Seasonal and spatial variability of polychlorinated biphenyls (PCBs) in vegetation and cow milk from a high altitude pasture in the Italian Alps

The seasonal and spatial variability of polychlorinated biphenyls (PCBs) in vegetation and cow milk was studied in a high altitude pasture in the Alps (1900 m a.s.l.). PCB contamination in vegetation shows a concentration peak in June, which is mainly interpreted as the consequence of a temporary PCB enrichment of the air layer above the ground due to net emission fluxes from the soil. A three compartment dynamic model was developed to test this hypothesis. The North/South enrichment factor in the vegetation was 1.5-1.6 for penta- and hexa-substituted congeners and 1.7 for hepta- and octa-PCBs, according to the effect of temperature on compounds having higher K_oa values. Milk concentrations followed the vegetation seasonal trend. The congener abundance in milk is in agreement with the biotransformation susceptibility, absorption efficiency and residence time of the different congeners in dairy cows.     

Temporal distribution and fractionation of polychlorinated biphenyl congeners in a contaminated Wisconsin lake

The most thorough field investigation, to date, of the temporal distribution and fractionation of polychlorinated biphenyl (PCB) congeners in an inland lake has been conducted in Little Lake Butte des Morts, WI. Distinct seasonal variations in dissolved and particle associated PCBs were observed over a two year period at the lake outlet; the lowest values occurred during ice-cover periods while the highest values occurred during summertime. Total dissolved PCBs ranged from 1.4–34 ng/L while total particle associated PCBs varied from 2.1–105 ng/L. An average of 71% of the total PCBs were associated with particles. Both PCB fractions were dominated by ortho-chlorinated di-, tri-, and tetrachlorobiphenyls with IUPAC #28+31 accounting for the greatest portion. Some changes appear to have taken place in the environmental composition of congeners since PCBs first entered this waterway through effluent discharges.     

Levels and congener profiles of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and dioxin-like polychlorinated biphenyls in cow’s milk collected in Campania, Italy

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and certain dioxin-like polychlorinated biphenyls (dl-PCBs) are a family of chemically-related lipophilic compounds characterized by similar toxicity. Due to their properties they are universally distributed in the environment and classified as persistent organic pollutants (POPs). From most of studies carried out to evaluate human dietary intake, milk and dairy products result as a major contributors of PCDD/Fs uptake. Of course the main source of milk contamination is animal feeds. Lactating ruminants, cows included, transfer these compounds to the food chain by ingestion of contaminated vegetables or soil. Their resistance to degradation and a high lipophilicity means that PCDD/Fs and dl-PCBs may be accumulated into fat tissues from which they are transferred to milk during lactation period.Seventy-nine cows milk samples, collected in the monitoring plan 2008, were analyzed for PCDD/Fs and dl-PCBs. Eleven milk samples were non-compliant corresponding to five breeding livestock located in Caserta province. The distribution of PCDD/Fs and dl-PCBs congeners in these samples was examined in order to determine the likely sources of dioxins. The results show that the congener profile is characterized by a prevalence of PCDFs in respect of PCDDs, that represents the typical pattern of thermal origin contamination.     

Seasonal fluxes and temperature-dependent accumulation of persistent organic pollutants in lakes: The role of internal biogeochemical cycling

A dynamic flux model for lakes taking into account the interactions between atmospheric depositional and biogeochemical processes (BIODEP model) was used to assess the importance of internal cycling and biogeochemical processes with respect to accumulation of four different polychlorinated biphenyls (PCBs) (congeners 28, 52, 101 and 153) in Lake Redo, a high-altitude lake in the Spanish Pyrenees. To investigate the effect of temperature on sediment accumulation, the model was run at different temperatures and corresponding sediment inventories were plotted vs. reciprocal temperature. In line with measurements from a previous study looking at sediment inventories of 19 European high-altitude lakes (MOLAR study), we found a stronger temperature dependence of lake sediment concentrations for the less volatile/less soluble PCBs. Seasonal and annual mass balances were investigated and highlighted the importance of internal lake processes controlling the differences in sediment accumulation for the different PCB congeners. For example, the higher temperature dependence of sediment inventories for the high chlorinated congeners is due to the fast dynamics of water-to-sediment transport in comparison to atmospheric deposition processes.     

