表面活性剂对二嗪磷在不同土壤中吸附迁移的影响

采用批量平衡法和薄层层析法, 分别研究了不同浓度的3种表面活性剂十二烷基苯磺酸钠(SDBS)、Tween80和十六烷基三甲基溴化胺(CTAB) 对二嗪磷在湖南省具有代表性的6大土类、9种不同母质土壤中吸附和迁移性能的影响. 结果表明, SDBS能够明显地降低各种土壤对二嗪磷的吸附, 促进二嗪磷的迁移作用, 并且吸附平衡系数(Kd)、比移值(Rf)分别随SDBS浓度增大而增大、减小.浓度成显著的负相关和正相关关系.Tween-80和CTAB对二嗪磷在土壤中的吸附和迁移表现出一定的相似性, Tween-80浓度在0.1~2倍临界胶束浓度(CMC)范围内(CTAB浓度为0.80~87.43 mg·L-1), 其Kd值、Rf值分别随表面活性剂浓度增大而增大、减小, 而Tween-80浓度在2~5倍临界胶束浓度的范围内(CTAB浓度为87.43~191.60 mg·L-1.), 则出现与之相反的变化趋势.     

Impact of acetochlor on ammonia-oxidizing bacteria in microcosm soils

Acetochlor is an increasingly used herbicide on corn in North China. Currently, the effect of acetochlor on soil ammonia-oxidizing bacteria (AOB) communities is not well documented. Here, we studied the diversity and community composition of AOB in soil amended with three concentrations of acetochlor (50, 150, 250 mg/kg) and the control (0 mg acetochlor/kg soil) in a microcosm experiment by PCR-DGGE (polymerase chain reaction-denaturing gradient gel electrophoresis) and the phylogenetic analysis of excised ...     

Characteristics of isothermal adsorption and desorption of aluminum ion to/from humic acids

The adsorption and desorption characteristics of Al3+ to/from humic acids at di erent pH, ionic strength, and temperature were studied by the C-25 glucosan-gel chromatography method. The results showed that the maximum adsorption amount (Qmax) and adsorption constant (k) increased, whereas, the absolute value of standard thermodynamic molar free energy change ( G0 m) decreased with the increase of pH at constant ionic strength and temperature. With ionic strength increasing from 0 to 0.15 mol/L, Qmax and k increased and the absolute value of G0 m decreased at constant pH and temperature. High temperature was unfavorable for the adsorption reaction, as indicated by the dramatic decrease of Qmax and the absolute value of G0 m with an increase in temperature. The standard thermodynamic molar free energy change ( G0 m) and the standard thermodynamic enthalpy change ( H0m ) of the adsorption reaction were both negative, suggesting that adsorption reaction was spontaneous and exothermic. The desorption rate of HA-Al3+ complex accelerated with the decrease of pH, and a significant linear relationship could be obtained between pH and the desorption rates of Al3+ from humic acids. These results demonstrated that the Al3+ adsorption reaction was a “biphase” reaction, and adsorption occurred at both the interior and exterior adsorption sites of humic acids.     

Adsorption and desorption characteristics of diphenylarsenicals in two contrasting soils

Diphenylarsinic acid(DPAA) is formed during the leakage of aromatic arsenic chemical weapons in soils,is persistent in nature,and results in arsenic contamination in the field.The adsorption and desorption characteristics of DPAA were investigated in two typical Chinese soils,an Acrisol(a variable-charge soil) and a Phaeozem(a constant-charge soil).Their thermodynamics and some of the factors influencing them(i.e.,initial pH value,ionic strength and phosphate) were also evaluated using the batch method in order to understand the environmental fate of DPAA in soils.The results indicate that Acrisol had a stronger adsorption capacity for DPAA than Phaeozem.Soil DPAA adsorption was a spontaneous and endothermic process and the amount of DPAA adsorbed was affected significantly by variation in soil pH and phosphate.In contrast,soil organic matter and ionic strength had no significant effect on adsorption.This suggests that DPAA adsorption may be due to specific adsorption on soil mineral surfaces.Therefore,monitoring the fate of DPAA in soils is recommended in areas contaminated by leakage from chemical weapons.     

