溶剂效应对有机氯农药测定的影响研究

采用气相色谱-质谱法(GC-MS)研究了不同溶剂对有机氯农药测定的影响。结果表明,有机氯农药在不同溶剂中的GC-MS响应值是有差异的,但保留时间不变,且随着有机氯农药质量浓度的增加,这种溶剂效应对大部分有机氯农药的作用减弱。经分析溶剂的极性对有机氯农药测定有显著的影响。     

中空纤维膜萃取-气相色谱法测定水中有机氯农药

提出了中空纤维膜萃取-气相色谱法测定水中有机氯农药的方法。首先研究了8种有机氯农药的线性范围,然后测定了中空纤维膜萃取对水中有机氯农药的回收率,最后用中空纤维膜萃取-气相色谱法对实际水样进行检测。结果表明,8种有机氯农药在0.5~10μg/L范围内具有良好的线性关系,中空纤维膜萃取法对水中8种有机氯农药的富集倍数为389~464,回收率为77%~92%,可以满足分析要求。     

微波萃取-气相色谱法测定土壤中有机氯残留

采用微波萃取-硅镁吸附剂净化-气相色谱法测定土壤中有机氯农药，优化了试验条件。方法线性良好，8种有机氯农药的检出限为0.09ng／g-0.62ng／g，样品测定的RSD为2.6％-13.2％，基质加标平均回收率为93.7％-112％，质控样的测定结果与参考值相吻合。     

兰州市郊蔬菜基地土壤及蔬菜中有机农药污染现状调查

通过对兰州市郊蔬菜基地土壤及蔬菜中，有机磷和有机氯农药残留量的测定，对其污染现状进行了综合分析。     

南四湖表层沉积物中有机氯农药的含量及分布特征

利用气相色谱-电子俘获检测(GC-ECD)方法对南四湖表层沉积物中13种有机氯农药进行了分析测定。每个采样点均检出了有机氯农药,与世界其它类似水体比较,南四湖表层沉积物中的有机氯农药处于低水平含量,属于低生态风险水平。多数点位有机氯农药均是由于历史上使用造成的,但不排除个别点位存在新的污染源。     

有机氯农药和多氯联苯测定的样品净化方法

介绍了多氯联苯和有机氯农药环境样品的弗罗里硅土小柱、浓硫酸的分离、净化方法。经实际样品测定检验该方法，测定结果可靠。     

鞍山大气中有机氯农药的污染特征研究

布设鞍钢工业区6个点位,周边2个点位,居民区2个点位和千山对照点等11个点位,分别在采暖期和非采暖期测定大气中有机氯农药的含量,掌握了鞍山市大气中有机氯农药空间和时间变化趋势。全年有机氯农药各组分和ΣOPC浓度最高的功能区均为工业区周边,最低的功能区是千山对照点,六六六、滴滴涕和ΣOPC浓度变化趋势为工业区周边工业区居住区千山对照点,全市各功能区采暖期有机氯农药各组分和ΣOPC总浓度均高于非采暖期。     

同位素稀释-气相色谱-质谱法测定国际比对样品中有机氯农药和指示性多氯联苯

介绍了参加联合国环境规划署组织的国际比对项目中的沉积物中有机氯农药和指示性多氯联苯的盲样比对实验,详细介绍了同位素稀释-气相色谱-质谱法测定有机氯农药和指示性多氯联苯的检测方法、测试数据的比对结果,并对结果进行了原因分析。     

北京工业废水和城市污水中有机氯农药残留分析

建立了基于HLB固相萃取柱和气相色谱-电子捕获(GC-ECD)测定水体中有机氯农药的方法,并对方法的回收率、灵敏度进行了评价,同时分析了北京市七类典型污染点源50个采样点位有机氯农药的浓度,检测到的有机氯农药包括γ-六六六、β-六六六、4,4’-滴滴涕、α-六六六、δ-六六六、硫丹Ⅰ、4,4’-滴滴伊、艾氏剂和异狄氏剂,它们的检出率分别为90%、60%、50%、46%、26%、8%、6%、2%和2%。主要有机氯农药污染残留为γ-六六六、β-六六六和4,4’-滴滴涕。检出有机氯农药浓度范围是0.20~76.40ng/L。方法对有机氯农药的回收率达到60.93%~141.50%,方法检测限为0.27~2.90ng/L。     