Seasonal air-water exchange fluxes of polychlorinated biphenyls in the Hudson River Estuary

Polychlorinated biphenyls (PCBs) were measured in the air and water over the Hudson River Estuary during six intensive field campaigns from December 1999 to April 2001. Over-water gas-phase SigmaPCB concentrations averaged 1100 pg/m3 and varied with temperature. Dissolved-phase SigmaPCB concentrations averaged 1100 pg/L and displayed no seasonal trend. Uncertainty analysis of the results suggests that PCBs with 5 or fewer chlorines exhibited net volatilization. The direction of net air/water exchange could not be determined for PCBs with 6 or more chlorines. Instantaneous net fluxes of SigmaPCBs ranged from +0.2 to +630 ng m(-2) d(-1). Annual fluxes of SigmaPCBs were predicted from modeled gas-phase concentrations, measured dissolved-phase concentrations, daily surface water temperatures and wind speeds. The net volatilization flux was +62 microg m(-2) yr(-1), corresponding to an annual loss of +28 kg/yr of SigmaPCBs from the Hudson River Estuary for the year of 2000.     

Painted surfaces--important sources of polychlorinated biphenyls (PCBs) contamination to the urban and marine environment

A study of a large number of samples of flaking old paint from various buildings in Bergen, Norway (N = 68) suggests that paint may be the most important contemporary source of PCBs in this urban environment with concentrations of PCB₇ up to 3.39 g/kg. Twenty-three of the samples were collected from a single building, and the concentrations were found to vary over 3 orders of magnitude. In addition, 16 concrete samples from a large bridge previously coated with PCB-containing paint were collected and separated into outer- and inner samples indicating that PCBs are still present in high concentrations subsequent to renovation. PCBs were found in several categories of paint from wooden and concrete buildings, potentially introduced to the environment by natural weathering, renovation, and volatilization. Consequently, this dispersion may lead to increased levels of PCBs in urban atmospheres, soils, and harbor sediments where high concentrations have resulted in Governmental advice against consumption of certain seafood.     

Characterization of polychlorinated biphenyls and brominated flame retardants in surface soils from Surabaya, Indonesia

In this study, soil contamination by PCBs, PBDEs, HBCDs and two novel BFRs such as 1,2-bis-(2,4,6-tribromopenoxy) ethane (BTBPE) and decabromodiphenyl ethane (DBDPE) in various locations such as industrial, urban, rural, dumping site and agricultural areas of Surabaya, Indonesia has been characterized in order to evaluate their contamination status, profiles, potential sources, fate and behavior. Range and median concentrations of PCBs, PBDEs, HBCDs, BTBPE and DBDPE were ND - 9.6 (1.2), 0.069 - 24 (7.4), ND - 1.8 (0.48), ND - 1.7 (0.14) and ND - 7.6 (2.2) ng g⁻¹ dw, respectively. Industrial, urban and dumping areas were inventoried as the main sources of these pollutants. Decreasing gradient levels were observed for these contaminants from industrial district, urban, dumping site, rural and agricultural areas, in that order. Furthermore, organic carbon contents and proximity to the point sources were found as the major controlling factors. Contaminant profiles were characterized by the predominance of hexa-, hepta- and penta-homologues for PCBs; deca-, nona- and octa- for PBDEs and α-isomer for HBCDs. Product mixtures such as Ar1260/KC600 and Ar1254/KC500 for PCBs, deca- and octa-BDEs for PBDEs were the possible common formulations used in study area. To our knowledge, this is a first comprehensive study on characterization of soil contamination by PCBs, PBDEs and HBCDs together with two novel BFRs in a highly industrialized city located in tropical region. This study provides baseline information for establishing national monitoring programs in Indonesia.     

