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UNIVERSIDADE FEDERAL DE MATO GROSSO
CAMPUS UNIVERSITÁRIO DE SINOP
Programa de Pós-Graduação em Ciências Ambientais
CARVÃO ATIVADO DO OURIÇO DA CASTANHA-DO-BRASIL:
CARACTERIZAÇÃO E ADSORÇÃO DO HERBICIDA ÁCIDO
DICLOROFENOXIACÉTICO (2,4-D)
MICHELLE FERREIRA DA SILVA RIMOLI
Sinop, Mato Grosso
Abril, 2018
MICHELLE FERREIRA DA SILVA RIMOLI
CARVÃO ATIVADO DO OURIÇO DA CASTANHA-DO-BRASIL:
CARACTERIZAÇÃO E ADSORÇÃO DO HERBICIDA ÁCIDO
DICLOROFENOXIACÉTICO (2,4-D)
Orientador: Dr. Evaldo Martins Pires
Coorientadora: Dra. Roberta Martins Nogueira
Dissertação apresentada ao Programa de
Pós-Graduação em Ciências Ambientais
da Universidade Federal de Mato Grosso,
Campus Universitário de Sinop, como
parte das exigências para a obtenção do
título de Mestre em Ciências Ambientais.
Área de concentração: Biodiversidade.
Sinop, Mato Grosso
Abril, 2018
SINOPSE:
Foi produzido carvão do ouriço da castanha-do-brasil, ativado em duas atmosferas
distintas, CO2 e vapor d’água, e testado para a remoção do herbicida ácido
diclorofenoxiacético. O carvão foi caracterizado pelo rendimento gravimétrico, teor de
água, materiais voláteis, teor de cinzas, carbono fixo, densidade aparente, pH, método
de Brunauer, Emmett e Teller (BET) e Microscopia Eletrônica de Varredura (MEV). O
teste de remoção de 2,4-D foi desenvolvido em CLAE.
PALAVRAS-CHAVE: Adsorção, Bertholettia excelsa, 2,4-D.
AGRADECIMENTOS
À Deus por todas as bênçãos e maravilhas que tem feito em minha vida.
À Universidade Federal de Mato Grosso (UFMT) por proporcionar as condições
necessárias para a realização deste trabalho.
À Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
pela bolsa concedida.
Ao meu pai Maurílio Pereira da Silva e a minha mãe Noêmia Maria Ferreira, por
sempre estarem ao meu lado me dando todo o apoio possível e me ensinarem o valor
que o estudo tem.
Ao meu esposo Leonardo Rimoli Pedro pela compreensão, apoio e amor.
Ao meu orientador Prof. Dr. Evaldo Martins Pires e à minha Coorientadora
Profa. Dra. Roberta Martins Nogueira, por terem me estendido a mão quando mais
precisei, por serem pessoas honradas e exemplo de dedicação ao trabalho. Agradeço
por suas correções e por me apoiarem em todos os momentos desta jornada, jamais
terei palavras suficientes para expressar toda a minha gratidão e admiração a vocês.
À Profa. Dra. Stela Ferrarini por ter contribuído tão grandemente ao meu
trabalho e também por ser um ombro amigo.
Às empresas Borello Alimentos Ltda e Eletrotécnica Pagliari que
disponibilizaram toda sua estrutura para o processo de produção dos carvões
ativados.
À minha amiga Pryscila Machado de Castro por ter contribuído em todos os
momentos deste trabalho e, principalmente, pelo apoio emocional.
Aos colegas do Programa de Pós-Graduação em Ciências Ambientais
(PPGCAM), por compartilharem das mesmas dores e vitórias.
Aos Professores do PPGCAM da UFMT Campus Universitário de Sinop, por
todo o conhecimento compartilhado.
RESUMO GERAL
O ouriço da castanha-do-brasil apresenta características desejáveis para a produção
de carvão ativado, dessa forma, pode ser um material precursor. O objetivo foi avaliar
o efeito da temperatura e da atmosfera de ativação na qualidade do carvão ativado do
ouriço da castanha-do-brasil e analisar a capacidade de adsorção em meio aquoso
do ácido 2,4-diclorofenoxiacético (2,4-D). O material foi carbonizado à 600, 700 e 800
°C, por cinco horas e ativado em duas atmosferas distintas, CO2 e vapor d’água, à
temperatura de carbonização por 40 minutos. Houve efeito da temperatura de pirólise
no rendimento gravimétrico, no teor de cinzas, no carbono fixo e no pH. A atmosfera
influenciou nos teores de água e cinzas e carbono fixo. Não houve efeito da interação
temperatura versus atmosfera nos parâmetros avaliados. A caracterização da
Espectroscopia de Infravermelho com Transformada de Fourier (FTIR) indicou que as
temperaturas e as atmosferas de ativação afetaram os grupos funcionais da superfície
do carvão ativado e a análise termogravimétrica, indicou estabilidade do material. A
temperatura de 800 °C e ativação com vapor d’água conferiram melhores índices de
carbono fixo, materiais voláteis e teor de água. Dessa forma, os carvões ativados
produzidos a 800 °C e ativados com CO2 ou vapor d’água foram utilizados para
estudar a adsorção do herbicida 2,4-D. A área superficial específica determinada pelo
método Brunauer, Emmett e Teller (BET) para os carvões ativados foi de 395 e 401
m2g-1, respectivamente. O diâmetro com a maior intensidade de poros foi de 1,17 nm
para os carvões ativados tanto com CO2 quanto com vapor d’água. As isotermas de
adsorção/dessorção de N2 foram do Tipo I, independente da atmosfera de ativação. A
análise por Microscopia Eletrônica de Varredura (MEV) mostrou que, para ambas
atmosferas de ativação, a formação de poros ocorreu em forma de crateras uniformes
do tipo colmeia. A cinética de adsorção seguiu o modelo de pseudo-segunda ordem.
O carvão ativado com vapor d’água a 800 °C também apresentou melhores resultados
para os testes de adsorção de 2,4-D, que associados aos melhores índices
qualitativos e ao menor custo em relação ao CO2, caracteriza como a melhor
alternativa para o processo proposto.
PALAVRAS-CHAVE: Consumo humano, contaminação, filtro, saúde.
ABSTRACT
“Ouriço” of Brazil nut presents desirable characteristics to produce activated carbon,
therefore, it can be a precursor material. The objective was to evaluate the effect of
the temperature and the atmosphere of activation on the quality of activated carbon
from “ouriço” and to analyze the adsorption capacity of 2,4-D in aqueous solution. The
material was carbonized at 600, 700 and 800 °C for five hours and activated in CO2 or
steam atmosphere at the carbonization temperature for 40 minutes. The results
showed that there was effect of the pyrolysis temperature on the gravimetric yield, ash
content, fixed carbon and pH. The atmosphere influenced the water, ash and fixed
carbon contents. There was no effect of the temperature x atmosphere interaction on
the evaluated parameters. The characterization of Fourier Transform Infrared
Spectroscopy (FTIR) indicated that the activation temperatures and the atmospheres
affected the functional groups of the activated carbon surface, and the
thermogravimetric analysis indicated stability of the material. The temperature of 800
°C and activation with steam presented better qualitative results. Thus, activated
carbons produced at 800 °C and activated with CO2 or steam were used to study the
adsorption of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). The specific
surface area determined by the Brunauer, Emmett and Teller (BET) method for the
activated carbons was 395 and 401 m2g-1, respectively. The highest pore intensity
occurred with 1.17 nm for the carbons activated with CO2 as well as with steam. The
plot of the adsorption/desorption isotherms of N2 presented Type I isotherms,
independent of the activation atmosphere. The Scanning Electron Microscopy (SEM)
analysis showed that, for both activation atmospheres, pore formation occurred in the
form of uniform hive-type craters. The adsorption kinetics followed the pseudo-second
order model. The activated carbon with steam at 800 °C also presented better results
for the 2,4-D adsorption tests, which, together with the best qualitative results and the
lowest cost in relation to CO2, characterize the best alternative for the proposed
process.
KEY WORDS: Contamination, filter, health, human consumption.
SUMÁRIO
INTRODUÇÃO GERAL ........................................................................................................ 10
ARTIGO 1 ............................................................................................................................. 14
Resumo ................................................................................................................................. 14
Abstract ................................................................................................................................. 15
1. Introdução ...................................................................................................................... 16
2. Material e métodos ........................................................................................................ 18
3. Resultados ..................................................................................................................... 20
4. Discussão ...................................................................................................................... 23
5. Conclusão ...................................................................................................................... 30
6. Agradecimentos ............................................................................................................. 30
7. Referências .................................................................................................................... 30
8. Legendas de figuras e tabelas .......................................................................................... 38
9. Tabelas e figuras ............................................................................................................... 38
ARTIGO 2 ............................................................................................................................. 62
Resumo ................................................................................................................................. 62
Abstract ................................................................................................................................. 63
1. Introdução ...................................................................................................................... 63
2. Material e métodos ........................................................................................................ 65
3. Resultados ..................................................................................................................... 68
4. Discussão ...................................................................................................................... 72
5. Conclusão ...................................................................................................................... 73
6. Agradecimentos ............................................................................................................. 74
7. Referências .................................................................................................................... 74
CONCLUSÃO GERAL ......................................................................................................... 95
10
INTRODUÇÃO GERAL
Nativa da região Amazônica, a castanheira (Bertholettia excelsa,
Lecythidaceae) pode alcançar até 60 metros de altura, seu fruto é chamado de ouriço
e sua semente é a castanha-do-brasil (SANTOS et al., 2006; YANG, 2009). Sua
semente é conhecida por ser agradável ao paladar e proporcionar benefícios para a
saúde, contendo entre seus componentes lipídios, proteínas, carboidratos e fibras
(MOODLEY; KINDNESS; JONNALAGADDA, 2007).
O beneficiamento da castanha-do-brasil é uma das principais atividades
econômicas na região Amazônica e gera grande volume de resíduos, cada ouriço
possui peso médio de 2,4 kg, sendo aproximadamente 1,4 kg de biomassa residual
(OLIVEIRA; LOBO, 2002).
Resíduos de plantas da Amazônia têm se mostrado importantes materiais
precursores para a produção de carvão ativado (MELO et al., 2015). O ouriço da
castanha-do-brasil possui características desejáveis a um material precursor, o que
pode permitir a obtenção de carvão ativado de boa qualidade e de baixo custo. Pois é
um material lignocelulósico, renovável e encontrado em abundância (MELO et al.,
2015; NOGUEIRA et al., 2014). Para transformar o material precursor em carvão
ativado, este é seco, carbonizado e em seguida ativado. As características finais do
carvão ativado se darão pela escolha do material precursor e o método de ativação
(BHATNAGAR E SILLANPÄÄ, 2010).
O carvão ativado é um produto que pode ser obtido pelos métodos químico
(ocorre em uma única etapa, o material precursor é impregnado em um agente
químico e a ativação ocorre na etapa da pirólise) e físico (ocorre em duas etapas,
primeiro o material precursor passa pelo processo de carbonização, em seguida é
ativado modificando a atmosfera) (ALSLAIBI et al., 2013).
11
O carvão ativado é utilizado com sucesso no tratamento de água para a
remoção de compostos orgânicos, pois um filtro com características físicas seria
incapaz de remover algumas moléculas, tais como aquelas que compõe agrotóxicos
(LETTERMAN et al., 1999). Estudos epidemiológicos sugerem que a contaminação
por compostos químicos é um problema relevante para a saúde humana, o consumo
de água contaminada é um dos principais mecanismos de ingestão desses compostos
pela população (FARIA et al., 2007; SALMAN E HAMEED, 2010).
O ácido diclorofenoxiacético (2,4-D) é o terceiro herbicida mais usado nos EUA
e no Canadá para o controle de ervas daninhas de folhas largas (JUNIOR et al., 2002),
no Brasil é amplamente utilizado na cultura da soja, impulsionado pelo baixo custo e
seletividade (AKSU E KABASAKAL, 2004; WHO, 2017).
Dessa forma, o objetivo foi avaliar o efeito da temperatura de pirólise e da
composição da atmosfera de ativação na qualidade do carvão ativado do ouriço da
castanha-do-brasil. Além de analisar a capacidade de adsorção em meio aquoso de
2,4-D deste carvão fisicamente ativado em atmosferas de CO2 ou vapor d’água.
12
REFERÊNCIAS
AKSU, Z.; KABASAKAL, E. Batch adsorption of 2,4-dichlorophenoxy-acetic acid (2,4-D) from aqueous solution by granular activated carbon. Separation and Purification Technology, v. 35, n. 3, p. 223–240, 2004.
ALSLAIBI, T. M. et al. A review: production of activated carbon from agricultural byproducts via conventional and microwave heating. Journal of Chemical Technology & Biotechnology, v. 88, n. 7, p. 1183–1190, Jul. 2013.
BHATNAGAR, A.; SILLANPÄÄ, M. Utilization of agro-industrial and municipal waste materials as potential adsorbents for water treatment—A review. Chemical Engineering Journal, v. 157, n. 2–3, p. 277–296, 1 Mar. 2010.
FARIA, N. M. X.; FASSA, A. G.; FACCHINI, L. A. Intoxicação por agrotóxicos no Brasil: os sistemas oficiais de informação e desafios para realização de estudos epidemiológicos. Ciência & Saúde Coletiva, v. 12, n. 1, p. 25–38, 2007.
JUNIOR, O. D. A. et al. Revisão das propriedades, usos e legislação ácido 2,4-diclorofenoxiacético (2,4-D). Caderno Pesquisa, v. 13, n. 1, p. 60–70, 2002.
LETTERMAN, R. D.; AMIRTHARAJAH, A.; O’MELIA, C. R. Coagulation and Flocculation. In: LETTERMAN, R. D. (Ed.). . Water Quality and Treatment: a Handbook of Community Water Supplies. 5th. ed. New York: McGraw-Hill, 1999. p. 6.1-6.66.
MELO, S. D. S. et al. Production and characterization of absorbent heat from the bark of residual Brazil nut bark (Bertholletia Excelsa l.). Chemistry Central Journal, v. 9, n. 1, p. 36, 2015.
MOODLEY, R.; KINDNESS, A.; JONNALAGADDA, S. B. Elemental composition and chemical characteristics of five edible nuts (almond, Brazil, pecan, macadamia and walnut) consumed in Southern Africa. Journal of Environmental Science and Health, Part B, v. 42, n. 5, p. 585–591, 11 Jun. 2007.