乌鲁木齐地表水饮用水源地水体有机氯农药健康风险评价

为了解乌鲁木齐市地表饮用水源地水体中有机氯农药(OCPs)对人体产生的潜在健康危害风险,从一号冰川、英雄桥、乌拉泊水库的9个采样点采集水样,采用液液萃取-气相色谱/质谱法对其中的有机氯农药残留状况进行了测定,水样中9种有机氯化合物的总质量浓度为15.1 ng/L～41.2 ng/L。应用美国国家环保局(US EPA)推荐的健康风险评价方法,对乌鲁木齐市地表饮用水源地水体中有机氯农药通过食用途径进入人体的危害进行了风险计算和初步评价。结果表明,各监测断面的致癌风险和非致癌风险低于ICRP和USEPA推荐的最大可接受风险水平,初步认为目前乌鲁木齐市地表饮用水源地水体中有机氯农药不会对人体产生明显的健康危害。     

Biomonitoring of polychlorinated biphenyls (PCBs) in heavily polluted aquatic environment in different fish species

The distribution and concentrations of polychlorinated biphenyls (PCBs) were determined in fish species (European perch Perca fluviatilis, northern pike Esox lucius, pike perch Sander lucioperca, wels catfish Silirus glanus, common carp Cyprinus carpio, European eel Anguilla anguilla, freshwater bream Abramis brama, goldfish Carassius auratus, and roach Rutilus rutilus) in a heavily polluted water reservoir Zemplínska ?írava (Slovakia). The study performed at two different time points 5?years apart (2004 and 2009) revealed serious PCB contamination of fish muscle tissue and significant interspecies as well as tissue-specific differences in PCB uptake by fish. Total PCBs broadly correlated with the trophic position of individual fish species within a food chain (P??0.05). The study has shown that the kind of fish, its feeding habit, and specific conditions of the habitat are mutually interrelated factors that are responsible for significant variations in fish body burdens. A tendency to PCB biomagnification was also proved in some fish species of this water reservoir.     

Contaminants in fish tissue from US lakes and reservoirs: a national probabilistic study

An unequal probability design was used to develop national estimates for 268 persistent, bioaccumulative, and toxic chemicals in fish tissue from lakes and reservoirs of the conterminous United States (excluding the Laurentian Great Lakes and Great Salt Lake). Predator (fillet) and bottom-dweller (whole body) composites were collected from 500 lakes selected randomly from the target population of 147,343 lakes in the lower 48 states. Each of these composite types comprised nationally representative samples whose results were extrapolated to the sampled population of an estimated 76,559 lakes for predators and 46,190 lakes for bottom dwellers. Mercury and PCBs were detected in all fish samples. Dioxins and furans were detected in 81% and 99% of predator and bottom-dweller samples, respectively. Cumulative frequency distributions showed that mercury concentrations exceeded the EPA 300 ppb mercury fish tissue criterion at nearly half of the lakes in the sampled population. Total PCB concentrations exceeded a 12 ppb human health risk-based consumption limit at nearly 17% of lakes, and dioxins and furans exceeded a 0.15 ppt (toxic equivalent or TEQ) risk-based threshold at nearly 8% of lakes in the sampled population. In contrast, 43 target chemicals were not detected in any samples. No detections were reported for nine organophosphate pesticides, one PCB congener, 16 polycyclic aromatic hydrocarbons, or 17 other semivolatile organic chemicals.     

Historical data review and source analysis of PCBs/Arochlors in the Lower Leon Creek Watershed

PCBs have been banned since the late 1970s, but concentrations still exist in sediments and riverine fish and continue to exceed regulatory limits which can result in negative health effects. This study looks at historical records of PCB and Arochlor concentrations in surface water, sediments, and fish tissue for the Lower Leon Creek, Bexar County in Texas. Temporal analysis on the concentrations of PCBs and Arochlors was conducted for detection and exceedance of selected screening criteria. In addition, the half-lives of select PCB congeners were calculated for 2007–2012 data to ascertain differences in PCB concentrations with their hydrophobicity. Source analysis was conducted to determine the potential contributing sources of PCB contamination using source data (landfills, outfalls, etc.) and the PCB exceedance data. For sediment and fish tissue sampling results, historic data shows high concentrations of PCB/Arochlors over the course of several decades. The historical data is characterized as being widely variable for detections in Arochlors and concentrations between years, with a dramatic drop in concentrations detected starting in 2009. Overall, the sampling locations adjacent to and downstream from the former Kelly Air Force Base have the highest concentrations of PCB/Arochlors over the longest period of time. The results of this work will aid regulatory agencies in addressing impairment.     

Modelling temporal and spatial changes of PCBs in fish tissue from Lake Huron

A model has been developed to assess temporal and spatial changes in the concentration of polychlorinated biphenyl (PCB) contaminant in whole fish from Lake Huron during the years 1980 to 2004. The model uses log PCB concentration as the response variable and includes time trend, within-lake variability and dependence on age, weight and length as explanatory variables. A preliminary examination of the data revealed that some values are recorded as below detection limits (thus leading to the left censoring), and the PCB concentration appears to show declines in latter years. To this end, parametric log-location-scale regression models used in survival analysis were employed. It has been found that the Weibull model yields a better fit than the log-logistic or the log-normal models. The analysis provides strong evidence that, starting in 1996, the level of PCB concentration showed steady decline, which is most contributed by the Canadian and US governments?? actions carried out earlier to reduce the load of toxic contaminants to the Great Lakes. Spatially, fish from the north of the lake is less contaminated than fish from the south. The pattern and magnitude of the estimated spatial and temporal trends can provide useful information regarding the safety of fish consumption, the setting of regularity limits, the identifiability of PCB sources and the effects of remedial actions in the future. In addition, the developed model is not restricted to the current application but could be used for the analysis of other contaminants.     

