水土比、pH和有机质对沉积物吸附四环素的复合影响
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摘要
为更深入了解抗生素在水环境迁移过程中受沉积物吸附影响的特征和规律,选取典型抗生素之四环素(TC)为代表,研究了不同水土比、pH及有机质对九龙江沉积物吸附TC的复合影响。通过在不同水土比条件下进行改变pH的吸附实验考察水土比和pH的复合影响,又以去除有机质前后的沉积物为吸附剂,在不同水土比、pH条件下对初始浓度范围为20~100 mg·L~(-1)的TC溶液进行等温平衡吸附试验,研究有机质在不同环境条件下对沉积物吸附TC的影响。结果显示pH的影响规律为:沉积物对TC的吸附率总是在酸性条件(pH=3~5)下出现最大值,并且吸附率总体上会随着pH的升高而降低。水土比的影响规律为:水土比的变化会使达到最大吸附率的pH位点和最大吸附率值都发生改变,如:水土比为0.125和0.25时,吸附率在pH=3时达到最大,分别是96.8%和95.3%;水土比0.5时,达到最大吸附率的pH值为5,且最大吸附率值降低至82.82%。这可能是吸附方式由阳离子交换转变为离子交换和配位络合的综合作用导致的。沉积物中有机质的影响研究发现,有机质不是单一的促进或抑制作用,而是在TC形态和沉积物的主要吸附方式发生变化的时候,其促进和抑制作用发生转换。
To understand the characteristic and mechanism of antibiotics migration in the aquatic environment influenced by sediment adsorption more clearly, this present study investigated the combination effects of pH, solution/soil ratio and inherent organic matter on the adsorption of tetracycline(TC)by sediments taken from Jiulong River. Composite effects of solution/soil ratio and pH on the adsorption was investigated by batch sorption experiments with different solution/soil ratio and pH value. The effects of inherent organic matter on the adsorp-tion at different solution/soil ratio and pH conditions were also reseached by batch sorption experiments with initial concentration of TC in the range of 20~100 mg·L~(-1). The results showed that the sorption of TC by sendiment was strongly pH-dependent, of which the adsorption efficiency reached the maximum value at the pH rang of 3~5. Moreover, the adsorption efficiency decreased with pH increasing. The variety of solution/soil ratios changed the optimum pH value at which the maximum adsorption efficiency reached, i.e. The maximum adsorption efficiencies were all reached at the optimum pH 3 when solution/soil ratio was 0.25 and 0.125 with the maximum value 95.3% and 96.8%,respectively. While the optimum pH value was changed to pH 5 when solution/soil ratio was 0.5(The maximum adsorption efficiency was decreased to 82.82%). The reason may be that the main way of adsorption was changed from cation exchange to combination of ion exchange and complexation. Furthermore, the effect of the inherent organic matter of the sendiment could promote or inhibit the sorption of TC depending on the different pH, TC fractions, equilibrium concentrations and other conditions.
To understand the characteristic and mechanism of antibiotics migration in the aquatic environment influenced by sediment adsorption more clearly, this present study investigated the combination effects of pH, solution/soil ratio and inherent organic matter on the adsorption of tetracycline(TC)by sediments taken from Jiulong River. Composite effects of solution/soil ratio and pH on the adsorption was investigated by batch sorption experiments with different solution/soil ratio and pH value. The effects of inherent organic matter on the adsorp-tion at different solution/soil ratio and pH conditions were also reseached by batch sorption experiments with initial concentration of TC in the range of 20~100 mg·L~(-1). The results showed that the sorption of TC by sendiment was strongly pH-dependent, of which the adsorption efficiency reached the maximum value at the pH rang of 3~5. Moreover, the adsorption efficiency decreased with pH increasing. The variety of solution/soil ratios changed the optimum pH value at which the maximum adsorption efficiency reached, i.e. The maximum adsorption efficiencies were all reached at the optimum pH 3 when solution/soil ratio was 0.25 and 0.125 with the maximum value 95.3% and 96.8%,respectively. While the optimum pH value was changed to pH 5 when solution/soil ratio was 0.5(The maximum adsorption efficiency was decreased to 82.82%). The reason may be that the main way of adsorption was changed from cation exchange to combination of ion exchange and complexation. Furthermore, the effect of the inherent organic matter of the sendiment could promote or inhibit the sorption of TC depending on the different pH, TC fractions, equilibrium concentrations and other conditions.
引文
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[15]邹献中,赵安珍,季国亮,等.可变电荷土壤吸附铜离子时氢离子的释放[J].土壤学报,2002,39(3):308-317.ZOU Xian-zhong,ZHAO An-zhen,JI Guo-liang,et al.Release of Hydrogen ions during adsorption of copper ions by variable charge soils[J].Acta Pedologica Sinica,2002,39(3):308-317.