NOGUEIRA, R. M. et al. Evaluation of carbonization of the hedgehog of Brazil nut in oven type metal drums. Scientific Electronic Archives, n. 6, p. 7–17, 2014.
OLIVEIRA, J. M. DA C. DE; LOBO, P. C. Avaliação do potencial energético de resíduos de biomassa Amazônica. Anais do 4o Encontro de energia no meio rural. Anais...Itajubá-MG: 2002Disponível em: <http://www.proceedings.scielo.br/scielo.php?script=sci_arttext&pid=MSC0000000022002000100026&lng=en&nrm=abn>
SALMAN, J. M.; HAMEED, B. H. Adsorption of 2,4-dichlorophenoxyacetic acid and carbofuran pesticides onto granular activated carbon. Desalination, v. 256, n. 1–3, p. 129–135, 2010.
SANTOS, J. U. M. DOS et al. Bertholletia excelsa Humboldt & Bonpland (Lecythidaceae): aspectos morfológicos do fruto, da semente e da plântula. Boletim do Museu Paraense Emílio Goeldi, v. 1, n. 2, p. 103–112, 2006.
13
WORLD HEALTH ORGANIZATION (WHO). Guidelines for Drinking-water Quality. fourth edi ed. Geneva: [s.n.].
YANG, J. Brazil nuts and associated health benefits: A review. LWT - Food Science and Technology, v. 42, n. 10, p. 1573–1580, 2009.
14
ARTIGO 1
Ouriço de Bertholletia excelsa (Lecythidaceae): parâmetros de carbonização e
ativação desse produto amazônico
Michelle Ferreira da Silva Rimoli¹, Roberta Martins Nogueira¹, Stela Regina
Ferrarini¹, Pryscila Machado de Catro¹, Evaldo Martins Pires¹*
¹Universidade Federal de Mato Grosso – Campus de Sinop, Avenida Alexandre
Ferronato, 1200, Sinop, Mato Grosso – 78557-267, Brasil.
*Autor para correspondência: [email protected]
Resumo
O objetivo foi avaliar o efeito da temperatura e da atmosfera de ativação na
qualidade dos carvões ativados preparados a partir do ouriço. Pedaços de “ouriço”
moídos foram carbonizados à 600, 700 e 800 °C por cinco horas e ativados em duas
atmosferas diferentes, CO2 e vapor d’água, à temperatura de carbonização por 40
minutos. Houve efeito da temperatura de pirólise sobre o rendimento gravimétrico,
teor de matéria volátil, teor de cinzas, carbono fixo e pH, e a atmosfera influenciou
no teor de água, teor de cinzas e carbono fixado. Não houve efeito da interação
temperatura x atmosfera nos parâmetros avaliados. A caracterização por FTIR
indicou que as temperaturas e as atmosferas de ativação afetaram os grupos
funcionais da superfície do carvão ativado e a análise termogravimétrica indicou
estabilidade do material. Áreas superficiais específicas determinadas pelo método
BET para carbonos ativados em atmosfera de CO2 à 600, 700 e 800 °C foram 15,8,
55,0 e 395,0 m2g-1, respectivamente. As áreas de superfície específicas dos carvões
15
ativadas com vapor d’água à 600, 700 e 800 °C foram de 125,0, 320,0 e 401 m2g-1,
respectivamente. A maior intensidade de poros ocorreu com 1,26, 1,17 e 1,17 nm
para os carvões ativados em atmosfera de CO2 à 600, 700 e 800 °C,
respectivamente. Para atmosfera de vapor de água, os carbonos ativados à 600,
700 e 800 °C apresentaram maior intensidade de poros com 1,26, 1,0 e 1,7 nm,
respectivamente. As isotermas de adsorção/dessorção do N2 apresentaram
isotermas do Tipo I, para ambas as atmosferas de ativação. A ativação com vapor à
800 ° C permitiu obter melhores índices qualitativos, o que, associado ao menor
custo em relação ao CO2, caracteriza-se como a melhor alternativa.
Palavras-chave: Adsorção, biocarvão, filtro, tratamento de água.
Abstract
“Ouriço” is the popular name for the fruit of Brazil nut tree and it may be used as a
material to produce activated carbon, as it is a lignocellulosic material, and the
carbonization and activation conditions may influence the final product. The objective
was to evaluate the effect of the temperature and the activation atmosphere on the
quality of the activated carbons prepared from “ouriço”. Pieces of ground “ouriço”
were carbonized at 600, 700 and 800 °C for five hours and activated in two different
atmospheres, CO2 and steam, at the carbonization temperature for 40 minutes.
There was an effect of the pyrolysis temperature on the gravimetric yield, volatile
matter content, ash content, fixed carbon and pH, and, the atmosphere influenced on
water content, ash content and fixed carbon. There was no effect of the temperature
x atmosphere interaction on the evaluated parameters. The Fourier Transform
Infrared Spectroscopy (FTIR) characterization indicated that the temperatures and
activation atmospheres affected the functional groups of the activated carbon surface
and the thermogravimetric analysis indicated stability of the material. Specific surface
16
areas determined by Brunauer, Emmett and Teller (BET) method for carbons
activated in CO2 atmosphere at 600, 700 and 800 °C were 15.8, 55.0 and 395.0 m2g-
1, respectively. Carbons’ specific surface areas activated with steam at 600, 700 and
800°C were 125.0, 320.0 and 401 m2g-1, respectively. The highest pore intensity
occurred with 1.26, 1.17 and 1.17 nm for carbons activated in CO2 atmosphere at
600, 700 and 800 °C, respectively. For water steam atmosphere, carbons activated
at 600, 700 and 800 °C showed highest pore intensity with 1.26, 1.0 and 1.7 nm,
respectively. The adsorption / desorption isotherms of N2 presented Type I isotherms,
for both activation atmospheres. Activation with steam at 800 °C granted better
qualitative indexes (fixed carbon, volatile materials and water content), which
associated to the lower cost in relation to CO2, is characterized as the best
alternative.
Keywords: Adsorption, biochar, filter, water treatment.
1. Introdução
O beneficiamento da castanha-do-brasil é uma das principais atividades
econômicas na região Amazônica, porém grande quantidade de resíduos são
produzidos após a etapa de coleta do ouriço até a aquisição da castanha sem casca
(principal produto comercializado). Somente a casca do “ouriço” pesa em média 1,4
kg de biomassa residual de um total de 2,4 kg em média quando ainda possui as
castanhas com casca em seu interior (Oliveira and Lobo, 2002).
Essa casca do “ouriço” possui elevado teor de lignocelulose, o que pode
qualificar esse material por apresentar características físicas em sua constituição
que favorecem à obtenção de um carvão de boa qualidade e, outro fator importante
17
é o fato de que a casca do “ouriço” é considerado resíduo da cadeia produtiva da
castanha-do-brasil, tendo por isso baixo custo de aquisição (Nogueira et al., 2014).
O uso de tecnologias para o processamento de material residual pode resultar
na valorização de determinados produtos, pois quando se agrega valor a um
determinado resíduo, de forma que este seja transformado em um produto
comercializável, há maior a geração de trabalho e consequente renda para as
populações envolvidas nessesprocessos (Rivela et al., 2006).
Uma das técnicas de processamento do resíduo é a produção de carvão
vegetal, que pode ser utilizado para a gerar energia, ou ainda, como material
precursor para a produzir carvão ativado. Este último tem seu uso no tratamento de
água de abastecimento (Borges et al., 2016), em aplicações médicas e ambientais
(Alkhatib and Zailaey, 2015), no armazenamento de gás natural (Gottipati et al.,
2012), na filtragem de compostos oriundos de atividade agrícola (Melo et al., 2015)
entre outras.
As características finais do carvão ativado se devem ao material precursor e o
método de ativação (Bhatnagar and Sillanpää, 2010) que pode ocorrer pelo método
químico, em que o material precursor é impregnado por um agente químico e a
ativação ocorre na etapa da pirólise, ou pelo método físico, em que o material
precursor passa pelo processo de carbonização e em seguida, é ativado em
temperatura e condição atmosférica controladas (Alslaibi et al., 2013).
A etapa de pirólise é realizada na ausência de ar e em temperaturas de 400 a
800 °C para enriquecer o conteúdo de carbono e promover o aumento da
porosidade do carvão. Dessa forma, a seleção dos parâmetros de carbonização é
importante para garantir a qualidade necessária do carvão ativado (Daud et al.,
2000).
18
A ativação da massa carbonizada ocorre em temperaturas de 600 a 1200 °C
com atmosfera saturada com vapor d’água ou CO2, podendo até mesmo ocorrer a
mistura desses agentes, por uma a até 10 horas (Melo et al., 2015)
O objetivo foi avaliar o efeito da temperatura de pirólise e da composição da
atmosfera de ativação na qualidade do carvão ativado do ouriço da castanha-do-
brasil.
2. Material e métodos
“Ouriços” de castanha-do-brasil foram obtidos em áreas de reflorestamento na
zona rural do município de Sinop, Mato Grosso, Brasil. Amostras pesando 350 g de
material foi obtida através da fragmentação do “ouriço” em pedaços de 2 a 3 cm,
lavadas em água corrente e mantidas em estufa com circulação forçada à 105 °C
por 24 horas para secagem visando a remoção de toda água livre.
Após esta etapa, as amostras foram acondicionadas em recipiente metálico
com 720 mm de comprimento e 68 mm de diâmetro interno e levado a um forno
tubular Fortelab FT-1200/H1Z com rampa de aquecimento de 10 °C/min até as
temperaturas de 600, 700 e 800 °C, condição que foram mantidas por cinco horas
para pirólise. Em seguida, as amostras foram ativadas com duas atmosferas
distintas, a primeira saturada com CO2 e a segunda com vapor d’água, nas mesmas
temperaturas atingidas na pirólise e mantidas por 40 minutos. As amostras foram
submetidas a pressão de 1 kgf/cm² em atmosfera de vapor d’água utilizando uma
caldeira vertical EIT–VL, enquanto que para a atmosfera com CO2 foi mantida a
pressão de 0,58 kgf/cm².
O processo de ativação foi realizado imediatamente após a pirólise, não
havendo resfriamento da massa entre a carbonização e a ativação.
19
O rendimento gravimétrico e a composição química imediata do carvão ativado
foram determinadas em quintuplicata no Laboratório Integrado de Pesquisas
Químicas (Lipeq) da Universidade Federal de Mato Grosso, Campus de Sinop.
Os teores de água, de materiais voláteis, de cinzas e de carbono fixo foram
determinados de acordo com a metodologia proposta pela norma internacional
ASTM D 1762-84 (ASTM D 1762-84, 2007). Os valores de pH foram aferidos
utilizando a metodologia proposta pela norma internacional ASTM D 3838-80 (ASTM
D 3838–80, 1999) e a densidade aparente pela norma internacional ASTM D 2854-
09 (ASTM D 2854-09, 2009). O rendimento gravimétrico foi determinado pesando o
material precursor antes do processo de ativação e o material retirado do forno, cujo
resultado foi expresso em percentual.
Os espectros de absorção na região do infravermelho das amostras de carvão
ativado para verificar os possíveis grupos funcionais presentes nos materiais
precursor e adsorventes foram determinados em espectofotômetro com
transformada de Fourier (FTIR) equipado com acessório para medidas de refletância
total atenuada (ATR), (Perkin Elmer, Spectrum BXII) na região entre 4000 e 400 cm-
¹, com resolução de 16 cm-1.
As curvas termogravimétricas (TGA) foram determinadas em analisador
termogravimétrico (TA Instruments, SDT Q600) para os carvões ativados que
apresentaram melhores resultados sobre os parâmetros físico-químicos. O intervalo
de temperatura explorado foi de 20 a 1000 °C com taxa de aquecimento de 10
°C/min, sob atmosfera inerte de ar sintético ultrapuro (100 mL/min).
Os carvões ativados foram submetidos à análise de BET (Brunauer, Emmett e
Teller) (Micromeritics Tristar II Kr 3020). A distribuição do tamanho de microporos foi
avaliada pelo método DFT (Density Functional Theory).
20
O experimento foi realizado em arranjo fatorial 3 x 2, sendo os dados submetidos
ao teste de normalidade. A análise dos efeitos dos fatores e de sua interação foi
realizada através do Teste F com p< 0,05 e as médias comparadas pelo teste Tukey
com p< 0,05 utilizando o programa Action Stat Pro (ESTATCAMP E DIGUP, 2017).
3. Resultados
Os dados obtidos para a composição físico-química das amostras de carvão
ativado seguiram distribuição normal pelo teste de Anderson-Darling. A interação
temperatura x atmosfera não influenciou nos valores obtidos para o rendimento
gravimétrico (F= 1,30; p= 0,28), para a densidade gravimétrica (F= 1,52; p= 0,24),
para o pH (F= 0,46; p= 0,63), para os teores de água (F= 0,29; p= 0,74), dos
materiais voláteis (F= 0,17; p= 0,84), de cinzas (F= 2,03; p= 0,15) e do carbono fixo
(F= 0,86; p= 0,44) (Tabela 1).
A temperatura influenciou o rendimento gravimétrico (F= 51,69; p< 0,05), no
pH (F= 35,95; p< 0,05), nos teores de materiais voláteis (F= 123,04; p< 0,05), de
cinzas (F= 8,56; p< 0,05) e de carbono fixo (F= 95,51; p< 0,05). A atmosfera
influenciou os teores de água (F= 45,54; p< 0,05), de cinzas (F= 5,09; p< 0,05) e de
carbono fixo (F= 38,60; p< 0,05) (Tabela 1).
Os maiores resultados observados para o rendimento gravimétrico foram
obtidos para o carvão ativado com CO2 na temperatura de 600 °C e para a ativação
com vapor d´água nas temperaturas de 600 e 700 °C. Os menores teores de
materiais voláteis foram conferidos as temperaturas de 700 e 800 °C para a
atmosfera de CO2, já para a atmosfera de vapor d’água, os menores valores para
este índice foram obtidos na temperatura de 800 °C. As amostras ativadas com
vapor d’água, a temperatura de 800 °C, produziram os maiores valores de teor de
21
cinzas. Para o teor de carbono fixo, tanto a atmosfera com vapor d’água, quanto a
com CO2, nas temperaturas de 700 e 800 °C, produziram os maiores resultados
deste índice. A temperatura de 800 °C, para ambas as atmosferas, conferiu maior
basicidade às amostras (Tabela 1).