Contaminants in water, sediment and fish biomonitor species from natural and artificial estuarine habitats along the urbanized Gold Coast, Queensland

Metal and pesticide contaminants were measured in water, sediment and fish species in various Gold Coast waterways, Queensland. With the exception of Cu, metal concentrations in water, measured using the diffuse gradients in a thin film (DGT) technique, complied with relevant Australian guidelines. Cu concentrations in these waterways have been related to recreational vessel activities previously. All sediment metal concentrations measured were below the national guidelines, although Cu, Zn and Pb were found to vary significantly between habitat types. Evidence of spikes in sediment pesticide concentrations (some banned over 50 years ago) was observed in some artificial residential waterways. Heavy metals and pesticides were measured in the tissue (muscle, gills and liver) of three economically important species of fish, with different feeding strategies (partly herbivore Arrhamphus sclerolepis, carnivore Acanthopagrus australis, detritivore Mugil cephalus). We tested the hypothesis that fish accumulate different amounts of contaminants from wetland habitats affected by different intensities of anthropogenic activities (i.e., marinas, artificial residential canals, artificial residential lakes, estuaries and natural, vegetated waterways). Significantly higher concentrations of Cu were found in the gills of each fish species from marinas compared to fish caught in other waterways. Furthermore, fish caught in canals had the second highest Cu and natural waterways the lowest. These results support the stated hypothesis for Cu and furthermore indicate that these fish species are suitable as biomonitors in estuarine waterways. Metal and pesticide concentrations in the edible muscle tissue of all fish complied with the Australian Food Standard Code recommended limits for human consumption, apart from As which is likely to be due to bioconcentration of lower toxicity organo-As species. These results indicate a low health risk for humans consuming fish, in terms of contaminant levels. The accumulated body of evidence on contaminants within Gold Coast waterways generally suggests that there are no major threats of metal or pesticide contamination, except for marina facilities which are a major source of Cu which also accumulates in fish. Water quality threats are also highlighted in residential canals, presumably as a consequence of their hydrological design.     

Sediment influence on congener-specific PCB bioaccumulation by Mytilus edulis: a case study from an intertidal hot spot, Clyde Estuary, UK

An intertidal site in the Clyde Estuary, UK, was selected to evaluate the role of sediment geochemistry on the bioaccumulation of polychlorinated biphenyls (PCBs) by mussels (Mytilus edulis). The area had previously been identified as showing anomalously high levels of PCB contamination (over 1,500 microg kg(-1) total PCB in sediment, 22 congeners). Samples of surface sediment and M. edulis were collected from two closely located sites, one within the anomalous area and another representing typical PCB contamination in the estuary. Sediment samples were separated into grain size fractions and analysed for a range of biomarker compounds, PCBs and sediment mineralogy. The anomalous site showed an atypical association of PCBs with sediment properties, despite both locations showing influence of both petrogenic and pyrogenic organic contamination. Interrogation of data using correlation and principal component analysis showed that sediment mineralogy as well as organic matter composition influenced PCB congener distribution. One sediment source was found to control the PCB concentration in mussels at both locations and clay mineralogy appears to control PCB uptake by biota with preference for higher molecular weight congeners. Overall bioavailability is determined by sediment TOC.     

Distribution and sources of PCBs (Aroclor 1268) in the Sapelo Island National Estuarine Research Reserve

Aroclor 1268 is a highly chlorinated PCB mixture that was released into the aquatic environment near Brunswick, GA (BR), as a result of decades of local industrial activity. This extensive contamination has led to US EPA Superfund designation in estuarine areas in and around Purvis Creek, GA. Roughly 50 km to the northeast is the Sapelo Island National Estuarine Research Reserve (SI) where previous studies have documented unexpectedly high Aroclor 1268-like PCB levels in blubber and plasma samples of resident bottlenose dolphins. This result led to a collaborative effort to assess the PCB patterns and concentrations in SI sediment and fish (as potential vectors for PCB transfer to SI resident dolphins). Thirty SI randomly assigned stations were sampled for sediment PCB levels. Additionally, fish were collected and analyzed from SI (n?=?31) and BR (n?=?33). Results were pooled with regional assessments of PCB concentrations from South Carolina and North Carolina in an effort to determine the association of Aroclor 1268 levels in SI samples. Results indicated that PCB levels in sediment and fish are much lower in the SI estuary compared to BR sediment and fish concentrations. However, PCB congener profiles for both sediments and fish were similar between the two locations and consistent with the Aroclor 1268 signature, indicating possible transport from the Brunswick area. A likely source of Aroclor 1268 in dolphins from SI is contaminated fish prey.     