Polychlorinated dibenzo-p-dioxins, dibenzofurans and polychlorinated biphenyls levels in human breast milk from different regions of Turkey

Human breast milk offers the optimal nutrition for all infants and have been widely used in biomonitoring programs to assess human exposure to lipophylic environmental contaminants such as polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF) and polychlorinated biphenyls (PCB). There are no previous reports from Turkey on chemically determined levels of PCDDs, PCDFs, and PCBs in human breast milk expressed as World Health Organization (WHO) toxic equivalents (TEQ). To get an overview of the levels of these contaminants in Turkish human milk, samples from 51 Turkish women living in the Ankara, İstanbul, Antalya, Kahramanmaraş, and Afyon provinces were analyzed by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) throughout 2007. The mean concentrations of WHO_PCDD/F-TEQ and WHO_PCB-TEQ of all samples from the five regions were 7.5 and 3.1 pg g⁻¹ on a lipid basis, respectively. PCDD/F concentrations ranged between 0.78 and 29.3 pg WHO-TEQ g⁻¹ fat (1.7 and 36.2 pg WHO-TEQ g⁻¹ fat, respectively, including PCB). Of the five studied locations, the lowest levels of ∑TEQs (PCDD/F + PCB) were found in the Afyon (6.8 pg WHO-TEQ g⁻¹ fat) and the highest in the Antalya (15.6 pg WHO-TEQ g⁻¹ fat) province. The results have been discussed in terms of regions and PCDD/F and PCBs for which analyses had been made. The mean levels of PCDD/Fs and PCBs in Turkish human milk are comparable to that found in other countries.     

Dietary uptake kinetics of polychlorinated biphenyls from sediment-contaminated sandworms in a marine benthic fish (Pseudopleuronectes yokohamae)

To evaluate the dietary uptake of polychlorinated biphenyls (PCBs) from live food, we investigated the dietary uptake and depuration kinetics of PCBs in a marine benthic fish (marbled sole, Pseudopleuronectes yokohamae) by using as food live sandworms (Perinereis nuntia) that were laboratory-exposed to field-collected PCB-contaminated sediment. Marbled sole were fed the PCB-contaminated sandworms for 28 d and then uncontaminated sandworms for 56 d. The assimilation efficiencies (AEs) of 84 PCB congeners via the gastrointestinal tract (GIT) to the muscle of the fish ranged from 0.21 to 0.78; whole-body AEs would be lower than those of muscle because of the lower PCB concentrations, on a lipid basis. The AEs determined in this study were lower than those in other studies that used PCB-spiked commercial pelletized food. The lower AEs found in this study might be attributable to differences in the food administered (live sandworms vs. commercial pellet food), possibly because of low digestibility of sandworm lipids by marbled sole. In addition, the AEs in this study tended to increase with increasing log octanol-water partition coefficients (K_OW) up to about seven, although AEs in the other studies using commercial pelletized food did not increase with increasing log K_OW. This result suggests the co-transport of highly hydrophobic PCB congeners along with lipids and fatty acids from the digested sandworms into the GIT epithelium cells. The growth-corrected half-lives of 26 PCB congeners in the muscle of fish ranged from 20 to 107 d.     

