高浓度DDTs污染土壤机械化学球磨试剂筛选

为了筛选DDTs(包括DDT及其衍生物——DDE、DDD)高污染土壤无害化处理的机械化学球磨试剂,以某退役DDT生产场地高污染土壤为研究对象,将不添加任何球磨试剂处理作为对照,分析添加不同球磨主剂(CaO、CaO₂和Fe粉)、球磨助剂(SiO₂、Al₂O₃)组合以及双金属(Fe-Ni、Fe-Zn)试剂对土壤中DDTs的去除效果. 结果表明:①对照处理下土壤w(DDTs)随球磨时间的延长而不断降低,8 h后降至404.0 mg/kg,仍远超过GB 5085.6—2007《危险废物鉴别标准 毒性物质含量鉴别》标准限值〔w(DDTs)为50 mg/kg〕;单一添加CaO₂处理球磨8 h后,土壤及球磨剂混合物中w(DDTs)仍为118.0 mg/kg;而单一添加CaO和Fe粉处理分别于球磨4和6 h后,土壤及球磨剂混合物中w(DDTs)低于GB 5085.6—2007标准,因此,CaO和Fe粉是较好的DDTs机械化学球磨主剂. ②与单一添加CaO处理相比,在CaO中加入球磨助剂SiO₂或Al₂O₃球磨4 h后,土壤及球磨剂混合物中 w(DDTs)由28.55 mg/kg分别显著降至18.70或17.57 mg/kg,DDTs去除率由99.16%升至99.45%或99.48%. 与单一添加Fe粉处理相比,在Fe粉中加入SiO₂或Al₂O₃球磨4 h后,土壤及球磨剂混合物中w(DDTs)由193.0 mg/kg分别显著降至54.25或69.98 mg/kg,虽然仍略超过GB 5085.6—2007标准限值,但却显示出SiO₂或Al₂O₃对机械化学去除土壤DDTs具有显著的促进作用. ③Fe-Ni和Fe-Zn双金属球磨处理4 h后,土壤及球磨剂混合物中w(DDTs)分别为27.00和4.00 mg/kg,DDTs去除率分别达到99.21%和99.88%. 因此,Fe-Zn双金属作为去除土壤DDTs的机械化学球磨试剂,具有潜在的应用前景.      

Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides (OCPs) were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX (DDD, DDE and DDT) had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p'-(DDD DDE)/DDT in soils under three land usages were: paddy field ＞ tree land ＞ fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p'-(DDD DDE)/DDT ＞1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.     

低温等离子体降解污染土壤热脱附尾气中DDTs

为优化低温等离子体技术对污染土壤热脱附尾气的处理效果,采用脉冲电晕放电等离子体处理含DDTs（滴滴涕）的热脱附尾气,控制进气中的ρ（DDTs）为2.873 mg/m3,考察了载气φ（O₂）、等离子体温度、载气湿度和脉冲电压对DDTs降解效果的影响,分析了O₃在降解过程中的作用.结果表明:①当氮气/氧气混合载气中φ（O₂）分别为0、3%、6%、10%、21%和100%时,DDTs降解率分别为80.1%、76.5%、78.4%、81.1%、88.8%和94.6%,ρ（O₃）分别为0、0.20、0.25、0.40、0.99和1.93 mg/L.随着φ（O₂）的增加,ρ（O₃）逐渐增大,除氮气气氛外,DDTs降解率均逐渐增大,当φ（O₂）超过10%时,DDTs降解率较氮气气氛下更高.p,p'-DDD降解率均为100%,p,p'-DDE和o,p'-DDT的降解率随φ（O₂）的增加而增大.氮气气氛下p,p'-DDT降解率高于低浓度氧气气氛,除氮气气氛外,p,p'-DDT降解率随φ（O₂）的增加而增大.②当等离子体温度分别为80、100和150 ℃时,DDTs降解率分别为88.8%、83.2%和56.3%,ρ（O₃）分别为0.99、0.65和0.35 mg/L.当载气湿度为0、1.0、2.7和20.5 g/m3时,DDTs降解率分别为88.8%、81.6%、68.6%和30.0%,ρ（O₃）分别为0.99、0.73、0.56和0.32 mg/L.随着等离子体温度升高、载气湿度增大,反应器内ρ（O₃）逐渐减小,DDTs降解率也随之降低.③DDTs降解率随脉冲电压的升高而增大,当脉冲电压为24 kV、脉冲频率为50 Hz、等离子体温度为80 ℃、气体在反应器中的停留时间为10 s时,DDTs降解率达86.9%.研究显示,脉冲电晕放电等离子体能够快速、有效地去除热脱附尾气中的DDTs.      

小海湾水体有机氯农药的浓度水平和特征

以海南省万宁市小海湾为研究区,按照美国EPA8080A方法,使用仪器GC-ECD对小海湾海水和汇入其中地表水中样品的OCPs含量进行分析,样品中18种有机氯农药均出,以HCHs和DDTs为主,它们的和占到OCPs含量的60%。外海HCH含量0.26ng/L,DDTs含量0.53ng/L,OCPs含量1.34ng/L。海水中HCHs含量范围:2.39～4.59ng/L,平均值是3.31ng/L;DDTs含量范围:0.27～6.34ng/L,平均值是3.42ng/L;OCPs含量范3.63～17.01ng/L,平均值是11.15ng/L。地表水中HCHs含量范围:0.95～3.46ng/L,总含量是9.70ng/L;DDTs含量:0.96～2.86ng/L,总含量是9.70ng/L;OCPs含量范围3.71～17.16ng/L,总含量是59.13ng/L后山村河以及桥头村河的OCPs含量高出其它河流很多,周围是农田、居民点。由数据及小海湾的地理状况,得出海水中OCPs来源于地表径流,小海湾是OCPs巨大的储存库,OCPs主要汇集在沉积物中。     

