1,2,4,5-四氯苯在沉积物中的解吸动力学

采用批量实验,研究了沉积物有机质特性、溶质负载量和温度对1,2,4,5-四氯苯在沉积物上解吸动力学的影响.用4参数2室一级动力学模型描述了1,2,4,5-四氯苯在沉积物上的解吸过程.结果表明,在本研究中的每个解吸体系,1,2,4,5-四氯苯慢解吸速率常数k_s要比快解吸速率常数k_r低2个数量级以上,说明慢解吸是整个解吸过程中的速控步骤;1,2,4,5-四氯苯在不同沉积物上的k_s范围为1.19×10^-3～2.88×10^-3 h^-1,解吸过程显著受沉积物NOM特性的影响,沉积物NOM的聚合度越高,1,2,4,5-四氯苯的解吸速度和程度越低;随着在沉积物中的初始负载量由13.3 μg·g^-1增加至25.3 μg·g^-1,1,2,4,5-四氯苯的k_s由1.26×10^-3 h^-1增加至2.52×10^-3 h^-1;1,2,4,5-四氯苯在沉积物上的解吸速度随着温度的升高而显著加快,慢解吸活化能E_a在9.45～21.43 　kJ·mol^-1之间,这为沉积物中污染物生物降解的可行性提供了科学依据.     

共存污染物对1,2,4-三氯苯在CTMAB-膨润土上吸附的影响

基于污染物分子本身的特性,实验研究了2种典型的有机污染物--1,4-二氯苯和苯胺对1,2,4-三氯苯在CTMAB-膨润土上吸附的影响.分别用CTMAB-膨润土和预负载了共溶质1,4-二氯苯和苯胺的CTMAB-膨润土对1,2,4-三氯苯进行了等温吸附和动力学实验.结果表明,当固定共溶质初始浓度时,对于以上2种吸附体系,在主溶质浓度较低时,非极性共溶质1,4-二氯苯对1,2,4-三氯苯的吸附有抑制作用,浓度较高时抑制作用逐渐消失.而对于极性共溶质苯胺来说,则是在混合吸附体系中与1,4-二氯苯对1,2,4-三氯苯吸附等温线的影响一致,而对于预负载体系,苯胺则在整个浓度范围内促进1,2,4-三氯苯的吸附.对于改变共溶质初始浓度的混合吸附体系,随着共溶质浓度的逐渐增大,1,4-二氯苯对1,2,4-三氯苯的抑制作用逐渐增强,最终达到稳定;苯胺则是在较低浓度时抑制1,2,4-三氯苯的吸附,随后抑制作用逐渐减小,最后甚至促进了1,2,4-三氯苯的吸附.在竞争吸附动力学实验中,除了预负载苯胺的体系中共溶质不影响1,2,4-三氯苯吸附速率外,对于其它竞争吸附体系,1,2,4-三氯苯的吸附速率都有所下降.     

北京东南郊化工区土壤和植物中氯苯类有机物的残留及分布特征

对2003-11采自北京东南郊化工区的土壤、植物样品中11种氯苯类有机物进行了分析测定. 结果表明,土壤（干重）中氯苯类有机物（CBs）的总量范围为0.232～51.15 ng·g^-1,均值为18.16 ng·g^-1,其中1,2-DCB、1,4-DCB和HCB分别占45.2％、15.3％和17.1％;植物（干重）中CBs的总量范围为5.635～31.99 ng·g^-1,均值为12.36 ng·g^-1,其中1,4-DCB和HCB分别占51.5％和14.9%. 土壤中∑CBsi>与土壤有机质含量的皮尔森（Pearson）相关系数为0.544（P≤0.05）,呈弱正相关关系. 此外,除1,4-DCB和1,2,4-TCB外,云杉针叶中CBs的土壤-植物富集因子（BCFs）随CBs挥发能力［lg(V_P/K_OW)的增强而降低,随CBs辛醇/空气分配系数（K_OA）的增大而升高.     