A ativação com vapor d’água, independente da temperatura, produziu teores
de água inferiores àqueles obtidos para as amostras ativadas com CO2. A
temperatura de 600 °C foi a única que apresentou diferença para o teor de cinzas
entre as atmosferas, conferindo menor valor à atmosfera de vapor d’água. A
atmosfera com vapor d’água, em todas as temperaturas, garantiu maiores valores de
teor de carbono fixo que aqueles obtidos em atmosfera de CO2 (Tabela 1).
Tabela 1
O espectro da região do infravermelho (IV) obtido do ouriço da castanha-do-
brasil apresentou bandas vibracionais em 3348, 2924, 1736, 1654, 1594, 1510,
1466, 1416, 1370, 1330, 1228, 1160, 1107, 1026 e 668 cm-1(Figura 1). Para o carvão
ativado com CO2 foram encontradas bandas vibracionais em 2884 cm-1 para as
temperaturas de 600, 700 e 800 °C, 1584 cm-1, para as temperaturas de 600 e 700
°C, 1563 cm-1, para 800 °C, 1134 cm-1 para 700 °C e 984 cm-1 para a temperatura de
800 °C (Figura 2). Para o carvão ativado com vapor d’água as bandas vibracionais
foram de 2928 cm-1 em 600 e 800 °C, 2891 cm-1 a 700 °C, 1127 cm-1 a 800 °C, 953
cm-1 a 700 e a 800 °C, 920 cm-1 a 600 °C, 847 e 771 cm-1, para a temperatura de
600 °C (Figura 3).
Figura 1
22
Figura 2
Figura 3
As análises termogravimétricas (TGA) das amostras do carvão ativado
obtidos em diferentes atmosferas, ativados fisicamente com CO2 ou com vapor
d’água (Figura 4), mostram dois pontos de inflexão para a perda de massa: um com
perda de massa de 3,80 % (100 para 96,20 %) para CO2 e de 9,79 % (100 para
90,21 %) para vapor d’água à temperatura menor que 150 °C e outro que ocorre
entre 600 e 700 °C, e que corresponde a perda de 0,67 % (96,20 para 95,53 %) para
CO2 e de 0,56 % (90,21 para 89,65 %) para vapor d´água. Ao final do intervalo de
degradação, a amostra ativada com CO2 reduziu 8,62 % (100 para 91,38 %) e
aquela ativada com vapor d’água reduziu 16,78 % (100 para 83,22 %) da massa
total.
Figura 4
A área superficial específica determinada pelo método BET para os carvões
ativados com CO2 a 600, 700 e 800 °C foram de 15,8, 55,0 e 395,0 m2g-1,
respectivamente. Para o carvão ativado com vapor d’água a 600, 700 e 800 °C
foram de 125,0, 320,0 e 401,0 m2g-1, respectivamente. As isotermas de
adsorção/dessorção de N2 para os carvões ativados com CO2 ou vapor d’água
indicaram alta adsorção de N2 a baixas pressões (Figuras 5 e 6) e maior intensidade
de poros com 1,26, 1,17 e 1,17 nm para os carvões ativados com CO2 a 600, 700 e
800 °C, respectivamente (Figura 7). Para os carvões ativados com vapor d’água, a
23
maior intensidade de poros para as temperaturas de 600, 700 e 800 °C foi com 1,26,
1,0 e 1,7 nm, respectivamente (Figura 8).
Figura 5
Figura 6
Figura 7
Figura 8
4. Discussão
Maiores rendimentos gravimétricos, obtidos para menores temperaturas de
carbonização/ativação também foram observados na produção de carvão ativado da
casca do pistache, que apresentou rendimentos de 20,9 e 7,2 %, para as
temperaturas de 725 e 825 °C, respectivamente (Yang and Lua, 2003).
Comportamento semelhante foi observado para o carvão ativado da madeira da
palma (dendê) com uma mistura de CO2 e vapor d’água, apresentando valores de
rendimento de 21,6, 18,6 e 13,4 %, respectivamente para as temperaturas de 619,
755 e 806 °C (Ahmad et al., 2007).
Os valores de rendimento gravimétrico foram afetados pela temperatura de
carbonização e não pela atmosfera de ativação. Logo, é possível dizer que este
parâmetro foi definido durante a etapa de carbonização. Altas temperaturas resultam
na maior liberação de materiais voláteis, levando a maior perda de massa (Lua and
Guo, 2001; Rodríguez-Reinoso et al., 1995; Yang and Lua, 2003), ou seja, quanto
24
maior a temperatura de carbonização, menor serão os valores de rendimento
gravimétrico.
Os resultados obtidos para o teor de água do carvão ativado mostram que
este parâmetro não foi influenciado pela temperatura, pois a água, durante o
processo de ativação volatiliza à temperatura inferior a 200 °C (Pastor-Villegas et al.,
1999). Para as temperaturas de 600, 700 e 800 °C a água está completamente
ausente da massa carbonizada, porém, o carvão ativado, em função de sua
natureza higroscópica, absorve a umidade da atmosfera circundante (Ahmad et al.,
2007), o que explica os valores de teor de água encontrados. Os vapores de água
preenchem os locais de adsorção dentro dos poros (Anisuzzaman et al., 2015),
dessa forma, o efeito da atmosfera de ativação sobre este indicador está relacionado
à influência do tratamento sobre a área superficial, o diâmetro e o volume dos poros.
Elevados valores do teor de água resultam na diminuição da resistência
mecânica dos carvões o que gera aumento de finos (Boas et al., 2010) e podendo
interferir negativamente no processo de adsorção. Os valores de teor de água
obtidos em todas as amostras de carvão produzidas estão abaixo de 2 %, o que é
desejável.
Com o aumento da temperatura, há a mudança para a fase vapor de
inúmeras moléculas, que deixam o interior do carvão, levando à redução do teor de
materiais voláteis (Silva and Brito, 1990).Tal processo também é auxiliado pela
mudança da atmosfera de ativação, pois, os gases penetram o material sólido e
contribuem para a dessorção, destilação e remoção dos materiais voláteis que ainda
existiam no carvão. Os gases de ativação também contribuem para a estabilização
dos radicais obtidos durante a decomposição térmica, potencializando a remoção de
voláteis (Ahmad et al., 2007). A perda de voláteis influencia na formação de macro e
25
microporos, ou seja, altos teores de matérias voláteis podem significar valores
baixos de área superficial (Zhang et al., 2004), o que não é desejável para um
carvão ativado. Teores de materiais voláteis acima de 11 % foram encontrados para
condições de carbonização e atmosfera de ativação semelhantes (Ahmad et al.,
2007; Róz et al., 2015; Yang and Lua, 2003) demonstrando a alta qualidade do
carvão ativado do ouriço da castanha-do-brasil.
O teor de cinzas dos carvões ativados está relacionado com o material
precursor e às condições no processo de carbonização e ativação, que possam
contaminar o carvão produzido com material inerte (Collet, 1956; Silva and Brito,
1990). Este é mais um indicador de qualidade de um carvão ativado (Jaguaribe et
al., 2005), pois, por serem aditivos minerais não carbônicos, elas prejudicam o
processo de adsorção, devido à modificação da interação entre a superfície do
carvão e a espécie que se deseja adsorver (Bautista-Toledo et al., 2005).
Além de bloquear os poros do carvão e em função do seu caráter hidrofílico,
há a preferência por adsorver água (Ahmedna et al., 2000), competindo com os
compostos de interesse (Brum et al., 2008). Carvões ativados comerciais
apresentam valores entre 10 e 15 % (Jaguaribe et al., 2005; Lopes et al., 2013), os
resultados obtidos neste trabalho encontram-se bem abaixo do teor de cinzas destes
carvões.
Alto teor de carbono fixo no carvão ativado confere ao produto uma matriz
capaz de gerar grupos funcionais, dando origem a complexos superficiais, que
servirão como sítios de ligação para a adsorção de compostos que se deseja reter
(Aznar, 2011; Mohan and Pittman, 2006). Correlação negativa com o rendimento
gravimétrico (Brito et al., 1987) e positiva com a temperatura (Róz et al., 2015) são
verificadas durante a pirólise. Pois com o aumento da temperatura há a perda de
26
compostos condensáveis e não condensáveis, como o CO e CO2 (Pinheiro et al.,
2005; Róz et al., 2015; Yang et al., 2007), reduzindo o re1
ndimento gravimétrico e fixando o carbono residual.
Valores de pH elevados indicam baixo índice de grupamentos ácidos na
superfície dos carvões produzidos (Strelko and Malik, 2002). Complexos formados
entre a matriz de carbono e átomos de oxigênio podem determinar as características
ácidas ou básicas dos carvões ativados (Aznar, 2011; Mohan and Pittman, 2006;
Wibowo et al., 2007). A característica básica do carvão ativado é função da alta
temperatura e da atmosfera de ativação, parâmetros estes que colaboram para a
quebra das ligações na matriz de carbono e para novo arranjo com os gases que
compõe a atmosfera (Leon y Leon et al., 1992; Mohan and Pittman, 2006; Pereira et
al., 2003; Wibowo et al., 2007).
A superfície química do carvão ativado determina capacidade em reter água,
propriedades catalíticas, caráter ácido-base e a capacidade de adsorção (Salame
and Bandosz, 2001) e está relacionada à presença de heteroátomos (oxigênio,
hidrogênio e nitrogênio), além de átomo de carbono dentro da matriz do carvão (El-
Sayed and Bandosz, 2004; Salame and Bandosz, 2001). Na ainterpretação do
espectro de infravermelho do precursor, o ouriço da castanha-do-brasil, uma banda
larga em 3348 cm-1 foi observada, atribuída ao estiramento vibracional do grupo
hidroxila (O-H) ligados a hidrogênio para álcoois e fenóis, possivelmente referente a
umidade da amostra (Ramos et al., 2009; Yang and Lua, 2003), esta mesma banda
também foi encontrada em outros materiais precursores utilizados na produção de
carvão ativado (Ramos et al., 2009).
Vibrações correspondentes a ѵ (C-H) de alcanos (CH3 e CH2) foram
observadas em 2924 cm-1 (Ramos et al., 2009; Yang and Lua, 2003). Os grupos CH3
27
e CH2 são confirmados pelas bandas nas regiões de 1466 e 1370 cm-1,
características de deformação angular desses grupos (Gomez-Serrano et al., 1996;
Jagtoyen et al., 1992; Yang and Lua, 2003).
Possíveis absorções olefínicas ѵ (C=C) presentes na amostra geraram sinal
em 1654 cm-1, já outras duas bandas por volta de 1510 cm-1 e 1416 cm-1 podem ser
provocadas por estiramento de C=C em anéis aromáticos (Yang and Lua, 2003).
Banda em 1330 cm-1 pode ser atribuída a vibrações ѵ (C=O) de grupos
carboxilados e vibrações de estiramento de C-O podem ser observadas entre 1300 e
900 cm-1. A banda em 1228 cm-1 e ombro em 1160 cm-1 indicam a presença de
ésteres (por exemplo, R-CO-O-R’), éteres (por exemplo, R-O-R’) ou grupos fenólicos
no ouriço. O outro ombro observado, em 1107 cm-1 associado à banda em 1026 cm-1
podem ser atribuídos a grupos álcoois (R-OH). Por fim, a banda em 668 cm-1
representa γ (OH) (Yang and Lua, 2003).
As bandas em 2928 cm-1, para as temperaturas de 600 e 800 °C com vapor
d’água, em 2891 cm-1, também para vapor, na temperatura de 700 °C e, a banda em
2884 cm-1, para todas as temperaturas da ativação CO2, podem ser atribuídas à
grupamento éter (-O-CH3) e/ou às ligações C-H simétricas e assimétricas de grupos
metilas e metilenos (Ahmad et al., 2007).
As bandas em 1584 cm-1, nos carvões ativados com CO2 nas temperaturas de
600 e 700 °C e, em 1563 cm-1, para a temperatura de 800 °C com CO2 representam
o estiramento do grupo carbonila em quinona, representando também a estrutura 𝛾-
pirona com fortes vibrações da combinação de C=O e C=C (Ahmad et al., 2007; Tsai
et al., 2001).
A banda em 1127 cm-1 da amostra ativada com vapor d’água na temperatura
de 800 °C, e, em 1134 cm-1 do carvão ativado com CO2 a 700 °C, representam
28
cetonas, álcoois, pironas e deformações aromáticas no plano C-H (Ahmad et al.,
2007).
As bandas em 984 cm-1 (carvão ativado a 800 °C com CO2); 953 cm-1 (ativado
com vapor a 700 e 800 °C) e 920 cm-1 (ativado com vapor a 600 °C) podem ser
atribuídas a vibrações de éteres (-C-O-C-) (Ahmad et al., 2007).
As bandas 847 e 771 cm-1 encontradas na amostra ativada com vapor a 600
°C podem estar relacionadas a C-H fora do plano em aldeídos -CHO, compostos da
piranose e outros derivados do benzeno (Ahmad et al., 2007).
O caráter básico do carvão confere maior capacidade de adsorção de
substâncias ácidas (Leon y Leon et al., 1992; Mohan and Pittman, 2006; Pereira et
al., 2003; Wibowo et al., 2007). A formação de bandas para estruturas do tipo pirona,
éter e grupos carbonila contribuem para este caráter básico das amostras de
carvões produzidas.
Nas curvas termogravimétricas, tanto o carvão ativado com CO2, quanto o
ativado com vapor d’água, na temperatura de 800 °C apresentaram estabilidade
térmica similar. A perda de massa inicial (3,80 % para CO2 e 9,79 % para vapor
d’água) observada em temperaturas menores que 200 °C, pode ser consequência
da evaporação da água (Pastor-Villegas et al., 1999), que pode ter sido adsorvida
durante o armazenamento das amostras (de Oliveira et al., 2016). A segunda perda
de massa entre 600 e 700 °C (0,67 % para CO2 e 0,56 % para vapor d’água) se deu,
possivelmente devido à decomposição dos grupos formados na superfície dos
carvões durante o processo de ativação (grupos carbonílicos, éteres, estruturas de
pirona) que ocorrem em temperaturas mais elevadas, e, também à decomposição do
esqueleto de carbono (de Oliveira et al., 2016). A perda de massa pequena para
29
ampla faixa de temperatura confere a característica de estabilidade desejada para o
carvão ativado.
Os valores para a área superficial específica tanto do carvão ativado com CO2
quanto do com vapor d’água estão dentro do esperado para carvões ativados obtidos
da pirólise da madeira (Herzog et al., 2006), indicando a qualidade do ouriço da
castanha-do-brasil como material precursor para a produção de carvão ativado, além
de ser um material de baixo custo, renovável e encontrado de forma abundante.
