有机质对污染土壤中DDTs热脱附行为的影响

采用2种不同性质土壤(黑土和棕壤)作为供试土壤,利用DDT农药自配滴滴涕类(DDTs,包括p,p'-DDT、o,p'-DDT、p,p'-DDD、p,p'-DDE)污染土壤.采用热脱附方法,研究了原土及去有机质后土壤中DDTs在300℃,6个停留时间(5、10、20、30、40和50 min)下的去除率以及脱附后土壤中D...     

热解吸对土壤中POPs农药的去除及土壤理化性质的影响

为探索土壤热解吸修复技术对POPs污染土壤的修复效果及修复后土壤可耕作性,选择北京某农药厂旧址的POPs农药污染土壤,研究了不同温度下热解吸处理后土壤中滴滴涕(DDTs)和六六六(HCHs)各组分的去除率以及土壤理化性质的变化。结果表明,热解吸修复技术可有效去除土壤中POPs农药,其中,p,p’-DDE与α-HCH组分去除率受热解吸温度的影响比其他组分更为明显。∑HCH与∑DDT在310℃、340℃时分别达到97%、99%的去除率,且此时土壤中的污染物含量低于我国《展览会用地土壤环境质量评价标准》,此后去除率受温度的影响不明显。热解吸温度对修复后土壤的理化性质有一定的影响,不同温度影响的程度各不相同,其中,有机质含量与全氮含量分别由0.78%、0.0352%降至0.14%、0.0107%;pH波动幅度较小,由7.80变至8.25;阳离子交换量变化存在波动,但呈整体下降趋势,由7.87 mg/kg降至5.00mg/kg;土壤中速效磷显著增加,由7.59 mg/kg升至21.8 mg/kg。而在最优温度条件下,土壤理化性质受热解吸温度的影响较小。由此可以说明,热解吸技术可以用于POPs污染土壤的修复,选择适当的热解吸温度对土壤的可耕作性影响有限,因而是一种潜在的绿色修复技术。     

混合燃料中含氧量对柴油机有害物质排放量的影响

通过柴油机试验,研究了混合燃料中含氧量对柴油机有害物质排放量的影响.试验结果显示,在混合燃料中含氧量低于10.4%(质量分数,下同)时,CO和HC排放量随含氧量增加而减少;但随着混合燃料中乙醇所占比例增加,当混合燃料中含氧量达25.3%时,CO和HC排放量均增加到含氧量为10.4%时的2.5倍左右;当混合燃料中含氧量低于10.4%时,NOx排放量随其增加而少量增加.但当混合燃料中含氧量达25.3%时,NOx排放量较燃用柴油时减少50%以上;碳烟排放量则随着混合燃料中含氧量增加而不断减少.     

载气含氧量及污染物浓度对土壤石油烃热脱附效率的影响

石油烃(TPHs)在土壤中难以降解,并具有生物毒性,异位热脱附(ESTD)在修复石油烃污染土壤方面极具应用潜力。采用实验室模拟异位热脱附装置,研究了热脱附载气含氧量及土壤石油烃污染浓度对可萃取石油烃(EPHs)中柴油段(DRO)和重油段(ORO)的5种组分去除率的影响。结果表明:在初始浓度为5 000～20 000mg·kg~(-1)时,在20 min内的脱附率均不超过50%;当初始浓度增加到40 000 mg·kg~(-1)、脱附时间为20 min时脱附率可以达到68.2%。热脱附时间为50 min时,40 000 mg·kg~(-1)污染土壤的残余浓度为407.1 mg·kg~(-1)。DOR组分相同时间的脱附率随污染浓度的升高而升高,ORO组分在50 min之内不能完全脱附,脱附率随着污染物浓度上升会出现先增大后减小的趋势。在250℃时,DRO中3个组分的去除率均随着气氛含氧量的增加而呈现明显的增长趋势。在400℃条件下,ORO中2个组分分别在含氧量为12%和15%时达到最高的去除率。本研究结果可为ESTD技术修复不同浓度的石油烃污染土壤的工程设计参数提供参考。     