Comparison of annual dry and wet deposition fluxes of selected pesticides in Strasbourg, France

This work summarizes the results of a study of atmospheric wet and dry deposition fluxes of Deisopropyl-atrazine (DEA), Desethyl-atrazine (DET), Atrazine, Terbuthylazine, Alachlor, Metolachlor, Diflufenican, Fenoxaprop-p-ethyl, Iprodione, Isoproturon and Cymoxanil pesticides conducted in Strasbourg, France, from August 2000 through August 2001. The primary objective of this work was to calculate the total atmospheric pesticide deposition fluxes induced by atmospheric particles. To do this, a modified one-dimensional cloud water deposition model was used. All precipitation and deposition samples were collected at an urban forested park environment setting away from any direct point pesticide sources. The obtained deposition fluxes induced by atmospheric particles over a forested area showed that the dry deposition flux strongly contributes to the total deposition flux. The dry particle deposition fluxes are shown to contribute from 4% (DET) to 60% (cymoxanil) to the total deposition flux (wet + dry).     

Seasonal variability of polychlorinated biphenyls (PCBs) and polychlorinated diphenyl ethers (PBDEs) congener profiles in butter in Poland: Dietary risk evaluation

Various statistical methods have been employed to analyse in details seasonal diversification of polychlorinated biphenyl (PCB)/polybrominated diphenyl ether (PBDE) congener profiles found in butter fat. The variability of the PCB/PBDE congener profiles indicates the presence of various sources of the milk fat contamination. The obtained results suggest that the environmental chemical background has the highest share in the contamination sources pattern. Ion trap mass spectrometry coupled to high-resolution gas chromatography with semi-permeable membrane dialysis sample cleanup was used for determination of PCBs and PBDEs in milk fat. Determined butter fat PCB profiles were similar to the profiles characteristic for Aroclor 1254 technical mixture. Our data indicate that dietary intake of PCB/PBDE with milk and milk products may be estimated to be about 717.5 pg kg b.w.^?1 day^?1 for six-indicator PCBs, 0.329 (equivalent toxicity, TEQ) pg kg b.w.^?1 day^?1 for 12 DL PCBs and 50 pg kg b.w.^?1 day^?1 for PBDEs (sum of 14 congeners).     

Survey of commercial pasteurised cows' milk in Wallonia (Belgium) for the occurrence of polychlorinated dibenzo-p-dioxins,dibenzofurans and coplanar polychlorinated biphenyls

Congener-specific analyses of 7 polychlorinated dibenzo-p-dioxins (PCDDs), 10 polychlorinated dibenzofurans (PCDFs) and 4 non-ortho (coplanar) polychlorinated biphenyls (cPCBs) were performed on 35 samples of commercial long-life pasteurised cows' milk issued from eight different brands available in Walloon supermarkets (Belgium). The observed congener profile was characteristic of milk samples issued from industrialised countries with good inter and intra-brand reproducibility's. The PCDDs to PCDFs ratio was equal to 1.8 in concentration. The toxic equivalent (TEQ based on WHO-TEF) value for PCDD/Fs in all analysed milks was 1.09+/-0.30 pg TEQ/g fat (range 0.86-1.59), which is below the recommended EU non-commercialisation threshold value of 3 pg TEQ PCDD/Fs/g of milk fat. The mean TEQ value including cPCBs was 2.23+/-0.55 pg TEQ/g fat. These PCBs actually contributed for 49+/-8.6% of the total TEQ. Among PCDD/Fs and cPCBs, tetrachloro dibenzo-p-dioxin (TCDD), pentachloro dibenzo-p-dioxin (PeCDD), pentachloro dibenzofurans (PeCDFs) and 3,3',4,4',5-pentachloro biphenyl (PCB-126) were the most important contributors to the TEQ. Estimated daily intake (EDI) due to consumption of such milks was 0.34 pg TEQ/kg of body weight/day for PCDD/Fs and 0.69 pg TEQ/kg of body weight/day when cPCBs were included.     

Myco- and phyco-remediation of polychlorinated biphenyls in the environment: a review

Environmental Science and Pollution Research - Polychlorinated biphenyls (PCBs) are toxic organic compounds and pose serious threats to environment and public health. PCBs still exist in different...     