Os carvões ativados, independente da atmosfera de ativação, apresentaram
perfil microporoso, este perfil é confirmado pelo maior volume de adsorção de N2 em
baixas pressões (Sun and Webley, 2010) e pela identificação dos picos com diâmetro
de poros inferior a 2 nm (20 Å) (Ahmad et al., 2007). Carvões ativados que apresentam
perfil microporoso proporcionam alta capacidade de adsorção de moléculas orgânicas
de dimensões pequenas, como potencial para retenção de gases e solventes comuns
(Nobre et al., 2015).
Através das análises de BET foi possível obter um gráfico das isotermas de
adsorção e dessorção do processo, cuja geometria foi definida pelas propriedades da
superfície e porosidade dos carvões ativados (Sing et al., 1985). As isotermas dos
carvões ativados com CO2 ou vapor d’água foram do Tipo I, que são típicas de
materiais microporosos com superfícies externas relativamente pequenas. Neste caso
a adsorção limitante é governada pelo volume de microporos acessíveis ao invés da
área superficial interna (Sing et al., 1985), isotermas do Tipo I são reveladas em casos
quando ocorre quimissorção (Shaji and Zachariah, 2017). O mesmo tipo de isoterma
foi encontrado para o carvão ativado da biomassa de babaçu (de Oliveira et al., 2016).
A análise de distribuição de poros mostrou que entre as duas atmosferas há
pouca variação na área superficial BET. Isto indica que a atmosfera de ativação não
30
influenciou na distribuição de poros e que o ouriço da castanha-do-brasil é
recomendado como material precursor para a produção de carvão ativado,
independentemente da ativação com CO2 ou vapor d’água.
5. Conclusão
Individualmente, tanto a temperatura quanto a atmosfera de ativação
produziram efeito significativo sobre os indicadores estudados. Considerando todos
os parâmetros estudados, a temperatura de 800 °C associada a atmosfera de
ativação composta por vapor d’água conferiu os melhores resultados qualitativos. As
amostras apresentaram perfil microporoso para ambas atmosferas, indicando sua
alta capacidade de adsorver de moléculas orgânicas de dimensões pequenas. A
distribuição de poros não foi influenciada pela atmosfera de ativação e os valores
para a área superficial específica confirmaram a qualidade do ouriço da castanha-
do-brasil como material precursor para a produção de carvão ativado.
6. Agradecimentos
À Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) pela
bolsa concedida e às empresas Borello Alimentos Ltda e Eletrotécnica Pagliari que
disponibilizaram toda sua estrutura para o processo de produção dos carvões
ativados.
.
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38
8. Legendas de figuras e tabelas
Figura 1 - Espectro na região do infravermelho do ouriço da castanha-do-brasil.
Figura 2 - Espectro na região do infravermelho do carvão fisicamente ativado com
CO2.
Figura 3 - Espectro na região do infravermelho do carvão fisicamente ativado com
vapor d’água.
Figura 4 – TGA curves dos carvões ativados com CO2 e vapor d'água a 800 °C.
Figura 5. Isoterma de adsorção/dessorção de N2 a 120 °C para os carvões ativados
com CO2 a 600, 700 e 800 °C.
Figura 6. Isoterma de adsorção/dessorção de N2 a 120 °C para os carvões ativados
com vapor d’água a 600, 700 e 800 °C.
Figura 7. Distribuição do volume de poros para os carvões ativados com CO2 a 600,
700 e 800 °C.
Figura 8. Distribuição do volume de poros para os carvões ativados com vapor
d’água a 600, 700 e 800 °C.
Tabela 1. Indicadores físico-químicos das amostras.
9. Tabelas e figuras
Tabela 1. Indicadores físico-químicos das amostras
Temperatura (°C) CO2 Vapor d’água p1
Rendimento Gravimétrico (%)
600 26,38±0,51 a 25,82±0,36 a 0,4004
39
700 23,78±0,46 b 24,48±0,46 a 0,3135
800 21, 86±0,42 c 21,34±0,43 b 0,4126
Teor de Água (%)
600 1,53±0,09 a 0,48±0,05 a < 0,001
700 1,55±0,18 a 0,58±0,20 a 0,0072
800 1,24±0,28 a 0,45±0,08 a 0,0284
Materiais Voláteis (%)
600 11,10±0,41 a 10,26±0,43 a 0,1935
700 7,47±0,32 b 6,96±0,14 b 0,1954
800 6,42±0,18 b 5,83±0,19 c 0,0588
Teor de Cinzas (%)
600 2,08±0,12 a 1,72±0,06 b 0,0308
700 1,79±0,08 a 1,69±0,09 b 0,4859
800 2,12±0,07 a 2,09±0,08 a 0,7813
Carbono Fixo (%)
600 85,27±0,42 b 87,53±0,40 b 0,0044
700 89,18±0,44 a 90,74±0,30 a 0,0198
800 90,20±0,17 a 91,61±0,24 a 0,0014
Densidade Aparente (g.cm-3)
600 0,24±0,01a 0,24±0,01 a 0,4323
700 0,25±0,01a 0,25±0,01 a 0,7355
800 0,25±0,01 a 0,23±0,02 a 0,0946
pH
600 9,00±0,08 b 9,17±0,04 b 0,1302
700 9,10±0,06 b 9,14±0,08 b 0,1302
40
800 9,58±0,04 a 9,64±0,08 a 0,4938
*Médias seguidas pela mesma letra na coluna não diferem pelo teste Tukey com p<
0,05.
1H0: μt vapor = μt CO2 e H1: μt vapor ≠ μt CO2
Figura 1 - Espectro na região do infravermelho do ouriço da castanha-do-brasil.
4000 3500 3000 2500 2000 1500 1000 500
Wave Number cm-1
% T
ransm
itta
nce
3348
2924
1736
16
54 15
94
15
10
14
66
14
16 13
70
13
30
1228
1026
668
1160
1107
41
Figura 2 - Espectro na região do infravermelho do carvão fisicamente ativado com
CO2.
4000 3500 3000 2500 2000 1500 1000 500
2884
2100
742
815
872
12501584
% T
ransm
itta
nce
2221
% T
ransm
itta
nce
% T
ransm
itta
nce
2884
1904
2364
1134
742
872 815
1584
2884
3742 1
904
2364
1563
984
2100
800 °C
700 °C
600 °C
Wave number cm-1
42
4000 3500 3000 2500 2000 1500 1000 500
% T
ransm
itta
nce
% T
ransm
itta
nce
847
771
1650
2928
2982
920
2333
2982
800 °C
700 °C
% T
ransm
itta
nce
600 °C
2354
1155
1127
815
953
2333
742
815
872
953
1078
11551
250
1378
2354
2891
1650
2013
21583349
1378
2333
2354
2928
2982
Wave number cm-1
Figura 3 - Espectro na região do infravermelho do carvão fisicamente ativado com
vapor d’água.
Figura 4 – TGA curves dos carvões ativados com CO2 e vapor d'água a 800 °C.
0 100 200 300 400 500 600 700 800 900 1000
80
85
90
95
100
We
igh
t (%
)
Temperature (°C)
Steam 800 °C
CO2 800 °C
43
0,0 0,2 0,4 0,6 0,8 1,0
0
10
20
30
40
50
60
70
80
90
100
110
120A
dso
rbe
d a
mo
un
t (c
m3g
-1)
Relative Pressure (P/P0)
Carbon activated with CO2 at 600 °C
Carbon activated with CO2 at 700 °C
Carbon activated with CO2 at 800 °C
Figura 5. Isoterma de adsorção/dessorção de N2 a 120 °C para os carvões ativados
com CO2 a 600, 700 e 800 °C.
0,0 0,2 0,4 0,6 0,8 1,0
0
20
40
60
80
100
120
Adso
rbe
d a
mo
un
t (c
m3g
-1)
Relative Pressure (P/P0)
Carbon activated with steam at 600 °C
Carbon activated with steam at 700 °C
Carbon activated with steam at 800 °C
Figura 6. Isoterma de adsorção/dessorção de N2 a 120 °C para os carvões ativados
com vapor d’água a 600, 700 e 800 °C.
44
0,8 1,0 1,2 1,4 1,6 1,8 2,0 2,2 2,4
0,0
0,2
0,4
0,6
0,8
1,0
1,2
1,4
1,6d
VdD
-1(c
m3g
-1)
Pore diameter (nm)
Carbon activated with CO2 at 600 °C
Carbon activated with CO2 at 700 °C
Carbon activated with CO2 at 800 °C
Figura 7. Distribuição do volume de poros para os carvões ativados com CO2 a 600,
700 e 800 °C.
0,8 1,0 1,2 1,4 1,6 1,8 2,0 2,2 2,4
0,0
0,2
0,4
0,6
0,8
1,0
1,2
1,4
1,6
dV
dD
-1(c
m3g
-1)
Pore diameter (nm)
Carbon activated with steam at 600 °C
Carbon activated with steam at 700 °C
Carbon activated with steam at 800 °C
Figura 8. Distribuição do volume de poros para os carvões ativados com vapor
d’água a 600, 700 e 800 °C.
45
BIORESOURCE TECHNOLOGY
AUTHOR INFORMATION
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TABLE OF CONTENTS XXX
Description p.1
Audience p.1
Impact Factor p.1
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ISSN: 0960-8524
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INTRODUCTION
Bioresource Technology publishes original articles, review articles, case studies and short
communications on the fundamentals, applications and management of bioresource
technology.
The journal's aim is to advance and disseminate knowledge in all the related areas of biomass,
biological waste treatment, bioenergy, biotransformations and bioresource systems analysis,
and technologies associated with conversion or production.
Topics include:
Biofuels: liquid and gaseous biofuels production, modeling and economics
Bioprocesses and bioproducts: biocatalysis and fermentations
Biomass and feedstocks utilization: bioconversion of agro-industrial residues
Environmental protection: biological waste treatment
Thermochemical conversion of biomass: combustion, pyrolysis, gasification, catalysis
For more details, authors should consult the Subject Classifications.
The journal does not consider articles dealing with crop cultivation, breeding and agronomy,
plant extracts and enzymes, composites, marine organisms (except microorganisms and algae
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The Executive Editor first evaluates all manuscripts on technical aspects such as compliance
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Manuscripts accepted at this stage are passed to the handling editor who can also reject on
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to accept or reject the article. Please note: Any Editor's decision is final.
Manuscripts previously rejected by the Journal will not be re-considered by the Editors, and
therefore will be rejected without review.
51
PREPARATION
Manuscript Preparation General:
Authors must follow guide for authors strictly, failing which the manuscripts would be rejected
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Follow this order when typing manuscripts: Title, Authors, Affiliations, Abstract, Keywords,
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To avoid unnecessary errors you are strongly advised to use the 'spell-check' and 'grammar-
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LaTeX
You are recommended to use the Elsevier article class elsarticle.cls to prepare your manuscript
and BibTeX to generate your bibliography.
52
Our LaTeX site has detailed submission instructions, templates and other information.
Article structure
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53
add your name between parentheses in your own script behind the English transliteration.
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Authors can make use of Elsevier's Illustration Services to ensure the best presentation of their
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54
ABBREVIATIONS
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Artwork
Electronic artwork General points
Make sure you use uniform lettering and sizing of your original artwork.
Embed the used fonts if the application provides that option.
55
Aim to use the following fonts in your illustrations: Arial, Courier, Times New Roman, Symbol,
oruse fonts that look similar.
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Figure captions
56
Ensure that each illustration has a caption. Supply captions separately, not attached
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Number tables consecutively in accordance with their appearance in the text. Place
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References
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This journal encourages you to cite underlying or relevant datasets in your manuscript
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repository, version (where available), year, and global persistent identifier. Add
57
[dataset] immediately before the reference so we can properly identify it as a data
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References in a special issue
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Reference management software
Most Elsevier journals have their reference template available in many of the most
popular reference management software products. These include all products that
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references and citations as shown in this Guide.
Users of Mendeley Desktop can easily install the reference style for this journal by
clicking the following link:
http://open.mendeley.com/use-citation-style/bioresource-technology
When preparing your manuscript, you will then be able to select this style using the
Mendeley plugins for Microsoft Word or LibreOffice.
Reference style
Text: All citations in the text should refer to:
Single author: the author's name (without initials, unless there is ambiguity) and the
year of publication;
Two authors: both authors' names and the year of publication;
Three or more authors: first author's name followed by 'et al.' and the year of
publication.
Citations may be made directly (or parenthetically).
Examples: 'as demonstrated (Allan, 2000a, 2000b, 1999; Allan and Jones, 1999).
Kramer et al. (2010) have recently shown ....'
List: References should be arranged first alphabetically, THEN NUMBERED
NUMERICALLY, and then further sorted chronologically if necessary. More than one
reference from the same author(s) in the same year must be identified by the letters
'a', 'b', 'c', etc., placed after the year of publication. Examples:
Reference to a journal publication:
Van der Geer, J., Hanraads, J.A.J., Lupton, R.A., 2010. The art of writing a scientific
article. J. Sci.
Commun. 163, 51–59.
58
Reference to a book:
Strunk Jr., W., White, E.B., 2000. The Elements of Style, fourth ed. Longman, New
York.
Reference to a chapter in an edited book:
Mettam, G.R., Adams, L.B., 2009. How to prepare an electronic version of your article,
in: Jones, B.S., Smith , R.Z. (Eds.), Introduction to the Electronic Age. E-Publishing
Inc., New York, pp. 281–304. [dataset] Oguro, M., Imahiro, S., Saito, S., Nakashizuka,
T., 2015. Mortality data for Japanese oak wilt disease and surrounding forest
compositions. Mendeley Data, v1. http://dx.doi.org/10.17632/ xwj98nb39r.1.
References in the list should be placed first alphabetically, then numbered
chronologically.
Mettam, G.R., Adams, L.B., 2009. How to prepare an electronic version of your article,
in: Jones,B.S., Smith , R.Z. (Eds.), Introduction to the Electronic Age. E-Publishing
Inc., New York, pp. 281-304.
Strunk Jr., W., White, E.B., 2000. The Elements of Style, fourth ed. Longman, New
York.
Van der Geer, J., Hanraads, J.A.J., Lupton, R.A., 2010. The art of writing a scientific
article. J. Sci.
Commun. 163, 51-59.
4....
Journal abbreviations source
Journal names should be abbreviated according to the List of Title Word Abbreviations.
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59
AudioSlides
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60
information about data citation. For more information on depositing, sharing and using
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61
methods to fit their specific needs or setting, but often without getting credit for this part
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For more information, visit the Data Statement page.