舟山近岸海域贝类中有机氯农药残留水平及人体健康风险评估

于2012年的7月在舟山群岛新区的海域采集贝类样本,测定了其中的有机氯农药残留量,并进行了人体健康风险评估和安全食用量推算。结果表明,采集的5种贝类样本中,六六六(BHCs)的各组分均未被检出,而滴滴涕(DDTs)在各种样本中均有检出,其中僧帽牡蛎和部分縊蛏样本中DDTs总量超过《海洋生物质量标准》(GB 18421—2001)一类标准(10μg/kg);健康风险评估结果显示,贝类样本中α-BHC、β-BHC、γ-BHC、p,p’-滴滴伊(p,p’-DDE)、p,p’-滴滴滴(p,p’-DDD)、p,p’-DDT的总致癌风险指数均低于10-4,致癌风险均在可接受的安全范围,α-BHC、β-BHC、γ-BHC、p,p’-DDE的总接触风险指数均小于1,接触风险指数未超过危害剂量参考值,人体食用舟山近岸海域的贝类是安全的;按可接受的致癌风险指数进行评估,人体的贝类安全消费量为9.8~138.0g/(kg·d)(按体重计,下同),而按可接受的接触风险指数进行评估,人体的贝类安全消费量在24.6~235.0g/(kg·d)。     

CABR处理分散式生活污水抗短期有机负荷潜能

为考察填料式厌氧折流板反应器（CABR）处理分散式生活污水抗短期有机负荷冲击的稳定性,从宏观运行性能、中间产物累积以及微观微生物活性3个层次来研究不同温度下短期有机负荷冲击对CABR运行性能影响。结果表明：宏观运行性能指标TCOD沿程变化曲线在28℃时受到有机负荷冲击仍呈现＂L＂型,容积负荷去除率也由基准条件下0.27kg/（m3.d）提高至0.73 kg/（m3.d）,但随温度的下降,沿程曲线逐渐接近＂／＂型,容积负荷去除率的增加幅度也逐渐变小。中间产物积累指标中VFA/碱度比值小于0.11～0.14时,TCOD去除率可达80%以上;SMP/SCOD比值沿水流方向呈上升趋势表明CABR抗负荷冲击性能较佳。而微观微生物酶活性受基质浓度提高的促进效应和温度下降的抑制效应相互作用表现各异。总体而言,在高温（28℃）条件下,分散式生活污水的有机负荷冲击不会对CABR出水造成显著影响,但在中温（18℃）和低温（10℃）条件下,CABR抗有机负荷冲击的稳定性随温度的下降而下降。     

热处理和pH调节协同作用下污泥调质过程研究

采用单因素实验和正交实验相结合的方式,考察了不同实验条件参数（温度、pH和反应时间）下,热处理和pH调节对污泥细胞溶出过程的影响。结果表明,污泥溶解性化学需氧量（SCOD）与反应温度、溶液pH、反应时间成正相关,其中pH对SCOD的影响最为显著,反应时间对其影响最小。污泥溶胞的最优条件：反应温度120℃,pH=11,反应时间为15 min,经过处理,SCOD可达14 810 mg/L,与总化学需氧量（TCOD）之比为49.29%,总有机碳（TOC）达4 560 mg/L,总氮（TN）则增加27%,总悬浮固体（TSS）和挥发性悬浮固体（VSS）去除率分别达22.85%和40.93%。热碱处理后污泥上清液分子量分布（MWD）状况结果显示：〉1 000 KDa MW物质含量随pH和温度的增加而增加,当pH=11时,该部分物质可从原污泥的20.94%增加到31.70%;当温度为120℃时,该部分物质可达49.83%。     

钻井废液的超临界水氧化处理及动力学分析

在反应温度为500～600℃、压力为25～30 MPa、停留时间为30～600 s的条件下,在连续式反应器中研究了钻井废液的超临界水氧化反应.结果表明:钻井废液的COD去除率可达90.00%以上;在600℃、停留时间为600 s时,钻井废液氧化后,剩余收集液的COD＜120 mg/L,满足《污水综合排放标准》(GB 8978-1996)中的二级标准.用幂函数方程描述了氧化剂过量时钻井废液超临界水氧化的反应动力学规律,反应速率常数与温度的关系符合Arrhenius公式,随停留时间的增加、温度的升高,有机物的去除率显著增加;反应速率常数随压力升高而增加,但反应速率常数的增幅随压力的升高而减小,反应活化体积不是常数.在25 MPa时,反应活化能和频率因子分别为(17 745.430 40±1 114.983 42)kJ/mol和1.152 3×10-4s-1模型计算值与实验值的误差在±15%以内.     

