Biomonitoring of polychlorinated byphenyls contamination in the supralittoral environment using the sandhopper Talitrus saltator (Montagu)

We evaluated the use of Talitrus saltator as biomonitor of polychlorinated byphenyls (PCBs) contamination of the supralittoral zone of Mediterranean sandy shores, an area not yet investigated about the presence of these pollutants. Twenty of 22 PCB congeners analysed were detected and quantified in sand and sandhoppers' samples collected in 6 different sites along the Tyrrhenian coast of Central Italy. Among the congeners analysed, PCB 153 and PCB 138 were the most abundant both in amphipods and sand samples and, regarding the congener pattern analysis, hexa-, hepta- and penta-PCBs were the most abundant congeners in sandhoppers. Though hydrophobic compounds, such as PCBs, bind strongly to sand and sediments, PCB concentrations were higher in T. saltator than in the sand revealing a good ability of this species to accumulate this class of contaminants. The concentration of each PCB congener recorded in tissues of sandhoppers showed significant differences among sampling sites revealing a good ability of these species to accumulate PCBs at different concentrations depending on the contamination levels of the sampling site. Therefore, our results suggest the possible utilisation of T. saltator as a biomonitor of PCB contamination of the supralittoral zone of Mediterranean sandy shores.     

Modelling the diagenetic fate of persistent organic pollutants in organically enriched sediments

The fate of persistent organic pollutants (POPs) in aquatic ecosystems is intimately linked to the cycling of organic matter. In this paper, we present a model of the effect of organic matter decomposition on the distribution of persistent organic pollutants in sediments. The model predicts a diagenetic (sediment-ageing) magnification of chemical concentrations in sediments enriched with labile organic matter. We predict two- to four-fold diagenetic magnification across a wide range of realistic parameter values, and higher levels (up to 20-fold) for labile organic matter in systems with low burial rates (i.e., residence times on the order of years). As an illustration, we apply our model to understand the fate of waste organic matter and associated PCBs discharged by marine fish farms. The available data support both the spatial pattern (as a function of burial rate) and the range of sediment PCB concentrations predicted by our model. This model explains why equilibrium models fail to predict the very high sediment-water partitioning coefficients often observed in the field. Effectively, diagenetic processes impose an additional biomagnification step at the bottom of the detritus-based food web, increasing the exposure to POPs of organisms at higher trophic levels.     

Biotransfer of persistent organic pollutants from a large site in China used for the disassembly of electronic and electrical waste

Samples of groundwater, river water, river sediment, paddy soil, rice seeds, hen eggs, fish, umbilical cord blood, and newborn meconium were collected from October 2002 to October 2003 near a large site in China used for the disassembly of obsolete transformers and other electronic or electrical waste. Six indicator PCB congeners, three non-ortho dioxin-like PCB congeners, and six organochlorine pesticides were determined in the samples by GC with electron capture detector. The results demonstrated that the local environment and edible foods had been seriously polluted by toxic PCBs and organochlorine pesticides. The actual daily intakes (ADIs) of these pollutants were estimated for local residents living in the area. The intake data showed that the contents of PCBs in these local residents were substantial, as the ADI estimates greatly exceed the reference doses set by the World Health Organization and the United States Agency for Toxic Substances and Disease Registry. The presence of the indicator PCB congeners in the cord blood and the meconium samples, as well as significant correlations (r ² > 0.80, p < 0.05) between these levels, suggests a potential biotransfer of these indicators from mothers to their newborns. This preliminary study showed that obsolete transformers and other electronic or electrical waste can be an important source for the emission of persistent organic pollutants into the local environment, such as through leakage, evaporation, runoff, and leaching. Contamination from this source appears to have reached the level considered to be a serious threat to environmental and human health around the disassembly site.     