桑沟湾养殖水域表层沉积物对磷酸盐的吸附特征

在室内模拟扰动条件下,研究了桑沟湾养殖水域表层沉积物对磷酸盐的吸附动力学及其吸附等温线,探讨了磷酸盐的吸附-解吸平衡质量浓度以及沉积物的源汇角色.结果表明,沉积物对磷酸盐的吸附主要发生在0～0.5 h,吸附平衡时间约为6 h,吸附动力学方程符合修正的Elovich模型,回归方程为： Q =85.536+35.512 ln t （r²=0.960 2）;低浓度条件下沉积物对磷酸盐的吸附等温线呈线性,线性方程为： Q =265.04 c _e-7.46（ Ｒ ²=0.965）,高浓度条件下沉积物对磷酸盐的吸附等温线符合Langmuir模型（ Ｒ ²=0.989）;沉积物中本底吸附态磷为7.46 μg/g,对磷的最大吸附量 Ｑ _max为769.23 μg/g;沉积物对磷酸盐的吸附-解吸平衡质量浓度EPC₀为0.028 mg/L,结合该区域水体磷酸盐含量情况,初步推断该区域的沉积物大多数时间充当的是磷源的角色.     

苯及其取代物与对硝基苯胺在沉积物上的竞争吸附

研究了沉积物-水体系中苯及其单取代化合物甲苯、氯苯、硝基苯、苯酚、苯胺和苯甲酸(作为共溶质)与对硝基苯胺(作为主溶质)之间的竞争吸附作用.结果表明,在相同的相对浓度下,易与沉积物有机质形成氢键的共溶质竞争能力强于不易形成氢键的共溶质;共溶质对主溶质吸附的竞争效应主要发生在表面吸附部分,对分配部分影响不大;有机化合物在单溶质体系中吸附等温线的非线性程度与其在多溶质体系中作为共溶质时的竞争能力具有相关性.     

1,2,4-三氯苯矿化菌的鉴定与功能分析

采用同位素示踪法从氯苯污染土壤中筛选到能高效降解1,2,4-三氯苯(1,2,4-TCB)为CO₂的细菌E3和F2,根据其表型特征、16S rDNA序列和荧光原位杂交(FISH)分析,鉴定E3和F2为博德特氏菌（Bordetella sp.）.E3和F2的16S rDNA序列相似性为100%;它们与菌株Bordetella sp. QJ2-5同源性最高,与Bordetella petrii(GDH030510)最接近,同源性分别为100%和99.4%.E3和F2能在含1,2,4-TCB的无机盐培养基中彻底降解1,2,4-TCB生成CO₂,30 d降解率达到90%以上,其中58%和46%矿化为CO₂,同时形成一定量的微生物生物量.     

有机改性蒙脱土对萘的吸附机制和影响因子

我国场地土壤中多环芳烃（PAHs）污染或PAHs-重金属复合污染是常见的污染类型,对公众健康与环境构成巨大威胁.本研究利用耗散型石英晶体微天平（QCM-D）技术和批量吸附实验,探究实验室制备的2种有机改性黏土对萘的吸附机制,以及萘与Cu²⁺共存时黏土颗粒吸附情况.结果表明,25℃时,十六烷基三甲基溴化铵改性蒙脱土（CTAB-SMF）的吸附等温线符合Freundlich模型（R²>0.92,n>1）,说明其对萘的吸附位点具有多样性,在较高萘平衡浓度（c_e=1 mmol ·L^-1）下吸附分配系数K_d为SMF的13.4倍;3-巯基丙基三甲氧基硅烷改性蒙脱土（TMSP-SMF）的吸附等温线符合Langmuir模型（R²>0.96）,在较高萘平衡浓度（c_e=1 mmol ·L^-1）下吸附分配系数K_d为SMF的1.14倍.说明2种有机改性黏土对萘的吸附效果优于SMF颗粒.3种黏土颗粒对萘的吸附焓在-30~-10 kJ ·mol^-1之间,均为自发物理吸附.溶液离子强度升高抑制了SMF吸附萘,但对改性黏土吸附萘无显著影响.萘平衡浓度较低（c_e=0.1 mmol ·L^-1）时,Cu²⁺的存在使TMSP-SMF对萘的吸附效果增加了3倍;同时萘能促进2种改性黏土对Cu²⁺的吸附.本研究通过原位在线QCM-D检测了黏土对萘的吸附机制,结果与批量吸附实验结果一致：CTAB-SMF对萘的吸附位点主要为黏土层间的改性剂基团,TMSP-SMF则位于黏土颗粒表面的改性剂基团.本项研究结果显示,QCM-D技术是一种有效的原位在线表征黏土膜吸附有机污染物的方法,2种有机改性的黏土颗粒可作为应用于PAHs或PAHs-重金属复合污染场地的修复材料.     