62
ARTIGO 2
NOVA ALTERNATIVA PARA ADSORVER ÁCIDO 2,4-DICLOROFENOXIACÉTICO
(2,4-D)
Michelle Ferreira da Silva Rimoli¹, Roberta Martins Nogueira¹, Stela Regina
Ferrarini¹, Pryscila Machado de Catro¹, Jacqueline Kerkhoff¹, Evaldo Martins Pires¹*
¹Universidade Federal de Mato Grosso – Campus de Sinop, Avenida Alexandre
Ferronato, 1200, Sinop, Mato Grosso – 78557-267, Brasil.
*Autor para correspondência: [email protected]
Resumo
Análises de isotermas foram realizadas com carvão ativado para investigar a
capacidade de adsorção em meio aquoso do ácido 2,4-diclorofenoxiacético (2,4-D)
pelo carvão do fruto da castanha-do-brasil, chamado ouriço. As amostras foram
carbonizadas em forno tubular a 800 °C por 5 horas e fisicamente ativadas em duas
atmosferas, CO2 e vapor d’água por 40 min na mesma temperatura de carbonização.
A análise por Microscopia Eletrônica de Varredura (MEV) mostrou que, para ambas
atmosferas de ativação, a formação de poros ocorreu em forma de crateras
uniformes do tipo colmeia e a cinética de adsorção seguiu o modelo de pseudo-
segunda ordem, indicando quimissorção. O carvão ativado do ouriço da castanha-
do-brasil, independente da atmosfera de ativação, foi eficiente para a adsorção de
63
2,4-D, porém, a ativação com vapor d’água foi superior em relação à quantidade do
herbicida adsorvido logo nos primeiros minutos.
Palavras-chave: Biocarvão, consumo humano, filtro, saúde.
Abstract
Isotherm analysis was carried out with activated carbon to investigate the adsorption
capacity of 2,4-dichlorophenoxyacetic acid (2,4-D) from aqueous solution onto
activated carbon from the fruit of Brazil nut, called “ouriço”. The samples were
carbonized in a tubular oven at 800 °C for 5 hours and physically activated in two
different atmospheres, CO2 and steam, at the same carbonization temperature for 40
minutes. Scanning Electron Microscopy (SEM) analysis showed that pore formation
occurred in the form of uniform hive-type craters and the adsorption kinetics followed
the pseudo-second order model, indicating chemisorption for both activation
atmospheres. The activated carbon from “ouriço”, independent of the activation
atmosphere, was efficient for adsorption of 2,4-D, however, the activation with steam
was superior in relation to the amount of herbicide adsorbed in the first minutes.
Key words: Biocarbon, filter, health, human consumption.
1. Introdução
O consumo de água contaminada por produtos fitossanitários é uma das
principais formas de ingestão desses compostos pela população [1,2], seguido pelo
consumo de alimentos, pela via dérmica e respiratória [3].
64
Entre os herbicidas mais utilizados mundialmente: o ácido diclorofenoxiacético
(2,4-D) é o terceiro mais usado nos EUA e Canadá, para controlar ervas daninhas
de folhas largas [4]. No Brasil, seu uso se destaca na cultura da soja, principalmente
para o controle de plantas daninhas e em pastagens, impulsionado pelo seu baixo
custo e seletividade [5,6].
Estudos epidemiológicos sugerem a associação da exposição humana a 2,4-
D e dois tipos de câncer: o sarcoma de partes moles e o linfoma não-Hodgkin. A
World Health Organization preconiza concentração máxima de 30 µg/L de 2,4-D na
água potável [6], sendo necessária a remoção de agrotóxicos de água e efluentes
[7]. Uma das técnicas de tratamento de água mais utilizadas é a filtração, porém,
sabe-se que um filtro com características físicas é incapaz de remover algumas
moléculas, tais como aquelas que compõe os agrotóxicos. A adsorção em carvão
ativado é uma das tecnologias usadas com sucesso na remoção de compostos
orgânicos (agrotóxicos, cianotoxinas, fármacos, etc) [8,9].
Carvões ativados produzidos a partir da pirólise da madeira possuem poros
interligados de dimensões menores que 2 nm e grande área superficial, variando
geralmente de 300 a 1500 m2.g-1, o que faz destes materiais adsorventes muito
efetivos [10]. Para o tratamento da água é desejado que o carvão ativado possua
propriedades como alta capacidade de adsorção do poluente e rápida cinética de
adsorção [11].
Encontrar um material precursor de baixo custo, que alie sustentabilidade e
desenvolvimento social, com as características técnicas ideais, é alvo de muitas
pesquisas. Inúmeros são os precursores oriundos das atividades agrícolas e/ou
florestais que têm potencial para produção do carvão ativado, principalmente
aqueles considerados resíduos. Ao serem utilizados como matéria-prima para a
65
produção de carvão ativado, os resíduos passam a ser coproduto, aumentando
assim a competitividade da atividade produtiva [12].
Resíduos de plantas da Amazônia têm-se mostrado importantes materiais
precursores para a produção de carvão ativado, pois são renováveis, geralmente
disponíveis em grandes quantidades e com baixo custo quando comparados à
outros materiais precursores [9]. O ouriço da castanha-do-brasil é o fruto da
castanheira (Bertholettia excelsa, Lecythidaceae) [13], árvore típica da região
Amazônica [14] que exerce a função de proteger as amêndoas [13–15]. Por ser um
resíduo da atividade de beneficiamento da castanha-do-brasil, o ouriço é um
material precursor de baixo custo, encontrado com facilidade e em grande
quantidade, além de ser lignocelulósico, característica que permite a obtenção de
carvão ativado de qualidade [16].
O objetivo foi analisar a capacidade de adsorção em meio aquoso de 2,4-D pelo
carvão do ouriço da castanha-do-brasil, fisicamente ativado em duas atmosferas
distintas, CO2 e vapor d’água.
2. Material e métodos
Os carvões ativados utilizados foram produzidos a partir da carbonização do
ouriço da castanha-do-brasil por cinco horas a 800 °C e ativados por meio físico,
através da associação da temperatura de 800 °C por 40 min, com atmosfera
modificada pela injeção de CO2 ou vapor d’água, no reator, durante o processo de
ativação (Tabela 1).
66
Tabela 1. Indicadores físico-químicos das amostras carbonizadas e ativadas à 800
°C em função das atmosferas de ativação
CO2 Vapor d’água
Rendimento Gravimétrico (%)
21,86 21,34
Teor de Água (%)
1,24 0,45
Materiais Voláteis (%)
6,42 5,83
Teor de Cinzas (%)
2,12 2,09
Carbono Fixo (%)
90,20 91,61
Densidade Aparente (g.cm-3)
0,25 0,23
pH
9,58 9,64
Foram obtidas imagens da superfície do carvão e a morfologia das amostras
a partir de microscopia eletrônica de varredura (MEV) com microscópio eletrônico de
varredura Jeol JSM 6060, tensão de 10 Kv.
A quantificação por CLAE foi feita pela construção de curvas analíticas com
padrão 2,4-D (Sigma Aldrich) com 98 % de pureza, construídas na faixa entre 0,6 a
30 µg mL-1, foram preparadas a partir de soluções-estoque na concentração de 500
µg.mL-1. O sistema utilizado foi de cromatografia líquida Varian Pro Star 325 com
detector ultravioleta (UV). A separação foi realizada em coluna C18 Phenomenex
Luna (250 x 4,6 mm, 5 µm). A fase móvel consistiu-se de 80% de H2O acidificada
com ácido fosfórico (pH 3,0), como eluente A e 20% de acetonitrila (eluente B). O
tempo de aquisição foi de 7 minutos, com fluxo de 1 mL min -1, volume de injeção de
20 µL e detecção em 230 nm.
Para o estudo da cinética de adsorção e de equilíbrio, 20,0 mL de solução de
trabalho (na concentração de 5 µg mL-1 de 2,4-D) foi preparada e adicionada em
67
tubo Falcon de 50 mL com 0,010 g de carvão ativado do ouriço da castanha-do-
brasil com CO2 ou vapor d’água a 800 °C. As amostras foram agitadas em
incubadora shaker da SP Labor a 150 rpm (25 °C) por períodos específicos (foram
analisadas amostras a cada 2 min para os primeiros 30 min, de 30 a 60 min, foram
analisadas amostras a cada 5 min, e, de 60 a 120 minutos, foram avaliadas
amostras a cada 30 min), filtradas e analisadas em CLAE.
Os ensaios de isotermas seguiram a norma internacional ASTM 3860-98 [17].
Modelos de cinética foram aplicados para interpretar os dados experimentais a fim
de compreender os mecanismos que controlam o processo de adsorção, assim
como a transferência de massa na solução e as interações químicas.
O primeiro modelo cinético usado para ajustar os dados experimentais foi o
de pseudo-primeira ordem, definido por Lagergren, que é baseado na capacidade de
adsorção de sistemas sólido-líquido [18]. A cinética de adsorção foi descrita pela
equação de pseudo-segunda ordem, segundo modelo usado para ajustar os dados
[19].
68
3. Resultados
A análise por MEV mostrou que tanto o carvão ativado com CO2 (Figura 1)
quanto o com vapor d’água (Figura 2) possuem formações de poros em forma de
crateras uniformes do tipo colmeia.
Figura 1. Micrografia obtida por MEV do carvão do ouriço da castanha-do-brasil com
CO2 a 800 °C.
Figura 2. Micrografia obtida por MEV do carvão do ouriço da castanha-do-brasil com
vapor d’água a 800 °C.
69
A quantidade adsorvida de 2,4-D após 2 minutos de contato com o carvão
ativado com CO2 foi de 3,48 mg.g-1, já para o carvão ativado com vapor d’água foi de
6,17 mg.g-1, ou seja, a porcentagem de remoção de 2,4-D em 2 minutos de contato
com o carvão ativado com CO2 foi de 54,62 %, enquanto que, no mesmo tempo, a
porcentagem de remoção de 2,4-D do carvão ativado com vapor d’água foi de 67,39
% (Figura 3).
Figura 3. Porcentagem de remoção de 2,4-D sobre o carvão ativado do ouriço da
castanha-do-brasil com CO2 ou vapor d'água em função do tempo.
O tempo necessário para se obter a adsorção máxima de 2,4-D no carvão
ativado com CO2 a 800 °C foi de 35 min (4,89 mg.g-1) e para o carvão ativado com
vapor d’água, também a 800°C, foi de 120 min (8,85 mg.g-1). No carvão ativado com
CO2, o tempo em que o processo de adsorção entrou em equilíbrio também foi de 35
min, já para o carvão ativado com vapor d’água, foi de 30 min (8,32 mg.g-1).
0 20 40 60 80 100 120
40
45
50
55
60
65
70
75
80
85
90
95
100
Rem
oval
(%)
t (min)
Carbon activated with CO2
Carbon activated with steam
70
Os modelos de pseudo-primeira ordem e pseudo-segunda ordem foram
usados para descrever o mecanismo de adsorção de 2,4-D, realizando ajustes não
lineares em condições de não equilíbrio. Para o carvão ativado com CO2, o modelo
de pseudo-primeira ordem apresentou valor de R2adj de 0,4024, k1 de 0,0219 min-1 e
qe de 0,9370 mg.g-1. O modelo de pseudo-segunda ordem obteve valor de R2adj de
0,9972, k2 de 0,0943 g.mg-1.min-1 e qe de 4,8197 mg.g-1 (Tabela 2).
O modelo de pseudo-primeira ordem ajustado aos dados experimentais do
carvão ativado com vapor d’água apresentou valor de R2adj de 0,5795, k1 de 0,0359
min-1 e qe de 2,1560 mg.g-1. O valor de R2adj do modelo de pseudo-segunda ordem
foi de 0,9942, k2 de 0,0283 g.mg-1.min-1 e qe de 8,8896 mg.g-1 (Tabela 2).
Tabela 2. Parâmetros dos modelos de cinética para a adsorção de 2,4-D em carvão
ativado com CO2 ou vapor d'água a 800 ºC
Parâmetros Carvão ativado com
CO2
Carvão ativado com
vapor d’água
C0 (mg.L-1) 3,1855 4,58
qe,exp (mg.g-1) 4,8900 8,32
Pseudo-primeira ordem
k1 (min-1) 0,0219 0,0359
qe (mg.g-1) 0,9370 2,1560
R2adj 0,4024 0,5795
Pseudo-segunda ordem
k2 (g.mg-1.min-1) 0,0943 0,0283
qe (mg.g-1) 4,8197 8,8896
71
R2adj 0,9972 0,9942
Com base no valor de R2adj, o modelo de pseudo-segunda ordem foi o que
mais se ajustou aos dados experimentais (Figuras 4 e 5).
Figura 4. Modelagem cinética para a adsorção de 2,4-D em carvão ativado com CO2
a 800 °C.
0 20 40 60 80 100 120
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.5
9.0
qt (m
g.g-1
)
t (min)
E xperimental data
qt Pseudo-first order
qt Pseudo-second order
0 20 40 60 80 100 120
0,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
4,0
4,5
5,0
5,5
6,0
6,5
7,0
7,5
8,0
8,5
9,0
qt (m
g.g-1
)
t (min)
Experimental data
Pseudo-first order
Pseudo-second order
72
Figura 5. Modelagem cinética para a adsorção de 2,4-D em carvão ativado com
vapor d'água a 800 °C.
4. Discussão
Os experimentos de cinética mostraram que a adsorção de 2,4-D foi
diretamente proporcional ao tempo de contato entre o adsorvente e adsorvato.
Também foi observado maior rapidez na adsorção durante os estágios iniciais e
maior lentidão quando se aproximou do equilíbrio. Tanto o carvão ativado com CO2
quanto o ativado com vapor d’água se mostraram eficientes na remoção de 2,4-D.
Porém, o carvão ativado com vapor d’água se mostrou superior na remoção de 2,4-
D logo nos primeiros minutos, sugerindo que a capacidade de adsorção deste
material está relacionada com as características químico-físicas (maior porcentagem
de carbono fixo e menores teores de água e materiais voláteis) e a superfície
química desenvolvida pela ativação com esta atmosfera.
A quantidade de 2,4-D adsorvida no equilíbrio reflete a capacidade de
adsorção máxima do carvão ativado em condições de operação [18]. Além da
porcentagem de adsorção ser maior para o carvão ativado com vapor d’água, este
entrou em equilíbrio em menor tempo. Esses resultados colaboram para a evidência
da superioridade do carvão ativado com vapor d’água sobre a ativação com CO2.
