

Irad2

05 kGy 31 lt10 (7) lt23

1 kGy 39 lt10 (7) lt18

20 kGy lt30 (28) lt10 (5) lt18

25



Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486


Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2




























a) 230 oC 50 bar b ) 200 oC 50 bar








H2O rarr

bullH eaq


2 H

2





bull)




OH

NaO

CH3

OH

CH3

OH

CH3

OH

Cl

OH

Cl

OH

Cl

OH

OH

O

O

ClCl

O

CH3O

OHO

CH3

OH

O

O

O

CH3

NHOH

Na

O

O

O

S

Na

OO

O

S

N

N

NH2

OH

NH2

OH

NH2

OH

CH3

ONH

OH

Cl

Cl

NH

OH

O

Cl Cl

NH2 CH3

O

O CH3

OH

OH

OH

OH

O

OH

O

OH

O

OH

O

OH

O

OH

0

500 000

1 000 000

1 500 000

2 000 000

2 500 000

Ibuprofen

Num

ber

of

boxes s

old

2001

2005

Ibuprofen (IBP)


(NSAID)



Rhinathiol Ibustar





OH

O





447 286ndash292 (2013)

200 250 300 350 400 45000

05

10

15

20

Abs

orba

nce

Wavelength nm

0 kGy

025 kGy05 kGy

075 kGy15 kGy

1 kGy

00 05 10 1500

02

04

06

08

10

Rel

co

ncen

trat

ion

Dose kGy




integraacutelja)


H3C

OH

CH3

O

CH3

CH3

O

CH3

O

OHO

CH3

CH3

CH3

CH3

CH3

CH3 OH

CH3

O O

OHO

OH

CH3

CH3

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OHOH

(1) mz 133 (2) mz 149 (3) mz 175 (4) mz 177

(6) mz 177 (8) mz 221(7) mz 221(5) mz 177

(9) mz 237

H3C

OH

CH3

O

CH3






0 1 2 3 40

5

10

15

20

25

30

35

40IBP 1 x 10-4 mol dm-3

Dose kGy

Inh

ibit

ion

00

05

10

cc

0

00 05 10 15 200

20

40

60

80

100

120

140

160

180 1633

1839

2303

2533

8997

Ab

so

rban

ce

Dose kGy



HPLC-diode array

detection





SampleFree Cl

mg dm-3

Total Cl

mg dm-3

Dose

kGy

Total

Coli

Fecal

Coli

Fec C

Total C

I01 - - - 730 75 102

IICl1 007 009 - 560 52 93

Irad1

- - 05 1 0 -

- - 1 1 0 -

- - 20 0 0 -

I02 - - - 900 90 99

IICl2 lt005 006 - 700 80 114

Irad2

- - 05 0 0 -

- - 1 0 0 -

- - 20 0 0 -






mg dm-3

BOD5

mg dm-3

BOD5CODk

I01 - 46 16 35

IICl1 Cl 62 16 26

Irad1

05 kGy 36 lt10 (6) lt17

1 kGy 32 lt10 (8) lt25

20 kGy 36 lt10 (5) lt14

I02 - 53 17 32

IICl2 Cl 58 15 26

Irad2

05 kGy 31 lt10 (7) lt23

1 kGy 39 lt10 (7) lt18

20 kGy lt30 (28) lt10 (5) lt18

25



Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486


Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2



























a) 230 oC 50 bar b ) 200 oC 50 bar








H2O rarr

bullH eaq


2 H

2





bull)




OH

NaO

CH3

OH

CH3

OH

CH3

OH

Cl

OH

Cl

OH

Cl

OH

OH

O

O

ClCl

O

CH3O

OHO

CH3

OH

O

O

O

CH3

NHOH

Na

O

O

O

S

Na

OO

O

S

N

N

NH2

OH

NH2

OH

NH2

OH

CH3

ONH

OH

Cl

Cl

NH

OH

O

Cl Cl

NH2 CH3

O

O CH3

OH

OH

OH

OH

O

OH

O

OH

O

OH

O

OH

O

OH

0

500 000

1 000 000

1 500 000

2 000 000

2 500 000

Ibuprofen

Num

ber

of

boxes s

old

2001

2005

Ibuprofen (IBP)


(NSAID)



Rhinathiol Ibustar





OH

O





447 286ndash292 (2013)