氯苯类化合物的生物降解

经过2个月的驯化,从某染料厂和某毛纺厂活性污泥中分离出能够生长于1,4-二氯苯、1,2,4-三氯苯和六氯苯的4种微生物.通过测定该混合菌降解氯苯类化合物过程中的累积好氧量、微生物生长曲线及降解产物Cl^-的释放,证明在好氧条件下该混合菌能够以1,4二氯苯和1,2,4-三氯苯为唯一碳源和能源,降解产物Cl^-浓度的变化与微生物生长周期有关.通过好氧振荡瓶培养法测得3种氯苯的生物降解顺序为:1,4-二氯苯[356.7μg/(L·d)]>1,2,4-三氯苯[110.4μg/(L·d)]>六氯苯[～6μg/(L·d)],说明氯取代数越多,氯苯类化合物越难被好氧降解.     

混合有机污染物在土壤中的竞争吸附研究

采用3种不同的溶质加入法研究溶质的吸附平衡,即方案①:先加入萘,然后再加入菲;方案②:萘和菲同时加入;方案③:先加入菲,然后再加入萘.研究结果表明同一溶质在有其它溶质竞争的情况下,表现出与单一纯溶质吸附时不同的吸附行为.随着竞争溶质浓度的增加,萘的吸附等温线的线性程度不断升高,吸附量降低.而菲则只是在实验方案③时,线性程度明显升高.随着竞争溶质初始浓度的增加,K_OC的值不断减小,当竞争浓度大约增加到0.5S_w后,K_OC基本不变化,达到了最小值.同时发现分子体积较大、厌水性较强的菲比分子体积较小、厌水性较弱的萘具有更强的竞争吸附能力.     

1,2,4-三氯苯双加氧酶和脱氢酶基因克隆与序列分析

通过PseudomonasnitroreducensJ5-1对不同氯苯类底物的降解实验,发现其降解能力大小顺序为:1,2,4-三氯苯,1,3-二氯苯,1,2-=氯苯,氯苯,与已报道的1,2,4-三氯苯降解菌株在底物利用的特性方面存在差异.采用PCR技术从J5-1中扩增获得氯苯降解过程中的关键酶--氯苯双加氧酶和脱氢酶的基因序列,分别命名为tcbA和tcbB,序列比对发现其与Burkholderia sp-PS12的氯苯双加氧酶和脱氢酶的基因序列同源性最高.通过J5-1的氯苯双加氧酶.亚基(TcbAa)与PS12的氯苯双加氧酶a亚基(TecAl)的氨基酸序列比对发现,在307-310位置有连续4个氨基酸残基的差异(1307L、M308T、1309V、Q310E),这可能是造成2株菌对1,2,4,5-四氯苯降解偏好性差异的原因.此外,通过催化芳香化合物降解的双力D氧酶a亚基的系统进化分析,认为TcbAa属于甲苯/联苯亚科,且与多取代氯苯双加氧酶e亚基的同源性最大.     