Detection of polychlorinated biphenyls employing chemical dechlorination followed by biphenyl whole cell sensing system

Polychlorinated biphenyls (PCBs) are a mixture of 209 individual chlorinated compounds commonly known as PCB congeners. These compounds are hydrophobic and are persistent in the environment. Their use was banned in the US a few decades ago because of harmful health effects. Therefore, detection of PCBs in environmental samples is increasingly important. To that end, we have developed a two-step simple and sensitive method for the detection of total PCBs. Specifically, our method involves dechlorination of PCBs to biphenyl followed by detection of biphenyl using a whole cell sensing system as the detection system. The whole cell sensing system consists of cells of the strain Pseudomonas pseudoalcaligenes KF707 harboring plasmid pSD7000. Plasmid pSD7000 contains the gene of lacZ, a reporter protein under the control of the bph operon. The detection is achieved through the emission of light afforded by the expression of reporter protein triggered by the presence of biphenyl. Due to the fact that this operon is activated only by few PCB congeners, a chemical dechlorination method was employed to convert all PCBs to biphenyl, and thus all the PCBs present in a given sample are able to be detected. The results showed that PCB congeners were rapidly (30?min) and efficiently (>98.5%) dechlorinated to biphenyl using a Mg/K₂PdCl₆ catalyst, and the biphenyl could be subsequently quantified using the whole cell sensing system. This hybrid analytical method that combines classical dechlorination with novel biosensing methods may find applications in the on-site monitoring of PCBs contamination levels.     

On the detoxification of benthic bivalves contaminated by POPs: insights from experimental and modelling approaches

Rearing benthic bivalves that are contaminated by persistent organic pollutants (POPs) in areas with low pollution levels permits their natural detoxification. Here, we present the results of novel detoxification experiments conducted with the Manila clam (Tapes philippinarum) in the Venice Lagoon; these experiments were conducted both in summer and winter. Measurements of dioxins (PCDD), furans (PCDF), polychlorinated biphenyl (PCB) and hexachlorobenzene (HCB) concentrations in clam flesh over time after their resettlement in cleaner areas allowed for determining the minimum time required to reach safe toxicity levels. Moreover, dioxin fingerprint dynamics demonstrated successful detoxification from industrial contaminants. A simple bioaccumulation/detoxification model applied to the collected data provided for the first time estimation of detoxification rates and half-lives for POP congeners in clam flesh. This work provides a basis for considering natural detoxification as a viable solution for safely exploiting resources otherwise restricted from human consumption due to associated health risks.     

Chorioallantoic membrane as a non-lethal sampling method for polychlorinated biphenyls analysis in the northern diamondback terrapin (Malaclemys terrapin terrapin)

Polychlorinated biphenyls (PCBs) are documented endocrine-disrupting chemicals. This study examined the bioaccumulation of PCBs and the utility of the chorioallantoic membrane (CAM) as a non-lethal sampling technique for PCB analysis in the northern diamondback terrapin (Malaclemys terrapin terrapin), a species endemic to US East Coast salt marshes. To determine the viability of the CAM as a surrogate for PCB burdens within this species, maternal transfer of PCBs to CAM and egg samples was studied. Egg and CAM samples were collected from populations in Cape May County, NJ and Jamaica Bay, NY; liver samples were collected only from NJ terrapins. PCB congeners were detected in all sample types, but less-chlorinated congeners preferentially partitioned in the CAM. Liver and egg sample PCB concentrations were strongly correlated (p=0.002, r _s=0.883), but PCB concentrations of CAM were not strongly correlated to liver (p=0.035, r _s=0.733) and egg samples (p=0.036, r _s=0.484). Examination of homologue groups indicated a strong correlation between penta- and hexachlorinated biphenyls for all sample types. This study shows that maternal transfer of PCB contaminants occurs with selective partitioning of congeners into the CAM, and that analysis of the CAM alone may not reflect total PCB body burdens in this species.     