200 250 300 350 400 45000

05

10

15

20

Abs

orba

nce

Wavelength nm

0 kGy

025 kGy05 kGy

075 kGy15 kGy

1 kGy

00 05 10 1500

02

04

06

08

10

Rel

co

ncen

trat

ion

Dose kGy




integraacutelja)


H3C

OH

CH3

O

CH3

CH3

O

CH3

O

OHO

CH3

CH3

CH3

CH3

CH3

CH3 OH

CH3

O O

OHO

OH

CH3

CH3

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OHOH

(1) mz 133 (2) mz 149 (3) mz 175 (4) mz 177

(6) mz 177 (8) mz 221(7) mz 221(5) mz 177

(9) mz 237

H3C

OH

CH3

O

CH3






0 1 2 3 40

5

10

15

20

25

30

35

40IBP 1 x 10-4 mol dm-3

Dose kGy

Inh

ibit

ion

00

05

10

cc

0

00 05 10 15 200

20

40

60

80

100

120

140

160

180 1633

1839

2303

2533

8997

Ab

so

rban

ce

Dose kGy



HPLC-diode array

detection





SampleFree Cl

mg dm-3

Total Cl

mg dm-3

Dose

kGy

Total

Coli

Fecal

Coli

Fec C

Total C

I01 - - - 730 75 102

IICl1 007 009 - 560 52 93

Irad1

- - 05 1 0 -

- - 1 1 0 -

- - 20 0 0 -

I02 - - - 900 90 99

IICl2 lt005 006 - 700 80 114

Irad2

- - 05 0 0 -

- - 1 0 0 -

- - 20 0 0 -






mg dm-3

BOD5

mg dm-3

BOD5CODk

I01 - 46 16 35

IICl1 Cl 62 16 26

Irad1

05 kGy 36 lt10 (6) lt17

1 kGy 32 lt10 (8) lt25

20 kGy 36 lt10 (5) lt14

I02 - 53 17 32

IICl2 Cl 58 15 26

Irad2

05 kGy 31 lt10 (7) lt23

1 kGy 39 lt10 (7) lt18

20 kGy lt30 (28) lt10 (5) lt18

25



Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486


Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2






























H2O rarr

bullH eaq


2 H

2





bull)




OH

NaO

CH3

OH

CH3

OH

CH3

OH

Cl

OH

Cl

OH

Cl

OH

OH

O

O

ClCl

O

CH3O

OHO

CH3

OH

O

O

O

CH3

NHOH

Na

O

O

O

S

Na

OO

O

S

N

N

NH2

OH

NH2

OH

NH2

OH

CH3

ONH

OH

Cl

Cl

NH

OH

O

Cl Cl

NH2 CH3

O

O CH3

OH

OH

OH

OH

O

OH

O

OH

O

OH

O

OH

O

OH

0

500 000

1 000 000

1 500 000

2 000 000

2 500 000

Ibuprofen

Num

ber

of

boxes s

old

2001

2005

Ibuprofen (IBP)


(NSAID)



Rhinathiol Ibustar





OH

O





447 286ndash292 (2013)

200 250 300 350 400 45000

05

10

15

20

Abs

orba

nce

Wavelength nm

0 kGy

025 kGy05 kGy

075 kGy15 kGy

1 kGy

00 05 10 1500

02

04

06

08

10

Rel

co

ncen

trat

ion

Dose kGy




integraacutelja)


