Seasonal variations of hydrophobic organic contaminant concentrations in the water-column of the Seine Estuary and their transfer to a planktonic species Eurytemora affinis (Calanoïda, copepoda). Part 1: PCBs and PAHs

Hydrophobic organic contaminants (HOC) (i.e. PAHs and PCBs) were measured in the water column and in Eurytemora affinis samples from the Seine Estuary collected from November 2002 to February 2005. Results showed seasonal variations of both total PCB and PAH levels in the suspended particulate matter (SPM) and in the copepods with maximum levels during winter times. PAH and PCB concentrations in the SPM ranged from 499 to 5819ngg(-1) and from 58 to 463ngg(-1), respectively. Phenanthrene, pyrene and benzo[b+j+k]fluoranthene (B[b+j+k]F) were the predominant PAH compounds in the water column, while CB 101, 118, 153 and 138 were the most abundant PCB congeners. PCBs and PAHs bioaccumulated by E. affinis (EA) varied between 383 and 1785ngg(-1) and 165-3866ngg(-1). CB101, 153, 138 and B[b+j+k] were, respectively, the major compounds of PCB and PAH fingerprints in EA. Thereby, the copepods could reach high accumulation factor (ACF) (91000 for PCBs and 17000 for PAHs). The principal component analyses of contaminant concentrations and environmental parameter datasets distinguished two groups of copepods. The winter time cluster, with high percentage of adult copepods, which bioaccumulated the highest PCB and PAH body-burdens, and the second cluster with juveniles showing the lowest HOC concentrations. Thus, PAH and PCB concentrations in EA exhibited significant correlations with the percentage of adults making up the samples.     

Assessment of bioavailable PAH, PCB and OCP concentrations in water, using semipermeable membrane devices (SPMDs), sediments and caged carp

Bioavailable water concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed at several freshwater sites in and around the city of Amsterdam. Carp (Cyprinus carpio) were caged for 4 weeks at 10 sites, together with semipermeable membrane devices (SPMDs). In addition, sediment samples were taken at each site. SPMDs and sediments were analysed for PAHs, PCBs and OCPs. Carp muscle tissues were analysed for PCBs and OCP, while PAH metabolites were assessed in fish bile. Contaminant concentrations in the water phase were estimated using three different methods: 1. Using fish tissue concentrations and literature bioconcentration factors (BCFs), 2. Using SPMD levels and a kinetic SPMD uptake model, and 3. Using sediment levels and literature sorption coefficients (K_ocs). Since PAH accumulation in fish is not considered an accurate indicator of PAH exposure, calculated aqueous PAH concentrations from SPMD data were compared with semiquantitatively determined biliary PAH metabolite levels. Contaminant concentrations in the water phase estimated with fish data (Cw_fish) and SPMD data (Cw_spmd) were more in line for compounds with lower K_ow than for compounds with higher K_ow values. This indicates that the assumption of fish–water sorption equilibrium was not valid. At most sites, sediment-based water levels (Cw_sed) were comparable with the Cw_spmd, although large differences were observed at certain sites. A significant correlation was observed between biliary PAH metabolite levels in fish and aqueous PAH concentrations estimated with SPMD data, suggesting that both methods may be accurate indicators of PAH exposure in aquatic ecosystems.     

Synthesis of novel polymer type sulfoxide solid phase combined with the porogen imprinting for enabling selective separation of polychlorinated biphenyls

We developed a novel polymer type sulfoxide-modified solid phase enabling to achieve selective separation of polychlorinated biphenyls (PCBs) from insulation oil. In this study, firstly we prepared base-polymer based on the concept of the molecular imprinting to capture PCBs in selectively, then, the sulfoxide groups were modified on the pore surface of base-polymers by changing preparation methods. As results of liquid chromatographic analyses for the polymers as columns, the base-polymer prepared by xylene as a porogenic solvent showed selective retention ability for chlorinated aromatic compounds by the porogen imprinting effect. Additionally, the polymer-type sulfoxide solid phases showed highly retention ability for PCBs by increasing amount of introduced sulfoxide groups. Consequently, the results of separation of PCBs comparing to insulation oil suggested that the prepared solid phase can be used for the selective separation of PCBs at the same level as a commercially available media utilized for the regulated method.     