泉州湾表层沉积物中残留DDTs污染现状及风险评价

运用GC／ECD对泉州湾表层沉积物下、上层共24个样品DDTs进行分析,结果表明：沉积物上层内湾、秀涂一石湖一线、外湾总DDTs浓度范围分别为3．23～25．23ng／g、4．13～10．36ng／g、0．03～0．84ng／g,平均浓度依次为13．88ng／g、7．78ng／g、1．72ng／g;下层分别为2．30～6．92ng／g、3．83～17．50ng／g、0．57～14．88ng／g,平均浓度依次为4．60ng／g、8．17ng／g、4．1lng／g。（DDD＋DDE）／DDTs比值为0．1l～1．00．上层沉积物DDE／DDTs比值远小于1。DDE／DDD表明降解主要处于厌氧环境下．污染物主要来自污水直接排放。风险评价表明,沉残留有机污染物毒性风险已经大于75％．会对泉州湾海产养殖产生一定影响。     

渤海表层沉积物中DDTs、PCBs及酞酸酯的空间分布特征

利用第2次全国海洋污染基线调查数据,研究渤海表层沉积物中DDTs、PCBs和酞酸酯的空间分布特征．结果表明：DDTs和PCBs的高值样点主要分布于秦皇岛近岸、辽东湾近岸和渤海湾近岸海区;酞酸酯的最高值和次高值样点分别出现在莱州湾近岸和辽东湾近岸,而秦皇岛近岸海区的平均水平高于其它海区．目前,渤海表层沉积物中PCBs和酞酸酯的含量相对较低,对周边底栖生物尚未构成威胁．另一方面,DDTs组成的比值关系显示秦皇岛近岸、渤海湾近岸和辽东湾近岸海区近期出现DDTs的输入,并且DDTs含量已超出相应的生态效应低值区间的标志水平,具有一定的生态风险．在渤海海区大多数样点,DDTs的主要代谢产物为厌氧条件下的DDD．     

Serum concentrations of persistent organic pollutants (POPs) in the inhabitants of a Sicilian city

Background

Polychlorinated biphenyls (PCBs) and organochlorine pesticides are common environmental contaminants that have been associated with human health problems.

Objectives

To assess serum concentrations of several organochlorine contaminants in general population living in a city with an ancient agricultural tradition and to identify possible exposure sources in Sicily.

Methods

A cross-sectional study was conducted on 101 individuals. Each participant answered a face-to-face questionnaire submitted by well-trained personnel and provided a serum sample which was analyzed for the concentrations of PCBs, HCB, HCHs and DDTs by using gas-chromatography coupled with mass spectrometry.

Results

HCB, p,p′-DDE, PCB 138, PCB 153 and PCB 180 were detected in more than 80% of the study participants. The ng g⁻¹ lipid median concentrations were: 18.6 for HCB; 175.1 for p,p′-DDE; 22. for PCB 138; 32.5 for PCB 153 and 23.0 for PCB 180. PCB 153 and PCB 138, PCB 138 and PCB 180, PCB 153 and PCB 180, and p,p′-DDE and HCB showed a high correlation each other (p < 0.05). HCB and p,p′-DDE concentrations were significantly higher in subjects >49 years old (adj-p = 0.03 in 50-69 years old and adj-p < 0.001 in >69 years old, respectively) whereas PCB 138, PCB 153 and PCB 180 concentrations were higher in males (adj-p = 0.03), in subjects >69 years old (adj-p = 0.04) and in current smokers (adj-p = 0.04).

Conclusions

The present study shows that serum concentrations of organochlorine compounds detected in subjects living in a small Sicilian city with ancient agricultural tradition are similar to those found in subjects living in urban areas of other countries. However, further investigations are needed to compare data from rural/urban areas in the same country, assessing correlations between serum concentrations of several chemical compounds and potential health effects in general population.     

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.     

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.     

广东罗非鱼养殖区水体和鱼体中重金属、HCHs、DDTs含量及风险评价

利用气相色谱(GC-ECD)、原子吸收和原子荧光法,对广东罗非鱼主要养殖区鱼塘水体及罗非鱼肌肉中Cu、Pd、Cd、As、HCHs和DDTs进行检测,同时应用了不同评价模型对罗非鱼食用安全进行健康风险评价.结果表明,Cu、Pd、Cd、As、BHCs和DDTs在4个不同养殖区水体中含量范围分别为:nd~0.101 mg·L-1、nd~0.097 mg·L-1、nd~0.003 27 mg·L-1、0.012 1~0.081 27mg·L-1、2.63~37.18 ng·L-1和2.05~12.21 ng·L-1.主要罗非鱼养殖区水体中BHCs、DDTs含量大小依次为:茂名>广州>惠州>肇庆,仍有新的γ-HCH输入.罗非鱼肌肉中残留Cu、Pd、Cd、As含量均值分别为0.805 6、0.409 6、0.070 6、0.257 mg·kg-1,BHCs和DDTs含量均值分别为12.21 mg·kg-1和13.21 mg·kg-1;采用美国国家环境保护署(EPA)推荐的评价模型对食用罗非鱼健康风险进行评价,结果表明除As可能存在致癌风险外,Cu、Pd、Cd、HCHs和DDTs的致癌和非致癌风险均低于国际放射性辐射防护委员会(ICRP)推荐的最大可接受风险水平,表明罗非鱼肌肉中HCHs、DDTs和重金属对人体健康风险处于较低水平.