H3C

OH

CH3

O

CH3

CH3

O

CH3

O

OHO

CH3

CH3

CH3

CH3

CH3

CH3 OH

CH3

O O

OHO

OH

CH3

CH3

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OHOH

(1) mz 133 (2) mz 149 (3) mz 175 (4) mz 177

(6) mz 177 (8) mz 221(7) mz 221(5) mz 177

(9) mz 237

H3C

OH

CH3

O

CH3






0 1 2 3 40

5

10

15

20

25

30

35

40IBP 1 x 10-4 mol dm-3

Dose kGy

Inh

ibit

ion

00

05

10

cc

0

00 05 10 15 200

20

40

60

80

100

120

140

160

180 1633

1839

2303

2533

8997

Ab

so

rban

ce

Dose kGy



HPLC-diode array

detection





SampleFree Cl

mg dm-3

Total Cl

mg dm-3

Dose

kGy

Total

Coli

Fecal

Coli

Fec C

Total C

I01 - - - 730 75 102

IICl1 007 009 - 560 52 93

Irad1

- - 05 1 0 -

- - 1 1 0 -

- - 20 0 0 -

I02 - - - 900 90 99

IICl2 lt005 006 - 700 80 114

Irad2

- - 05 0 0 -

- - 1 0 0 -

- - 20 0 0 -






mg dm-3

BOD5

mg dm-3

BOD5CODk

I01 - 46 16 35

IICl1 Cl 62 16 26

Irad1

05 kGy 36 lt10 (6) lt17

1 kGy 32 lt10 (8) lt25

20 kGy 36 lt10 (5) lt14

I02 - 53 17 32

IICl2 Cl 58 15 26

Irad2

05 kGy 31 lt10 (7) lt23

1 kGy 39 lt10 (7) lt18

20 kGy lt30 (28) lt10 (5) lt18

25



Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486


Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2





























H2O rarr

bullH eaq


2 H

2





bull)




OH

NaO

CH3

OH

CH3

OH

CH3

OH

Cl

OH

Cl

OH

Cl

OH

OH

O

O

ClCl

O

CH3O

OHO

CH3

OH

O

O

O

CH3

NHOH

Na

O

O

O

S

Na

OO

O

S

N

N

NH2

OH

NH2

OH

NH2

OH

CH3

ONH

OH

Cl

Cl

NH

OH

O

Cl Cl

NH2 CH3

O

O CH3

OH

OH

OH

OH

O

OH

O

OH

O

OH

O

OH

O

OH

0

500 000

1 000 000

1 500 000

2 000 000

2 500 000

Ibuprofen

Num

ber

of

boxes s

old

2001

2005

Ibuprofen (IBP)


(NSAID)



Rhinathiol Ibustar





OH

O





447 286ndash292 (2013)

200 250 300 350 400 45000

05

10

15

20

Abs

orba

nce

Wavelength nm

0 kGy

025 kGy05 kGy

075 kGy15 kGy

1 kGy

00 05 10 1500

02

04

06

08

10

Rel

co

ncen

trat

ion

Dose kGy




integraacutelja)


H3C

OH

CH3

O

CH3

CH3

O

CH3

O

OHO

CH3

CH3

CH3

CH3

CH3

CH3 OH

CH3

O O

OHO

OH

CH3

CH3

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OHOH

(1) mz 133 (2) mz 149 (3) mz 175 (4) mz 177

(6) mz 177 (8) mz 221(7) mz 221(5) mz 177

(9) mz 237

H3C

OH

CH3

O

CH3






0 1 2 3 40

5

10

15

20

25

30

35

40IBP 1 x 10-4 mol dm-3

Dose kGy

Inh

ibit

ion

00

05

10

cc

0

00 05 10 15 200

20

40

60

80

100

120

140

160

180 1633

1839

2303

2533

8997

Ab

so

rban

ce

Dose kGy



HPLC-diode array

detection





SampleFree Cl

mg dm-3

Total Cl

mg dm-3

Dose

kGy

Total

Coli

Fecal

Coli

Fec C

Total C

I01 - - - 730 75 102

IICl1 007 009 - 560 52 93

Irad1

- - 05 1 0 -

- - 1 1 0 -

- - 20 0 0 -

I02 - - - 900 90 99

IICl2 lt005 006 - 700 80 114

Irad2

- - 05 0 0 -

- - 1 0 0 -

- - 20 0 0 -






mg dm-3

BOD5

mg dm-3

BOD5CODk

I01 - 46 16 35

IICl1 Cl 62 16 26

Irad1

05 kGy 36 lt10 (6) lt17

1 kGy 32 lt10 (8) lt25

20 kGy 36 lt10 (5) lt14

I02 - 53 17 32

IICl2 Cl 58 15 26

Irad2

05 kGy 31 lt10 (7) lt23

1 kGy 39 lt10 (7) lt18

20 kGy lt30 (28) lt10 (5) lt18

25



Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486


Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2
























H2O rarr

bullH eaq


2 H

2





bull)




