Polychlorinated biphenyls in contaminated soil samples evaluated by GC-ECD with dual-column and GC-HRMS

We present and compare results obtained from the analysis of polychlorinated biphenyls (PCBs) of a limited number of contaminated soil samples collected in three areas of Basilicata region (south of Italy). The levels of PCBs were evaluated by using two analytical methods: (i) parallel dual-column gas-chromatography with dual electron capture detectors (GC-ECD) and (ii) gas-chromatography coupled to high-resolution mass spectrometry (GC-HRMS) via electron impact ionization (EI) in the multiple ion monitoring mode (MIM, two ions per compound). Two extraction methods prior to sample cleanup were also examined: microwave-assisted extraction (MAE) and ultrasonic-assisted extraction (UAE). The MAE was the extraction procedure adopted using acetone/n-hexane (1:1, v/v) as it is mainly characterized by higher sample throughput and allowed reduced consumption of organic solvents. While extraction and analysis of spiked soil samples showed the applicability of both methods, systematic differences between the results were obtained for the sum of PCBs as a result of some non-detected congeners by GC-ECD compared with GC-HRMS. Indeed, high resolution MS using EI mode (electron energy 40eV) with a resolving power of 10,000 provides additional information about the contamination pattern. The GC-ECD screening of 11 soil samples led to just one sample non-compliant to as it was close to the guide value for soils fixed by the Italian legislation (i.e., 60ppb for private or urban soil). Using GC-HRMS, the amount of all PCBs found ranged from 5.4 to 127ppb with five soil samples non-compliant to the guide value. The number of identified congeners ranged from 1 to 9 and 9 to 18 using dual-column GC-ECD and GC-HRMS, respectively.     

Polychlorinated biphenyls (PCBs) in Africa: a review of environmental levels

Several studies have shown an increase in PCB sources in Africa due to leakage and wrongly disposed transformers, continuing import of e-waste from countries of the North, shipwreck, and biomass burning. Techniques used in the recycling of waste such as melting and open burning to recover precious metals make PCBs contained in waste and other semivolatile organic substances prone to volatilization, which has resulted in an increase of PCB levels in air, blood, breast milk, and fish in several regions of Africa. Consequences for workers performing these activities without adequate measures of protection could result in adverse human health effects. Recent biodegradation studies in Africa have revealed the existence of exotic bacterial strains exhibiting unique and unusual PCB metabolic capability in terms of array of congeners that can serve as carbon source and diversity of congeners attacked, marking considerable progress in the development of effective bioremediation strategies for PCB-contaminated matrices such as sediments and soils in tropical regions. Action must be taken to find and deal with the major African sources of these pollutants. The precise sources of the PCB plume should be pinned down and used to complete the pollutant inventories of African countries. These nations must then be helped to safely dispose of the potentially dangerous chemicals.     

Polychlorinated biphenyls in small mammals from contaminated landfill sites

PCBs in small mammals living in a contaminated landfill site varied in both concentration and congener composition, reflecting both the feeding strategy of each species and the chlorination of the congeners. Body concentrations of SigmaPCB on a 1:1:1 Arochlor (1242:1254:1260) basis gave a rank order of Sorex araneus > Apodemus sylvaticus > Microtus agrestis. Comparisons with data for other PCB-contaminated sites suggest that the SigmaPCB values in S. araneus from the landfill site may be of sufficient magnitude to inhibit reproductive capability and to cause other major organ dysfunction. There were also inter-specific differences in the whole body concentrations of the individually quantified congeners. For S. araneus, the rank order of concentrations of the selected ICES 7 marker PCB congeners was: No. 153>138>180>118>28>101>52. In M. agrestis the rank order was: No. 28>118>153>138>180, 52>101. The congener order for A. sylvaticus differed from both S. araneus and M. agrestis, but was more similar to the latter, being: No. 153>138>118>180>28>52, 101. The contribution of the different congeners to SigmaPCB in the mammals reflects the degree of chlorination of different congeners but varies with feeding strategy of the species. In the insectivorous S. araneus, heavily chlorinated congeners (Nos 153, 138 and 180) are most abundant, whereas the herbivore, M. agrestis showed congeners Nos 28 and 118 to be present in the highest amounts, whilst the equivalent pattern for the more omnivorous A. sylvaticus was intermediate between S. araneus and M. agrestis. The high concentrations of PCBs in S. araneus relative to the other species, suggests that it may serve as a useful biomarker of terrestrial environmental pollution by organochlorines.     

