腐殖酸对生物炭吸附水环境中雌激素的影响
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摘要
以玉米秸秆为原料,通过500℃限氧裂解制备生物炭(记为500BC),并采用批量吸附实验对比500BC及腐殖酸负载后生物炭(记为500BC-HA)对于水环境中两种雌激素(双酚A(BPA)和17α-乙炔雌二醇(EE2))的吸附性能及作用机制。结果表明,腐殖酸分子可阻塞部分500BC孔隙,使500BC的孔径、孔容及比表面积下降,负载腐殖酸后,500BC的比表面积由8.43m~2/g减小至4.40m~2/g,孔径从26.1nm减小至3.2nm,孔容由0.018cm~3/g下降至0.001cm~3/g;与500BC相比,500BC-HA对BPA、EE2的吸附能力均明显降低,一方面是因为腐殖酸分子占据了500BC表面的吸附点位并堵塞部分孔隙,使其吸附能力降低,另一方面腐殖酸负载后引入更多的含氧官能团,使500BC表面疏水性降低,与雌激素间的疏水作用减弱。腐殖酸负载质量浓度为0～10mg/L时,增加负载质量浓度对500BC吸附性能影响明显,当负载质量浓度大于10mg/L时,腐殖酸在500BC表面达到饱和,继续增加负载浓度对500BC的吸附性能不再产生影响。
In this paper,corn straw was oxygen-limited pyrolyzed at 500 ℃ to produce biochar(500BC).The batch adsorption approach was conducted to compare the adsorption process and mechanism of 500BC and humic acid loaded biochar(500BC-HA)to two estrogens(bisphenol A(BPA)and 17 alpha-ethinyl estradiol(EE2))in aquatic environment.The results indicated that humic acid molecules could block part of the pores and result in the decrease of pore diameter,pore volume and specific surface area of 500 BC.After humic acid loading,the specific surface area of 500BC decreased from 8.43 m~2/g to 4.40 m~2/g,the pore diameter decreased from 26.1 nm to 3.2 nm,and the pore volume decreased from 0.018 cm~3/g to 0.001 cm~3/g.Compared with 500BC,the adsorption ability of the biochar was significantly decreased.It was because the humic acid occupied the adsorption sites on the surface of biochar and blocked some pores,resulting in the decrease of BPA and EE2 adsorption ability.On the other hand,the loaded humic acid could introduce oxygen-containing functional groups,thus the hydrophobicity of the biochar was reduced,and the hydrophobic interaction between the biochar and the estrogens was weakened.When the humic acid loading concentration was 0-10 mg/L,the adsorption ability of estrogen was significantly affected by the humic acid loading concentration.When the humic acid loading concentration was greater than 10 mg/L,the humic acid adsorption reached saturation,the further effect of increasing humic acid loading concentration on adsorption capacity was negligible.
In this paper,corn straw was oxygen-limited pyrolyzed at 500 ℃ to produce biochar(500BC).The batch adsorption approach was conducted to compare the adsorption process and mechanism of 500BC and humic acid loaded biochar(500BC-HA)to two estrogens(bisphenol A(BPA)and 17 alpha-ethinyl estradiol(EE2))in aquatic environment.The results indicated that humic acid molecules could block part of the pores and result in the decrease of pore diameter,pore volume and specific surface area of 500 BC.After humic acid loading,the specific surface area of 500BC decreased from 8.43 m~2/g to 4.40 m~2/g,the pore diameter decreased from 26.1 nm to 3.2 nm,and the pore volume decreased from 0.018 cm~3/g to 0.001 cm~3/g.Compared with 500BC,the adsorption ability of the biochar was significantly decreased.It was because the humic acid occupied the adsorption sites on the surface of biochar and blocked some pores,resulting in the decrease of BPA and EE2 adsorption ability.On the other hand,the loaded humic acid could introduce oxygen-containing functional groups,thus the hydrophobicity of the biochar was reduced,and the hydrophobic interaction between the biochar and the estrogens was weakened.When the humic acid loading concentration was 0-10 mg/L,the adsorption ability of estrogen was significantly affected by the humic acid loading concentration.When the humic acid loading concentration was greater than 10 mg/L,the humic acid adsorption reached saturation,the further effect of increasing humic acid loading concentration on adsorption capacity was negligible.
引文
[1]CARGOUET M,PERDIZ D,MOUATASSIM SOUALI A,et al.Assessment of river contamination by estrogenic compounds in Paris area(France)[J].Science of the Total Environment,2004,324(1/2/3):55-66.
[2]YING G G,KOOKANA R S,KUMAR A,et al.Occurrence and implications of estrogens and xenoestrogens in sewage effluents and receiving waters from South East Queensland[J].Science of the Total Environment,2009,407(18):5147-5155.
[3]隋倩,黄俊,余刚.中国城市污水处理厂内分泌干扰物控制优先性分析[J].环境科学,2009,30(2):384-390.
[4]李轶,饶婷,胡洪营.污水中内分泌干扰物的去除技术研究进展[J].生态环境学报,2009,18(4):1540-1545.
