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Biossorção de íons chumbo da solução aquosa por Sargassum

fi lipendula: Estudos de equilíbrio e cinética

Ayushi Verma, Shashi Kumar, Surendra Kumar *

Departamento de Químico Engenharia, Instituto Indiano de Tecnologia Roorkee, Roorkee, 247 667, Uttaranchal, Índia

ARTICLEINFO RESUMO

Artigo história:
Recebido 3 Agosto de 2016 Recebido em formulário revisado em 5 A remoção do Pb + 2 íons por Sargassum fi lipendula foi estudado usando o processo em lote. A caracterização biossorvente foi realizada pelas técnicas
de outubro de 2016 Aceito 23 October 2016 Disponível online xxx FESEM-EDX e FTIR. O projeto composto central foi usado para otimizar o Pb + 2 processo de biossorção de íons variando quatro parâmetros diferentes
do processo independente (temperatura, pH, dosagem de biossorvente e concentração inicial de Pb + 2 íons). A adequação do modelo da superfície de
resposta foi verificada por análise de variância (ANOVA). Os parâmetros ideais do processo para a remoção de Pb + 2 íons foram encontrados como
temperatura (34,8 C), pH (4,99), concentração inicial (152,10 mg / L) e dosagem de biossorvente (0,49 g / L) na qual foram alcançados 96% de remoção.
Palavras-chave: As capacidades preditivas de seis tipos de modelos cinéticos e seis tipos de modelos isotérmicos de adsorção foram examinadas S. fi lipendula. Para este
Biossorção Pesada metais Central projeto
estudo, o modelo isotérmico de Fritz e o modelo cinético de Bangham foram os melhores fi modelos modificados para a biossorção de Pb + 2 íons. Estudos
compósito Isotermas Cinética
de dessorção mostraram que após quatro ciclos consecutivos de biossorção-dessorção 77,53% e 90,84% de dessorção e biossorção ef fi foram
alcançadas, respectivamente. Os parâmetros termodinâmicos estudados mostraram que a biossorção de Pb + 2 íons em S. fi lipendula eram de natureza
viável, espontânea e endotérmica. Assim, tendo em vista as observações experimentais, pode-se concluir que S. fi lipendula pode ser usado como um ef fi biossorvente
eficiente para Pb + 2 biossorção de íons da solução aquosa.

uma 2016 Publicado por Elsevier Ltd.

1 Introdução
No recente anos, poluição causada por metais pesados ​é uma causa global problema devido à sua
toxicidade e bioacumulação na cadeia alimentar causando um sérios problemas de saúde e ecológicos [1]
. A maioria dos pesado metais liberados de várias indústrias são considerados não biodegradáveis, o
que pode causar fi perigo para o ser humano saúde. Entre metais pesados ​diferentes (como, Pb, Cr, Cu,
Co, Zn, Hg, e Ni) o chumbo é um metal altamente tóxico, mesmo em concentrações muito baixas;
chumbo causa danos cerebrais em crianças. O chumbo pode causar muitos efeitos na saúde humana,
como danos nos rins, cérebro, reprodutivos sistema, fígado e sistema nervoso central. Exposição
severa ao chumbo resulta em aborto, esterilidade, natimortos e neonatais mortes. Portanto, é importante
remover o chumbo de águas residuais e descargas.
No ef industrial fl como mostrado em tabela 1 , Pb + 2 concentração de íons abordagens para até
200 - 500 mg / l; esta concentração é muito alta em comparação com os padrões descritos por QUEM.
o limites máximos de descarga de íons de chumbo em
águas residuais é 0,05 mg / L e a pasta de esgoto aplicada às terras agrícolas é de 420 mg / L, conforme
definido pela Agência de Proteção Ambiental [8,9] . Assim, a concentração de íons de chumbo nas águas
residuais deve ser reduzida a um nível de 0,05 mg / L antes da descarga para corpos d'água
[10,11] . Existem vários métodos convencionais usados ​para a remoção de Pb + 2 íons de águas
residuais industriais. Esses métodos são troca iônica, precipitação, fi ltração, osmose reversa,
separação por membrana, evaporação, tratamento eletroquímico e adsorção por carvão ativado.
Mas esses métodos convencionais possuem várias desvantagens, pois são caros, ineficazes quando
o Pb + 2 estão presentes em baixa concentração e gera grande quantidade de resíduos secundários
(lodo) fi culto para tratar [12 - 15] . Em comparação com os métodos físico-químicos convencionais, a
biossorção é promissora para o Pb + 2 remoção de íons das águas residuais industriais devido ao seu
baixo custo, alta adsorção ef fi eficiência em baixo Pb + 2 concentração de íons, método livre de lodo
com ef fi ciência e af fi tempo de operação curto, possibilidade de recuperação de metais e
regeneração de biossorventes [16,17] . A biossorção envolve a captação passiva de Pb + 2 íons por
materiais biológicos inativos / mortos, como bactérias, fungos e algas. Os principais mecanismos
responsáveis ​pelo Pb + 2 A acumulação de íons por biossorventes envolve interações iônicas e
formação complexa entre

* Autor correspondente.
O email endereços: skumar.iitroorkee@gmail.com , skumar@iitr.ac.in (S. Kumar).

http://dx.doi.org/10.1016/j.jece.2016.10.026
2213-3437 / uma 2016 Publicado por Elsevier Ltd.

Cite este artigo no prelo como: A. Verma, et al., Biossorção de íons chumbo da solução aquosa por Sargassum fi lipendula: Equilíbrio e cinética estudos, J. Environ. Chem. Eng. (2016), http://dx.doi.org/10.1016/j.jece.201
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A. Verma et al. / Revista de Engenharia Química Ambiental xxx (2016) xxx - xxx

tabela 1
Nível de Pb + 2 íons em águas residuais de várias indústrias.

S. Não. Indústria Pb + 2 concentração de íons nas águas residuais (mg / L) Referência

11 Químico fábrica, Glubczyce (Polônia) 326,4 [2]

2 NM 200 - 500 [3]
3 Óleo 125 - 150 [4]
4 Bateria fábrica 5 - 15 [5]
5 Galvanoplastia 116,42 [6]
6 Planta industrial 19.1 [7]

NM: Não mencionado. 2

Pb + 2 íons e ligantes presente em superfície biossorvente. As algas marinhas estamos provou ser mais
eficaz para a atividade de ligação de metais devido a baixo custo, alta capacidade de biossorção de
metais e fontes renováveis natureza [18 - 20] . As algas marinhas, geralmente conhecidas como algas,
são abundantemente disponível em muitas partes do mundo e pode ser obtido economicamente do
oceano em larga escala
2.2 Técnicas de caracterização
Para determinar a morfologia da superfície do biossorvente e sua composição, foi utilizado o
instrumento analítico FESEM-EDX (FESEM QUANTA 200 FEG da FEI Netherland). O biossorvente
antes e depois da biossorção de Pb + 2 íons foram submetidos a análise pelo instrumento.