Change in levels of persistent organic pollutants in human plasma after consumption of a traditional northern Norwegian fish dish-mølje (cod,cod liver,cod liver oil and hard roe)

The traditional northern Norwegian fish dish "m?lje", consisting of boiled cod, cod liver, cod liver oil and hard roe, is still consumed frequently during the winter months January to March. The liver of the cod is rich in lipids and the levels of persistent organic pollutants (POPs) are relatively high. To better understand the short-term consequences of this traditional meal on the plasma levels of PCBs and p,p'-DDE, individual intake of liver and cod liver oil during one meal was measured. Blood samples were collected from 33 participants before the meal, and then 4 h, 12 h and 5 days after it. Lipid-weight and wet-weight levels of 10 PCB congeners and p,p'-DDE were determined in the plasma samples and the food. The plasma levels of p,p'-DDE was found to increase significantly from 0 to 4 h, both when expressed as wet-weight (35% change) and lipid-weight (20% change). The corresponding changes (0-4 h) in wet-weight levels of the most prevalent PCB congeners were non significant. By contrast, PCB congeners with low levels in the food showed a significant drop in lipid-weight levels during the first 4 h. The observed changes were independent of amount consumed. Significant differences in fasting and non-fasting samples were found for most PCBs and p,p'-DDE. For the lipid weight levels of sum PCBs there was a significant decrease of 16% from non-fasting to fasting samples. To obtain reliable data on human levels of POPs it is, on the basis of these findings, recommended that blood samples should be collected from fasting individuals and both wet-weight and lipid-weight levels should be reported.     

Impact assessment of pesticide residues in fish of Ganga river around Kolkata in West Bengal

An investigation was conducted from 2001 to 2005 for determining the residual concentration of five pesticides, viz., total-HCH, total-DDT, total-Endosulfan, Dimethoate and Malathion in fish samples collected from various points of the river Ganga. Fish samples were analyzed for pesticide residues using standard laboratory procedures by GC method. It was found that total-HCH concentration remains above the MRL values for maximum number of times in comparison to four other pesticides. The pesticide contamination to fish may be due to indiscriminate discharge of polluted and untreated sewage-sludge to the river. The pesticide contents in some places are alarming. Thus proper care, maintenance, treatment and disposal of sewage water and sludge are most vital and should be the prime thrust for the nation.     

Large variation in breast milk levels of organohalogenated compounds is dependent on mother's age, changes in body composition and exposures early in life

We identified factors that are important determinants of body burdens (breast milk levels) of polychlorinated biphenyls (PCBs), dioxins (polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs)) and polybrominated diphenyl ethers (PBDEs). PCBs, PCDD/Fs and PBDEs were analysed in breast milk from up to 325 first-time mothers in Uppsala, Sweden, who delivered between 1996 and 2006. Hierarchical clustering was used as a method for identification of groups of compounds with common sources of exposure and similar toxicokinetics. Based on correlations between levels of single compounds/congeners in breast milk, distinctly separated clusters were formed, strongly dependent on structural similarities of the organohalogen molecules. In a multiple regression model, levels of PCBs (except PCB 28), PCDD/Fs and BDE-153 were positively associated with age of the mother and weight loss after delivery and inversely associated with pre-pregnancy BMI (body mass index) and weight gain during pregnancy. Higher levels of mono-ortho PCB TEQ, non-ortho PCB TEQ and BDE-153 in milk were found among women with high physical activity. Women who were breastfed during infancy and grew up on the Baltic coast of Sweden, with high availability of contaminated fish from the Baltic sea, had higher levels of PCBs and PCDD/Fs in breast milk indicating that exposure early in life from breast milk and contaminated fish may still affect body burdens at the time of pregnancy. The importance of current consumption of fatty Baltic fish as a source of exposure was supported by the positive association with breast milk levels of mono-ortho PCB TEQ, PCDF TEQ and BDE-153. The results show that, in contrast to the lower brominated PBDE congeners, the hexa-brominated BDE-153 resembles the chlorinated compounds with regards to determinants in breast milk. This suggests that some of the PBDEs may have toxicokinetic properties and that are similar to the PCBs and PCDD/Fs. Our results show that a few simple advices to women regarding weight changes in connection with pregnancy and consumption of contaminated fatty fish during the whole lifetime may lower the levels of dioxins in breast milk by up to 60%.