OH

NaO

CH3

OH

CH3

OH

CH3

OH

Cl

OH

Cl

OH

Cl

OH

OH

O

O

ClCl

O

CH3O

OHO

CH3

OH

O

O

O

CH3

NHOH

Na

O

O

O

S

Na

OO

O

S

N

N

NH2

OH

NH2

OH

NH2

OH

CH3

ONH

OH

Cl

Cl

NH

OH

O

Cl Cl

NH2 CH3

O

O CH3

OH

OH

OH

OH

O

OH

O

OH

O

OH

O

OH

O

OH

0

500 000

1 000 000

1 500 000

2 000 000

2 500 000

Ibuprofen

Num

ber

of

boxes s

old

2001

2005

Ibuprofen (IBP)


(NSAID)



Rhinathiol Ibustar





OH

O





447 286ndash292 (2013)

200 250 300 350 400 45000

05

10

15

20

Abs

orba

nce

Wavelength nm

0 kGy

025 kGy05 kGy

075 kGy15 kGy

1 kGy

00 05 10 1500

02

04

06

08

10

Rel

co

ncen

trat

ion

Dose kGy




integraacutelja)


H3C

OH

CH3

O

CH3

CH3

O

CH3

O

OHO

CH3

CH3

CH3

CH3

CH3

CH3 OH

CH3

O O

OHO

OH

CH3

CH3

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OHOH

(1) mz 133 (2) mz 149 (3) mz 175 (4) mz 177

(6) mz 177 (8) mz 221(7) mz 221(5) mz 177

(9) mz 237

H3C

OH

CH3

O

CH3






0 1 2 3 40

5

10

15

20

25

30

35

40IBP 1 x 10-4 mol dm-3

Dose kGy

Inh

ibit

ion

00

05

10

cc

0

00 05 10 15 200

20

40

60

80

100

120

140

160

180 1633

1839

2303

2533

8997

Ab

so

rban

ce

Dose kGy



HPLC-diode array

detection





SampleFree Cl

mg dm-3

Total Cl

mg dm-3

Dose

kGy

Total

Coli

Fecal

Coli

Fec C

Total C

I01 - - - 730 75 102

IICl1 007 009 - 560 52 93

Irad1

- - 05 1 0 -

- - 1 1 0 -

- - 20 0 0 -

I02 - - - 900 90 99

IICl2 lt005 006 - 700 80 114

Irad2

- - 05 0 0 -

- - 1 0 0 -

- - 20 0 0 -






mg dm-3

BOD5

mg dm-3

BOD5CODk

I01 - 46 16 35

IICl1 Cl 62 16 26

Irad1

05 kGy 36 lt10 (6) lt17

1 kGy 32 lt10 (8) lt25

20 kGy 36 lt10 (5) lt14

I02 - 53 17 32

IICl2 Cl 58 15 26

Irad2

05 kGy 31 lt10 (7) lt23

1 kGy 39 lt10 (7) lt18

20 kGy lt30 (28) lt10 (5) lt18

25



Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486


Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2























OH

NaO

CH3

OH

CH3

OH

CH3

OH

Cl

OH

Cl

OH

Cl

OH

OH

O

O

ClCl

O

CH3O

OHO

CH3

OH

O

O

O

CH3

NHOH

Na

O

O

O

S

Na

OO

O

S

N

N

NH2

OH

NH2

OH

NH2

OH

CH3

ONH

OH

Cl

Cl

NH

OH

O

Cl Cl

NH2 CH3

O

O CH3

OH

OH

OH

OH

O

OH

O

OH

O

OH

O

OH

O

OH

0

500 000

1 000 000

1 500 000

2 000 000

2 500 000

Ibuprofen

Num

ber

of

boxes s

old

2001

2005

Ibuprofen (IBP)


(NSAID)



Rhinathiol Ibustar





OH

O





447 286ndash292 (2013)

200 250 300 350 400 45000

05

10

15

20

Abs

orba

nce

Wavelength nm

0 kGy

025 kGy05 kGy

075 kGy15 kGy

1 kGy

00 05 10 1500

02

04

06

08

10

Rel

co

ncen

trat

ion

Dose kGy




integraacutelja)