Modelling the fate of hydrophobic organic contaminants in a boreal forest catchment: A cross disciplinary approach to assessing diffuse pollution to surface waters

The fate of hydrophobic organic compounds (HOCs) in soils and waters in a northern boreal catchment was explored through the development of a chemical fate model in a well-characterised catchment system dominated by two land types: forest and mire. Input was based solely on atmospheric deposition, dominated by accumulation in the winter snowpack. Release from soils was governed by the HOC concentration in soil, the soil organic carbon fraction and soil-water DOC content. The modelled export of selected HOCs in surface waters ranged between 11 and 250 ng day⁻¹ during the snow covered period, compared to 200 and 9600 ng/d during snow-melt; highlighting the importance of the snow pack as a source of these chemicals. The predicted levels of HOCs in surface water were in reasonable agreement to a limited set of measured values, although the model tended to over predict concentrations of HOCs for the forested sub-catchment, by over an order of magnitude in the case of hexachlorobenzene and PCB 180. This possibly reflects both the heterogeneity of the forest soils and the complicated and changing hydrology experienced between the different seasons.     

Concentrations of polychlorinated dibenzo-p-dioxins, dibenzofurans and non-ortho substituted biphenyls in polar bear milk from Svalbard (Norway)

Polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and non-ortho substituted biphenyls (PCB, CB) were determined in 6 polar bear milk samples from Svalbard (Norway). For these compounds, no data for polar bears have been reported before from this region. Most of the PCDD/PCDF congeners were found at detectable levels. Concentrations expressed as 2,3,7,8-TCDD equivalents (Nordic model) were in the order of 1–3 pg/g⁻¹ fat (0.2–1.6 pg ml⁻¹ milk) which is comparable with ringed and harp seal blubber from the same region. On whole milk basis, concentrations were similar to those found in human milk. An estimation of the daily uptake via milk showed that the intake is lower for polar bears compared to humans. As in human milk, relatively high levels of OCDD were found in some polar bear milk samples. The PCDD/PCDF congener pattern in the milk was different to that found in polar bear fat from the Canadian Arctic. Non-ortho substituted PCB levels in polar bear milk were similar to those found in polar bear fat from the Canadian North. However, CB 77 or 169 dominated in the milk while CB 126 was the most abundant congener in fat. PCDD/PCDF levels expressed as 2,3,7,8-TE were highly correlated with the fat content of the milk. No correlation between CB and PCDD/PCDF concentrations was found. Some data indicate that PCDD/PCDF concentrations in polar bear milk decrease with increasing time after delivery.     

Dry deposition and soil-air gas exchange of polychlorinated biphenyls (PCBs) in an industrial area

Ambient air and dry deposition, and soil samples were collected at the Aliaga industrial site in Izmir, Turkey. Atmospheric total (particle + gas) ∑₄₁-PCB concentrations were higher in summer (3370 ± 1617 pg m⁻³, average + SD) than in winter (1164 ± 618 pg m⁻³), probably due to increased volatilization with temperature. Average particulate ∑₄₁-PCBs dry deposition fluxes were 349 ± 183 and 469 ± 328 ng m⁻² day⁻¹ in summer and winter, respectively. Overall average particulate deposition velocity was 5.5 ± 3.5 cm s⁻¹. The spatial distribution of ∑₄₁-PCB soil concentrations (n = 48) showed that the iron-steel plants, ship dismantling facilities, refinery and petrochemicals complex are the major sources in the area. Calculated air-soil exchange fluxes indicated that the contaminated soil is a secondary source to the atmosphere for lighter PCBs and as a sink for heavier ones. Comparable magnitude of gas exchange and dry particle deposition fluxes indicated that both mechanisms are equally important for PCB movement between air and soil in Aliaga.     