Polychlorinated biphenyls and their hydroxylated metabolites in the serum of e-waste dismantling workers from eastern China

A number of studies have reported on the exposure of e-waste dismantling workers to significantly high concentrations of halogenated organic pollutants such as polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers. Such exposure can have adverse health effects. However, little information on the metabolites of these contaminants exists. In this study, we investigated PCBs levels and their hydroxylated metabolites (OH-PCB) in the serum of e-waste workers in Taizhou in eastern China. Our results indicate elevated PCB and OH-PCB levels in the serum of the workers, with medians of 443.7 and 133.9 ng/g lw, respectively. Tri- to hexachlorinated PCB congeners were the dominant homologue groups in all of the samples. 4-OH-CB107 was the predominant homologue among the hydroxylated metabolites, accounting for 88.9% of the total OH-PCB concentrations. While dietary sources (e.g., fish) appear to be an important route for PCB accumulation in non-occupational exposure groups, exposure via ingestion of house dust and inhalation of pollutants derived from the recycling of PCB-containing e-wastes may primarily contribute to the high body burden observed in the occupational groups. Since we found concentrations of metabolites higher than those of their parent compounds, further studies need to pay more attention to their bioaccumulation and toxicity.     

Congener-specific analysis of polychlorinated biphenyl in human blood from Japanese

Polychlorinated biphenyl (PCB) congeners were analyzed by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) of whole blood samples taken from 24 healthy adult Japanese volunteers (12 males and 12 females; age range 25–46 years). On average, 95 PCB congeners were detected in whole blood samples. The mean of total PCB concentration in whole blood was 771.9 pg g^–1 whole blood (139.6 ng per g-lipid). Congener-specific analysis identified the predominant PCB congeners as #153 (22.2), #180 (11.6), #138 (8.4), #182/187 (6.6), #118 (5.6), #163/164 (5.0), #99 (3.9), #74 (3.6), #146 (3.3), #170 (3.0) and #156 (2.2), representing 75.6 of all PCBs detected in the human blood samples. Among the predominant PCB congeners, #153, #180, #138, #187 #118, #99 and #74 had chlorine as the substituent at the 2-, 4- and 5- positions of the phenyl-ring. In human blood in Japanese individuals, it is assumed that these congeners would be characteristic of the entire population, based on the relation between PCB ingestion and metabolism. Measuring 209 PCB congeners has the advantage of providing detailed information regarding the congener distribution within the blood samples, which can be compared to congener patterns in other matrices. Congener-specific analysis of 209 PCB congeners is especially useful in evaluating human exposure to PCBs.     

环境监测中POPs分析的关键问题与对策

系统介绍了采用EPA8081A与8082方法进行环境样品中持久性有机污染物(POPs)分析的关键问题与对策。包括POPs的气相色谱分析与验证双柱系统,DDT与异狄氏剂在进样系统中的分解及其处理方法,应用目测识别法、手型法与透明复印胶片法等经验方法快速定性多氯联苯(PCBs)、氯丹与毒杀芬等多峰化合物,影响外标法准确定量PCBs、氯丹与毒杀芬等多峰POPs的关键因素,以及质量控制要求。提出应根据中国POPs的环境污染特点,建立相应的POPs标样库与标准图谱库,为中国的POPs污染调查与环境监测提供技术支持。     

电子垃圾拆解区土壤中典型手性PCBs分布及对映体特征

龙塘镇位于广东省清远市,是国内最大的进口电子垃圾集中处理处置地之一.通过对龙塘镇土壤中7种手性PCBs对映体浓度和对映体百分数(enantiomer fractions,EF)值的测定,发现龙塘镇土壤样品除PCB45和PCB174外,其余5种手性PCBs在土壤中均有不同程度的检出.土壤中5种目标手性PCBs(PCB91、PCB95、PCB132、PCB136和PCB149)的总浓度为145.4—286.7 ng·g^-1,这与先前文献中测定清远市土壤中手性PCBs污染水平基本一致.5种同系物的含量排序为PCB95>PCB132>PCB136>PCB149>PCB91.在距离电子垃圾拆解区10km以外的区域也检测到手性PCBs,证实这些污染物已经迁移到周边地区.土壤中手性PCB91、PCB95、PCB132、PCB136和PCB149的EFs值分别为0.519±0.005、0.4443±0.006、0.427±0.003、0.379±0.016和0.494±0.008,其中PCB149具有双向选择性.在全部检出样品中26%的PCB91、78%的PCB95、100%的PCB132、86%的PCB136和53%的PCB149具有非外消旋特征,表明该地区土壤中手性对映体选择性降解的显著性.     