[16]Gu C,Karthikeyan K G,Sibley S D,et al.Complexation of the antibiotic tetracycline with humic acid[J].Chemosphere,2007,66(8):1494-1501.
[17]Wang Y P,Xu R K,Li J Y.Effect of Fe/Al hydroxides on desorption of K+and NH+4from two soils and kaolinite[J].Pedosphere,2013,23(1):81-87.
[18]Rubert IV K F,Pedersen J A.Kinetics of oxytetracycline reaction with a hydrous manganese oxide[J].Environmental Science and Technology,2006,40(23):7216-7221.
[19]Figueroa R A,Mac Kay A A.Sorption of oxytetracycline to iron oxides and iron oxide-rich soils[J].Environmental Science&Technology,2005,39(17):6664-6671.
[20]陈蕾,郑西来,王婷,等.表层沉积物主要矿化组分对Mn(Ⅱ)的吸附特性与贡献[J].环境科学研究,2014,27(11):1345-1350.CHEN Lei,ZHENG Xi-lai,WANG Ting,et al.Characteristics and contribution of major mineralized components of the surface sediment to Mn(Ⅱ)adsorption[J].Research of Environmental Sciences,2014,27(11):1345-1350.
[21]卢龙飞,蔡进功,刘文汇,等.泥岩与沉积物中粘土矿物吸附有机质的三种赋存状态及其热稳定性[J].石油与天然气地质,2013,34(1):16-26.LU Long-fei,CAI Jin-gong,LIU Wen-hui,et al.Occurrence and thermostability of absorbed organic matter on clay minerals in mudstones and muddy sediments[J].Oil and Gas Geology,2013,34(1):16-26.
[22]崔桂芳,关连珠,孙琳,等.有机质含量对棕壤表面电荷及NH+4的吸附解吸特性的影响[J].土壤肥料,2006(1):17-20.CUI Gui-fang,GUAN Lian-zhu,SUN Lin,et al.Effect of organic matter content on surface electric charge and NH+4adsorption-desorption characteristics in brown soil[J].Soils and Fertilizers,2006(1):17-20.
[23]Kulshrestha P,Giese R F,Aga D S,et al.Investigating the molecular interactions of oxytetracycline in clay and organic matter:Insights on factors affecting its mobility in soil[J].Environmental Science&Technology,2004,38(15):4097-4105.
[24]Li Y,Wang X L,Guo S H,et al.Cu and Zn adsorption onto non-residual and residual components in the natural surface coatings samples(NSCSs)in the Songhua River,China[J].Environmental Pollution,2006,143(2):221-227.
[2]Watanabe N,Bergamaschi B A,Loftin K A,et al.Use and environmental occurrence of antibiotics in freestall dairy farms with manured forage fields[J].Environmental Science&Technology,2010,44(17):6591-6600.
[3]Liu H,Zhang G,Liu C Q,et al.The occurrence of chloramphenicol and tetracyclines in municipal sewage and the Nanming River,Guiyang City,China[J].Journal of Environmental Monitoring,2009,11(6):1199-1205.
[4]Zhou L J,Ying G G,Zhao J L,et al.Trends in the occurrence of human and veterinary antibiotics in the sediments of the Yellow River,Hai River and Liao River in Northern China[J].Environmental Pollution,2011,159(7):1877-1885.
[5]Zhang D,Lin L,Luo Z,et al.Occurrence of selected antibiotics in Jiulongjiang River in various seasons,South China[J].Journal of Environmental Monitoring,2011,13(7):1953-1960.
[6]Zhao Y P,Geng J J,Wang X R,et al.Adsorption of tetracycline onto goethite in the presence of metal cations and humic substances[J].Journal of Colloid and Interface Science,2011,361(1):247-251.
[7]秦晓鹏,刘菲,王广才,等.抗生素在土壤/沉积物中吸附行为的研究进展[J].水文地质工程地质,2015,42(3):142-148.QIN Xiao-peng,LIU Fei,WANG Guang-cai,et al.Adsorption of antibiotics in soils/sediments:A review[J].Hydrogeology and Engineering Geology,2015,42(3):142-148.
[8]凌婉婷,徐建民,高彦征,等.溶解性有机质对土壤中有机污染物环境行为的影响[J].应用生态学报,2004,15(2):326-330.LING Wan-ting,XU Jian-min,GAO Yan-zheng,et al.Influence of dissolved organic matter(DOM)on environmental behaviors of organic pollutants in soils[J].Chinese Journal of Applied Ecology,2004,15(2):326-330.