不同温度下曝气生物滤池运行效能与微生物群落结构

采用Biostyr曝气生物滤池(BAF)处理城市污水,研究了温度变化对其处理效果与微生物群落结构的影响。结果表明,温度低于18℃(低温)时,BAF对COD和NH_4~+-N去除率均低于60%;当水温在18~22℃(中温)之间变化时,BAF对COD和NH_4~+-N的去除效果稳定且明显高于低温时的去除率;当水温高于22℃(高温)后,BAF对COD和NH_4~+-N去除率与水温正相关,去除率随温度的升高而显著提高。PCR-DGGE分析表明,温度越高BAF内总细菌微生物群落多样性越好;定量PCR分析表明,BAF内总细菌、氨氧化细菌和硝化细菌的菌群密度均随温度升高而增大,与其对污染物的去除率变化趋势一致。BAF在低温环境下,滤池内的菌群结构变得简单、菌群密度降低,但出水水质仍能满足要求,表明BAF工艺具有良好的抗低温冲击能力。     

复配介质去除地下水中腐殖酸

以模拟地下水为研究对象,进行了复配介质去除地下水中腐殖酸的实验研究。探讨了配比、粒径、固液比、pH和温度对腐殖酸去除效果的影响。腐殖酸的浓度通过紫外分光光度法测定。结果表明:在不加活性炭的条件下,H物质∶X物质∶Q物质=1∶8∶8时,其硬度较好;在初始pH=6.34、反应时间为4 h时,去除率可达到95%以上;当反应时间≤1 h时,去除率随粒径增大而减小,而当反应时间为2～6 h时,小粒径和中等粒径复配介质对腐殖酸去除率略高于大粒径;一定浓度范围内,腐殖酸的去除率与固液比呈正相关,但固液比增大时,并不能无限提高去除率,当固液比为1∶200～1∶50时,去除率呈现平台;pH对复配介质去除效果影响不大,而温度对腐殖酸的去除有显著影响,较低温度(16.8℃)下的去除率比较高温度(35.0℃)下的去除率高5%。该复配介质去除地下水中腐殖酸是有效可行的,可作为PRB(permeable reactive barrier,渗透反应格栅)的潜在反应介质。     

Isolation and characterization of an Alcaligenes sp. strain DG-5 capable of degrading DDTs under aerobic conditions

In this study, an Alcaligenes sp. strain DG-5 that can effectively degrade dichlorodiphenyltrichloro-ethanes (DDTs) under aerobic conditions was isolated from DDTs-contaminated sediment. Various factors that affect the biodegradation of DDTs by DG-5 were investigated. About 88 %, 65 % and 45 % of the total DDTs were consumed within 120 h when their initial concentrations were 0.5, 5 and 15 mg L^?1, respectively. However, almost no degradation was observed when their concentration was increased to 30 mg L^?1, but the addition of nutrients significantly improved the degradation, and 66 % and 90 % of the total DDTs were degraded at 336 h in the presence of 5 g L^?1 peptone and yeast extract, respectively. Moreover, the addition of 20 mM formate also enhanced the ability of DG-5 to transform DDTs, and its DDT transformation capacity (T_c) value was increased by 1.8 - 2.7 fold for the pure (p,p’-DDT or o,p’-DDT only) and mixed systems (p,p’-DDT, o,p’-DDT, p,p’-DDD and p,p’-DDE). Furthermore, it was found that competitive inhibition in the biodegradation by DDT compounds occurred in the mixed system.     