Accumulation, distribution and transformation of DDT and PCBs by Phragmites australis and Oryza sativa L.: II. Enzyme study

Two wetland plant species, Phragmites australis and Oryza sativa, were grown in a glasshouse under hydroponics conditions. Enzyme extracts from different parts of the plants were used to determine the transformation rate of o,p′-DDT, p,p′-DDT and PCBs. The organic pollutants were directly spiked into the enzyme extracts, and samples were collected every 30 min and analyzed with a GC-ECD. Root extracts of P. australis readily degraded and transformed DDT and some PCB congeners with a low degree of chlorination. In contrast, crude extracts of O. sativa showed no appreciable degradation or transformation of DDT or PCBs. Inhibition studies indicated that the degradation and transformation of both DDT and PCBs by P. australis enzymes were partly mediated by peroxidase and the plant P-450 system. PCBs with a high degree of chlorination were highly resistant to transformation or degradation by plant enzymes. Both wetland plant species accumulated substantial quantities of the persistent organic chemicals but had different degradation capacities. The enzyme systems in P. australis were much more effective that those in rice in the degradation and transformation of the organic pollutants.     

Polychlorinated biphenyl (PCB) residues in European roe deer (Capreolus capreolus) and red deer (Cervus elaphus) from north-western Poland

The purpose of this study was to evaluate polychlorinated biphenyls (PCBs) contamination levels in roe and red deer from north-western Poland and to assess environmental pollution in this area. A quantitative analysis was conducted using a capillary gas chromatography/mass spectrometry method. The mean concentrations of ΣPCBs (sum of PCBs: 28, 52, 101, 138, 153, 180) in liver samples were 30.24±12.35 ng·g^?1 of lipid weight (l.w.) in roe deer and 60.13±14.23 ng·g^?1 l.w. in red deer, compared with 24.21±10.02 and 45.22±9.77 ng·g^?1 in the lungs of roe and red deer, respectively. PCBs 138, 153 and 180 were the dominant congeners in the liver samples of the analysed animals, whereas PCB 138 and 153 in the lungs. TEQs levels calculated for only dioxin-like PCBs were low: 0.32 and 0.29 pg WHO-PCB-TEQ·g^?1 fat in liver of red deer and roe deer, respectively. The mean PCB concentrations obtained in our study for organs of roe deer and red deer were several times lower than those reported elsewhere. These findings show that the investigated roe and red deer originated from an area with low levels of PCB contamination.     

持久性有机污染物(POPs)的生物降解与外生菌根真菌对POPs的降解作用

综述了持久性有机污染物(POPs)的生物降解途径,以及国内外在外生菌根真菌降解POPs方面的研究进展,阐述了其机制与优势.根据作用的微生物和环境条件的不同,POPs如PCBs、DDT等可以通过脱氯或开环等途径生物降解.外生菌根真菌能降解多种POPs,具有较大的潜力.图2表2参30     

Occurrence of PCBs and PAHs in an urban soil of Madrid (Spain)

Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were analysed in surface soil samples collected in 2001–2002 at an open urban area of Madrid. In order to obtain representative samples, three collection points at the site were chosen. The most abundant PAHs and PCBs were phenanthrene, fluorene, pyrene, chrysene and benzo[a]pyrene and hexa- and heptachlorinated PCBs, respectively. The sum of selected PAHs (13 compounds) and PCBs (15 congeners) averaged 1 and 0.1?µg?g^?1, respectively. PCB levels in winter were 2–10 times higher than summer ones, while seasonal variation for most of PAHs were not observed. Good correlations among all PCBs were found. Five PAHs were also well correlated.     