[9]万莹,鲍艳宇,周启星,等.四环素在土壤中的吸附与解吸以及镉在其中的影响[J].农业环境科学学报,2010,29(1):85-90.WAN Ying,BAO Yan-yu,ZHOU Qi-xing,et al.Adsorption and desorption of tetracycline and effect of cadmium on these in two typical soils of China[J].Journal of Agro-Environment Science,2010,29(1):85-90.
[10]胡佶,王江涛.四环素在海洋沉积物上的吸附[J].高等学校化学学报,2010,31(2):320-324.HU Ji,WANG Jiang-tao.Adsorption of tetracycline on marine sediment[J].Chemical Journal of Chinese Universities,2010,31(2):320-324.
[11]Mac Kay A A,Canterbury B.Oxytetracycline sorption to organic matter by metal-bridging[J].Journal of Environmental Quality,2005,36(6):1964-1971.
[12]Sassman S A,Lee L S.Sorption of three tetracyclines by several soils:Assessing the role of p H and cation exchange[J].Environmental Science and Technology,2005,39(19):7452-7459.
[13]Chang P H,Li Z,Jiang W T,et al.Adsorption and intercalation of tetracycline by swelling clay minerals[J].Applied Clay Science,2009,46(1):27-36.
[14]彭亚君,王玉珏,刘东艳,等.酸化过程对海洋沉积物中有机碳同位素分析的影响[J].海洋学报,2015,37(12):85-92.PENG Ya-jun,WANG Yu-jue,LIU Dong-yan,et al.Acid treatment effects on the carbon stable isotope value of marine sediments[J].Acta Oceanologica Sinica,2015,37(12):85-92.
[15]邹献中,赵安珍,季国亮,等.可变电荷土壤吸附铜离子时氢离子的释放[J].土壤学报,2002,39(3):308-317.ZOU Xian-zhong,ZHAO An-zhen,JI Guo-liang,et al.Release of Hydrogen ions during adsorption of copper ions by variable charge soils[J].Acta Pedologica Sinica,2002,39(3):308-317.
[16]Gu C,Karthikeyan K G,Sibley S D,et al.Complexation of the antibiotic tetracycline with humic acid[J].Chemosphere,2007,66(8):1494-1501.
[17]Wang Y P,Xu R K,Li J Y.Effect of Fe/Al hydroxides on desorption of K+and NH+4from two soils and kaolinite[J].Pedosphere,2013,23(1):81-87.
[18]Rubert IV K F,Pedersen J A.Kinetics of oxytetracycline reaction with a hydrous manganese oxide[J].Environmental Science and Technology,2006,40(23):7216-7221.
[19]Figueroa R A,Mac Kay A A.Sorption of oxytetracycline to iron oxides and iron oxide-rich soils[J].Environmental Science&Technology,2005,39(17):6664-6671.
[20]陈蕾,郑西来,王婷,等.表层沉积物主要矿化组分对Mn(Ⅱ)的吸附特性与贡献[J].环境科学研究,2014,27(11):1345-1350.CHEN Lei,ZHENG Xi-lai,WANG Ting,et al.Characteristics and contribution of major mineralized components of the surface sediment to Mn(Ⅱ)adsorption[J].Research of Environmental Sciences,2014,27(11):1345-1350.
[21]卢龙飞,蔡进功,刘文汇,等.泥岩与沉积物中粘土矿物吸附有机质的三种赋存状态及其热稳定性[J].石油与天然气地质,2013,34(1):16-26.LU Long-fei,CAI Jin-gong,LIU Wen-hui,et al.Occurrence and thermostability of absorbed organic matter on clay minerals in mudstones and muddy sediments[J].Oil and Gas Geology,2013,34(1):16-26.
[22]崔桂芳,关连珠,孙琳,等.有机质含量对棕壤表面电荷及NH+4的吸附解吸特性的影响[J].土壤肥料,2006(1):17-20.CUI Gui-fang,GUAN Lian-zhu,SUN Lin,et al.Effect of organic matter content on surface electric charge and NH+4adsorption-desorption characteristics in brown soil[J].Soils and Fertilizers,2006(1):17-20.
[23]Kulshrestha P,Giese R F,Aga D S,et al.Investigating the molecular interactions of oxytetracycline in clay and organic matter:Insights on factors affecting its mobility in soil[J].Environmental Science&Technology,2004,38(15):4097-4105.
[24]Li Y,Wang X L,Guo S H,et al.Cu and Zn adsorption onto non-residual and residual components in the natural surface coatings samples(NSCSs)in the Songhua River,China[J].Environmental Pollution,2006,143(2):221-227.