[21] . Eles podem ef fi remova cientificamente muito baixo concentração de Pb + 2

íons variando de poucas ppm a várias centenas de ppm [22] . Há três tipos de algas vermelhas (Rhodophyta), Espectros de FTIR para a forma bruta e tratados com chumbo S. fi lipendula

marrom (Phaeophyta) e verde (Clorofita). Entre elas, as algas marrons são mais eficientes fi suficiente foram obtidos pelo método de pellets KBr usando o espectrômetro infravermelho por transformada de
para biossorção de Pb + 2 íons devido ao seu polissacarídeo ácido conteúdo presente em sua parede Fourier (Thermo Scienti fi c, Índia), que foi usada para estudos espectrais de IV de biossorvente. Para
celular. A eficácia de biossorção para remover Pb + 2 íons depende do pH de a solução, ef fl uent composição,
esses estudos, a amostra seca foi misturada com KBr na proporção 1:10 e transformada em pellets para
biossorvente concentração, reação temperatura e cinética [23 - 25] . Comparado com diferentes tipos de algaobservar os grupos funcionais existentes no S. fi lipendula.
marinha, biossortivo desempenho mostrado por Sargassum

2.3 Preparação de solução metálica

gênero de a alga marrom provou ser a melhor devido à sua alta biossorção capacidade para Pb + 2 íons A solução estoque de 1000 mg / L foi preparada dissolvendo
em baixa concentração de equilíbrio [26] . este gênero de alga marrom é amplamente distribuído na 1,56 g Pb (NO 3) 2 em água deionizada. As soluções de teste de várias concentrações foram
maioria dos tropical países e é disponível em grandes quantidades como uma alga residual biomassa [27 preparadas diluindo a solução estoque. O pH inicial de Pb + 2 solução de íons foi controlada usando NaOH
- 30] . O principal constituintes de Sargassum sp. Castanho algas são alginato de polissacarídeos, 0,1 M e 0,1 M HNO 3)
geralmente alginatos de Ca e Na [31 - 33] . Assim, tem um alto efeito fi eficiência em acumular Pb + 2 íons
em comparação com algas de outros gêneros [34] . o a Principal O objetivo deste trabalho foi remover
íons de chumbo de solução utilizando a forma seca de algas marinhas mortas, S. 2.4 Experimentos de biossorção em lote

Todos os experimentos de biossorção em lotes foram conduzidos para observar os efeitos de

fi lipendula. o foram planejados experimentos de acordo com projeto de experimentos usando a
Metodologia da superfície de resposta (RSM). O efeito de temperatura, pH, Pb + inicial 2
íons concentração e dosagem de biossorvente. A isoterma e cinético modelos foram fi tted to dados
experimentais. Estudo termodinâmico (determinação de D G e D S ) foi realizada para julgar o viabilidade
do processo. O estudo de dessorção também foi feito para verificar o capacidade de regeneração do
biossorvente. Todos a resultados de biossorção capacidades de diferentes algas castanhas, isotermas, cinético
de biossorvente (0,2 - 0,5 g / L). Em todas as experiências, as amostras foram coletadas após um
e estudos termodinâmicos foram comparados com o resultados relatados na literatura para tornar o
presente estude completo.
vários parâmetros experimentais como temperatura, pH, Pb + inicial 2 concentração de íons, tempo de
biossorção e dosagem de biossorvente na remoção do chumbo. Os experimentos de biossorção
foram conduzidos em Erlenmeyer fl pede 250 mL por agitação especi fi quantidade reduzida de
biossorvente em 50 mL de solução de chumbo com diferentes parâmetros de processo por 85 min a
150 rpm em uma incubadora-agitadora (Metrex Scienti fi c Instruments Private Limited, Índia). A
otimização da biossorção de chumbo foi estudada variando parâmetros importantes da reação, como
pH (2,0 - 5.0), temperatura (25 - 35 C), Pb + inicial 2 concentração de íons (100 - 300 mg / L) e dosagem
intervalo de tempo regular. Para determinar a concentração de Pb + 2 íons na solução, a solução
tratada foi fi filtrado com Whatman No. 1 fi lter papel. o

2) Materiais e métodos fi O ltrato foi examinado quanto a Pb + residual 2 concentração de íons usando o espectrofotômetro de
absorção atômica com chama (GBC Avantha, Alemanha) e quanti fi contra uma solução padrão
2.1 Biomassa preparação conhecida de chumbo. Sempre que necessário, as amostras foram diluídas com água destilada para
melhorar a precisão da estimativa. Todas as experiências foram realizadas em triplicado e os
o seco forma de S. fi lipendula foi comprado de Aushadh Agri Ciência Privado Limited, Gujarat (Índia) resultados foram analisados ​estatisticamente. Os resultados foram expressos em termos de% de
a uma taxa de Rs 80 / kg seco peso o impurezas e íons como Ca + 2 ou Na + presente na superfície do biossorvente,
remoção de Pb + 2 íons, como indicado abaixo pela equação:% Removal = (( C o C e) / C o) 100
que pode afetar o processo de biossorção, foram removido por lavagem da biomassa com quantidade
abundante de desionizada água várias vezes. Depois disso, foi seco a 80 ° C por 24 h e mantido no exsicador.
A alga seca foi então moída em uma liquidificador. o alga aterrada foi peneirada através de 212 mm
(1)
peneira e a subdimensionar A fração assim obtida foi utilizada como biossorvente biossorção processo.
A capacidade de biossorção q e de um biossorvente é a quantidade de metal biossorvido por
unidade de quantidade de biossorvente (mg / g) em equilíbrio. Pode ser obtido usando a Eq. 2) :

q e = ( C o C e) V / m 2)

Por favor, cite isso artigo na imprensa como: A. Verma, et al., Biossorção de íons chumbo da solução aquosa por Sargassum fi lipendula: Equilíbrio e cinética estudos, J. Environ. Chem. Eng. (2016), http://dx.doi.org/10.1016
G Modelo
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A. Verma et al. / Revista de Engenharia Química Ambiental xxx (2016) xxx - xxx 3

o quantidade de Pb + biossorvido 2 iões por unidade de massa de biossorvente a qualquer Tempo t O total de 30 experimentos em lote (16 + 8 + 6) desenhados a partir do CCD foram realizados em
(q t mg / g) foi obtido usando a seguinte equação: triplicata com seis repetições dos pontos centrais e o valor médio foi relatado. O modelo CCD com a
resposta sob diferentes condições de operação é fornecido Tabela 3 . O delineamento experimental e
a análise dos dados foram realizados utilizando-se
q t = ( C o C t) V / m (3)

No Eqs. (1) - ( 3) C o é inicial concentração de iões metálicos, C e é equilíbrio concentração de íons " Especialista em Design " versão do software 9.0, Stat-Ease, Inc., Minneapolis, EUA).
metálicos e C t é a concentração de íons metálicos a qualquer momento t na solução (mg / L), V é o
volume da solução (L), m é massa de biossorvente (g). Para correlacionar as respostas com quatro variáveis ​independentes, foi utilizada uma equação
polinomial de segundo grau, dada abaixo:
o experimentos para estudo cinético de Pb + 2 biossorção de íons S.
fi lipendula estavam realizada a 35 ° C usando fi cinco concentrações iniciais diferentes de Pb + 2 íons: 100, Y ¼ boº Sk Eu ¼ 1 1 b Eu x Eu º S k Eu ¼ 1 1 b ii x Eu 2 º S k Eu ¼ 1 1 S kj>
kj> 1 1 b eu j x Eu x j
ð4º