Polychlorinated biphenyls in polysulfide sealants--occurrence and emission from a landfill station

Approximately 80,000 kg polysulfide sealant containing 10,000-18,000 kg polychlorinated biphenyls (PCB) was deposited at a Swedish municipal landfill station during 1965-1973. Investigations during 1994 showed that soil layers underneath the landfill had concentration of PCB not alarmingly high. The concentration of PCB congeners in ground water samples was elevated 4-750 times compared to a reference sample. Based on samples of ground water, leachate water, and flux chambers measuring evaporation of PCB from the landfill surface, the emission of PCB was estimated to be 1 g sigmaPCB/yr. This very low rate was attributed to the high sorptive capacity of the sealant. Compared to a reference site, the evaporation flux was elevated for the most volatile congeners, but factors 20-1400 lower than from another landfill which was contaminated with PCB in paper-pulp fibres.     

Polychlorinated biphenyls and their hydroxylated metabolites in placenta from Madrid mothers

Introduction  

Concentrations and congener profiles of polychlorinated biphenyls (PCBs) and their hydroxylated metabolites (OH-PCBs) in placenta samples from a Madrid population (Spain) are reported. Structure dependent retentions of OH-PCBs are known to occur in both humans and wildlife, making it of interest to assess placental transfer of both parent compounds and their metabolites to the developing foetus.     

Polychlorinated biphenyls in Mexican cereals and their packings

The content of polychlorinated biphenyls in Mexican cereals and in their packaging materials was determined. All the samples had polychlorinated biphenyls. In all the food samples and in 73% of the packings, the concentrations of polychlorinated biphenyls exceeded the tolerance limits established by the U.S. Food and Drug Administration. A correlation was found between the values for polychlorinated biphenyls in the cereals and those in their packings, therefore, it is concluded that the main source of polychlorinated biphenyls in Mexican cereals is the transference of those present in the recycled paperboard used for the packings.     

Polychlorinated biphenyls and organochlorine pesticides in various bird species from northern China

Little data are available on organochlorine contamination in Chinese terrestrial birds of prey. This study examined the presence of PCBs, DDTs and other organochlorine pesticides in various raptors from northern China. DDE exhibited the highest concentrations among targeted compounds. Greatest levels (23.5-1020 mg/kg lipid weight) were observed in Eurasian sparrowhawks. This may be due to their stopover in southeastern China, where high DDT and dicofol applications have been documented. Residential kestrels exhibited much lower DDE, but similar PCB and HCH concentrations. ΣTEQs and PCB-126/-77 concentration ratios exhibited significant positive correlations with ΣPCB concentrations, respectively. Similar results were also demonstrated by a meta-analysis of previously published data across avian species. Possible hepatic sequestration of coplanar PCB-77, -126, -169 and -118 was observed as liver TEQs increased in Eurasian sparrowhawks. These observations may indicate an induction of CYP1A enzymes, as a result of elevated contamination in some species.     

Lichens as an integrating tool for monitoring PAH atmospheric deposition: A comparison with soil, air and pine needles

The aim of this study was to validate lichens as biomonitors of PAH atmospheric deposition; for that, an inter-comparison between the PAH profile and concentrations intercepted in lichens with those of air, soil and pine needles was performed. The study was conducted in a petro-industrial area and the results showed that PAH profiles in lichens were similar to those of the air and pine needles, but completely different from those of soils. Lichens accumulated higher PAH concentrations when compared to the other environmental compartments and its concentrations were significantly and linearly correlated with concentrations of PAHs in soil; we showed that a translation of the lichen PAHs concentrations into regulatory standards is possible, fulfilling one of the most important requirements of using lichens as biomonitors. With lichens we were then able to characterize the air PAHs profile of urban, petro-industrial and background areas.     