Estudos de cinética de adsorção de 2,4-D encontraram tempos de equilíbrio
de 8 h para o carvão da espiga de milho ativado quimicamente com H3PO4 [18].
Entre 4 e 7 h e 30 min para o carvão ativado de caroço de tâmara [7]. E entre 4 e 6
dias para carvão comercial granular (6 – 16 mesh) [5], demonstrando a alta
qualidade do carvão do ouriço da castanha-do-brasil ativado com CO2 ou vapor
d’água.
73
O estudo da cinética de adsorção possibilitou a otimização dos processos e
determinou a taxa de adsorção do soluto que controla o tempo de residência do
adsorvente na interface sólido-solução [20].
Dados experimentais do estudo de cinética de adsorção de 2,4-D e pesticidas
de carbofurano com carvão ativado granular comercial foram melhor descritos pelo
modelo de pseudo-segunda ordem [2]. A remoção de 2,4-D da solução aquosa
utilizando carvão ativado pode ocorrer através do transporte de 2,4-D da camada
limite para a superfície externa do adsorvente. Ou seja, pela difusão de filme na
transferência de 2,4-D da superfície para os sítios ativos intraparticulares e pela
adsorção de 2,4-D pelos sítios ativos do sorvente [5]. O modelo de pseudo-segunda
ordem sugere que a taxa de adsorção é mais dependente da disponibilidade de
sítios de adsorção na superfície do carvão ativado do que da concentração de 2,4-D
na solução [21]. Essa expressão descreve a quimissorção envolvendo forças de
valência através do compartilhamento ou troca de elétrons entre o 2,4-D e o carvão
ativado como forças covalentes e troca iônica [22]. O modelo de pseudo-segunda
ordem tem sido aplicada com sucesso para a adsorção de herbicidas [22] e foi a que
melhor se ajustou aos dados experimentais.
5. Conclusão
O modelo de pseudo-segunda ordem obteve o melhor ajuste para os dados
experimentais de cinética, tanto para as amostras ativadas com CO2 quanto para as
com vapor d’água, indicando que a adsorção do 2,4-D nos carvões ativados foi por
quimissorção. Os carvões se mostraram eficientes na remoção de 2,4-D,
independente da atmosfera de ativação, porém, o carvão ativado com vapor d’água
foi superior em relação à quantidade adsorvida logo nos primeiros minutos.
74
6. Agradecimentos
À Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) pela
bolsa concedida e às empresas Borello Alimentos Ltda e Eletrotécnica Pagliari que
disponibilizaram toda sua estrutura para o processo de produção dos carvões
ativados.
7. Referências
[1] N.M.X. Faria, A.G. Fassa, L.A. Facchini, Intoxicação por agrotóxicos no Brasil: os sistemas oficiais de informação e desafios para realização de estudos epidemiológicos, Cien. Saude Colet. 12 (2007) 25–38. doi:10.1590/S1413-81232007000100008.
[2] J.M. Salman, B.H. Hameed, Adsorption of 2,4-dichlorophenoxyacetic acid and carbofuran pesticides onto granular activated carbon, Desalination. 256 (2010) 129–135. doi:10.1016/j.desal.2010.02.002.
[3] M.A.T. Dos Santos, M.A. Areas, F.G.R. Reyes, Piretróides - uma visão geral, Aliment. E Nutr. - Brazilian J. Food Nutr. 18 (2007) 339–349. http://serv-bib.fcfar.unesp.br/seer/index.php/alimentos/article/viewFile/173/181.
[4] O.D.A. Junior, T. Santos, N. Brito, M.L. Ribeiro, T. Cristina, R. Santos, Revisão das propriedades, usos e legislação ácido 2,4-diclorofenoxiacético (2,4-D)., Cad. Pesqui. 13 (2002) 60–70.
[5] Z. Aksu, E. Kabasakal, Batch adsorption of 2,4-dichlorophenoxy-acetic acid (2,4-D) from aqueous solution by granular activated carbon, Sep. Purif. Technol. 35 (2004) 223–240. doi:10.1016/S1383-5866(03)00144-8.
[6] World Health Organization (WHO), Guidelines for Drinking-water Quality, fourth edi, Geneva, 2017.
[7] B.H. Hameed, J.M. Salman, A.L. Ahmad, Adsorption isotherm and kinetic modeling of 2,4-D pesticide on activated carbon derived from date stones, J. Hazard. Mater. 163 (2009) 121–126. doi:10.1016/j.jhazmat.2008.06.069.
[8] R.D. Letterman, A. Amirtharajah, C.R. O’Melia, Coagulation and Flocculation, in: R.D. Letterman (Ed.), Water Qual. Treat. a Handb. Community Water Supplies, 5th ed., McGraw-Hill, New York, 1999: p. 6.1-6.66.
[9] S.D.S. Melo, J.E.D.M. Diniz, J.H. Guimarães, J.D.S. Costa, D.D.S.B. Brasil, S.S.D.S. de Morais, D.C. Brito, J.C.T. Carvalho, C.B.R. dos Santos, D.L. da Silva, Production and characterization of absorbent heat from the bark of residual Brazil nut bark (Bertholletia Excelsa l.), Chem. Cent. J. 9 (2015) 36. doi:10.1186/s13065-015-0114-3.
75
[10] A. Herzog, B. Reznik, T. Chen, T. Graule, U. Vogt, Structural changes in activated wood-based carbons: correlation between specific surface area and localization of molecular-sized pores, Holzforschung. 60 (2006) 85–92. doi:10.1515/HF.2006.015.
[11] J.P. Kearns, L.S. Wellborn, R.S. Summers, D.R.U. Knappe, 2,4-D adsorption to biochars: Effect of preparation conditions on equilibrium adsorption capacity and comparison with commercial activated carbon literature data, Water Res. 62 (2014) 29–28. doi:10.1016/j.watres.2014.05.023.
[12] O. Ioannidou, A. Zabaniotou, Agricultural residues as precursors for activated carbon production—A review, Renew. Sustain. Energy Rev. 11 (2007) 1966–2005. doi:10.1016/J.RSER.2006.03.013.
[13] V.M. Scussel, D. Manfio, G.D. Savi, E.H.S. Moecke, Stereoscopy and Scanning Electron Microscopy of Brazil Nut (Bertholletia excelsa H.B.K.) Shell, Brown Skin, and Edible Part: Part One-Healthy Nut, J. Food Sci. 79 (2014) 1–11. doi:10.1111/1750-3841.12502.
[14] J. Yang, Brazil nuts and associated health benefits: A review, LWT - Food Sci. Technol. 42 (2009) 1573–1580. doi:10.1016/j.lwt.2009.05.019.
[15] J.U.M. dos Santos, M. de N. do C. Bastos, E.S.C. Gurgel, A.C.M. Carvalho, Bertholletia excelsa Humboldt & Bonpland (Lecythidaceae): aspectos morfológicos do fruto, da semente e da plântula, Bol. Do Mus. Para. Emílio Goeldi. 1 (2006) 103–112.
[16] R.M. Nogueira, S. Ruffato, J.S. Carneiro, E.M. Pires, V.S. Álvares, Evaluation of carbonization of the hedgehog of Brazil nut in oven type metal drums, Sci. Electron. Arch. (2014) 7–17.
[17] ASTM D 3860-98, Standard Practice for Determination of Adsorptive Capacity of Activated Carbon by Aqueous Phase Isotherm Technique, 2008. doi:10.1520/D3860-98R08.2.
[18] V.O. Njoku, B.H. Hameed, Preparation and characterization of activated carbon from corncob by chemical activation with H3PO4 for 2,4-dichlorophenoxyacetic acid adsorption, Chem. Eng. J. 173 (2011) 391–399. doi:10.1016/j.cej.2011.07.075.
[19] Y.. Ho, G. McKay, Pseudo-second order model for sorption processes, Process Biochem. 34 (1999) 451–465. doi:10.1016/S0032-9592(98)00112-5.
[20] L.F. Zeferino, I. Gaubeur, M.E. V Suárez-iha, P.A.M. Freitas, nucifera L .): Kinetic and Isotherms, (2014) 37–52.
[21] Y. Liu, New insights into pseudo-second-order kinetic equation for adsorption, Colloids Surfaces A Physicochem. Eng. Asp. 320 (2008) 275–278. doi:10.1016/J.COLSURFA.2008.01.032.
[22] Y.S. Ho, Review of second-order models for adsorption systems, J. Hazard. Mater. 136 (2006) 681–689. doi:10.1016/j.jhazmat.2005.12.043.
76
JOURNAL OF HAZARDOUS MATERIALS
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ISSN: 0304-3894
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J.M. Park, Pohang, Gyeongbuk, The Republic of Korea
H.J. Pasman, Delft, Netherlands
S.G. Pavlostathis, Atlanta, Georgia, USA
M.J. Plewa, Urbana, Illinois, USA
X. Quan, Dalian, China
S.D. Richardson, Columbia, South Carolina, USA
M.A. Rodrigo, Real, Spain
P. Stepnowski
S. Tunali Akar, Meselik/Eskisehir, Turkey
S.-B. Wang, Perth, Western Australia, Australia
X. Wang, Beijing, China
J. Yu, Wuhan, China
Z. Svatopluk, Pardubice, Czech Republic
A.I. Zouboulis, Thessaloniki, Greece
GUIDE FOR AUTHORS
INTRODUCTION
The Journal of Hazardous Materials full-length research papers, review articles, and case
studies that improve our understanding of the hazards and risks that certain materials pose to
public health, and the environment. Papers that deal with ways of controlling and mitigating
risks of hazardous materials (HM) are within the scope of the journal. However, the following
areas are excluded: non-hazardous materials, work place health and safety, standard
municipal waste and wastewater treatment processes including nutrient removal, greenhouse
gas mitigation, toxicology of hazardous materials below the organism level (i.e. at the cellular,
metabolic, or molecular level) and the manufacturing of explosives.
The Journal publishes high-impact contributions on: Characterization of the Harmful Effects of
Chemicals and Materials (including contaminants of emerging concern) Measurement and
Monitoring of HM Transport and Fate of HM in the Environment Risk Assessment and
Management Physicochemical and Separation Processes for HM Removal (Adsorption, Ion
Exchange, Coagulation/ Flocculation/Precipitation, Membrane Processes, Flotation,
Stabilization/Solidification) Thermal Processes for HM Removal (Incineration, Pyrolysis,
Gasification, Plasma) Advanced Oxidation Processes for HM Removal
(Photodegradation/Photocatalysis, H2O2-UV, Fenton, Ozone, Sonolysis,
.
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Plasma Processes, etc.) Biological Processes for HM Removal(Biodegradation,
Phytoremediation, Combined Degradation Processes) Safer and Cleaner Technologies
Material and Energy Resource Recovery from Hazardous Waste (Medical waste, Electronic
waste, etc.) Micropollutants and Endocrine Disrupting Chemicals.
The Journal publishes papers with significant novelty and scientific impact. The Editors reserve
the right to decline, without external review, papers that do not meet these criteria, including
papers that: Are very similar to previous publications, with changed target substrates,
employed materials, analyzed sites or experimental methods, Deal with parameter
optimization of known processes without new concepts and/or interpretations, Report the
environmental analysis and monitoring of specific geographic areas without presenting new
insights and/or hypothesis testing, or Do not focus on the environmental relevance and
significance of the studied systems or materials.
A 100 word (maximum) "statement of novelty" explaining why the work should be published in
Journal of Hazardous Materials must be provided as a separate document upon submission
of your manuscript. The "statement of novelty" must not be a retelling of the abstract. When
preparing the statement please make sure to address (a) the significance and novelty of the
work, with respect to existing literature, and (b) the scientific impact and interests to our
readership. Papers that lack significant novelty will be rejected.
Types of Paper
Full-length research papers within the above stated Aims and Scope are welcome. Such
contributions are not to be submitted in two parts (i.e. Part I and Part II) - these must be
consolidated into one manuscript. Short communications are not considered.
The Editors welcome proposals for review articles. Proposals must contain the following
components for consideration: (1) a brief summary of the proposed review article content, (2)
a clear indication of the novelty and urgency of such a review paper at this time, in light of other
review articles on the same topic, (3) a brief description of the authors' academic background
and research areas, and (4) a list of all authors' publications related to the proposed review
article topic. Please send your proposals to one of the Editors directly using the e-mail
addresses available on the Journal homepage: http://www.elsevier.com/locate/hazmat. Note
that submission of review articles is by invitation only, pending approval of the proposal by the
Editors.
Letters to the Editor will undergo review. Any Letters to the Editor received will be circulated to
all Editors before a decision is made whether to publish. Authors of earlier papers, if the Letter
concerns a prior publication, will also be given an opportunity to respond.
To ensure conciseness, follow these maximum word count guidelines: research paper: 5,000
words; review article: 15,000 words. Cover letters must state the manuscript word count, which
includes text, figures captions, and table legends, but not references.
Submission checklist
You can use this list to carry out a final check of your submission before you send it to the
journal for review. Please check the relevant section in this Guide for Authors for more details.
Ensure that the following items are present:
One author has been designated as the corresponding author with contact details:
E-mail address
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Full postal address
All necessary files have been uploaded:
Manuscript:
Include keywords
All figures (include relevant captions)
All tables (including titles, description, footnotes)
Ensure all figure and table citations in the text match the files provided
Indicate clearly if color should be used for any figures in print
Graphical Abstracts / Highlights files (where applicable)
Supplemental files (where applicable)
Further considerations
Manuscript has been 'spell checked' and 'grammar checked'
All references mentioned in the Reference List are cited in the text, and vice versa
Permission has been obtained for use of copyrighted material from other sources (including
theInternet)
A competing interests statement is provided, even if the authors have no competing interests
todeclare
Journal policies detailed in this guide have been reviewed
Referee suggestions and contact details provided, based on journal requirements
For further information, visit our Support Center.
BEFORE YOU BEGIN
Ethics in publishing
Please see our information pages on Ethics in publishing and Ethical guidelines for journal
publication.
Declaration of interest
All authors must disclose any financial and personal relationships with other people or
organizations that could inappropriately influence (bias) their work. Examples of potential
conflicts of interest include employment, consultancies, stock ownership, honoraria, paid
expert testimony, patent applications/ registrations, and grants or other funding. Authors must
disclose any interests in two places: 1. A summary declaration of interest statement in the title
page file (if double-blind) or the manuscript file (if single-blind). If there are no interests to
declare then please state this: 'Declarations of interest: none'. This summary statement will be
ultimately published if the article is accepted. 2. Detailed disclosures as part of a separate
Declaration of Interest form, which forms part of the journal's official records. It is important for
potential interests to be declared in both places and that the information matches. More
information.