150, 200, 250 e 300 mg / L. Em cada fl pedir, um fi xed quantidade de biossorvente (0,5 g / L) foi
Onde Y é a resposta prevista (variável dependente), b o é coefo constante fi cient, x Eu e x j são variáveis b Eu,
adicionado. O pH de solução foi ajustado em 5.0 adicionando NaOH 0,1 M ou 0,1 M HNO 3 Como necessário.
b ii e b eu j são coefas de interação fi clientes por termos lineares, quadráticos e de segunda ordem,
Após especi fi intervalo de tempo determinado, as amostras foram retiradas e fi filtrado imediatamente
respectivamente.
para interromper o processo de biossorção. o fi ltrate As amostras foram analisadas usando o AAS para
estimar a remanescente concentração de Pb + 2 íons na solução,
O valor ótimo das variáveis ​selecionadas foi alcançado através da resolução da equação de
regressão e da análise do gráfico de resposta 3D. A adequação de cada modelo foi verificada por
Análise de Variância (ANOVA) e a qualidade do modelo polinomial
C t.
No fim de determinar Pb + 2 íons isotermas de biossorção em diferentes temperaturas, experimentos
fi foi indicado pelo coeficiente de correlação fi suficiente ( R 2) [ 38. - 40] .
foram realizados em quatro diferentes temperaturas (20, 25, 30 e 35 C) variando a concentração inicial
de 100 a 300 mg / L com dosagem constante de biossorvente de 0,5 g / L. Estes dados experimentais
2.6 Método de dessorção / regeneração
com diferentes valores de

A reciclagem de biossorvente é um passo mais importante do ponto de vista econômico.

C e para cada corrida foi fi para seis modelos isotérmicos e parâmetros de modelo com o valor de R 2 foram
Portanto, o processo de biossorção-dessorção foi realizado até 4 ciclos, adicionando 0,5 g de Pb + 2 iões
obtidos usando a curva
carregados S.
fi tting ferramenta de MATLAB 2013 no Windows XP. O padrão normalizado desvio entre valores
fi lipendula em 50 mL de HCl 0,2 M para cada ciclo. Uma sequência de ciclo único compreende
experimentais e previstos para cada isoterma modelo era determinado á discriminar entre os
biossorção seguida de dessorção. Para reutilizar a biomassa para o próximo ciclo, a biomassa foi
concorrentes modelos.
lavada com Solução de HCl 0,2 M e água destilada, consecutivamente. A dessorção ef fi eficiência foi
dada pela seguinte equação:
o estudo termodinâmico foi realizado para avaliar a viabilidade do Pb + 2 íons biossorção em S. fi lipendula.
Para esse fim, o biossorção de Pb + 2 íons foram realizados em quatro diferentes temperaturas: 20 25,
30 e 35 C, mantendo todos os outros biossorção processo parâmetros constantes, como dosagem
Eficiência de dessorção ð% Þ ¼ Quantidade de íons metálicos dessorvidos
biossorvente (0,5 g / L), inicial concentração de Pb + 2 íons (150 mg / L) e pH (5.0) Quantidade de íons metálicos biossorvidos 100

ð5º

3 Resultados e discussão

2.5 Design experimental

3.1 Caracterização de S. fi lipendula

RSM é um bem conhecido técnica matemática usada para projetar o experimentos, desenvolver
3.1.1 FESEM - Análise EDX
modelos e avaliar os efeitos de variáveis ​em um variável de resposta de interesse. O objetivo é
Figura 1 ( a) mostra a forma bruta de S. fi lipendula antes da biossorção.
otimizar esse resposta e obter valores ótimos de variáveis [35] . A fim de projetar estatisticamente o experimentos
Figura 1 ( b) mostra que após a biossorção de Pb + 2 íons os poros e superfície de S. fi lipendula foram
e calcular o interativo efeitos de quatro parâmetros independentes (pH, temperatura, biossorvente dosagem
cobertos e a superfície ficou lisa. É evidente que a estrutura de S. fi lipendula mudou após a
e metal inicial concentração) para otimizar o biossorção de chumbo em S. fi lipendula, uma central
biossorção.
fatorial completa foi utilizado o projeto composto (CCD) com modelo quadrático

Análise EDX do biossorvente antes e após a biossorção de Pb + 2

íons con fi rms esta observação como mostrado em Figura 2 ( uma & b) Um pico de Pb + 2 íons foi notado
quando S. fi lipendula as amostras foram expostas ao Pb (NO 3) 2 solução. Alguns dos cátions inicialmente
[36] . No Em geral, o número total de execuções necessárias para o CCD é (2 k + 2 k + N 0), Onde k é o
presentes na matriz da parede celular foram substituídos por Pb + 2 íons e criou uma forte ligação
número de variáveis, 2 k são pontos fatoriais, 2 k estamos axial pontos e N 0 0 é o número de experimentos
cruzada. A imagem EDX mostra que o principal componente do S. fi lipendula
realizados no Centro [37] . Os níveis mais baixo e mais alto de quatro parâmetros são dados em mesa
2.
parede celular era C juntamente com pequenas quantidades de Mg, Na, S, Ca e K.

3.1.2 Análise FTIR

O estudo FTIR foi realizado para detectar os grupos funcionais presentes na superfície do

mesa 2 biossorvente e sua interação com os íons metálicos. Fig. 3 mostra os picos correspondentes aos
Alcance e nível da variáveis ​independentes. grupos funcionais de
S. fi lipendula biomassa antes e depois da biossorção de íons de chumbo.
Independente variáveis Faixa e níveis (codificados)
Quadro 4 mostra a mudança na frequência vibracional de grupos funcionais de S. fi lipendula após
uma 11 00 +1 + uma
biossorção de Pb + 2 íons.
Temperatura, C ( A) 20 25 30 35 40.
O pico de biossorção em 3407.9 cm 1 1 corresponde ao alongamento do grupo OH deslocado
Inicial concentração, mg / L ( B) 75 150 225 300 375
para 3405.9 cm 1 2925,35 cm 1 1 corresponde ao alongamento de
Biossorvente Dosagem, g / L ( C) 0,05 0,2 0,35 0,5 0,65
O grupo OH e o grupo CH passaram para
pH ( D) 2 3 4 5 6
2924,3 cm 1 1633.89 cm 1 1 corresponde ao alongamento de C¼C

Cite este artigo no prelo como: A. Verma, et al., Biossorção de íons chumbo da solução aquosa por Sargassum fi lipendula: Equilíbrio e cinética estudos, J. Environ. Chem. Eng. (2016), http://dx.doi.org/10.1016/j.jece.201
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JECE 1306 No. of Pages 13

4 A. Verma et al. / Journal of Environmental Chemical Engineering xxx (2016) xxx – xxx

Tabela 3

Experimental design baseado no CCD e sua resposta para Pb + 2 remoção de íons.