H3C

OH

CH3

O

CH3

CH3

O

CH3

O

OHO

CH3

CH3

CH3

CH3

CH3

CH3 OH

CH3

O O

OHO

OH

CH3

CH3

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OHOH

(1) mz 133 (2) mz 149 (3) mz 175 (4) mz 177

(6) mz 177 (8) mz 221(7) mz 221(5) mz 177

(9) mz 237

H3C

OH

CH3

O

CH3






0 1 2 3 40

5

10

15

20

25

30

35

40IBP 1 x 10-4 mol dm-3

Dose kGy

Inh

ibit

ion

00

05

10

cc

0

00 05 10 15 200

20

40

60

80

100

120

140

160

180 1633

1839

2303

2533

8997

Ab

so

rban

ce

Dose kGy



HPLC-diode array

detection





SampleFree Cl

mg dm-3

Total Cl

mg dm-3

Dose

kGy

Total

Coli

Fecal

Coli

Fec C

Total C

I01 - - - 730 75 102

IICl1 007 009 - 560 52 93

Irad1

- - 05 1 0 -

- - 1 1 0 -

- - 20 0 0 -

I02 - - - 900 90 99

IICl2 lt005 006 - 700 80 114

Irad2

- - 05 0 0 -

- - 1 0 0 -

- - 20 0 0 -






mg dm-3

BOD5

mg dm-3

BOD5CODk

I01 - 46 16 35

IICl1 Cl 62 16 26

Irad1

05 kGy 36 lt10 (6) lt17

1 kGy 32 lt10 (8) lt25

20 kGy 36 lt10 (5) lt14

I02 - 53 17 32

IICl2 Cl 58 15 26

Irad2

05 kGy 31 lt10 (7) lt23

1 kGy 39 lt10 (7) lt18

20 kGy lt30 (28) lt10 (5) lt18

25



Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486


Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2























0

500 000

1 000 000

1 500 000

2 000 000

2 500 000

Ibuprofen

Num

ber

of

boxes s

old

2001

2005

Ibuprofen (IBP)


(NSAID)



Rhinathiol Ibustar





OH

O





447 286ndash292 (2013)

200 250 300 350 400 45000

05

10

15

20

Abs

orba

nce

Wavelength nm

0 kGy

025 kGy05 kGy

075 kGy15 kGy

1 kGy

00 05 10 1500

02

04

06

08

10

Rel

co

ncen

trat

ion

Dose kGy




integraacutelja)


H3C

OH

CH3

O

CH3

CH3

O

CH3

O

OHO

CH3

CH3

CH3

CH3

CH3

CH3 OH

CH3

O O

OHO

OH

CH3

CH3

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OHOH

(1) mz 133 (2) mz 149 (3) mz 175 (4) mz 177

(6) mz 177 (8) mz 221(7) mz 221(5) mz 177

(9) mz 237

H3C

OH

CH3

O

CH3






0 1 2 3 40

5

10

15

20

25

30

35

40IBP 1 x 10-4 mol dm-3

Dose kGy

Inh

ibit

ion

00

05

10

cc

0

00 05 10 15 200

20

40

60

80

100

120

140

160

180 1633

1839

2303

2533

8997

Ab

so

rban

ce

Dose kGy



HPLC-diode array

detection





SampleFree Cl

mg dm-3

Total Cl

mg dm-3

Dose

kGy

Total

Coli

Fecal

Coli

Fec C

Total C

I01 - - - 730 75 102

IICl1 007 009 - 560 52 93

Irad1

- - 05 1 0 -

- - 1 1 0 -

- - 20 0 0 -

I02 - - - 900 90 99

IICl2 lt005 006 - 700 80 114

Irad2

- - 05 0 0 -

- - 1 0 0 -

- - 20 0 0 -






mg dm-3

BOD5

mg dm-3

BOD5CODk

I01 - 46 16 35

IICl1 Cl 62 16 26

Irad1

05 kGy 36 lt10 (6) lt17

1 kGy 32 lt10 (8) lt25

20 kGy 36 lt10 (5) lt14

I02 - 53 17 32

IICl2 Cl 58 15 26

Irad2

05 kGy 31 lt10 (7) lt23

1 kGy 39 lt10 (7) lt18

20 kGy lt30 (28) lt10 (5) lt18

25



Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486


Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2























200 250 300 350 400 45000

05

10

15

20

Abs

orba

nce

Wavelength nm

0 kGy

025 kGy05 kGy

075 kGy15 kGy

1 kGy

00 05 10 1500

02

04

06

08

10

Rel

co

ncen

trat

ion

Dose kGy




integraacutelja)