Submission declaration and verification
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Submission of an article implies that the work described has not been published previously
(except in the form of an abstract, a published lecture or academic thesis, see 'Multiple,
redundant or concurrent publication' for more information), that it is not under consideration for
publication elsewhere, that its publication is approved by all authors and tacitly or explicitly by
the responsible authorities where the work was carried out, and that, if accepted, it will not be
published elsewhere in the same form, in English or in any other language, including
electronically without the written consent of the copyrightholder. To verify originality, your
article may be checked by the originality detection service Crossref Similarity Check.
Preprints
Please note that preprints can be shared anywhere at any time, in line with Elsevier's sharing
policy. Sharing your preprints e.g. on a preprint server will not count as prior publication (see
'Multiple, redundant or concurrent publication' for more information).
Changes to authorship
Authors are expected to consider carefully the list and order of authors before submitting their
manuscript and provide the definitive list of authors at the time of the original submission. Any
addition, deletion or rearrangement of author names in the authorship list should be made only
before the manuscript has been accepted and only if approved by the journal Editor. To request
such a change, the Editor must receive the following from the corresponding author: (a) the
reason for the change in author list and (b) written confirmation (e-mail, letter) from all authors
that they agree with the addition, removal or rearrangement. In the case of addition or removal
of authors, this includes confirmation from the author being added or removed.
Only in exceptional circumstances will the Editor consider the addition, deletion or
rearrangement of authors after the manuscript has been accepted. While the Editor considers
the request, publication of the manuscript will be suspended. If the manuscript has already
been published in an online issue, any requests approved by the Editor will result in a
corrigendum.
Article transfer service
This journal is part of our Article Transfer Service. This means that if the Editor feels your article
is more suitable in one of our other participating journals, then you may be asked to consider
transferring the article to one of those. If you agree, your article will be transferred automatically
on your behalf with no need to reformat. Please note that your article will be reviewed again
by the new journal. More information.
Copyright
Upon acceptance of an article, authors will be asked to complete a 'Journal Publishing
Agreement' (see more information on this). An e-mail will be sent to the corresponding author
confirming receipt of the manuscript together with a 'Journal Publishing Agreement' form or a
link to the online version of this agreement.
Subscribers may reproduce tables of contents or prepare lists of articles including abstracts
for internal circulation within their institutions. Permission of the Publisher is required for resale
or distribution outside the institution and for all other derivative works, including compilations
and translations. If excerpts from other copyrighted works are included, the author(s) must
obtain written permission from the copyright owners and credit the source(s) in the article.
Elsevier has preprinted forms for use by authors in these cases.
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For gold open access articles: Upon acceptance of an article, authors will be asked to complete
an 'Exclusive License Agreement' (more information). Permitted third party reuse of gold open
access articles is determined by the author's choice of user license.
Author rights
As an author you (or your employer or institution) have certain rights to reuse your work. More
information.
Elsevier supports responsible sharing
Find out how you can share your research published in Elsevier journals.
Role of the funding source
You are requested to identify who provided financial support for the conduct of the research
and/or preparation of the article and to briefly describe the role of the sponsor(s), if any, in
study design; in the collection, analysis and interpretation of data; in the writing of the report;
and in the decision to submit the article for publication. If the funding source(s) had no such
involvement then this should be stated.
Funding body agreements and policies
Elsevier has established a number of agreements with funding bodies which allow authors to
comply with their funder's open access policies. Some funding bodies will reimburse the author
for the gold open access publication fee. Details of existing agreements are available online.
Open access
This journal offers authors a choice in publishing their research:
Subscription
Articles are made available to subscribers as well as developing countries and patient groups
throughour universal access programs.
No open access publication fee payable by authors.
The Author is entitled to post the accepted manuscript in their institution's repository and make
this public after an embargo period (known as green Open Access). The published journal
article cannot be shared publicly, for example on ResearchGate or Academia.edu, to ensure
the sustainability of peerreviewed research in journal publications. The embargo period for this
journal can be found below.
Gold open access
Articles are freely available to both subscribers and the wider public with permitted reuse.
A gold open access publication fee is payable by authors or on their behalf, e.g. by their
researchfunder or institution.
Regardless of how you choose to publish your article, the journal will apply the same peer
review criteria and acceptance standards.
For gold open access articles, permitted third party (re)use is defined by the following Creative
Commons user licenses:
Creative Commons Attribution (CC BY)
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Lets others distribute and copy the article, create extracts, abstracts, and other revised
versions, adaptations or derivative works of or from an article (such as a translation), include
in a collective work (such as an anthology), text or data mine the article, even for commercial
purposes, as long as they credit the author(s), do not represent the author as endorsing their
adaptation of the article, and do not modify the article in such a way as to damage the author's
honor or reputation.
Creative Commons Attribution-NonCommercial-NoDerivs (CC BY-NC-ND)
For non-commercial purposes, lets others distribute and copy the article, and to include in a
collective work (such as an anthology), as long as they credit the author(s) and provided they
do not alter or modify the article.
The gold open access publication fee for this journal is USD 2500, excluding taxes. Learn more
about Elsevier's pricing policy: https://www.elsevier.com/openaccesspricing.
Green open access
Authors can share their research in a variety of different ways and Elsevier has a number of
green open access options available. We recommend authors see our green open access
page for further information. Authors can also self-archive their manuscripts immediately and
enable public access from their institution's repository after an embargo period. This is the
version that has been accepted for publication and which typically includes author-incorporated
changes suggested during submission, peer review and in editor-author communications.
Embargo period: For subscription articles, an appropriate amount of time is needed for journals
to deliver value to subscribing customers before an article becomes freely available to the
public. This is the embargo period and it begins from the date the article is formally published
online in its final and fully citable form. Find out more.
This journal has an embargo period of 24 months.
Elsevier Researcher Academy
Researcher Academy is a free e-learning platform designed to support early and mid-career
researchers throughout their research journey. The "Learn" environment at Researcher
Academy offers several interactive modules, webinars, downloadable guides and resources to
guide you through the process of writing for research and going through peer review. Feel free
to use these free resources to improve your submission and navigate the publication process
with ease.
Language (usage and editing services)
Please write your text in good English (American or British usage is accepted, but not a mixture
of these). Authors who feel their English language manuscript may require editing to eliminate
possible grammatical or spelling errors and to conform to correct scientific English may wish
to use the English Language Editing service available from Elsevier's WebShop.
Submission
Submission to this journal proceeds totally online. Use the following guidelines to prepare your
article. Via the homepage of this journal (http://ees.elsevier.com/hazmat/) you will be guided
stepwise through the creation and uploading of the various files. The system automatically
converts source files to a single Adobe Acrobat PDF version of the article, which is used in the
peer-review process. Please note that even though manuscript source files are converted to
PDF at submission for the review process, these source files are needed for further processing
after acceptance. All correspondence, including notification of the Editor's decision and
85
requests for revision, takes place by e-mail and via the author's homepage, removing the need
for a hard-copy paper trail.
Manuscripts must conform to the following guidelines for revised manuscripts or they will be
rejected.
Should Authors be requested by the Editor to revise their submission, the revised version
should be submitted within two months. Please note that revised manuscripts will be sent out
for review because revising a manuscript does not automatically mean it will be accepted for
publication.
In the revision letter, authors must transcribe each reviewer's comments into the letter, followed
by the author's responses. Any associated changes in the manuscript(DO NOT include page
and line numbers) must be copied down in the revision letter. This will help the Editor compare
the reviewer comments with both the replies and the changes made in the manuscript. The
replies to the reviewers' comments must also be reflected in the revised manuscript wherever
possible (not just in the revision letter). Authors must give clear reasons if they choose not to
make changes according to the reviewer suggestions. In the revised manuscript, authors must
indicate how the manuscript was changed according to the reviewer comments by highlighting
the revisions (all new text/data/figures) with colour. Only one final revised version the
manuscript must be uploaded.
Authors must provide the original manuscript number, the name of the original handling Editor,
and state whether the revised manuscript is a resubmission of a rejected manuscript both in
EES and in the cover letter in order to ensure that it is assigned to the original handling Editor.
Upon resubmission of a rejected manuscript, Authors will be required to upload the decision
letter from the Editor requesting submission of the rejected manuscript, the original Reviewer
comments of the rejected manuscript, the responses to the Reviewer comments, and the
original manuscript number. The resubmitted manuscript must indicate, in color, where the
revisions were made in the paper in response to the Reviewer comments.
Please be aware that manuscripts rejected for "out of scope" or "lack of novelty" will not be
accepted as a resubmission.
PREPARATION
Peer review
This journal operates a single blind review process. All contributions will be initially assessed
by the editor for suitability for the journal. Papers deemed suitable are then typically sent to a
minimum of two independent expert reviewers to assess the scientific quality of the paper. The
Editor is responsible for the final decision regarding acceptance or rejection of articles. The
Editor's decision is final. More information on types of peer review.
Use of word processing software
It is important that the file be saved in the native format of the word processor used. The text
should be in single-column format. Keep the layout of the text as simple as possible. Most
formatting codes will be removed and replaced on processing the article. In particular, do not
use the word processor's options to justify text or to hyphenate words. However, do use bold
face, italics, subscripts, superscripts etc. When preparing tables, if you are using a table grid,
use only one grid for each individual table and not a grid for each row. If no grid is used, use
tabs, not spaces, to align columns. The electronic text should be prepared in a way very similar
to that of conventional manuscripts (see also the Guide to Publishing with Elsevier). Note that
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source files of figures, tables and text graphics will be required whether or not you embed your
figures in the text. See also the section on Electronic artwork.
To avoid unnecessary errors you are strongly advised to use the 'spell-check' and 'grammar-
check' functions of your word processor.
Article structure
Subdivision - numbered sections
Divide your article into clearly defined and numbered sections. Subsections should be
numbered 1.1 (then 1.1.1, 1.1.2, ...), 1.2, etc. (the abstract is not included in section
numbering). Use this numbering also for internal cross-referencing: do not just refer to 'the
text'. Any subsection may be given a brief heading. Each heading should appear on its own
separate line.
Introduction
State the objectives of the work and provide an adequate background, avoiding a detailed
literature survey or a summary of the results.
Experimental
Provide sufficient detail to allow the work to be reproduced. Methods already published should
be indicated by a reference: only relevant modifications should be described.
Results
Results should be clear and concise.
Discussion
This should explore the significance of the results of the work, not repeat them. A combined
Results and Discussion section is often appropriate. Avoid extensive citations and discussion
of published literature.
Conclusions
The main conclusions of the study may be presented in a short Conclusions section, which
may stand alone or form a subsection of a Discussion or Results and Discussion section.
Appendices
If there is more than one appendix, they should be identified as A, B, etc. Formulae and
equations in appendices should be given separate numbering: Eq. (A.1), Eq. (A.2), etc.; in a
subsequent appendix, Eq. (B.1) and so on. Similarly for tables and figures: Table A.1; Fig. A.1,
etc.
Essential title page information
Title. Concise and informative. Titles are often used in information-retrieval systems. Avoid
abbreviations and formulae where possible.
Author names and affiliations. Where the family name may be ambiguous (e.g., a double
name), please indicate this clearly. Present the authors' affiliation addresses (where the actual
work was done) below the names. Indicate all affiliations with a lower-case superscript letter
immediately after the author's name and in front of the appropriate address. Provide the full
postal address of each affiliation, including the country name, and, if available, the e-mail
address of each author.
87
Corresponding author. Clearly indicate who is willing to handle correspondence at all stages
of refereeing and publication, also post-publication. The submitting author and the
corresponding author must be the same person. Ensure that telephone and fax numbers (with
country and area code) are provided in addition to the e-mail address and the complete postal
address. Present/permanent address. If an author has moved since the work described in the
article was done, or was visiting at the time, a "Present address"' (or "Permanent address")
may be indicated as a footnote to that author's name. The address at which the author actually
did the work must be retained as the main, affiliation address. Superscript Arabic numerals are
used for such footnotes.
Abstract
A concise and factual abstract is required (100-200 words). The abstract should state briefly
the purpose of the research, the principal results and major conclusions. An abstract is often
presented separately from the article, so it must be able to stand alone. For this reason,
References should be avoided, but if essential, they must be cited in full, without reference to
the reference list. Also, non-standard or uncommon abbreviations should be avoided, but if
essential they must be defined at their first mention in the abstract itself.
Graphical abstract
Although a graphical abstract is optional, its use is encouraged as it draws more attention to
the online article. The graphical abstract should summarize the contents of the article in a
concise, pictorial form designed to capture the attention of a wide readership. Graphical
abstracts should be submitted as a separate file in the online submission system. Image size:
Please provide an image with a minimum of 531 × 1328 pixels (h × w) or proportionally more.
The image should be readable at a size of 5 × 13 cm using a regular screen resolution of 96
dpi. Preferred file types: TIFF, EPS, PDF or MS Office files. You can view Example Graphical
Abstracts on our information site.
Authors can make use of Elsevier's Illustration Services to ensure the best presentation of their
images and in accordance with all technical requirements.
Highlights
Highlights are mandatory for this journal. They consist of a short collection of bullet points that
convey the core findings of the article and should be submitted in a separate editable file in the
online submission system. Please use 'Highlights' in the file name and include 3 to 5 bullet
points (maximum 85 characters, including spaces, per bullet point). You can view example
Highlights on our information site.
Keywords
Immediately after the abstract, provide a maximum of 5 keywords, using American spelling
and avoiding general and plural terms and multiple concepts (avoid, for example, "and", "of").
Be sparing with abbreviations: only abbreviations firmly established in the field may be eligible.
These keywords will be used for indexing purposes.
Abbreviations
Define abbreviations that are not standard in this field in a footnote to be placed on the first
page of the article. Such abbreviations that are unavoidable in the abstract must be defined at
their first mention there, as well as in the footnote. Ensure consistency of abbreviations
throughout the article.
Acknowledgements
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Collate acknowledgements in a separate section at the end of the article before the references
and do not, therefore, include them on the title page, as a footnote to the title or otherwise. List
here those individuals who provided help during the research (e.g., providing language help,
writing assistance or proof reading the article, etc.).
Formatting of funding sources
List funding sources in this standard way to facilitate compliance to funder's requirements:
Funding: This work was supported by the National Institutes of Health [grant numbers xxxx,
yyyy]; the Bill & Melinda Gates Foundation, Seattle, WA [grant number zzzz]; and the United
States Institutes of Peace [grant number aaaa].
It is not necessary to include detailed descriptions on the program or type of grants and awards.