Isolation and characterization of an Alcaligenes sp. strain DG-5 capable of degrading DDTs under aerobic conditions

In this study, an Alcaligenes sp. strain DG-5 that can effectively degrade dichlorodiphenyltrichloro-ethanes (DDTs) under aerobic conditions was isolated from DDTs-contaminated sediment. Various factors that affect the biodegradation of DDTs by DG-5 were investigated. About 88 %, 65 % and 45 % of the total DDTs were consumed within 120 h when their initial concentrations were 0.5, 5 and 15 mg L?1, respectively. However, almost no degradation was observed when their concentration was increased to 30 mg L?1, but the addition of nutrients significantly improved the degradation, and 66 % and 90 % of the total DDTs were degraded at 336 h in the presence of 5 g L?1 peptone and yeast extract, respectively. Moreover, the addition of 20 mM formate also enhanced the ability of DG-5 to transform DDTs, and its DDT transformation capacity (T(c)) value was increased by 1.8 - 2.7 fold for the pure (p,p'-DDT or o,p'-DDT only) and mixed systems (p,p'-DDT, o,p'-DDT, p,p'-DDD and p,p'-DDE). Furthermore, it was found that competitive inhibition in the biodegradation by DDT compounds occurred in the mixed system.     

Potential of different species for use in removal of DDT from the contaminated soils

Dichlorodiphenyltrichloroethane (DDT) and its main metabolites, p,p'-DDD and p,p'-DDE (DDTs in this study included DDT, DDD and DDE), are frequently detected in agricultural soils even though its usage in agriculture was banned in 1980s or earlier. In this study, eleven plants including eight maize (Zea mays) cultivars and three forage species (alfalfa, ryegrass and teosinte) widely cultivated in China were grown in the soils spiked with DDTs to investigate their potential for removal of DDT from the contaminated soils. The plants varied largely in their ability to accumulate and translocate DDTs, with the bioconcentration factor (BCF; DDT concentration ratio of the plant tissues to the soils) ranging from 0.014 to 0.25 and the translocation factor (TF; DDT concentration ratio of the shoots to the roots) varying from 0.35 (Zea mays cv Chaotian-23) to 0.76 (Zea mays spp. mexicana). The amount of DDT phytoextraction ranged from 3.89mug (ryegrass) to 27.0mug (teosinte) and accounted for <0.1% of the total initial DDTs spiked in the soils. After 70d, the removal rates reached 47.1-70.3% of the total initial DDTs spiked in the soils with plants while that was only 15.4% in the soils without plant. Moreover, the higher removal rates of DDTs occurred at the first 20d of experiment, and then the removal rate decreased with time. The highest amount of DDTs phytoextracted was observed in teosinte, followed by Zea mays spp. mexicana, but the highest removal rate of DDTs was found in maize (Zea mays cv Jinhai-6). Even though phytoextraction is not the main removal process for DDTs, the plant species especially Zea mays cv Jinhai-6 showed high potential for removing DDTs from the contaminated soils.     

Development of enzyme immunoassay for detection of DDT

Dichlorodiphenyltrichloroethane (DDT) is one of the persistent organic pollutants (POPs) widely found in the environment and in the general population. In this study, a direct competitive enzyme immunoassay (EIA) has been developed for the quantitative analysis of DDT. To generate a specific polyclonal antibody for EIA, p, p'-DDT was conjugated to porcine thyroglobulin for rabbit immunization. At optimized EIA conditions, the standard curves ranged from 0.137 to 100 ng/mL with the quantification limit of 0.41 ng/mL. The coefficients of variation (CV%) were 5.42-10.53% for intra-assay and 6.04-7.26% for inter-assay. Cross-reactivities with DDT metabolites (DDTs, including o, p'-DDT, p, p'-DDD, o, p'-DDD, p, p'-DDE, o, p'-DDE, p, p'-dichlorobenzophenone (DCBP), o, p'-DCBP) were investigated. The polyclonal antibody showed relatively low and/or no cross-reactivity with these compounds, and the assay was seen to be highly selective for p, p'-DDT. Moreover, the DDTs could be ranked by their reactivity: DDT > DDD > DDE > DCBP. In addition, the characterization of the polyclonal antibody indicated that the antiserum possesses a high specificity for p, p'-isomers. The results indicated that the developed EIA using this antibody could be a convenient and supplemental analytical tool for monitoring DDT.     