[5]YANG W,WANG Y,SHANG J,et al.Antagonistic effect of humic acid and naphthalene on biochar colloid transport in saturated porous media[J].Chemosphere,2017,189:556-564.
[6]YANG Y,WEI Z,ZHANG X,et al.Biochar from Alternanthera philoxeroides could remove Pb(Ⅱ)efficiently[J].Bioresource Technology,2014,171(1):227-232.
[7]林雪原,荆延德,巩晨,等.生物炭吸附重金属的研究进展[J].环境污染与防治,2014,36(5):83-87.
[8]李沛辰,毋伟,张丰松,等.秸秆生物炭的结构特征及其对17β-雌二醇的吸附性能[J].环境科学研究,2015,28(8):1260-1266.
[9]张博,李杰,谈广才,等.生物炭对双酚A和17α-乙炔基雌二醇在土壤中吸附的影响[J].环境工程学报,2016,10(9):5255-5261.
[10]PIGNATELLO J J,KWON S,LU Y.Effect of natural organic substances on the surface and adsorptive properties of environmental black carbon(char):attenuation of surface activity by humic and fulvic acids[J].Environmental Science&Technology,2006,40(24):7757-7763.
[11]CORNELISSEN G,ELMQUIST M,GROTH I,et al.Effect of sorbate planarity on environmental black carbon sorption[J].Environmental Science&Technology,2004,38(13):3574-3580.
[12]QIU Y,XIAO X,CHEN H,et al.Influence of environmental factors on pesticide adsorption by black carbon:pH and model dissolved organic matter[J].Environmental Science&Technology,2009,43(13):4973-4978.
[13]HYUNG H,KIM J H.Natural organic matter(NOM)adsorption to multi-walled carbon nanotubes:effect of NOMcharacteristics and water quality parameters[J].Environmental Science&Technology,2008,42(12):4416-4421.
[14]PIGNATELLO J J.Dynamic interactions of natural organic matter and organic compounds[J].Journal of Soils&Sediments,2012,12(8):1241-1256.
[15]KASOZI G N,ZIMMERMAN A R,NKEDIKIZZA P,et al.Catechol and humic acid sorption onto a range of laboratoryproduced black carbons(biochars)[J].Environmental Science&Technology,2010,44(16).
[16]汪华,方程冉,王群,等.腐殖酸对生物炭吸附四环素的影响[J].环境污染与防治,2018,40(4):423-428.
[17]JONKER M T O,HOENDERBOOM A M,KOELMANS AA.Effects of sedimentary sootlike materials on bioaccumulation and sorption of polychlorinated biphenyls[J].Environmental Toxicology&Chemistry,2010,23(11):2563-2570.
[18]WANG F,SUN H,REN X,et al.Effects of humic acid and heavy metals on the sorption of polar and apolar organic pollutants onto biochars[J].Environmental Pollution,2017,231:229-236.
[19]WANG X,TAO S,XING B S.Sorption and competition of aromatic compounds and humic acid on multi-walled carbon nanotubes[J].Environmental Science&Technology,2009,43(16).
[20]LAWRINENKO M,LAIRD D A,JOHNSON R L,et al.Accelerated aging of biochars:impact on anion exchange capacity[J].Carbon,2016,103:217-227.
[21]KANG S,XING B.Phenanthrene sorption to sequentially extracted soil humic acids and humins[J].Environmental Science&Technology,2005,39(1):134-140.
[22]CHEN B,JOHNSON E J,CHEFETZ B,et al.Sorption of polar and nonpolar aromatic organic contaminants by plant cuticular materials:role of polarity and accessibility[J].Environmental Science&Technology,2005,39(16):6138-6146.
[23]ZHANG M,SHU L,GUO X,et al.Impact of humic acid coating on sorption of naphthalene by biochars[J].Carbon,2015,94:946-954.
[24]XIE M,CHEN W,XU Z,et al.Adsorption of sulfonamides to demineralized pine wood biochars prepared under different thermochemical conditions[J].Environmental Pollution,2014,186:187-194.
[25]LIAN F,SUN B,CHEN X,et al.Effect of humic acid(HA)on sulfonamide sorption by biochars[J].Environmental Pollution,2015,204:306-312.
[26]SUN K,RO K,GUO M,et al.Sorption of bisphenol A,17alpha-ethinyl estradiol and phenanthrene on thermally and hydrothermally produced biochars[J].Bioresource Technology,2011,102(10).
[27]LU L,WANG J,CHEN B.Adsorption and desorption of phthalic acid esters on graphene oxide and reduced graphene oxide as affected by humic acid[J].Environmental Pollution,2018,232:505-513.
[28]WANG F,YAO J,YU C,et al.Mutual effects of dialkyl phthalate esters and humic acid sorption on carbon nanotubes in aqueous environments[J].ACS Sustainable Chemistry&Engineering,2014,2(5):1219-1227.
[2]YING G G,KOOKANA R S,KUMAR A,et al.Occurrence and implications of estrogens and xenoestrogens in sewage effluents and receiving waters from South East Queensland[J].Science of the Total Environment,2009,407(18):5147-5155.