低分子量有机酸影响可变电荷土壤吸附铜的机制

采用平衡实验法研究了水杨酸和邻苯二甲酸对砖红壤吸附铜的影响,并通过吸附铜的解吸实验探讨了有机酸对铜吸附的影响机制.结果表明,有机酸可以增加土壤对铜的吸附量,与对照相比,有机酸体系中吸附的铜的解吸量高.有机酸对铜吸附的影响随体系pH值的增加而增大,约在pH4.3(水杨酸体系)或pH4.5(邻苯二甲酸体系)达最大,然后逐渐减小.土壤对有机酸的吸附量越高,有机酸对铜吸附的影响程度越大.有机酸可以通过形成表面三元络合物和改变土壤的表面电荷2种机制影响土壤对铜的吸附.水杨酸体系中铜的解吸增量与吸附增量的百分比在76%～89%之间,说明水杨酸主要是通过增加土壤表面的净负电荷量来增加铜的静电吸附量.     

Biodegradation of acetanilide herbicides acetochlor and butachlor in soil

The biodegradation of two acetanilide herbicides, acetochlor and butachlor in soil after other environmental organic matters addition were measured during 35 days lal)oratory incubations. The herbicides were applied to soil alone, soiI-SDBS (sodium dodecylbenzene sulfonate) mixtures and soil-HA (humic acid) mixtures. Herbicide biodegradation kinetics were compared in the different treatment. Biodegradation products of herbicides in soil alone samples were identified by GC/MS at the end of incubation. Addition of SDBS and HA to soil decreased acetochlor biodegradation, but increased butachlor biodegradation. The biodegradation half-life of acetochlor and butachlor in soil alone, soilSDBS mixtures and soil-HA mixtures were 4.6d, 6, ld and 5.4d and 5.3d, 4.9d and 5.3d respectively. The biodegradation products were hydroxyacetochlor and 2-melhvl-6-ethvlaniline for acetochlor, and hvdroxvbutachlor and 2,6-diethvlaniline for butachlor.     

Cu2+存在下腐殖酸对磺胺嘧啶吸附解吸的影响

为探究重金属与抗生素共存时不同条件下土壤有机组分对抗生素吸附解吸的影响,通过批量静态吸附试验方法,研究了不同污染物浓度、初始pH、离子强度及阳离子类型下腐殖酸对磺胺嘧啶（sulfadiazine）和重金属Cu共存时吸附解吸行为及其交互作用,并做了显著性差异分析;采用Freundlich、Langmuir等温吸附模型和线性等温吸附模型对试验数据进行拟合,对吸附前后的样品进行红外光谱扫描分析.结果表明:①不同w（Cu2+）对腐殖酸吸附磺胺嘧啶的状况不同,当w（Cu2+）为1、10、100 mg/kg时,Cu2+的存在起促进吸附的作用;当w（Cu2+）为300 mg/kg时,Cu2+的存在起抑制吸附的作用;随着初始pH的增大,吸附量变化不明显,但略有减小;高离子强度促进吸附,低离子强度抑制吸附;高价态阳离子的存在抑制腐殖酸对磺胺嘧啶的吸附.②显著性差异分析显示,P均小于0.05,说明w（Cu2+）、pH、离子强度及阳离子类型对吸附量均有显著影响.③运用Freundlich、Langmuir等温吸附模型和线性等温吸附模型对不同条件下的吸附特征进行拟合,其拟合效果均较好,R2均大于0.952,其中线性等温吸附模型拟合效果最好;HI（滞后系数）在0.995~1.120之间,接近于1,表明腐殖酸对磺胺嘧啶的吸附解吸过程中不存在滞后现象.△G（吉布斯自由能变化量）在18.921~20.412 kJ/mol之间,均小于40 kJ/mol,属于物理吸附.④红外光谱分析表明,腐殖酸对磺胺嘧啶的吸附机制主要是形成氢键或发生络合反应.研究显示,不同条件下腐殖酸对磺胺嘧啶吸附解吸的影响不同,w（Cu2+）、初始pH、离子强度及阳离子类型的改变,均会导致腐殖酸对磺胺嘧啶的吸附情况有所差异.      