Organochlorine contaminants in hair of adolescents from Iassy, Romania

Human hair samples (n=42) from Iassy county (Eastern Romania) collected in 2002-2003 from adolescents were analyzed for hexachlorocyclohexane (HCH) isomers, p,p'-DDT and its metabolites, hexachlorobenzene (HCB), chlordane and metabolites and 5 polychlorinated biphenyl (PCB) congeners. Very low levels were found for HCB and oxychlordane (0.8 and 2.5 ng g(-1)) indicating a low usage of these pesticide formulations in the studied area. In case of HCHs, gamma-HCH isomer was measured at higher median concentrations (79 ng g(-1) hair) compared to the beta-HCH isomer (55 ng g(-1)), which generally is the most prevalent from HCHs. The DDTs profile consisted in p,p'-DDE and p,p'-DDT which levels correspond to 81% of sum DDTs. Very high median concentrations measured for p,p'-DDT (192 ng g(-1)) combined with lower values for p,p'-DDE/p,p'-DDT of 0.4 (from 0.20 to 2.0) in all hair samples suggest recent exposure to "fresh" DDT. When gender was considered, significantly higher concentrations for most of the investigated contaminants were found in girls hair compared to boys. Very high levels were found in the present study for HCHs and DDTs compared to samples from Greece, Western Europe and China. In case of PCBs, the levels found in Romanian samples were found to be in the same range compared to other previously published data.     

Presence of DDT metabolites in water,sediment and fish muscle tissue from Lake Prespa,Republic of Macedonia

Organochlorine pesticides were determined in water and sediment samples collected from the littoral zone of Lake Prespa, as well as from its three main tributaries (the rivers Golema, Brajcinska and Kranska), during the period 2004 to 2006. In addition, muscle tissue samples of barbus fish (Barbus prespensis Karaman, 1928) collected from the littoral zone of Lake Prespa were also analysed. The obtained results give an overview of the contamination levels of these problematic compounds at their potential sources in the river mouths, in the potentially affected, species-rich littoral section of the lake and in the muscle tissue of one selected fish species, collected near the rivers’ deltas. Special attention was paid to the presence of some DDT metabolites (1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (p,p′–DDE); (1,1-dichloro-2,2-bis(p-chlorophenyl)ethane (p,p′–DDD) and 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (p,p′–DDT). The extraction of pesticides from water samples was done by liquid-liquid partition in dichloromethane. For the sediment and fish tissue we used solid-liquid extraction. The extracted residues were analyzed on a gas chromatograph equipped with an electron capture detector (GC-ECD). The results of the respective studies indicated the presence of DDT metabolic forms in the samples of the three analysed matrixes. The highest levels of presence for these pollutants were found in the muscle tissue of the fish samples. The total DDTs content in the analysed muscle tissue samples range from 11.67 to 13.58 μg kg^?1of fresh tissue. The average total DDTs content for the sediment samples were within the range of 2.32 to 4.17 μg kg^?1 of dry sediment. Higher DDT metabolites content were found in the sediments collected from the rivers than in the samples from the littoral zone. The lowest average total concentrations of DDTs, on the other hand, were recorded in the water samples and ranged between 0.036 and 0.057 μg L^?1. The obtained results indicated that the dominant metabolic form in the samples of the three investigated matrixes (water, sediment and fish tissue) from Lake Prespa was p,p′-DDE. There was a very good linear correlation in this study between the content of DDT's (total DDT metabolites) detected and the percentage of total organic material in the sediment. The detected concentrations are clearly below the toxicity thresholds; consequently, severe effects on the endemic species of Lake Prespa are not very likely.     