中国东海抹香鲸体内多氯联苯的组成特征及毒性当量

用气相色谱-质谱联用仪测定了一只中国东海海域抹香鲸(Physeter macrocephalus)皮脂24种多氯联苯(PCBs)同系物的含量,并分析了其组成特征以及国际毒性当量.结果表明,东海海域抹香鲸皮脂PCBs的湿重含量为1.12μg.g-1;PCBs同族体中以含6和5个氯原子的化合物为主,高氯代PCBs占总量的92.10%;PCBs同系物中以PCB153、PCB138、PCB101和PCB149居多,分别占到PCBs总量的21.28%、15.97%、10.29%和10.23%;抹香鲸皮脂的TEQs含量为1663.07 pg.g-1,其毒性主要来自PCB126,其次是PCB123和PCB118;初步推断中国东海海域的抹香鲸受PCBs污染程度较轻.     

Bioindikation mit Wanderfalken

Goal and Scope

The Stockholm convention bans 12 prominent persistent organic pollutants (POPs), and the pertinent global monitoring programme recommends birds’ eggs as bio-indicators for the terrestrial food web. As top predators, Peregrine falcons are uniquely suited indicators because of their accumulating power for persistent and lipophilic compounds. On the other hand, the Peregrine falcon as a sentinel species was closer to extinction than other birds of prey. Only unremitting efforts of private omithologists throughout the past four decades in conjunction with the timely banning of organochlorine pesticides like DDT succeeded in saving the Peregrine population of Baden-Wueriternberg from extinction, in contrast to the Peregrine falcons of other German states or other European countries.

Methods

See vd Trenck et al. (2006).

Results and Conclusions

New results confirm the findings of the past long-term bio-monitoring. The main pollutants are PCBs (ca. 20 μg/g) and pp′-DDE (ca. 11 μg/g), the latter contributing >96% of all organochlorine pesticide residues (all concentrations on a dry matter basis). Both substances have followed a slightly increasing trend since 2004. The sum of the polychlorinated diphenyl ethers (PBDE) has fluctuated strongly in the past four years, and in 2006 amounted to 0.6 μg/g (mean without outliers), just as the mercury contamination of the eggs. PCB-156 as the main dioxin-like PCB followed with an average concentration of 0.35 μg/g. Only 10 out of 23 eggs analysed contained hexabromocyclododecane (HBCD) in measurable concentrations; the mean concentration of these eggs was 0.024 μg/g. Tetrabromobisphenol A (TBBA) was detected in all egg samples with a mean of 0.004 μg/g. Due to the many and diverse effects exerted by PCBs; the assessment of this group of compounds, with the aid of European and German regulations for food, proves to be a complex matter, which is currently in a state of flux. There is no doubt, however, that the mean pollution of the Peregrine eggs with toxic dioxin equivalents (WHO TEQ) has reached the no observed adverse effect level (NOAEL) known for chickens and osprey chicks, and the most polluted eggs exceed this threshold considerably. The toxic profile of PBDEs is similar to that of PCBs. They are known to promote tumour growth, to interfere with the thyroid hormone system resulting in toxicity for the neuronal development, to suppress the immune system, and to trigger stress reactions. Tests with highly purified BDE-47 have ruled out dioxin-like effects via Ah-receptor binding for this congener and such effects are therefore very unlikely for the whole class of compounds. At the present time, quantitative criteria for the assessment of the risk posed by PBDEs are not sufficiently reliable, and less so for HBCD and TBBA.