Polychlorinated biphenyls contamination in urban soil of Shanghai: level, compositional profiles and source identification

Surface soil samples taken from 55 sampling sites at the urban areas of Shanghai were collected and analyzed for the occurrence of 144 polychlorinated biphenyls (PCBs) by GC-μECD. The results showed that totally 74 PCB congeners were identified and the mean concentration of total PCBs was 3057 ng kg⁻¹ with a range of 232 to 11325 ng kg⁻¹. Compared with the related reports, the level of PCBs contamination in this study was approximately equal to the global background value in soils, but higher than Chinese background for rural and urban soils. According to the compositional profiles of PCBs homologues, a higher proportion of low chlorinated (from tri-CBs to hexa-CBs) was observed. The results indicated that PCB15 + 13, PCB18, PCB28, PCB104 + 47 and PCB153 were the most dominant congeners among the identified PCBs. Through homologues analysis, cluster analysis and principal component analysis (PCA), it was found that PCBs were stretched from mixed local sources, and appeared to be mostly originated by Aroclor 1260- and 1254-like mixtures as well as some samples influenced by Aroclor 1232 and 1242. The correlation analysis showed the relatively good correlation among the PCB homologues and soil total organic carbon (TOC), suggesting important influence of soil TOC on PCBs contamination in soil matrix in Shanghai region. The toxic equivalency (TEQ) concentrations of these six dioxin-like PCBs detected in urban soil samples range from 2.71 to 24.9 pg kg⁻¹-PCDDeq with a mean 8.18 pg kg⁻¹-PCDDeq.     

Polychlorinated biphenyls in sediments of the Venice Lagoon

Twenty-four surficial sediment samples, representing different environments within the Venice Lagoon, were analyzed for polychlorinated biphenyls (PCBs) in order to assess degrees of pollution, sources, areal distribution, and potential risk for the environment. Concentrations in surficial sediments range from 2 to more than 2049 microg kg(-1) dw. The maximum is probably due to the discharge of industrial wastes into the Brentella Canal, within the first Industrial Area. Lagoon samples are 11-205 times less contaminated, being influenced by pollutants stored in the canals only occasionally. Congener profiles distinguish PCBs in two main categories. The baseline pollution is probably due to a variety of sources within the lagoon system, whereas less chlorinated PCBs were discharged into the Brentella Canal. Our estimates suggest that, due to high concentrations, toxic equivalents (TEQs) of PCBs are comparable to those relative to PCDD/Fs for the least contaminated samples, whereas they are lower in case of heavy PCDD/F contamination.     

Polychlorinated biphenyls in different trophic levels from a shallow lake in Argentina

Polychlorinated biphenyls (PCBs) were determined in a aquatic community from Los Padres Lake, Argentina. Twenty four PCB congeners from tri- to octa-chlorinated isomers were detected and quantified using conventional gas chromatography with electron capture detector (GC-ECD). The aim of this study was to investigate the concentrations of PCBs in freshwater organisms from a shallow lake of Argentina. Stems of bulrush (Schoenoplectus californicus), whole tissues of false loosestrife (Ludwigia sp.) and grass shrimp (Palaemonetes argentinus), and liver, gonads, muscle and mesenteric fat (if present) of fish species (Rhamdia sapo) and (Oligosarcus jenynsi) were analyzed. Two areas were selected to macrophytes sampling: the input area, main PCB source of the lake (Station 1), and the output area, a potential anoxic zone (Station 2). Macrophytes from Station 1 bioconcentrated higher total PCB levels than Station 2, showing that the former have received PCBs washed down from upstream areas. Penta- and hexa-congeners were enriched relative to other congeners in animal biota and macrophytes from Station 1, consistent with commercial mixture of Aroclor 1254 used in this region. In bulrush from Station 2 a predominance of tri- and tetra-chlorinated congeners was observed. Grass shrimp showed the lowest PCB values among animal biota. PCB concentrations in fish tissues varied with the species and the gonadal development. Mesenteric fat, only present in post-spawning organisms of R. sapo, had the highest values of PCBs relative to other tissues. A clearance of total PCBs in ovaries of post-spawning females of R. sapo was observed, but not in testes. O. jenynsi/P. argentinus biomagnification factor (BMF) had a mean value of 18.7. Congeners 44, 52 and 151, showed the highest BMF values, being 64, 66 and 62, respectively. These values would be a consequence of the low depuration rate of 44 and 52 congeners with orthochlorine substitution conducted by O. jenynsi and the high depuration rate of congener 151, which lacks 4 4^′- chlorine substitution, carried out by grass shrimp. Although the most of congeners have been biomagnified, they did not clearly displayed a concomitantly increasing with log K_ow.     