Detailed study on the levels of polychlorinated dibenzo-p-dioxins,polychlorinated dibenzofurans and polychlorinated biphenyls in Yusho rice oil

One bottle of Yusho rice oil was obtained from a Yusho family in 1998. The levels of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in the causal oil were investigated with two different approaches and the individual concentrations of all the 17 2,3,7,8-substituted PCDD/F and 14 coplanar PCB (Co-PCB) congeners were elucidated for the first time. The concentrations of PCDDs and PCDFs were found to be 0.60 and 8.8 ppm, respectively. For PCBs, more than 130 PCB peaks were observed and a total concentration of 850 ppm including 170 ppm of Co-PCBs was obtained. The toxic equivalents (TEQs) of PCDDs, PCDFs, and Co-PCBs were calculated to be 17, 470, and 120 ppb, respectively. The relative contribution of these classes to the total TEQ in Yusho oil is 3%, 77%, and 20%, respectively, indicating that PCDFs play a major role in the toxicity of Yusho oil. Furthermore, it was confirmed that 2,3,4,7,8-penta-CDF contributes 58% to the total TEQ, supporting the view that this compound is the principal causal agent in Yusho poisoning. It is noteworthy that the most toxic 2,3,7,8-tetra-CDD was newly discovered, although it contributes only 0.1% to the total TEQ. Based on our data, the smallest TEQ intake during the latent period was estimated to be 0.067 mg for Yusho patients. This value is about 60% of that previously reported, suggesting a lower minimum threshold level for the development of the toxic symptoms of Yusho.     

The air-water exchange of polychlorinated biphenyls and polybrominated diphenyl ethers at an urban lake, a receipt water body for the effluent from a municipal sewage treatment plant

The effluents and sludge from municipal sewage treatment plants (MSTPs) are considered as potential sources of many contaminants to the ambient environments. In the present work, the air-water exchange of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) was studied using passive air samplers at an urban lake, which receives the effluents from a MSTP in Beijing, China. The concentrations of PCBs and PBDEs in atmosphere were in the range 15.5-108 ng sample⁻¹ and 2.37-27.8 ng sample⁻¹, respectively, during the sampling period (August, 2007-July, 2008). The predominant PCBs and PBDEs were lowly halogenated congeners. The calculation for the exchange fluxes of PCBs and PBDEs using fugacity model showed that, the net exchange fluxes in different seasons were closely related to the halogen number of different congeners. Except for CBs-28 and 52, the net exchange fluxes was mainly directed from air to water for most of predominant congeners, which implied that the lower chlorinated CBs were dominated by volatilization process rather than the dry/wet depositions and diffusion between air-water interface, additionally, for heavy congeners, the dry/wet deposition process was an important source of PCBs and PBDEs in this lake.     

典型城市湖泊沉积物污染特征与清淤深度

城市湖泊外源污染阻断后,沉积物污染物向上覆水体扩散成为水质主要威胁,探明城市湖泊沉积物污染分布特征和来源是实现湖泊清淤的前提。以龙亭湖和包公湖沉积物为对象,分析了沉积物OM、TN和TP分布特征并进行源解析,基于有机指数和有机氮指数探讨了其清淤深度。结果表明,龙亭湖和包公湖表层 (深度20~30 cm) 沉积物污染严重且分布差异显著,OM (93.08~8.67 mg·g⁻¹,120 cm深度变化) 和TN (5.42~0.26 mg·g⁻¹,40 cm深度变化) 随深度显著降低,TP (1.04~0.55 mg·g⁻¹,110 cm深度变化) 纵向分布变化不显著。龙亭湖沉积物OM来源与取样位置相关,且沉积物形成早期存在大量外源OM输入 (C/N>14) ;包公湖取样点OM以陆源输入占主导 (C/N=5.008~52.808) 。基于此,提出有机指数≥0.5或有机氮指数≥0.133的沉积物层及以上部分应清除,龙亭湖和包公湖所选点位最大清淤深度分别为100和70 cm,湖泊取样点底泥清淤削减量分别达到33.33%~100%和33.33%~53.84%。该研究结果对城市湖泊水质长效保持提供实践参考。