Corre Temperatura ( C) Concentração inicial (mg / L) Dosagem de biossorvente (g / L) pH Remoção (%)

Experimental Predicted

1 25 150 0.2 3 33.98 33.33

2 35 150 0.2 3 41.64 43.85
3 25 300 0.2 3 16.48 17.78
4 35 300 0.2 3 34.9 29.46
5 25 150 0.5 3 61.84 64.47
6 35 150 0.5 3 78.56 80.65
7 25 300 0.5 3 33.67 36.00
8 35 300 0.5 3 54.17 53.33
9 25 150 0.2 5 42.68 45.58
10 35 150 0.2 5 57.33 52.83
11 25 300 0.2 5 29.26 25.00
12 35 300 0.2 5 33.97 33.40
13 25 150 0.5 5 80.59 83.85
14 35 150 0.5 5 96.50 96.76
15 35 300 0.5 5 50.49 50.34
16 35 300 0.5 5 65.94 64.41
17 20 225 0.35 4 40.96 37.22
18 40 225 0.35 4 57.95 61.80
19 30 75 0.35 4 92.34 87.93
20 30 375 0.35 4 35.50 40.03
21 30 225 0.05 4 12.78 17.23
22 30 225 0.65 4 83.71 79.38
23 30 225 0.35 2 31.18 29.31
24 30 225 0.35 6 50.64 52.63
25 30 225 0.35 4 53.53 53.21
26 30 225 0.35 4 51.53 53.21
27 30 225 0.35 4 54.53 53.21
28 30 225 0.35 4 53.59 53.21
29 30 225 0.35 4 52.53 53.21
30 30 225 0.35 4 53.53 53.21

Fig. 1. FESEM images for Pb+ 2 ions biosorption on S. fi lipendula ( a) Before biosorption (b) After biosorption.

grupo mudou para 1628.96 cm 1 1426,39 cm 1 1 corresponde ao grupo CH alongamento e C ¼ A flexão do

grupo C mudou para 1417,63 cm 1 1
3.2 Efeito do tempo de contato

e 606,88 cm 1 1 corresponde a O grupo C Cl mudou para

622,57 cm 1 o picos em 1245.13 cm 1 1 e 1048.13 cm 1 1 Observou-se experimentalmente que a taxa de biossorção inicial era muito alta e a remoção de
corresponde a CO grupos alongamento são deslocados para 80% ef fi eficiência foi alcançada em 15 minutos iniciais. Posteriormente, a taxa de biossorção foi
1250.90 cm 1 1 e 1049,47 cm 1 O novo pico em 3140.54 cm 1 1 gradualmente diminuída com o tempo até atingir o equilíbrio ( Fig. 4 ) É devido ao fato de que
corresponde a Grupo OH alongamento aparece. A mudança na vibração frequência de grupos inicialmente havia uma grande área superficial do biossorvente disponível para a biossorção de íons
funcionais após biossorção de Pb + 2
metálicos, mas após um certo período de tempo, a acessibilidade dos locais ativos na superfície do
íons mostra que esses grupos estão envolvidos no processo de biossorção biossorvente diminui, o que diminui a taxa de biossorção [13] . O equilíbrio
[41] .

Please cite this article in press as: A. Verma, et al., Biosorption of lead ions from the aqueous solution by Sargassum fi lipendula: Equilibrium and kinetic studies, J. Environ. Chem. Eng. (2016), http://dx.doi.org/10.1016/j.jece
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JECE 1306 No. of Pages 13

A. Verma et al. / Journal of Environmental Chemical Engineering xxx (2016) xxx – xxx 5

Fig. 2. EDX images for Pb+ 2 ions biosorption on S. fi lipendula ( a) Before biosorption (b) After biosorption.

time for Pb+ 2 ions biosorption onto S. fi lipendula was 40 min at which 96.54% removal ef fi ciency of Pb+ 2
ions was achieved.
0.6 Before biosorption
After biosorption
3.3. Experimental design and factorial model for Pb+ 2 ions biosorption process
0.5

0.4
In the experimental design, the selected range and level of variables were selected on the basis
Absorbance

of literature reported for Pb+ 2

0.3
ions biosorption by other brown algae. The optimized conditions of higher biosorption ef fi ciency for
Pb+ 2 ions were analyzed by using CCD under RSM. The matrix of four variables pH,
0.2
initial
concentration, biosorbent dosage, and temperature of Pb+ 2 ions were varied at 5 levels (-2, 1, 0, +1, +2).
0.1
The higher and lower levels of variables were symbolized as ‘+’ and ‘-’, respectively. Removal ef fi ciency
(%) of Pb+ 2 ions obtained from the experiments at the end of equilibrium time for each experiment is
0.0
4000 3500 3000 2500 2000 1500 1000 500 presented in

Wavenumber (cm- 1 )
Table 3 . The mathematical expression of relationship of four independent variables with response is
Fig. 3. FTIR image of S. fi lipendula surface before and after biosorption of Pb+ 2 ions. given as:

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Table 4
IR vibration wavenumber and functional groups observed on untreated and Pb+ 2 ions treated S. fi lipendula biomass.

Wavenumber (cm 1) Functional groups

Unloaded biomass Metal ion loaded biomass

3407.9 3407.15 OH stretching

– 3140.54 OH stretching
2925.35 2924.43 CH & OH stretching
1633.89 1628.96 C ¼ C stretching
1426.39 1417.63 C H stretching & C ¼ C bending
1245.13 1250.9 C O stretching
1048.13 1049.47 C O stretching
606.88 622.57 C Cl stretching

biosorbent dosage and pH, temperature and pH, respectively. The six runs were replicated for central

120 point.
The statistical signi fi cance and interaction of factors are determined by ANOVA. Table 5 shows
100 the regression coef fi cient and analysis of variance of second-order polynomial models. The

80
p-value ( P < 0.0001) and F-value ( 53.94) shows that the model is signi fi cant. The “ Lack of fi t F-value ” of 21.36

60 shows that Lack of fi t is signi fi cant. A low value of coef fi cient of variance (CV) 7.73 indicates that the
% Removal

deviation between experimental and predicted values is low. The goodness of fi t of the model is tested
40 by coef fi cient of determination ( R 2). The R 2 value close to 1.0 show that the model is more signi fi cant.
For this model R 2 value is found to be 0.98 which shows that more than 98% of the experimental data
20
are compatible with predicted data. The value of predicted R 2 ( 0.88) is in reasonable agreement with adjusted

0 R 2 value (0.96). Adequate precision

0 20 40 60 80 100
Time (min)

Fig. 4. Effect of contact time on biosorption of Pb+ 2 ions by S. fi lipendula ( pH 5.0, temperature 35 C, biosorbent dosage of 0.5measures the ratio of signal to noise. A ratio greater than 4 is desirable [42] . In this work, the ratio was 28.41
g/L, initial concentration of Pb+ 2 ions 150 mg/L).
which indicate an adequate signal. The value of Prob. > F less than 0.050 indicates that the model terms
are signi fi cant. Here, for biosorption of Pb+ 2 ions A,

Y = + 53.21 + 6.15A 11.98B + 15.54C + 5.83D + 0.29AB + 1.42AC 0.82 AD 3.23BC 1.26BD + 1.78CD 0.92A 2 + 2.69B
B, C, D, B 2, D 2 and BC were signi fi cant model terms. The p-value
2 1.23C 2 3.06 D 2
greater than 0.10 shows that model terms A 2, C 2, AB, AC, AD and BD
(6)
are not signi fi cant. Fig. 5 shows that the predicted response values of reduced quadratic model are
where Y is percent removal of Pb+ 2 ions and A, B, C and D are coded values of temperature ( C), initial concentration
well in agreement with actual ones in the range of operating variables. The 3D graphs for Pb+ 2 ions
(mg/L) of Pb+ 2
removal ef fi ciency are presented in Fig. 6 . The pH of the solution plays a signi fi cant role in the
ions, biosorbent dosage (g/L), and pH, respectively. A 2, B 2, C 2 and D 2 protonation of functional group present on biosorbent surface. Fig. 6 ( a) illustrates the effect of pH on
are the measure of main effect of variables such as temperature ( C), initial concentration (mg/L) of Pb+ 2 ions,
removal ef fi ciency of Pb+ 2 ions. It is noticed that removal ef fi ciency of Pb+ 2 ions increases with the
biosorbent dosage (g/ increase in pH from 3 to 5. At low pH, the biomass surface becomes positively charged due to
L), and pH, respectively. Whereas, AB, BC, CD and AD represent interaction effect of temperature and
initial concentration of Pb+ 2

ions, initial concentration of Pb+ 2 ions and biosorbent dosage,

Table 5
ANOVA results for response surface quadratic model.