氟啶胺在土壤中的吸附解吸与淋溶特性

采用批量平衡法研究了氟啶胺在南京黄棕壤、江西红壤、东北黑土中的吸附解吸特性.结果表明,25℃下,氟啶胺在3种供试土壤中的等温吸附-解吸曲线能较好地符合Freundlich模型,其吸附常数分别为南京黄棕壤119.34,江西红壤202.23,东北黑土311.88,与土壤有机质含量、阳离子代换量和粘粒含量有良好的相关性,相关系数分别为0.9973,0.9690,0.8586.土壤对氟啶胺的吸附自由能变化均小于40kJ/mol,属于物理吸附.氟啶胺在3种土壤中均难淋溶.     

胡敏酸在土壤中的迁移

研究了不同条件下胡敏酸在土壤中的迁移过程.结果表明,其迁移过程表现出较大的差异,在溶液pH值、胡敏酸浓度和溶液流速均较高时,胡敏酸迁移的阻滞因子和在土壤中的吸附系数均较低,有利于胡敏酸在土壤中的迁移;在溶液pH值、胡敏酸浓度和溶液流速均较低时,土壤对胡敏酸迁移的阻滞作用较大.胡敏酸的迁移还与土壤性质有关,土壤黏粒含量和阳离子交换量越高,胡敏酸在土壤中吸附的越多,越不利于迁移.在土壤中的吸附是胡敏酸迁移的主要控制因素,在预测胡敏酸在水土环境中迁移时,应该充分考虑不同条件下胡敏酸在不同性质土壤中的吸附.     

Adsorption and desorption of herbicide monosulfuron-ester in Chinese soils

Monosulfuron-ester is a new, low rate, sulfonylurea herbicide that is being promoted for annual broadleaf and gramineal weed control; however, there is a lack of published information on its behavior in soils. The adsorption and desorption of monosulfuronester by seven type soils were measured using a batch equilibrium technique. The results showed that the Freundlich equation fitted its adsorption and desorption well, and the Freundlich constant values (Kf-ads) ranged from 0.88 to 5.66. Adsorption isotherms were nonlinear with 1/nf-ads values < 1. Soil pH, organic matter (OM), and clay content were the main factors influencing its adsorption and desorption. Adsorption and desorption were negatively correlated with pH 4.0–8.0 while positively correlated with OM and clay content. The adsorption of monosulfuron-ester was mainly a physical process, because its free energy (ΔG) in seven soils was less than 40 kJ/mol. Monosulfuron-ester adsorption by three soils increased with increasing CaCl2 concentration using CaCl2 as a background electrolyte. Monosulfuron-ester desorption was hysteretic in all tested soils.     

土壤有机质对土霉素在土壤中吸附-解吸的影响

采用批量平衡方法,研究了土霉素在原土及去除有机质土壤中的吸附和解吸.结果表明,土霉素在原土和去除有机质土壤中的吸附和解吸等温线均不同程度地偏离线性模型,其中Freundlich模型可以对吸附和解吸数据进行良好的非线性拟合,在不同土壤以及不同土壤处理中的拟合相关系数(r)均达到极显著水平.去除有机质能够降低土霉素在土壤中的吸附容量(lgKf),但增加了吸附强度(1/n).土霉素在土壤上的解吸过程存在明显的滞后现象,在所设土霉素浓度范围内,土霉素在褐土和红壤中的平均滞后系数(HIa)分别为0.039和0.015;去除有机质后的褐土和红壤对土霉素的解吸滞后现象显著增强(P<0.01),其HIa分别增加到0.068和0.028.     