H3C

OH

CH3

O

CH3

CH3

O

CH3

O

OHO

CH3

CH3

CH3

CH3

CH3

CH3 OH

CH3

O O

OHO

OH

CH3

CH3

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OHOH

(1) mz 133 (2) mz 149 (3) mz 175 (4) mz 177

(6) mz 177 (8) mz 221(7) mz 221(5) mz 177

(9) mz 237

H3C

OH

CH3

O

CH3






0 1 2 3 40

5

10

15

20

25

30

35

40IBP 1 x 10-4 mol dm-3

Dose kGy

Inh

ibit

ion

00

05

10

cc

0

00 05 10 15 200

20

40

60

80

100

120

140

160

180 1633

1839

2303

2533

8997

Ab

so

rban

ce

Dose kGy



HPLC-diode array

detection





SampleFree Cl

mg dm-3

Total Cl

mg dm-3

Dose

kGy

Total

Coli

Fecal

Coli

Fec C

Total C

I01 - - - 730 75 102

IICl1 007 009 - 560 52 93

Irad1

- - 05 1 0 -

- - 1 1 0 -

- - 20 0 0 -

I02 - - - 900 90 99

IICl2 lt005 006 - 700 80 114

Irad2

- - 05 0 0 -

- - 1 0 0 -

- - 20 0 0 -






mg dm-3

BOD5

mg dm-3

BOD5CODk

I01 - 46 16 35

IICl1 Cl 62 16 26

Irad1

05 kGy 36 lt10 (6) lt17

1 kGy 32 lt10 (8) lt25

20 kGy 36 lt10 (5) lt14

I02 - 53 17 32

IICl2 Cl 58 15 26

Irad2

05 kGy 31 lt10 (7) lt23

1 kGy 39 lt10 (7) lt18

20 kGy lt30 (28) lt10 (5) lt18

25



Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486


Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2























CH3

O

CH3

O

OHO

CH3

CH3

CH3

CH3

CH3

CH3 OH

CH3

O O

OHO

OH

CH3

CH3

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OH

CH3

CH3

CH3

OH

O

OHOH

(1) mz 133 (2) mz 149 (3) mz 175 (4) mz 177

(6) mz 177 (8) mz 221(7) mz 221(5) mz 177

(9) mz 237

H3C

OH

CH3

O

CH3






0 1 2 3 40

5

10

15

20

25

30

35

40IBP 1 x 10-4 mol dm-3

Dose kGy

Inh

ibit

ion

00

05

10

cc

0

00 05 10 15 200

20

40

60

80

100

120

140

160

180 1633

1839

2303

2533

8997

Ab

so

rban

ce

Dose kGy



HPLC-diode array

detection





SampleFree Cl

mg dm-3

Total Cl

mg dm-3

Dose

kGy

Total

Coli

Fecal

Coli

Fec C

Total C

I01 - - - 730 75 102

IICl1 007 009 - 560 52 93

Irad1

- - 05 1 0 -

- - 1 1 0 -

- - 20 0 0 -

I02 - - - 900 90 99

IICl2 lt005 006 - 700 80 114

Irad2

- - 05 0 0 -

- - 1 0 0 -

- - 20 0 0 -






mg dm-3

BOD5

mg dm-3

BOD5CODk

I01 - 46 16 35

IICl1 Cl 62 16 26

Irad1

05 kGy 36 lt10 (6) lt17

1 kGy 32 lt10 (8) lt25

20 kGy 36 lt10 (5) lt14

I02 - 53 17 32

IICl2 Cl 58 15 26

Irad2

05 kGy 31 lt10 (7) lt23

1 kGy 39 lt10 (7) lt18

20 kGy lt30 (28) lt10 (5) lt18

25



Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486


Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2


























0 1 2 3 40

5

10

15

20

25

30

35

40IBP 1 x 10-4 mol dm-3

Dose kGy

Inh

ibit

ion

00

05

10

cc

0

00 05 10 15 200

20

40

60

80

100

120

140

160

180 1633

1839

2303

2533

8997

Ab

so

rban

ce

Dose kGy



HPLC-diode array

detection





SampleFree Cl

mg dm-3

Total Cl

mg dm-3

Dose

kGy

Total

Coli

Fecal

Coli

Fec C

Total C

I01 - - - 730 75 102

IICl1 007 009 - 560 52 93

Irad1

- - 05 1 0 -

- - 1 1 0 -

- - 20 0 0 -

I02 - - - 900 90 99

IICl2 lt005 006 - 700 80 114

Irad2

- - 05 0 0 -

- - 1 0 0 -

- - 20 0 0 -






mg dm-3

BOD5

mg dm-3

BOD5CODk

I01 - 46 16 35

IICl1 Cl 62 16 26