共存氯苯类同系物对六氯苯厌氧降解活性的影响

微生物厌氧降解六氯苯已经成为国内外六氯苯污染土壤修复技术研发的前沿和热点.研究了在不同的初始pH值、反应温度及固液比等环境条件下,3种共存氯苯类同系物五氯苯、1,2,4,5-四氯苯、1,2,4-三氯苯对染料厂污染土壤中六氯苯厌氧降解活性的影响.结果表明,在降解过程中,共存氯苯类同系物的累积对六氯苯的厌氧降解产生了反馈抑制作用,影响了六氯苯的降解活性,且在不同的环境条件下,累积规律不同,反馈抑制作用不同.反应的初始pH值较低时,五氯苯的的反馈抑制作用更突出,反应的初始pH值较高时,1,2,4-三氯苯的反馈抑制作用更突出;常温下,五氯苯的反馈抑制作用更突出,较高温度下,1,2,4-三氯苯的反馈抑制作用更突出;固液比越小,五氯苯的反馈抑制作用越突出.因此,针对性地采取提高低氯苯类同系物降解活性的措施,降低共存低氯苯类同系物在六氯苯厌氧降解过程中的累积,不失为提高污染土壤中六氯苯降解率的一种好的选择.     

Effects of different sediment fractions on sorption of galaxolide

Sorption isotherms of galaxolide (HHCB) of different fractions from two sediments with different mineral and organic carbon contents were determined to compare HHCB sorption behavior and contribution to the total sorption. The HHCB sorption isotherms that used the batch equilibration method were studied on different sediments of different fractions. The sorption isotherms of 600°C heating fractions were detailed using the linear model, while the other fractions were nonlinear and fitted well with the Freundlich model. The dissolved organic carbon (DOC) removed, NaOH extracted, and 375°C heating fractions showed more nonlinear sorption than the original sediments, which suggested more heterogeneous sorption sites in these fractions. Compared to the original sediments, the 375°C heating fractions had higher carbonnormalized distribution coefficient (K _oc) values, indicating a higher sorption affinity for HHCB. Among the different sediment fractions, the contribution of the 600°C heating fractions to the overall sorption were the lowest (< 20%), while the 375°C heating fractions were the highest (up to 85%).     

水稻秸秆主要组分的提取及其对芘的吸附作用

从水稻秸秆中提取主要组分--木质素、纤维素、半纤维素,利用元素分析和红外光谱对其性质进行了表征,并研究了芘在秸秆及其3种组分上的吸附行为.结果表明,各组分性质差异很大,木质素具有较高的芳香性和较低的极性,而纤维素和半纤维素具有较高的极性和脂肪性.不同组分对芘的吸附等温线均符合Freundlich方程,但吸附能力因其结构的差异而不同,木质素对芘的吸附能力最强, 吸附容量KF为5.04×104,比纤维素高100倍左右,而芘在半纤维素上的吸附能力略低于纤维素.低浓度(水相平衡浓度ce=0.01 Sw)下,秸秆对芘的吸附主要受木质素的控制,而且分配系数Kd略低于按照木质素质量分数计算的预测值,可能是由于木质素的烷基和芳香结构被周围的极性结构所覆盖.但在高浓度(ce = 0.5 Sw)时,秸秆对芘的吸附高于各组分的加和,芘向秸秆其他组分的分配作用不能忽略.芘在木质素上的吸附表现为非线性(非线性指数,n = 0.89),而其它3种吸附剂对芘的吸附更趋向于线性(n > 0.96).n值与芳香性呈负相关关系,而与极性呈正相关关系,表明芳香性导致的特殊作用力是造成吸附非线性的主要原因.有机碳标化分配系数Koc随吸附剂芳香性的增强而增大,但随极性的增强而减小.     