Spatial and temporal distribution of acetochlor in sediments and riparian soils of the Songhua River Basin in northeastern China

The Songhua River Basin is a burgeoning agricultural area in the modern times in China. Particularly in recent years, increasing chemical fertilizers and pesticides have been applied with the development of agricultural production. However, the situation of non-point source pollution (NSP) from agricultural production in this basin is still obscure. In order to solve the problem, the occurrence and distribution of acetochlor in sediments and riparian soils of the Songhua River Basin before rain season and after rain season were investigated. In addition, total organic carbon was analyzed. The result showed that the concentration of acetochlor ranged from 0.47 to 11.76 μg/kg in sediments and 0.03 to 709.37 μg/kg in riparian soils. During the high flow period in 2009, the mean concentration was 4.79 μg/kg in sediments and 0.75 μg/kg in riparian soils, respectively. Similarly, the mean concentration was 2.53 μg/kg in sediments and 61.36 μg/kg in riparian soils, during the average flow period in 2010. There was a significant correlation between the concentration of acetochlor and total organic carbon in surface sediments. Moreover, the distribution of acetochlor in sediments of the Songhua River was significantly correlated to land use and topography of the watershed. The investigated data suggested that the concentration of acetochlor in the Songnen Plain and the Sanjiang Plain was higher than that in the other areas of the basin, and riparian buffering zones in these areas had been destroyed by human activities. The optimal agricultural measures to alleviate the contamination of pesticides should be adopted, including controlling agricultural application of acetochlor and ecological restoration of riparian buffering strips.     

新烟碱类农药在土壤中环境行为的研究进展

目前新烟碱类农药已占据了世界最大的杀虫剂市场份额,同时土壤是该类农药进入环境系统的源头,厘清其在土壤中的环境行为对探索新烟碱类农药的环境归趋和生态评价均具有重要的意义.本文总结并梳理了新烟碱类农药在土壤中主要环境行为的研究现状,包括吸附、解吸及降解行为;分析了农药本身性质、土壤成分及类型、pH值、温度、含水量等因子对该类农药吸附和解吸的影响机制;同时探讨了降解土壤新烟碱类农药的微生物菌群、光解和水解机理,并对新烟碱类农药未来的研究重点和方向提出了展望.     

太湖地区几种水稻土团聚体颗粒组中PAHs的分布及其环境意义

以太湖地区代表性的青紫泥、黄泥土、白土等3种水稻土为研究对象,采用低能量分离-分散法提取得到不同粒径的团聚体颗粒组,用HPLC测定了本土和分离得到的团聚体颗粒组中16种PAHs的含量.结果表明,供试水稻土不同粒径的团聚体颗粒组中PAHs含量分布存在差异,PAHs总含量以＜2μm粒径的团聚体颗粒组最高,其次是200～2000μm粒径的团聚体颗粒组,PAHs在这2个团聚体颗粒组有明显富集现象(富集系数为1.25～3.92);而20～200μm和2～20 μm粒径的团聚体颗粒组中PAHs含量小于本土,呈现亏缺现象(富集系数为0.64～0.88).考虑到不同粒径团聚体颗粒组的相对组成,水稻土中PAHs主要分布于20～200μm和200～2000μm 2个团聚体颗粒组中,而在＜2μm粒径的团聚体颗粒组中最少.PAHs在不同粒径的团聚体颗粒组中的含量分布与其总有机碳、腐殖质碳、胡敏酸碳的含量有关,并在很大程度上受芳构化疏水性有机物含量的控制.因此,水稻土不同粒径团聚体颗粒中有机碳及其组分的性质影响着这些团聚体颗粒组分对PAHs的吸持与固定.     