Source Sum of square df Mean square F value p-value Remarks

Model 11832.02 14 845.14 53.94 < 0.0001 Signi fi cant

A- Temperature 906.51 1 906.51 57.86 < 0.0001 Signi fi cant
B- Initial concentration 3442.09 1 3442.09 219.69 < 0.0001 Signi fi cant
C- Dosage 5793.31 1 5793.31 369.76 < 0.0001 Signi fi cant
D- pH 815.97 1 815.97 52.08 < 0.0001 Signi fi cant
AB 1.35 1 1.35 0.086 0.7735
AC 32.04 1 32.04 2.04 0.1732
AD 10.69 1 10.69 0.68 0.4217
BC 167.06 1 167.06 10.66 0.0052 Signi fi cant
BD 25.35 1 25.35 1.62 0.2227
CD 50.91 1 50.91 3.25 0.0916
A2 23.39 1 23.39 1.49 0.2406
B2 198.88 1 198.88 12.69 0.0028 Signi fi cant
C2 41.23 1 41.23 2.63 0.1256
D2 256.8 1 256.8 16.39 0.0011 Signi fi cant
Residual 235.02 15 15.67
Lack of fi t 229.64 10 22.96 21.36 0.0017 Signi fi cant
Pure error 5.38 5 1.08
Total 12067.03 29

R 2 = 0.9805; Adjusted R 2 = 0.9623; Predicted R 2 = 0.8897; Adequate precision = 28.415. 6

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positively charged metal ions. At pH greater than 5, precipitation of Pb+ 2 ions occurs as lead
120
hydroxides [43] . The biosorbent dosage has a great impact on biosorption process at a speci fi ed

100 initial metal ions concentration. The effect of biomass dosage on removal ef fi ciency of Pb+ 2 ions has
been studied by changing biosorbent dosage from 0.2 to 0.5 g/L and the results are presented in Fig. 6 (
80 a). It is observed that Pb+ 2 ions removal ef fi ciency increases with increase in dosage of S. fi lipendula. This
Predicted removal (%)

trend is due to the availability of more active sites available on S.

60

40

20 fi lipendula surface [45] . The effect of initial concentration on Pb+ 2 ions removal ef fi ciency has been
studied in the range 150 – 300 mg/L. The results are shown in Fig. 6 ( b). The removal ef fi ciency of Pb+ 2 ions
0 decreases on increasing the initial concentration of Pb+ 2 ions. It could be possible that all biosorbents
0 20 40 60 80 100 120
have certain number of active binding sites which are accessible for binding of metal ions at low initial
Actual removal (%)
concentration while at high initial concentration the binding sites become saturated [46] .

Fig. 5. Correlation of actual versus predicted removal of Pb+ 2 ions by S. fi lipendula.

which repulsion for binding of metal ions occurs [43,44] . With rise in pH of the solution, the concentration
of H+ ions decreases and negatively charged ligands like phosphate, carboxyl, and amino groups present Fig. 6 ( c) illustrates the effect of temperature on Pb+ 2 ions removal ef fi ciency. It has been noticed
on biomass surface is exposed because of deprotonation of metal binding sites which can interact with that there is an increase in removal ef fi ciency of Pb+ 2 ions with rise in temperature from 25 to 35 C
indicating that the reaction for Pb+ 2 ions biosorption is

100 100

60 80
Removal (%)

60 80
Removal (%)

20 40 20 40

0 0

5 0.5 5 300
0.44 270
4.5 4.5
0.38 240
4 4
0.32 210
3.5 3.5
pH 0.26 Biosorbent dosage (g/L) pH 180 Initial concentration (mg/L)
3 0.2 3 150

(c) (d)

34.8529 25 35 152.107 150 300

A:Temperature = B:initial concentration =

100

60 80
Removal (%)

20 40 0.2 0.5 4.99992 3 5

0 C:dosage = 0.499904 D:pH =

Desirability = 1.000
5 35

33
4.5
31
4 12.78 96
29
3.5
pH 27 Temperature (degree celsius)
3 25 removal = 96.0077

Fig. 6. ( a) Interactive effect of pH and biosorbent dosage (b) Interactive effect of pH and initial concentration of Pb+ 2 ions (c) Interactive effect of pH and temperature (d) Desirability ramp for numerical optimization of four independent variables and
the responses.

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endothermic in nature. On increasing temperature, the thickness of layer that surrounds the biosorbent 3.5.3. Elovich model
decreases. This results in the decrease of external layer resistance. Micro-pores become widen and deepen This model is expressed as follows [51] :
which provide more surface area for biosorption and the increased availability of active sites in the
dq t
biosorbent [47] . ð Þ ð 13 Þ
dt ¼ a exp b q t

Simplifying Eq. (13) in form of Eq. (14) by considering ab >> 1 and with initial conditions t = 0, q t = 0; t = t, q t
3.4. Optimization using the desirability function = q t one obtains [52] :

To obtain the maximum point for desirability function, numerical optimization was done by fi xing the qt¼ 1 ð Þþ1 ðÞ ð 14 Þ
b ln ab b ln t
values of reaction parameters within their ranges and maximizing the removal ef fi ciency of Pb+ 2 ions [38]
. It can be seen in Fig. 6 ( d), that the best local maximum value is noticed at initial solution pH of 4.99, where both a and b are constants and their values are determined from the linear plot of q t vs. ln t. The
temperature of 34.85 C, constant a ( mg/g. min) indicates initial rate of biosorption, b ( g/mg) is associated with the extent of
surface coverage and activation energy for chemisorption and q t ( mg/g) is amount of Pb+ 2 ions
initial Pb+ 2 ion concentration of biosorbed at time t ( min).
152.10 mg/L, and biosorbent dosage of 0.5 g/L. In this condition, Pb+ 2 ions removal ef fi ciency and the desirability
value are found to be 96.0% and 1.0, respectively. This optimum condition has been tested experimentally
and results reveal that removal ef fi ciency is
3.5.4. Bangham model (Pore diffusion model)
96.5%. The high degree of agreement between the predicted optimum conditions and repeated experimental Bangham model was used to determine whether the biosorption of Pb+ 2 ions on S. fi lipendula is
results shows that RSM can be used as an ef fi cient and reliable tool to evaluate and optimize the effects pore diffusion or not. The equation for this model is given below:
of biosorption parameters on Pb+ 2 ions removal ef fi ciency using S. fi lipendula.