When funding is from a block grant or other resources available to a university, college, or
other research institution, submit the name of the institute or organization that provided the
funding.
If no funding has been provided for the research, please include the following sentence:
This research did not receive any specific grant from funding agencies in the public,
commercial, or not-for-profit sectors.
Nomenclature and units
Follow internationally accepted rules and conventions: use the international system of units
(SI). If other quantities are mentioned, give their equivalent in SI. You are urged to consult the
International Union of Pure and Applied Chemistry (IUPAC) http://www.iupac.org/ for further
information.
Footnotes
Footnotes should be used sparingly. Number them consecutively throughout the article. Many
word processors can build footnotes into the text, and this feature may be used. Otherwise,
please indicate the position of footnotes in the text and list the footnotes themselves separately
at the end of the article. Do not include footnotes in the Reference list.
Artwork
Electronic artwork General points
Make sure you use uniform lettering and sizing of your original artwork.
Embed the used fonts if the application provides that option.
Aim to use the following fonts in your illustrations: Arial, Courier, Times New Roman, Symbol,
oruse fonts that look similar.
Number the illustrations according to their sequence in the text.
Use a logical naming convention for your artwork files.
Provide captions to illustrations separately.
Size the illustrations close to the desired dimensions of the published version.
Submit each illustration as a separate file.
A detailed guide on electronic artwork is available.
89
You are urged to visit this site; some excerpts from the detailed information are given here.
Formats
If your electronic artwork is created in a Microsoft Office application (Word, PowerPoint, Excel)
then please supply 'as is' in the native document format.
Regardless of the application used other than Microsoft Office, when your electronic artwork
is finalized, please 'Save as' or convert the images to one of the following formats (note the
resolution requirements for line drawings, halftones, and line/halftone combinations given
below):
EPS (or PDF): Vector drawings, embed all used fonts.
TIFF (or JPEG): Color or grayscale photographs (halftones), keep to a minimum of 300 dpi.
TIFF (or JPEG): Bitmapped (pure black & white pixels) line drawings, keep to a minimum of
1000 dpi. TIFF (or JPEG): Combinations bitmapped line/half-tone (color or grayscale), keep to
a minimum of 500 dpi.
Please do not:
Supply files that are optimized for screen use (e.g., GIF, BMP, PICT, WPG); these typically
have alow number of pixels and limited set of colors;
Supply files that are too low in resolution;
Submit graphics that are disproportionately large for the content.
Color artwork
Please make sure that artwork files are in an acceptable format (TIFF (or JPEG), EPS (or
PDF), or MS Office files) and with the correct resolution. If, together with your accepted article,
you submit usable color figures then Elsevier will ensure, at no additional charge, that these
figures will appear in color online (e.g., ScienceDirect and other sites) regardless of whether
or not these illustrations are reproduced in color in the printed version. For color reproduction
in print, you will receive information regarding the costs from Elsevier after receipt of your
accepted article. Please indicate your preference for color: in print or online only. Further
information on the preparation of electronic artwork.
Figure captions
Ensure that each illustration has a caption. Supply captions separately, not attached to the
figure. A caption should comprise a brief title (not on the figure itself) and a description of the
illustration. Keep text in the illustrations themselves to a minimum but explain all symbols and
abbreviations used.
Tables
Please submit tables as editable text and not as images. Tables can be placed either next to
the relevant text in the article, or on separate page(s) at the end. Number tables consecutively
in accordance with their appearance in the text and place any table notes below the table body.
Be sparing in the use of tables and ensure that the data presented in them do not duplicate
results described elsewhere in the article. Please avoid using vertical rules and shading in
table cells.
References
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Manuscripts must contain at least 10 references. The references must cite recent and relevant
research only. At least half (50%) of the references should be published within the last 10
years.
Citation in text
Please ensure that every reference cited in the text is also present in the reference list (and
vice versa). Any references cited in the abstract must be given in full. Unpublished results and
personal communications are not recommended in the reference list, but may be mentioned
in the text. If these references are included in the reference list they should follow the standard
reference style of the journal and should include a substitution of the publication date with
either 'Unpublished results' or 'Personal communication'. Citation of a reference as 'in press'
implies that the item has been accepted for publication.
Web references
As a minimum, the full URL should be given and the date when the reference was last
accessed. Any further information, if known (DOI, author names, dates, reference to a source
publication, etc.), should also be given. Web references can be listed separately (e.g., after
the reference list) under a different heading if desired, or can be included in the reference list.
Data references
This journal encourages you to cite underlying or relevant datasets in your manuscript by citing
them in your text and including a data reference in your Reference List. Data references should
include the following elements: author name(s), dataset title, data repository, version (where
available), year, and global persistent identifier. Add [dataset] immediately before the reference
so we can properly identify it as a data reference. The [dataset] identifier will not appear in your
published article.
Reference management software
Most Elsevier journals have their reference template available in many of the most popular
reference management software products. These include all products that support Citation
Style Language styles, such as Mendeley and Zotero, as well as EndNote. Using the word
processor plug-ins from these products, authors only need to select the appropriate journal
template when preparing their article, after which citations and bibliographies will be
automatically formatted in the journal's style. If no template is yet available for this journal,
please follow the format of the sample references and citations as shown in this Guide.
Users of Mendeley Desktop can easily install the reference style for this journal by clicking the
following link:
http://open.mendeley.com/use-citation-style/journal-of-hazardous-materials
When preparing your manuscript, you will then be able to select this style using the Mendeley
plugins for Microsoft Word or LibreOffice.
Reference style
Text: Indicate references by number(s) in square brackets in line with the text. The actual
authors can be referred to, but the reference number(s) must always be given.
Example: '..... as demonstrated [3,6]. Barnaby and Jones [8] obtained a different result ....' List:
Number the references (numbers in square brackets) in the list in the order in which they
appear in the text.
91
Examples:
Reference to a journal publication:
J. van der Geer, J.A.J. Hanraads, R.A. Lupton, The art of writing a scientific article, J. Sci.
Commun.163 (2010) 51–59.
Reference to a book:
W. Strunk Jr., E.B. White, The Elements of Style, fourth ed., Longman, New York, 2000.
Reference to a chapter in an edited book:
G.R. Mettam, L.B. Adams, How to prepare an electronic version of your article, in: B.S. Jones,
R.Z.Smith (Eds.), Introduction to the Electronic Age, E-Publishing Inc., New York, 2009, pp.
281–304.
Reference to a website:
Cancer Research UK, Cancer statistics reports for the UK.
http://www.cancerresearchuk.org/aboutcancer/statistics/cancerstatsreport/, 2003 (accessed
13 March 2003).
Reference to a dataset:
[dataset] [5] M. Oguro, S. Imahiro, S. Saito, T. Nakashizuka, Mortality data for Japanese oak
wilt disease and surrounding forest compositions, Mendeley Data, v1, 2015.
https://doi.org/10.17632/ xwj98nb39r.1.
Journal abbreviations source
Journal names should be abbreviated according to the List of Title Word Abbreviations.
Video
Elsevier accepts video material and animation sequences to support and enhance your
scientific research. Authors who have video or animation files that they wish to submit with
their article are strongly encouraged to include links to these within the body of the article. This
can be done in the same way as a figure or table by referring to the video or animation content
and noting in the body text where it should be placed. All submitted files should be properly
labeled so that they directly relate to the video file's content. . In order to ensure that your video
or animation material is directly usable, please provide the file in one of our recommended file
formats with a preferred maximum size of 150 MB per file, 1 GB in total. Video and animation
files supplied will be published online in the electronic version of your article in Elsevier Web
products, including ScienceDirect. Please supply 'stills' with your files: you can choose any
frame from the video or animation or make a separate image. These will be used instead of
standard icons and will personalize the link to your video data. For more detailed instructions
please visit our video instruction pages. Note: since video and animation cannot be embedded
in the print version of the journal, please provide text for both the electronic and the print
version for the portions of the article that refer to this content.
AudioSlides
The journal encourages authors to create an AudioSlides presentation with their published
article. AudioSlides are brief, webinar-style presentations that are shown next to the online
article on ScienceDirect. This gives authors the opportunity to summarize their research in
their own words and to help readers understand what the paper is about. More information and
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examples are available. Authors of this journal will automatically receive an invitation e-mail to
create an AudioSlides presentation after acceptance of their paper.
Data visualization
Include interactive data visualizations in your publication and let your readers interact and
engage more closely with your research. Follow the instructions here to find out about available
data visualization options and how to include them with your article.
Supplementary material
Supplementary material such as applications, images and sound clips, can be published with
your article to enhance it. Submitted supplementary items are published exactly as they are
received (Excel or PowerPoint files will appear as such online). Please submit your material
together with the article and supply a concise, descriptive caption for each supplementary file.
If you wish to make changes to supplementary material during any stage of the process, please
make sure to provide an updated file. Do not annotate any corrections on a previous version.
Please switch off the 'Track Changes' option in Microsoft Office files as these will appear in the
published version.
Research data
This journal encourages and enables you to share data that supports your research publication
where appropriate, and enables you to interlink the data with your published articles. Research
data refers to the results of observations or experimentation that validate research findings. To
facilitate reproducibility and data reuse, this journal also encourages you to share your
software, code, models, algorithms, protocols, methods and other useful materials related to
the project.
Below are a number of ways in which you can associate data with your article or make a
statement about the availability of your data when submitting your manuscript. If you are
sharing data in one of these ways, you are encouraged to cite the data in your manuscript and
reference list. Please refer to the "References" section for more information about data citation.
For more information on depositing, sharing and using research data and other relevant
research materials, visit the research data page.
Data linking
If you have made your research data available in a data repository, you can link your article
directly to the dataset. Elsevier collaborates with a number of repositories to link articles on
ScienceDirect with relevant repositories, giving readers access to underlying data that gives
them a better understanding of the research described.
There are different ways to link your datasets to your article. When available, you can directly
link your dataset to your article by providing the relevant information in the submission system.
For more information, visit the database linking page.
For supported data repositories a repository banner will automatically appear next to your
published article on ScienceDirect.
In addition, you can link to relevant data or entities through identifiers within the text of your
manuscript, using the following format: Database: xxxx (e.g., TAIR: AT1G01020; CCDC:
734053; PDB: 1XFN).
Mendeley Data
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This journal supports Mendeley Data, enabling you to deposit any research data (including raw
and processed data, video, code, software, algorithms, protocols, and methods) associated
with your manuscript in a free-to-use, open access repository. Before submitting your article,
you can deposit the relevant datasets to Mendeley Data. Please include the DOI of the
deposited dataset(s) in your main manuscript file. The datasets will be listed and directly
accessible to readers next to your published article online.
For more information, visit the Mendeley Data for journals page.
Data in Brief
You have the option of converting any or all parts of your supplementary or additional raw data
into one or multiple data articles, a new kind of article that houses and describes your data.
Data articles ensure that your data is actively reviewed, curated, formatted, indexed, given a
DOI and publicly available to all upon publication. You are encouraged to submit your article
for Data in Brief as an additional item directly alongside the revised version of your manuscript.
If your research article is accepted, your data article will automatically be transferred over to
Data in Brief where it will be editorially reviewed and published in the open access data journal,
Data in Brief. Please note an open access fee of 500 USD is payable for publication in Data in
Brief. Full details can be found on the Data in Brief website. Please use this template to write
your Data in Brief.
MethodsX
You have the option of converting relevant protocols and methods into one or multiple
MethodsX articles, a new kind of article that describes the details of customized research
methods. Many researchers spend a significant amount of time on developing methods to fit
their specific needs or setting, but often without getting credit for this part of their work.
MethodsX, an open access journal, now publishes this information in order to make it
searchable, peer reviewed, citable and reproducible. Authors are encouraged to submit their
MethodsX article as an additional item directly alongside the revised version of their
manuscript. If your research article is accepted, your methods article will automatically be
transferred over to MethodsX where it will be editorially reviewed. Please note an open access
fee is payable for publication in MethodsX. Full details can be found on the MethodsX website.
Please use this template to prepare your MethodsX article.
Data statement
To foster transparency, we encourage you to state the availability of your data in your
submission. This may be a requirement of your funding body or institution. If your data is
unavailable to access or unsuitable to post, you will have the opportunity to indicate why during
the submission process, for example by stating that the research data is confidential. The
statement will appear with your published article on ScienceDirect. For more information, visit
the Data Statement page.
AFTER ACCEPTANCE
Online proof correction
Corresponding authors will receive an e-mail with a link to our online proofing system, allowing
annotation and correction of proofs online. The environment is similar to MS Word: in addition
to editing text, you can also comment on figures/tables and answer questions from the Copy
Editor. Web-based proofing provides a faster and less error-prone process by allowing you to
directly type your corrections, eliminating the potential introduction of errors.
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If preferred, you can still choose to annotate and upload your edits on the PDF version. All
instructions for proofing will be given in the e-mail we send to authors, including alternative
methods to the online version and PDF.
We will do everything possible to get your article published quickly and accurately. Please use
this proof only for checking the typesetting, editing, completeness and correctness of the text,
tables and figures. Significant changes to the article as accepted for publication will only be
considered at this stage with permission from the Editor. It is important to ensure that all
corrections are sent back to us in one communication. Please check carefully before replying,
as inclusion of any subsequent corrections cannot be guaranteed. Proofreading is solely your
responsibility.
Offprints
The corresponding author will, at no cost, receive a customized Share Link providing 50 days
free access to the final published version of the article on ScienceDirect. The Share Link can
be used for sharing the article via any communication channel, including email and social
media. For an extra charge, paper offprints can be ordered via the offprint order form which is
sent once the article is accepted for publication. Both corresponding and co-authors may order
offprints at any time via Elsevier's Webshop. Corresponding authors who have published their
article gold open access do not receive a Share Link as their final published version of the
article is available open access on ScienceDirect and can be shared through the article DOI
link.
AUTHOR INQUIRIES
Visit the Elsevier Support Center to find the answers you need. Here you will find everything
from Frequently Asked Questions to ways to get in touch.
You can also check the status of your submitted article or find out when your accepted article
will be published.
© Copyright 2018 Elsevier | https://www.elsevier.com
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CONCLUSÃO GERAL
O ouriço da castanha-do-brasil se mostrou eficiente como material precursor
para a produção de carvão ativado. O carvão ativado com vapor d’água à 800 °C
conferiu melhores resultados para a porcentagem de carbono fixo, o teor de água e
materiais voláteis, assim como demonstrou melhor desempenho na adsorção de 2,4-
D quando comparado ao carvão ativado com CO2.