PCB138在两种土壤及其有机质组分中解吸特征研究

为探讨多氯联苯在污染土壤中的解吸特性,选用南北方两种典型土壤,红壤和黑土为研究介质,以六氯联苯PCB138为目标污染物,探讨PCB138在红壤和黑土原土,以及从两种土壤中提取出的有机质组分胡敏酸和胡敏素中的解吸行为,并探讨土壤理化性质与解吸速率和解吸量之间的关系。实验结果表明,PCB138在两种土壤及其有机质组分中的解吸在360 min时达到动态平衡。准一级、准二级、叶洛维奇和内扩散模型四种动力学模型拟合结果显示,准二级动力学方程R²值为0.911~0.998,拟合效果最好。PCB138在黑土中的解吸速率和解吸量要略大于红壤中的相应数值。Freundlich、Langmuir和D-R等温模型拟合结果显示,Freundlich模型能更好的描述PCB138在土壤及其有机质组分中的解吸过程,有机碳归一化分配系数K_oc值由大到小依次为胡敏素>原土>胡敏酸。当温度由25℃升高到45℃时,PCB138在土壤及其组分中的解吸量随之减小。热力学数据计算结果显示ΔG^°>0,ΔH^°和ΔS^°值均小于0,说明PCB138在两种土壤及其组分中的解吸是非自发的放热反应,同时在解吸过程中固液界面的无序性和体系混乱度减小。Pearson相关性分析结果显示,PCB138在土壤中的解吸速率、解吸量与其组分中有机质质量分数和比表面积相关性不显著。     

3种四环素类抗生素在褐土上的吸附和解吸

以OECD Guideline 106为基础,采用批量平衡方法研究3种四环素类抗生素在褐土上的吸附和解吸作用.结果表明,3种四环素类抗生素的吸附和解吸不同程度地偏离线性模型,其中Freundlich模型可以对吸附和解吸数据进行良好的非线性拟合,平均拟合相关系数为0.991;其中金霉素的吸附等温线呈“S型”,土霉素的吸附等温线呈“L型”,而四环素的吸附等温线呈线性.在2种褐土中,金霉素吸附容量(lgKf) (4.307和4.003)高于四环素,而四环素lgKf (3.252和3.198)高于土霉素lgKf (2.932和2.724).对于同一种抗生素,在2种褐土中的吸附容量和吸附强度并无显著差异性.此类抗生素在褐土中的吸附均以物理性吸附为主.土霉素在褐土中的滞后系数显著高于四环素和金霉素(P<0.01),而四环素和金霉素的解吸滞后系数之间无显著差异.     

腐植酸对重金属铅镉的吸附特征

为了揭示腐植酸对单一Pb、单一Cd和Pb、Cd复合污染物的吸附特征,笔者通过吸附模拟实验分析了pH、温度、反应时间和初始浓度等因素变化对风化煤腐植酸吸附重金属离子Pb~(2+)和Cd~(2+)的影响.结果表明,腐植酸对Pb~(2+)的吸附受pH值变化的影响很小,但对Cd~(2+)的吸附随着pH增加而增加;腐植酸对Pb~(2+)和Cd~(2+)吸附饱和的时间均为240 min;对Pb~(2+)和Cd~(2+)的吸附量均随温度的增加而增加;Langmuir吸附模型对腐植酸吸附单一Pb~(2+)、单一Cd~(2+)和铅镉复合态中Pb~(2+)的拟合较好,Freundlich吸附模型则对腐植酸吸附铅镉复合态中Cd~(2+)的拟合较好;准二级动力学模型能较好地拟合腐植酸吸附Pb~(2+)和Cd~(2+)的过程,说明腐植酸对铅镉的吸附为物理吸附和化学吸附的复合吸附过程;铅镉复合态下Pb~(2+)和Cd~(2+)存在竞争吸附,单一Pb~(2+)溶液中加入Cd~(2+)对腐植酸吸附Pb~(2+)基本无影响,但单一Cd~(2+)溶液中加入Pb~(2+)时,Pb~(2+)会与Cd~(2+)产生竞争吸附,从而降低Cd~(2+)的吸附量.本研究结果可为利用腐植酸稳定土壤中Pb~(2+)、Cd~(2+)等重金属离子的技术开发提供参考.     