Co
ln ln ð 15 Þ
C o q t m ¼ ln k o m Vþ a o ln ð t Þ

3.5. Biosorption kinetics where a o (< 1) and k o are constants which are calculated from the intercept
and slope of the straight line plot of
h i vs: l n ð t Þ [ 53] .
The biosorption mechanism and rate controlling step are investigated by using six kinetic models
ln ln C o Co qt m
as discussed below:

3.5.5. Intraparticle diffusion model

3.5.1. Pseudo fi rst order
In intraparticle diffusion there is a migration of Pb+ 2 ions from liquid phase to the solid phase.
This model is expressed as follows [48 – 50] :
According to Weber and Morris theory, equation for this model is given below [53,54] :

dq t
ð Þ ð7Þ
dt ¼ k 1 q e q t
q t = K id t 0.5+ C (16)
Integration of Eq. (7) with initial conditions, t = 0, q t = 0; t = t, q t = q t
where C is constant, K id is intraparticle diffusion rate constant (mg/ g min 0.5). If the plot of q t vs. t 0.5 shows
gives:
a linear relationship then biosorption process involves the intraparticle diffusion. In intraparticle
ln qðe q t Þ ¼ ln q e k 1: t ð8Þ diffusion the uptake is proportional to t 0.5 instead of time t.

The values of K id and C are obtained from the slope and intercept of plot q t vs. t 0.5, respectively. The value
of intercept C is proportional to boundary layer thickness. It implies that larger the intercept more will be
ln q e q t ¼ k 1: t ð9Þ
qe the boundary layer effect. The value of C equal to zero shows that the intraparticle diffusion is the rate
controlling step.
where k 1 ( min 1) is pseudo fi rst order biosorption rate constant. The value of k 1 is calculated from the slope
of plot of ln q e q t vs: t:
qe

3.5.2. Pseudo second order 3.5.6. Modi fi ed freundlich model

This model is expressed as follows [49,50] : Kuo and Lotse [53,55] developed the Modi fi ed Freundlich equation for kinetics of biosorption. This
model is expressed as follows:
dq t
ð Þ2 ð 10 Þ
dt ¼ k 2 q e q t

Integration of Eq. (10) with initial conditions, t = 0, q t = 0; t = t, q t = q t q t ¼ k 3ðC o Þt1

m1
ð 17 Þ

gives:

t
¼1 þ1 t ð 11 Þ
qt k2q2e qe lnq t ¼ lnk 3 C o þ 1 ðÞ ð 18 Þ
m 1 ln t

where k 3 is uptake rate constant (L/g min), t is contact time (min),

1 m 1 is Kuo-Lotse constant. The values of k 3 and m 1 are used to fi nd out the effect of ionic strength and
ð1 Þ q2e¼ 1 ð 12 Þ
qt qe k2 t surface loading in biosorption process.

where k 2 ( g/mg min) is pseudo second order biosorption rate constant. The value of k 2 is evaluated from The best fi tted kinetic model is chosen on the basis of correlation coef fi cient ( R 2) and normalized
the slope of plot of standard deviation
1
ð q1t qe Þ vs: 1 t :

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( D q%) estimated according to Eq. (19) . Normalized standard deviation at a constant temperature, there is no contact between the biosorbed molecules and all vacant sites
on biosorbent surface, and all active sites are of same intensity [56,57,60] . The Langmuir isotherm
ð D q% Þ
vuut ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi model equation is as follows:

X ½ q e ð exp Þ q e ðpred Þ= q e ð exp Þ 2

¼ 100 ð 19 Þ
N
q e ¼ q o bC e ð 20 Þ
1 þ bC e
In Eq. (19) , q e ð exp Þ is the experimental q e and q e pred ð Þ is the
corresponding predicted q e according to the equation under study with the best fi tted parameters, N is the where q o ( mg/g) is maximum biosorption capacity i.e. the maximum amount of Pb+ 2 ions biosorbed per
number of measurements. Lower the values of D q%, the better are the fi t of experimental data. The values gram of S. fi lipendula
of parameters, R 2 and D q% for all the kinetic models are evaluated and given in Table 6 (values for to form a complete monolayer on surface, b ( L/mg) is biosorption equilibrium constant.
Pseudo fi rst order and Pseudo second order have not been mentioned as their R 2 values are very much lower).
The R 2 values for Bangham, Elovich, Modi fi ed Freundlich, and Intra particle diffusion models are
greater than 0.90 while the value of normalized standard deviation ( D q%) is low (1.36) in case of
Bangham model in comparison to other kinetic models ( Table 6 ). According to these results, it can be 3.6.2. Freundlich isotherm

concluded that Bangham model gives a good correlation for Pb+ 2 This model is applicable to multilayer biosorption of Pb+ 2 ions on a heterogeneous surface [57,61] .
The equation for this model is given below:

q e ¼ k f C 1= ne ð 21 Þ

ions biosorption on S. fi lipendula. where k f and n are Freundlich constants which represent the biosorption capacity and biosorption
intensity, respectively [62] . According to this model, the value of 1/n should lie between 0 and 1 for good
3.6. Biosorption isotherm model study biosorption. The limitation of this isotherm model is that it does not obey Henry ’ s law at low
concentration and doesn ’ t reach a maximum biosorption at high concentration.
Biosorption isotherm describes the relationship between amount of biosorbate biosorbed per unit

mass of biosorbent q e
(mg/g) at equilibrium and biosorbate concentration in the bulk phase at equilibrium C e ( mg/L). Biosorption
isotherm gives the evidence about biosorption capacity of biosorbent or amount of biosorbent required 3.6.3. Redlich-Peterson isotherm
to adsorb a unit mass of biosorbate [61] . The experimental data are assessed using six different This model involves the features of both Langmuir and Freundlich isotherm equations [57,61] .
isotherm models namely Langmuir, Freundlich, Radke-Prausnitz, RedlichPeterson, Fritz and Toth isotherm The equation for this model is given below:
models. Out of these isotherms, Langmuir and Freundlich both are two parameter models,
RadkePrausnitz, Toth, and Redlich-Peterson are three parameter models, and Fritz is four parameter
model. qe¼ K1 Ce ð 22 Þ
1 þ K 2 C be

where K 1 and K 2 are Redlich-Peterson isotherm constants and b is Redlich-Peterson isotherm exponent
which lies between 0 and 1.
For b = 1 this model is converted to Langmuir isotherm, for K 2
3.6.1. Langmuir isotherm C eb >> 1, it becomes Freundlich isotherm, and for K 2 C eb<< 1 it obeys Henry ’ s law.
This model relies on the assumptions that a monolayer of biosorbate is biosorbed above homogenous
surface of biosorbent

Table 6
Kinetic models parameter for Pb+ 2 ion biosorption using S. fi lipendula.