Phenanthrene sorption to environmental black carbon in sediments from the Song-Liao watershed (China)

Black carbon (BC) in ten contaminated sediments from the Song-Liao watershed, NE China, was isolated upon treatments using a combustion method at 375°C, and the isolates’ sorption isotherms for phenanthrene (Phen) were determined. All sorption isotherms were nonlinear and fitted well by the Freundlich model. A negative relation was found between Freundlich sorption nonlinearity parameter (n values) and BC/total organic carbon (TOC) content of the original sediments (r ² = 0.687, p<0.01), indicating the dominance of BC in Phen sorption nonlinearity. The BC isolates from this industrialized region had n values of 0.342 to 0.505 and logK _FOC values of 6.02 to 6.42 (μg·kg⁻¹·OC⁻¹)/(μg·L⁻¹) ⁿ for Phen. At a given C _e, the BC had higher K _oc value than the original sediments, revealing a higher sorption capacity for BC. BC was responsible for 50.0% to 87.3% of the total sorption at C _e= 0.05 S _w, clearly indicating the dominance of BC particles in overall sorption of Phen by sediments.     

Characteristics of the natural organic matter sorption affects of organic contaminants

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Characteristics of the natural organic matter sorption affects of organic contaminants

Several soil samples were used to study how the characteristics of natural organic matter(NOM)affect sorption of organic compounds.These soils contains different amounts and types of NOM.Aromaticity of NOM(percentage of aromatic carbons)was determined from solid-state CPMAS^13 C NMR spectra and the soil effective polarity was computed from the equation developed by Xing et al.Naphthalene was used to examine the sorption characteristics of NOM.Both aromaticity and polarity of NOM strongly affected sorption of naphthalene.Old NOM showed higher affinity than that in the surface,young soils.Sorption increased with increasing aromaticity and decreasing polarity.Thus,the sorption coefficients of organic contaminants cannot be accurately predicted without some considerstion of NOM characteristics.     

Characteristics of natural organic matter affect sorption of organic contaminants

Several soil samples were used to study how the characteristics of natural organic matter (NOM) affect sorption of organic compounds. These soils contains different amounts and types of NOM. Aromaticity of NOM (percentage of aromatic carbons) was determined from solid-state CPMAS 13C NMR spectra and the soil effective polarity was computed from the equation developed by Xing et al. Naphthalene was used to examine the sorption characteristics of NOM. Both aromaticity and polarity of NOM strongly affected sorption of naphthalene. Old NOM showed higher affinity than that in the surface, young soils. Sorption increased with increasing aromaticity and decreasing polarity. Thus, the sorption coefficients of organic contaminants cannot be accurately predicted without some consideration of NOM characteristics.     

Competitive sorption between 17α-ethinyl estradiol and bisphenol A/4-n-nonylphenol by soils

The sorption of 17α-ethinyl estradiol(EE2),bisphenol A(BPA),and 4-n-nonylphenol(NP) in single systems and the sorption of EE2 with different initial aqueous concentrations of BPA or NP were examined using three soils.Results showed that all sorption isotherms were nonlinear and fit the Freundlich model.The degree of nonlinearity was in the order BPA(0.537-0.686) > EE2(0.705-0.858) > NP(0.875-0.0.951) in single systems.The isotherm linearity index of EE2 sorption calculated by the Freundlich model for Loam,Silt Loam and Silt increased from 0.758,0.705 and 0.858,to 0.889,0.910 and 0.969,respectively,when BPA concentration increased from 0 to 1000 μg/L,but the effect of NP was comparably minimal.Additionally,EE2 significantly suppressed the sorption of BPA,but insignificantly suppressed that of NP.These findings can be attributed to the difference of sorption affinity of EE2,NP and BPA on the hard carbon(e.g.,black carbon) of soil organic matter that dominated the sorption in the low equilibrium aqueous concentration range of endocrine-disrupting chemicals(EDCs).Competitive sorption among EDCs presents new challenges for predicting the transport and fate of EDCs under the influence of co-solutes.