甲胺磷、乙草胺和铜单一与复合污染对黑土环境安全的胁迫研究

以黑土为环境介质,通过急性毒性试验法研究了东北黑土区普遍存在的2种农用化学品甲胺磷和乙草胺与重金属Cu对赤子爱胜蚓(Eiseniafoetida)的单一与复合毒性效应.单一毒性试验结果表明,3者对蚯蚓均有毒性,顺序为甲胺磷>乙草胺>Cu.复合毒性实验结果表明,2种有机农药与重金属Cu复合毒性效应十分复杂,与不同的浓度组合及染毒历时有关,一般随时间的延长,毒性加剧.2种有机农药通过不同途径毒害蚯蚓,复合毒性效应表现为协同作用.可见,3者对土壤生态系统环境安全性和土壤健康质量存在潜在危害,同时这几种污染物的共存进一步加大了潜在危害性,且复合毒性效应与各组浓度组合及污染暴露时间密切相关.     

Comparative characterization of two natural humic acids in the Pearl River Basin, China and their environmental implications

Two humic acids (HAs) were isolated from contaminated river sediments present under comparative conditions in the Pearl River Basin, China. YFHA (the HA extracted at an open pyrite mining area in Yunfu) exhibited a lower absorption intensity for certain bands in the Fourier transform infrared spectra, a lower E4/E6 value (the UV absorbances at 465 nm (E4) and 665 nm (E6)), a lower apparent molecular weight, a lower polarity and a lower oxygen functionality in comparison with GZHA (the HA isolated at an urban living area in Guangzhou). All these differences indicated a higher degree of humification of YFHA than GZHA. Overall, the enrichment patterns of permanent heavy metals in the studied HAs were similar to those in corresponding sediments. In particular, YFHA exhibited high enrichment of trace element Tl, a characteristic concomitant from the mining of the pyrite minerals. The adsorption isotherms of two HAs for goethite and pyrolusite, two representative geological materials, conformed to the Langmuir equation. Based on the qualitative relationships between the Langmuir constants of the adsorption isotherms and the chemical characteristics of HAs, the main mechanism of HA adsorption on these materials was suggested to be hydrophobic interaction. This study highlighted the promising use of HA as a peculiar bio-indicator of uncommon trace metal contaminations. The HA adsorption mechanism on representative geological materials further provided a theoretical basis for the study on the unusual metal behavior in complex environmental settings.     

Adsorption of chloroacetanilide herbicides on soil and its components Ⅲ. Influence of clay acidity, humic acid coating and herbicide structure on acetanilide herbicide adsorption on homoionic clays

Adsorption of chloroacetanilide herbicides on homoionic montmorillonite, soil humic acid, and their mixtures was studied by coupling batch equilibration and FT-IR analysis. Adsorption isotherms of acetochlor, alachlor, metolachlor and propachlor on Ca2 + -, Mg2 + -. Al3 + -and Fe3 + -saturated clays were well described by the Freundlich equation. Regardless of the type of exchange cations, Kf decreased in the order of metolachlor ＞ acetolachlor ＞ alachlor ＞ propachlor on the same clay. FT-IR spectra showed that the carbonyl group of the herbicide molecule was involved in binding, probably via H-bond with water molecules in the clay interlayer. The type and position of substitutions around the carbonyl group may have affected the electronegativity of oxygen, thus influencing the relative adsorption of these herbicides. For the same herbicide, adsorption on clay increased in the order of Mg2+ ＜ Ca2+ ＜ Al3+ ≤ Fe3+ which coincided with the iucreasing aciditv of homoionic clays. Acidity of cations may have affected the protonation of water, and thus the strength of H-bond between the clay water and herbicide. Complexation of clay and humic acid resulted in less adsorption than that expected from independent adsorption by the individual constituents. The effect varied with herbicides, but the greatest decrease in adsorption occurred at a 60:40 clay-to-humic acid ratio for all the herbicides. Causes for the decreased adsorption need to be characterized to better understand adsorption mechanisms and predict adsorption from soil compositions.