Kinetic model Parameters Initial concentration (mg/L) D q%

100 150 200 250 300

Elovich q e ( mg/g) 198 289.22 336.32 363.78 393.6 1.94

q t ( mg/g) 200.789 297.903 330.11 371.584 393.675
a 1.628 10 5 8.364 10 3 1.86 10 4 2.297 10 3 6.24 10 2
b 0.067 0.033 0.0324 0.022 0.0169
R2 0.98 0.92 0.94 0.95 0.95

Bangham q e ( mg/g) 198 289.22 336.32 363.78 393.6 1.36

q t ( mg/g) 196.831 291.083 329.069 370.407 396.725
ao 0.355 0.3792 0.219 0.2491 0.289
ko 89.32 68.392 67.139 46.06 31.04
R2 0.94 0.90 0.93 0.95 0.968

Intraparticle diffusion model q e ( mg/g) 198 289.22 336.32 363.78 393.6 5.72
q t ( mg/g) 206.093 309.757 344.461 389.363 418.86
K id ( mg min 0.5/ g) 6.73 13.96 14.92 21.24 27.96
C 147.81 188.86 215.25 205.42 176.72
R2 0.90 0.89 0.98 0.94 0.95

Modi fi ed Freundlich q e ( mg/g) 198 289.22 336.32 363.78 393.6 2.79

q t ( mg/g) 201.995 300.78 331.897 375.72 403.58
k3 1.403 1.190 1.037 0.781 0.566
m1 11.862 8.825 9.182 6.605 4.995
R2 0.98 0.93 0.95 0.96 0.97

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3.6.4. Radke-Prausnitz isotherm

450
This model equation is expressed as follows:
400

350
q e ¼ q o KC e ð 23 Þ
1 þ q o C ae 300 Langmuir Freundlich

250 Radke-Prausnitz

where q o is Radke-Prausnitz maximum biosorption capacities (mg/ Redlich-Peterson Toth

q e ( mg/g)
200
g), K is Radke-Prausnitz equilibrium constant and a is RadkePrausnitz model exponent. At low concentration, Fritz Experimental
150
Radke- Prausnitz isotherm reduces to a linear isotherm and at high concentration it changes to Freundlich
100
isotherm [61] .
50

0
0 20 40 60 80 100 120
3.6.5. Toth isotherm C e ( mg/L)
This model is the modi fi ed form of Langmuir isotherm which is applicable to heterogenous biosorption
Fig. 7. Comparison of different isotherm models for biosorption of Pb+ 2 ions on S.
[57] . This isotherm follows Henry ’ s law at low Pb+ 2 ions concentration. The Toth isotherm equation is expressed
fi lipendula.
as follows:

qe¼ q1eCe ð 24 Þ where a 1 and a 2 are Fritz parameters, b 1 and b 2 are Fritz equation exponents. Fritz isotherm has higher
1= n 1
a þ C n1e degree of fl exibility to fi t the experimental data as it contains more parameters than any other equation
isotherm. Therefore, Fritz isotherm described the high level of accuracy and able to fi t experimental
where a ( mg/L) is Toth isotherm constant and n 1 is dimensionless constant generally n 1< 1.
data over a wide range of concentration. Fritz isotherm is a hybrid of Langmuir and Freundlich
isotherms. It contains the heterogeneity factor ( b 1 and

3.6.6. Fritz isotherm

This model equation is expressed as follows [57] :
b 2) that report for the biosorbent heterogeneity and show a high level of irreversibility which
characterizes diffusion in the micropores [58,59] . The value of parameters for each isotherm model
q e ¼ a 1 C b1
e
ð 25 Þ
with their correlation coef fi cient ( R 2) and normalized standard deviation ( D q %) are shown in Table 7 . Fig.
1 þ a 2 C b2e
7 shows the comparison of different isotherm models with experimental results. The shape of isotherm
models can be used to fi nd out favorable biosorption system. For Fritz model, the value of R 2 is greater
than 0.99 and D q% is very small for all the temperatures. This shows that Fritz model is the best fi tted
isotherm model for Pb+ 2 ions biosorption on S.

Table 7
Isotherm model constants for Pb+ 2 ions biosorption onto S. fi lipendula at different temperatures.

Isotherm model Parameters Temperature ( C) fi lipendula.

20 25 30 35

Langmuir qo 455.68 427.635 376.907 367.942

3.7. Thermodynamic study
b 0.021 0.0412 0.178 1.024
R2 0.983 0.986 0.979 0.923 The nature of biosorption process and feasibility, are assessed by thermodynamic study. The
D q% 4.466 3.794 2.209 5.89
equilibrium constant changes with temperature on the basis of which Gibbs free energy change ( D G ),
Freundlich kf 43.023 75.308 152.69 215.342
n 2.339 3.033 5.245 7.720 entropy change ( D S ) and enthalpy change ( D H ) are estimated. The biosorption of Pb+ 2 ions is a
R2 0.957 0.929 0.929 0.96 reversible process, which represents a heterogenous equilibrium. Pb+ 2 ( solution) + biosorbent $ Pb
D q% 7.5 8.542 5.574 5.396
biosorbent

Radke- Prausnitz q 0.009 0.013 0.247 3.139 (26)

K 912.914 1051.8 318.721 263.832
a 1.133 1.179 0.963 0.918
R2 0.984 0.994 0.996 0.988
D q% 3.91 2.202 2.334 2.168

Redlich- Peterson K 1 8.589 13.645 78.726 828.258

K2 0.009 0.013 0.247 3.139
295 300 305 310
b 1.138 1.179 0.963 0.918 - 1 0 290
R2 0.984 0.994 0.996 0.988
-2
D q% 3.91 2.177 2.334 2.168
-3
Toth qe 385.889 368.906 384.317 473.129
Δ G ° (kJ/mol)

-4
a 329.596 385.194 4.176 0.314
n1 1.478 1.724 0.901 0.321 -5
y = -0.443x + 128.34
R2 0.985 0.996 0.996 0.981
-6 R² = 0.9771
D q% 3.58 1.531 2.312 2.89
-7
Fritz a1 69.8132 176.738 2.297 242.445
-8
a2 1.1448 10 6 331.774 0.011 0.2245
b1 0.322 0.145 0.3270 0.100 -9

b2 4.733 2.210 3.145 13.896 Temperature (K)

R2 0.996 0.999 0.999 0.994
D q% 2.10 0.442 0.732 1.505 Fig. 8. Plot of D G vs. T for the estimation of thermodynamic parameters for biosorption of Pb+ 2 ions by S. fi lipendula.

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Table 8
Comparison of thermodynamic parameters for Pb+ 2 ions adsorption with different adsorbents.

Adsorbent T ( C) D G0 D H0 D S0 Reference
(kJ/mol) (kJ/mol) (J/mol.K)

Solanum melongena 30, 40, 50 8.74 to 7.98 3.698 0.039 [64]

Peanut shells 20, 30, 40 24.25 to 25.00 16.68 25.16 [4]
Sargassum ilicifolium 20, 25, 30 2.6 to 3.6 0.027 0.102 [65]
Cucumis melo 20, 30, 40 23.22 to 29.97 75.67 337 [66]
Caulerpa 20, 30, 40 17.9 to 19.7 8.28 0.0893 [67]
lentillifera
Rice husk ash 25, 40, 50, 75 17.24 to 18.15 11.82 18.26 [68]
Olive tree pruning waste 25, 40, 60 23.46 to 23.84 19.8 11.34 [69]
Sargassum fi lipendula 20, 25, 30, 35 1.75 to 8.52 0.128 0.443 This study

Thermodynamic constants were evaluated by the following equations: 3.8. Desorption and reuse ef fi ciency

Four consecutive cycles of biosorption and desorption of Pb+ 2

D G 0 = - RT ln K e (27)
ions were carried out in a batch system to fi nd the reusability of S.
fi lipendula for Pb+ 2 ions biosorption ( Fig. 9 ). After four cycles, the biosorption and desorption of Pb+ 2 ions
was decreased by 5.7% and
D G0= D H0 T D S0 (28)
15.68%, respectively. Hence, S. fi lipendula has shown the better reusability during four consecutive

where K e is equilibrium constant, calculated as ratio of equilibrium metal concentration on the cycles of biosorption and desorption for Pb+ 2 ions. The results indicate that S. fi lipendula can be reused

biosorbent surface, C a in Pb+ 2 ions biosorption studies without any signi fi cant loss of their biosorption capacities.