Concentrations and composition of organochlorine contaminants in different species of cephalopod molluscs from the Italian waters (Adriatic Sea)

Persistent organochlorines, such as polychlorinated biphenyls including coplanar congeners and DDT compounds were measured in the liver of different species of mollusc cephalopods: broadtail squid (Illex coindetii), horned octopus (Eledone moschata) and spider octopus (Octopus salutii) collected in two different areas of the Adriatic Sea (central and southern Adriatic Sea). The concentration of PCBs exceeded DDT ones in horned octopus (PCBs: 617.0 ngg(-1) lipid weight, DDTs: 188.0 ngg(-1) lipid weight) and in spider octopus (PCBs: 590.0 ngg(-1) lipid weight, DDTs: 293.0 ngg(-1) lipid weight), while in broadtail squid PCB load (748.0 ngg(-1) lipid weight) was similar to those of DDTs (514.5 ngg(-1) lipid weight). No significant difference in PCB levels was observed among species, while DDT concentrations were higher in broadtail squid than in horned octopus and spider octopus. DDTs composition showed slight differences in relation to species, thought p,p'-DDE was the predominant compound in all cephalopod species (broadtail squid: 88.1%, horned octopus 94.1%, spider octopus: 97.5%). PCB isomer profiles were similar among species being hexachlorinated isomers the most abundant, followed by penta- and heptachlorobiphenyls, while tri- and tetrachlorobiphenyls made up a small percentage of the total PCB residues. Regarding coplanar congeners, non-ortho PCBs were below the detection limit in all samples and the 2,3,7,8-TCDD toxic equivalent (TEQ) concentrations were very low. The influence of biological and ecological factors (size/weight and location) on the bioaccumulation of organochlorine compounds has been discussed.     

Distribution and change of DDT and HCH levels in oysters (Crassostrea rivularis) from coast of Guangdong,China between 2003 and 2007

This investigation was undertaken to understand the temporal trend, the spatial distribution and the residue level of dichloro-diphenyl-trichloroethanes (DDTs) and hexachlorobenzenes(HCHs) in bivalves from the coast of the South China in recent years. Jinjiang oysters (Crassostrea rivularis) were sampled from 15 bays along the coast of Guangdong province, China between 2003 and 2007. Gas chromatography with electron capture detector was used to quantify the contents of HCH isomers (α-, β-, γ-, δ-HCH), DDT isomers (p,p′-, o,p′-DDT), p,p′-DDD and p,p′-DDE in the oyster tissues. The results demonstrate that annual level of DDTs in the tissue increase throughout the study, particularly between 2004 and 2006. The DDTs content in the tissue varied significantly among sampling regions and some sampling sites (p < 0.05). On the other hand, the HCHs content was significantly lower than DDTs content in the tissue (p < 0.01), and remain constant among sampling years, sampling regions and sampling sites (p > 0.10). Predominance of isomer form of DDTs and higher ratio of γ-HCH/HCHs at some sites indicated that recent input of DDT and lindane in the coastal waters of Guangdong, which might be caused by dicofol spraying in crop planting and lacquer painting on fisher boat. In the soft tissues of the oysters, the highest content of HCHs was 1.21 ng/g (wet weight), and DDTs levels ranged from 0.11 ng/g to 76.3 ng/g (wet weight), far below the Maximum Residual Limits in China and many developed nations.     

Organochlorine pesticides (DDTs and HCHs) in soils from the outskirts of Beijing, China

Concentrations of HCH (hexachlorocyclohexane) and DDT (Dichlorodiphenyltrichloroethane) were determined in shallow subsurface (5-30 cm depth) and deep soil layers (150-180 cm depth) from the outskirts of Beijing, China. Concentrations of total HCHs (including alpha, beta, gamma, delta-isomers) and total DDTs (including p,p'-DDT, p,p'-DDE, p,p'-DDD, o,p'-DDT) in shallow subsurface soils ranged from 1.36 to 56.61 ng/g dw (median 5.25 ng/g), and from 0.77 to 2178 ng/g (median 38.66 ng/g), respectively, and those in the deeper layers were approximately an order of magnitude less. The spatial distribution of HCHs and DDTs reflected the known historical usage of these pesticides. No correlation between the concentrations of pesticides and soil organic matter content or clay content can be found. The factors affecting residue levels and compositions of DDT and HCH were discussed. The contour maps of beta/gamma ratios and DDT/DDE ratios for both the shallow subsurface and deep layer soils were drawn.