Irad1

05 kGy 36 lt10 (6) lt17

1 kGy 32 lt10 (8) lt25

20 kGy 36 lt10 (5) lt14

I02 - 53 17 32

IICl2 Cl 58 15 26

Irad2

05 kGy 31 lt10 (7) lt23

1 kGy 39 lt10 (7) lt18

20 kGy lt30 (28) lt10 (5) lt18

25



Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486


Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2

























0 1 2 3 40

5

10

15

20

25

30

35

40IBP 1 x 10-4 mol dm-3

Dose kGy

Inh

ibit

ion

00

05

10

cc

0

00 05 10 15 200

20

40

60

80

100

120

140

160

180 1633

1839

2303

2533

8997

Ab

so

rban

ce

Dose kGy



HPLC-diode array

detection





SampleFree Cl

mg dm-3

Total Cl

mg dm-3

Dose

kGy

Total

Coli

Fecal

Coli

Fec C

Total C

I01 - - - 730 75 102

IICl1 007 009 - 560 52 93

Irad1

- - 05 1 0 -

- - 1 1 0 -

- - 20 0 0 -

I02 - - - 900 90 99

IICl2 lt005 006 - 700 80 114

Irad2

- - 05 0 0 -

- - 1 0 0 -

- - 20 0 0 -






mg dm-3

BOD5

mg dm-3

BOD5CODk

I01 - 46 16 35

IICl1 Cl 62 16 26

Irad1

05 kGy 36 lt10 (6) lt17

1 kGy 32 lt10 (8) lt25

20 kGy 36 lt10 (5) lt14

I02 - 53 17 32

IICl2 Cl 58 15 26

Irad2

05 kGy 31 lt10 (7) lt23

1 kGy 39 lt10 (7) lt18

20 kGy lt30 (28) lt10 (5) lt18

25



Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486


Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2



























SampleFree Cl

mg dm-3

Total Cl

mg dm-3

Dose

kGy

Total

Coli

Fecal

Coli

Fec C

Total C

I01 - - - 730 75 102

IICl1 007 009 - 560 52 93

Irad1

- - 05 1 0 -

- - 1 1 0 -

- - 20 0 0 -

I02 - - - 900 90 99

IICl2 lt005 006 - 700 80 114

Irad2

- - 05 0 0 -

- - 1 0 0 -

- - 20 0 0 -






mg dm-3

BOD5

mg dm-3

BOD5CODk

I01 - 46 16 35

IICl1 Cl 62 16 26

Irad1

05 kGy 36 lt10 (6) lt17

1 kGy 32 lt10 (8) lt25

20 kGy 36 lt10 (5) lt14

I02 - 53 17 32

IICl2 Cl 58 15 26

Irad2

05 kGy 31 lt10 (7) lt23

1 kGy 39 lt10 (7) lt18

20 kGy lt30 (28) lt10 (5) lt18

25



Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486


Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2




























mg dm-3

BOD5

mg dm-3

BOD5CODk

I01 - 46 16 35

IICl1 Cl 62 16 26

Irad1

05 kGy 36 lt10 (6) lt17

1 kGy 32 lt10 (8) lt25

20 kGy 36 lt10 (5) lt14

I02 - 53 17 32

IICl2 Cl 58 15 26

Irad2

05 kGy 31 lt10 (7) lt23

1 kGy 39 lt10 (7) lt18

20 kGy lt30 (28) lt10 (5) lt18

25



Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486


Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2























25



Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486


Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2























Compounds m

TOFISOPAM 119

METHANOL 31

AMMON Cl 92

ACETIC ACID 1364

WATER 4486

0 2 4 6 8 10 12 14 163800

4000

4200

TO

C m

g dm-3C

OD

mg

dm-3

Dose kGy

TOC

COD

1100

1200

1300

1400

O CH3

OCH3

CH3

CH3

N

NH3C

O

H3CO

20 bar O2




















































































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Katalitikus éééés sug áááárkrrkkrk éééémiai elj áááárrrrááások a ...aekimhp/EK/hirek/KOTEB_13_02... · 2013. 2. 28. · MTA Energiatudom áááányi Kutat óóóókkkköööözpont