and in the solution C e ( K e = C a/ C e), R is universal gas constant (8.314 10 3 kJ/mol K) and T is temperature in
Kelvin. From Fig. 8

the values of D H 0 ( 128.34 kJ/mol) and D S 0 ( 0.443 J/mol K) are evaluated from intercept and slope of a
plot of D G 0 vs. T according to Eq. (26) . The evaluated thermodynamic parameters are listed in 3.9. Comparison with other seaweeds

A comparative table ( Table 9 ) on the basis of brief review of different kinetic models, isotherm
Table 8 . The positive value of D H 0 indicates endothermic nature of physical biosorption [63] . It is evident
that the extent of metal ion biosorption increases with the increase in the temperature of process. The negative models, and uptake capacity of brown algae for Pb+ 2 ions is presented. The removal ef fi ciency of

value of D G 0 shows the feasibility and spontaneous nature of biosorption [49,60] . Few reported results different biosorbents for Pb+ 2 ions varies due to different properties of adsorbents like structural,

in the literature on thermodynamic study for other adsorbent – Pb+ 2 functional groups, and surface area. In addition to these properties, the degree of biosorption can also
be affected by reaction parameters like temperature, pH, and presence of other competing cations.
The amount of metal ions that binds on biomass surface depends on the number of active binding
sites present [71] . The value of biosorption capacity for Pb+ 2 ions in this work is signi fi cantly greater
ions systems are listed in Table 8 . It can be clearly observed from this table that the temperature for
than ( ffi 285 mg/g) other reported biosorbents. Thus, S.
every system favors the extent of adsorption as D G 0 tends to become more negative. The increase in biosorption
with temperature can be either due to increase in the number of metal binding sites which are accessible
for biosorption on surface of biosorbent or due to decrease in boundary layer thickness surrounding the
biosorbent, which intern reduces the mass transfer resistance of biosorbate [70] . The positive values of D
S 0 indicate the enhancement in randomness of biosorbed species at solid and liquid interface with
fi lipendula can be used as an ef fi cient biosorbent for Pb+ 2 ions uptake.
progress of biosorption.

4. Conclusions

A batch experimental study for the biosorptive removal of Pb+ 2

ions on S. fi lipendula algae has been presented. The RSM has been used to obtain the optimum
conditions for biosorption of Pb+ 2 ions from the aqueous solution by S. fi lipendula. The optimum
parameters for biosorption have been obtained as pH (4.99), temperature (34.8 C), initial
concentration of Pb+ 2 ions (152 mg/L), and biosorbent dosage (0.49 g/L) at which 96% removal ef fi ciency

120
has been achieved. The removal ef fi ciency of Pb+ 2 ions is increased with increasing biosorbent
dosage and reaction temperature while decreased with rise in initial concentration of Pb+ 2 ions. The
100
Desorption efficiency Adsorption efficiency percentage of Pb+ 2 ions removal is decreased at both low and high pH. Therefore, further biosorption
studies have been performed at pH of 5. The biosorption experimental data of Pb+ 2 ions removal using S.
80
fi lipendula have been very well fi tted with Fritz isotherm and Bangham kinetic model. Thermodynamic
% Efficiency

studies has shown that the reaction for biosorption of Pb+ 2 ions is spontaneous, feasible and
60
endothermic in nature. After four consecutive cycles of biosorption- desorption, 77.53% of Pb+ 2 ions

40 has been recovered. The observations of this study indicates that S. fi lipendula can be

20

0
1 2 3 4
No. of cycles

Fig. 9. Biosorption-desorption ef fi ciency vs. the number of cycles.

Please cite this article in press as: A. Verma, et al., Biosorption of lead ions from the aqueous solution by Sargassum fi lipendula: Equilibrium and kinetic studies, J. Environ. Chem. Eng. (2016), http://dx.doi.org/10.1016/j.j
G Model
JECE 1306 No. of Pages 13

12 A. Verma et al. / Journal of Environmental Chemical Engineering xxx (2016) xxx – xxx

Table 9
Comparison of adsorption isotherm, kinetics, and uptake capacity of brown algae for Pb+ 2 ions.

Biosorbent pH T Adsorption Isotherms Kinetic model Reference

( C) Initial Pb+
ions concentration
2 capacity (mg/g)

Padina sp. 5 22 662 122.6 Langmuir – [72]

Sargassum 5 25 75 – 100 38.2 – Pseudo fi rst order, Pseudo [73]
muticum second order
Cytoseira baccata 4.5 35 10 – 2000 134.68 Langmuir, Freundlich – [74]
Gelidium algae 5 25 100 64 Langmuir, Langmuir-Freundlich Pseudo fi rst order, Pseudo [75]
second order
Chlamydomonas 5 25 100 96.3 Langmuir, Freundlich Pseudo fi rst order, Pseudo [44]
reinhardtii second order
Sargassum 3.7 25 200 195 Langmuir, Freundlich Pseudo fi rst order, Pseudo [65]
illicifolium second order
Nizimuddiniazan 5.5 25 165.5 50.41 Langmuir, Toth, Freundlich, Sips, Khan, DubininRadushkavich, Pseudo fi rst order, Pseudo [61]
ardini Temkin, Redlich-Peterson, RadkePrausnitz second order

Sargassum 5 35 150 – 300 285.65 Langmuir, Fritz, Toth Freundlich, RadkePrausnitz, Pseudo fi rst order, Pseudo second order, Elovich, This
fi lipendula Redlich-Peterson Bangham, Modi fi ed Freundlich Intraparticle diffusion study

used effectively as a biosorbent for the removal of Pb+ 2 ions from industrial wastewater. [15] N.H. Yarkandi, Removal of lead (II) from waste water by adsorption, Int. J. Curr.
Microbiol. App. Sci. 3 (2014) 207 – 228 .
[16] N. Dasy, R. Vimla, P. Karthika, Biosorption of heavy metals – an overview, Int. J. Biotechnol. 7 (2008) 159 – 169 .

Acknowledgements
The authors are thankful to the Ministry of Human Resource Development, New Delhi, India for
providing fi nancial support (Fellowship to Ayushi Verma), and Institute Instrumentation Center, Indian Institute
of Technology Roorkee, India for making its analytical instruments available for the research work.
[17] W. Huang, Z. Liu, Biosorption of Cd (II)/Pb (II) from aqueous solution by
biosurfactant-producing bacteria: isotherm kinetic characteristic and mechanism studies, Colloids
Surf. B 105 (2013) 113 – 119 .
[18] Y.G. Bermudeza, I.L.R. Ricoa, E. Guibalb, M.C. de Hocesc, M.A. Martin-Larac,
Biosorption of hexavalent chromium from aqueous solution by Sargassum muticum brown alga: application of
statistical design for process optimization, Chem. Eng. J. 183 (2012) 68 – 76 .

[19] P. Lodeiro, R. Herrero, M.E. Sastre de Vicente, The use of protonated Sargassum
muticum as biosorbent for cadmium removal in a fi xed-bed column, J. Hazard. Mater. B137 (2006) 244 – 253 .

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