Organohalogenated compounds in pine needles from Beijing city, China

Pine needles collected from 22 sites of six areas in Beijing city, China, were analyzed by instrumental neutron activation analysis (INAA) combined with organic extraction for extractable organohalogens (EOX) and extractable persistent organohalogens (EPOX). The concentrations of EOX (EOX = ECl + EOBr + EOI) were in the order of EOCl > EOBr > EOI. About 1.6-34% of EOCl remained as extractable persistent organochlorine (EPOCl) after treatment with concentrated sulfuric acid, which suggested that major fractions of EOCl in pine needles were an acid-liable or acid-soluble fraction. The fact that pine needle contained higher EOCl contents in chemical industrial and traffic hub areas indicated that chemical industries and exhaust emission from vehicle were the main sources of organochlorines in the Beijing's air. The relative proportions of the known organochlorines (such as HCHs, DDTs, chlordanes, HCB and PCBs) to total EOCl and EPOCl were 0.32-0.76% and 2.5-11.4%, respectively, which implied that a major portion of the EOCl and EPOCl measured in pine needles was unknown. The organochlorinated pesticides (OCPs) and PCBs concentrations in six areas were as follows: sigma HCH (sigma HCH = alpha- + beta- + gamma- + delta-HCH), 11.7-20.8 ng/g; sigma DDT (p,p'-DDT + p,p'-DDE + p,p'-DDD), 12.5-113.3 ng/g; hexachlorobenzene (HCB), 1.1-5.3 ng/g; sigma chlordane (cis-chlordane + trans-chlordane + heptachlor), 1.7-9.5 ng/g, sigma PCB, 41.8-270.5 ng/g, on dry weight basis. The samples from chemical industrial area and residential area nearby chemical industries contained the highest concentrations of sigma DDT, HCB, sigma chlordane and sigma PCB, while the contamination levels of most OCPs and PCBs in iron-steel industrial area were the lowest. The ratios of alpha/gamma-HCH (ranged from 0.9-1.5) and p,p'-DDT/DDTs (ranged from 72.1% to 91.0%) revealed the presence of the recent use of lindane and DDTs or impure dicofol in Beijing.     

Polychlorinated biphenyls and chlorinated pesticides in mussels from the Egyptian Red Sea coast

The residues of 17 organochlorine pollutants were analyzed in bivalve Brachiodontes sp. collected from 11 different locations in April 2000 along the Egyptian Red Sea coast. The pollutants studied were 10 individual polychlorinated biphenyl (PCB) congeners, alpha,alpha,alpha-hexachlorocyclohexane (HCHs), cyclodienes (heptachlor, heptachlorepoxide, aldrin, dieldrin) and dichlorodiphenyltrichloroethanes (DDTs) (p,p'-DDE, p,p'-DDD and p,p'-DDT). The concentration of total DDTs ranged between 125 and 772 ng/g of wet weight whereas the concentration of the PCBs, HCHs and cyclodienes ranged from 6.7 to 66.4 ng/g; 16.2 to 183.4 ng/g and 8.8 to 221.6 ng/g of wet weight, respectively. The levels are low to moderate in relation to the published data from other coastal areas. The present results indicate low to moderate PCBs and pesticides contamination in the investigated mussels except DDTs.     

Polychlorinated biphenyls in freshwater salmonids from the Kerguelen Islands in the Southern Ocean

The Subantarctic Kerguelen Islands (49°S, 70°E) contain freshwater ecosystems among the most isolated in the world. Concentrations of polychlorinated biphenyls (PCBs) were assessed in the muscle of 48 brook trout and 38 brown trout caught during summer and spring 2006 in the rivers, lakes and ponds of Kerguelen. The sum of 29 PCBs averaged 404 and 358 ng g⁻¹ lipid, and dioxin-like PCB was 19 and 69 ng g⁻¹ lipid, in brook and brown trout, respectively. The values showed a high variability and some fish accumulated PCBs at levels similar to those of fish from impacted areas. While inter-sex differences were limited, the season and the morphotype appeared to have the most influence. Fish captured in summer had muscle PCB concentrations about three times higher than those caught in spring and the ‘river’ morphotype of brook trout showed the highest PCB levels.     