Recommendations and Perspectives

It is necessary to continue the bio-monitoring of POPs and similar pollutants in the terrestrial food web and to establish NOAELs as quantitative criteria for their assessment. Possible sources of dioxin-like PCBs and PCDD/Fs are to be pinpointed, and abatement measures are to be considered where background concentrations are significantly exceeded.     

多溴联苯醚在啮齿类动物体内的代谢动力学研究进展

多溴联苯醚(PBDEs)是一类持久性有机污染物(POPs),其作为一种广泛使用的溴化阻燃剂在环境中普遍存在.PBDEs对生物体和人体存在内分泌干扰等毒性危害,正受到人们越来越多的关注.然而目前PBDEs对人体造成的影响都是由动物实验(主要是啮齿类动物)外推而得,因此研究不同的PBDEs同系物在啮齿类动物体内的代谢动力学...     

Monitoring and risk assessment of polychlorinated biphenyls (PCBs) in agricultural soil from two industrialized areas

For monitoring and risk assessment, levels and distributions of Σ₂₉ PCBs in paddy soil samples collected from Gwangyang (10 sites) and Ulsan (20 sites), heavily industrialized cities in Korea, were investigated using high-resolution gas chromatography/high-resolution mass spectrometry. Overall, total concentrations of Σ₂₉ PCBs in Gwangyang (216.4–978.6 pg g^?1 dw) and Ulsan (273.8–1824.1 pg g^?1 dw) were higher than those (106.6–222.6 pg g^?1 dw) in agricultural soil from Anseong in Korea. The TEQ (toxic equivalency) values from Gwangyang (0.06–0.40 ng TEQ kg^?1 dw) and Ulsan (0.06–0.22 ng TEQ kg^?1 dw) were higher than those (0.04–0.11 ng TEQ kg^?1 dw) in Anseong but lower than the WHO threshold level (20 ng TEQ kg^?1). However, one of the most toxic congeners, PCB 126, gave the highest concentration, possibly posing a risk to the biota. Seven indicator PCB congeners contributed to 50–80% of the total concentration of Σ₂₉ PCBs, indicating the 7 PCBs can be used as valuable indicators for monitoring. The principal component analysis and cluster analysis for the homologue profiles of PCBs indicated that all the samples from both cities had the similar PCB contamination patterns, and the major sources of the PCB contamination were most likely from the usage of Aroclor 1254 than those of Aroclors 1242 and 1260. These PCB technical mixtures were possibly significantly used by various industries including iron and steel industries in Gwangyang and petrochemical and shipbuilding industries in Ulsan.     

Polychlorinated biphenyls and organochlorine pesticides in amniotic fluids of pregnant women in south-central Turkey†

The concentrations of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) were determined in amniotic fluid of 200 pregnant women from the Cukurova region of Turkey. The concentrations of OCPs [hexachlorocyclohexane (HCH), hexachlorobenzene (HCB), dichlorodiphenyl trichloroethane (p,p′-DDT), and various metabolites], and different PCB congeners (28, 52, 101, 118, 138, 153, 180) were determined by gas chromatography with electron capture detection as follows: HCB 6.6 ± 4.7, ΣHCH 21.6 ± 14.2, ΣDDT 12.5 ± 7.5, and ΣPCBs 74.0 ± 54 ng mL^?1. Correlations of maternal or gestational age and levels of OCPs and PCBs were not significant. The levels of these organochlorine compounds (OCs) were below detection limit for 5% of the samples, 80% contained more than one OC. This study illustrates that prenatal exposure of a fetus to OCs is prevalent in the Cukurova region.     

植物--实时富集大气持久性有机污染物的被动采样平台

对植物富集大气持久性有机污染物(POPs)的机理及其在大气POPs污染监测中的应用,主要是地衣、苔藓、树叶、树皮作为大气POPs的被动采样器在大气POPs监测中的应用做了介绍,指出树木“时间隧道”作为实时记录大气历史污染状况的又一“新标本”将在大气污染“历史监测”中发挥重要作用．