[3]隋倩,黄俊,余刚.中国城市污水处理厂内分泌干扰物控制优先性分析[J].环境科学,2009,30(2):384-390.
[4]李轶,饶婷,胡洪营.污水中内分泌干扰物的去除技术研究进展[J].生态环境学报,2009,18(4):1540-1545.
[5]YANG W,WANG Y,SHANG J,et al.Antagonistic effect of humic acid and naphthalene on biochar colloid transport in saturated porous media[J].Chemosphere,2017,189:556-564.
[6]YANG Y,WEI Z,ZHANG X,et al.Biochar from Alternanthera philoxeroides could remove Pb(Ⅱ)efficiently[J].Bioresource Technology,2014,171(1):227-232.
[7]林雪原,荆延德,巩晨,等.生物炭吸附重金属的研究进展[J].环境污染与防治,2014,36(5):83-87.
[8]李沛辰,毋伟,张丰松,等.秸秆生物炭的结构特征及其对17β-雌二醇的吸附性能[J].环境科学研究,2015,28(8):1260-1266.
[9]张博,李杰,谈广才,等.生物炭对双酚A和17α-乙炔基雌二醇在土壤中吸附的影响[J].环境工程学报,2016,10(9):5255-5261.
[10]PIGNATELLO J J,KWON S,LU Y.Effect of natural organic substances on the surface and adsorptive properties of environmental black carbon(char):attenuation of surface activity by humic and fulvic acids[J].Environmental Science&Technology,2006,40(24):7757-7763.
[11]CORNELISSEN G,ELMQUIST M,GROTH I,et al.Effect of sorbate planarity on environmental black carbon sorption[J].Environmental Science&Technology,2004,38(13):3574-3580.
[12]QIU Y,XIAO X,CHEN H,et al.Influence of environmental factors on pesticide adsorption by black carbon:pH and model dissolved organic matter[J].Environmental Science&Technology,2009,43(13):4973-4978.
[13]HYUNG H,KIM J H.Natural organic matter(NOM)adsorption to multi-walled carbon nanotubes:effect of NOMcharacteristics and water quality parameters[J].Environmental Science&Technology,2008,42(12):4416-4421.
[14]PIGNATELLO J J.Dynamic interactions of natural organic matter and organic compounds[J].Journal of Soils&Sediments,2012,12(8):1241-1256.
[15]KASOZI G N,ZIMMERMAN A R,NKEDIKIZZA P,et al.Catechol and humic acid sorption onto a range of laboratoryproduced black carbons(biochars)[J].Environmental Science&Technology,2010,44(16).
[16]汪华,方程冉,王群,等.腐殖酸对生物炭吸附四环素的影响[J].环境污染与防治,2018,40(4):423-428.
[17]JONKER M T O,HOENDERBOOM A M,KOELMANS AA.Effects of sedimentary sootlike materials on bioaccumulation and sorption of polychlorinated biphenyls[J].Environmental Toxicology&Chemistry,2010,23(11):2563-2570.
[18]WANG F,SUN H,REN X,et al.Effects of humic acid and heavy metals on the sorption of polar and apolar organic pollutants onto biochars[J].Environmental Pollution,2017,231:229-236.
[19]WANG X,TAO S,XING B S.Sorption and competition of aromatic compounds and humic acid on multi-walled carbon nanotubes[J].Environmental Science&Technology,2009,43(16).
[20]LAWRINENKO M,LAIRD D A,JOHNSON R L,et al.Accelerated aging of biochars:impact on anion exchange capacity[J].Carbon,2016,103:217-227.
[21]KANG S,XING B.Phenanthrene sorption to sequentially extracted soil humic acids and humins[J].Environmental Science&Technology,2005,39(1):134-140.
[22]CHEN B,JOHNSON E J,CHEFETZ B,et al.Sorption of polar and nonpolar aromatic organic contaminants by plant cuticular materials:role of polarity and accessibility[J].Environmental Science&Technology,2005,39(16):6138-6146.
[23]ZHANG M,SHU L,GUO X,et al.Impact of humic acid coating on sorption of naphthalene by biochars[J].Carbon,2015,94:946-954.
[24]XIE M,CHEN W,XU Z,et al.Adsorption of sulfonamides to demineralized pine wood biochars prepared under different thermochemical conditions[J].Environmental Pollution,2014,186:187-194.
[25]LIAN F,SUN B,CHEN X,et al.Effect of humic acid(HA)on sulfonamide sorption by biochars[J].Environmental Pollution,2015,204:306-312.
[26]SUN K,RO K,GUO M,et al.Sorption of bisphenol A,17alpha-ethinyl estradiol and phenanthrene on thermally and hydrothermally produced biochars[J].Bioresource Technology,2011,102(10).
[27]LU L,WANG J,CHEN B.Adsorption and desorption of phthalic acid esters on graphene oxide and reduced graphene oxide as affected by humic acid[J].Environmental Pollution,2018,232:505-513.
[28]WANG F,YAO J,YU C,et al.Mutual effects of dialkyl phthalate esters and humic acid sorption on carbon nanotubes in aqueous environments[J].ACS Sustainable Chemistry&Engineering,2014,2(5):1219-1227.