Distribution of some organochlorine compounds in pine needles from Central and Northern Europe

Levels of selected organochlorine compounds in pine needles were measured in two sampling series. The first series collected in 1989 covered Southern Germany to Northern Scandinavia, and the second collected in 1990 covered Czechoslovakia to Estonia. The levels of alpha-hexachlorocyclohexane (alpha-HCH) and hexachlorobenzene (HCB) were relatively uniform throughout Europe, while the levels of gamma-hexachlorocyclohexane (gamma-HCH) and the DDT group show higher levels in the southern parts of the investigated area. The deposition patterns of all compounds except alpha-HCH indicate a dependence on fresh release from diffuse or point sources rather than global fractionation. The analytes accumulate in the needles until senescence starts and, generally, the oldest needles have the highest concentrations. The accumulation rate of the analytes in mountain pine needles is about half that of Scots pine needles indicating the importance of species differences.     

Accumulation of chlorinated hydrocarbon vapours in pine needles

Needles with different ages from four pines have been analysed for PCB's, HCB, α- and γ-HCH, p,p'DDT and DDE. The accumulation found has been discussed and provisional accumulation rates under actual background conditions have been calculated.     

Polychlorinated biphenyls and organochlorine pesticides in Baltic Sea sediments and bivalves

Insecticide resistance is an evolutionary response to insecticides and, as such, important for environmental biomonitoring and for pest management. Fitness disadvantage in the absence of insecticide is a frequent assumption in models of insecticide resistance evolution, which was observed in different insect species. Fitness studies are based in demographic performance of isolated populations without direct interaction between insecticide-resistant and -susceptible populations. Here we reported a study of direct competition following a factorial bivariate design between an insecticide-susceptible population of the maize weevil, Sitophilus zeamais Motschulsky (Coleoptera: Curculionidae), and one of two insecticide-resistant populations - one exhibiting fitness disadvantage based on demographic studies (Juiz de Fora) and other not exhibiting it (Jacarezinho). Total number of insects, mortality by insecticide, insect body mass and respiration rate were recorded after three generations of competition. Indeed, fitness disadvantage was observed in the resistant population from Juiz de Fora, but not in the population from Jacarezinho, as expected. The higher body mass and respiration rate of the insecticide-resistant insects from Jacarezinho are probably mitigating the physiological costs associated with the insecticide resistance minimizing their fitness disadvantage, what does not take place with the insecticide-resistant insects from Juiz de Fora. These distinct responses between the insecticide-resistant populations are probably related to the length and intensity of field-selection with insecticides.     

Polychlorinated dibenzo-p-dioxins/furans and polychlorinated biphenyls in fresh fishes from Qiantangjiang River, China

Muscles of two species of fish collected in Qiangtangjiang River were analyzed for polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS). Average concentrations of total PCDD/Fs in Crucian carp and White Amur bream were 1.14-7.88 pg g(-1)ww and 1.02-8.18 pg g(-1)ww respectively. Corresponding values for PCBs were 469.36-10972 pg g(-1)ww and 364.79-4948.0 pg g(-1)ww. Average total WHO-TEQ of Crucian carp and White Amur bream from five areas ranged from 0.25 to 2.33 pg g(-1)ww and 0.30 to 1.70 pg g(-1)ww. The contamination level was compared with other studies and risk assessment was discussed.     

Polychlorinated biphenyls and organochlorine pesticides in EELS (Anguilla anguilla L.) from Welsh rivers

Organochlorine concentrations in the muscle tissues of eels at 41 freshwater sites across Wales were surveyed in 1993. Positive but weak relationships were detected between eel age or length and the concentration of some organochlorines. Isomers of HCH were below detection at most sites. Dieldrin was widespread at 10-100 microg kt(-1) wet weight, despite its ban in sheep dip in 1989. Total DDT residue concentrations averaged 73 microg kg(-1). Total PCB burdens expressed as Arochlor 1260, were > 50 microg kg(-1) at 76% of sites and > 100 microg kg(-1) at 46% of sites. The range of concentrations was comparable with other UK data. Rural sites had relatively low levels of PCBs, highest contamination occurring in the lower reaches of industrialised catchments. The inferences for environmental effects are discussed.