Evaluation of sequentially-coupled POP fluxes estimated from simultaneous measurements in multiple compartments of an air-water-sediment system

Bulk atmospheric deposition fluxes, air-water exchange fluxes, particle settling fluxes out of the upper water column, sediment trap fluxes in deep waters, and sediment burial fluxes of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured in the Koster Fjord, eastern Skagerak, on the Swedish west coast. The aim of the study was to compare the magnitude and direction of the compound fluxes in the system in order to diagnose key fate processes. The PCB and PAH fluxes via net atmospheric deposition, settling particles out of the surface and through deep waters, as well as into the accreting underlying sediments were shown to be remarkably similar, agreeing within a factor of a few for any given target compound. Fluxes of all PCB and PAH target compounds remained fairly constant with water column depth. Thus there was no evidence for net desorption from sinking particles. The net unidirectional and near balancing of vertical fluxes suggests a net transport of PCBs and PAHs from the atmosphere to the continental shelf sediments in the Koster Fjord, which is consistent with the hypothesis that the shelf sediments are important sinks for these compounds.     

Emissions from simulated deep-seated fires in domestic waste

The emissions from deep-seated fires in domestic waste have been investigated. The gas phase yields of PAH, PCDD/F, PCB, HCB, particles, and metals associated to the particulate matter were analysed during a series of simulated deep-seated fires. The method of extinguishment was varied and in cases where water was used for extinguishment, the runoff water was analysed for PAH, PCDD/F, PCB, hexachlorobenzene, and metals. In total six tests were performed. In four of the tests, samples of the fire residue were analysed for PCDD/F, PCBs, and chlorobenzenes.     

Uptake of PAHs into polyoxymethylene and application to oil-soot (lampblack)-impacted soil samples

Polyoxymethylene (POM) is a polymeric material used increasingly in passive sampling of hydrophobic organic contaminants such as PAHs and PCBs in soils and sediments. In this study, we examined the sorption behavior of 12 PAH compounds to POM and observed linear isotherms spanning two orders of magnitude of aqueous concentrations. Uptake kinetic studies performed in batch systems for up to 54 d with two different volume ratios of POM-to-aqueous phase were evaluated with coupled diffusion and mass transfer models to simulate the movement of PAHs during the uptake process and to assess the physicochemical properties and experimental conditions that control uptake rates. Diffusion coefficients of PAHs in POM were estimated to be well correlated with diffusants' molecular weights as D(POM) proportional, variant(MW)(-3), descending from 2.3 x 10(-10) cm(2) s(-1) for naphthalene to 7.0 x 10(-11) cm(2) s(-1) for pyrene. The uptake rates for PAHs with log K(ow)<5.8 were controlled by the POM phase and the hydrophobicity of PAH compounds. For more hydrophobic PAH compounds, the aqueous boundary layer played an increasingly important role in determining the overall mass transfer rate. The POM partitioning technique was demonstrated to agree well with two other procedures for measuring PAH soil-water distribution coefficients in oil-soot (lampblack) containing soil samples.     

Development of GC capillary column for isomer-specific separation of toxic isomer of PCDDs and PCDFs in environmental samples

Analysis of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) has been performed using gas chromatography mass spectrometry (GC-MS). Analysis of the most toxic isomers, in particular, 2,3,7,8-substituted PCDD/PCDF in the presence of other isomers requires a special isomer specific capillary column or high performance liquid chromatography (HPLC) fractionation prior to GC-MS analysis. Commercially available long (>50 m) polar columns can separate 2,3,7,8-TCDD from other tetra isomers. However, those columns are not satisfactory for the analyses of total PCDD/PCDF in the environmental samples. Gas chromatography -high resolution mass spectrometry (GC-HRMS) and GC-MS/MS techniques are not helpful in the analysis of 2,3,7,8-TCDD unless it is separated from the other tetra isomers. The analysis of 2,3,7,8-TCDD and total PCDD and PCDF in a single GC-MS run can ease the laborious techniques presently used. In this study we have developed a new stationary phase for the GC capillary column. The capillary column developed using this new stationary phase showed unsurpassed selectivity for the separation of 2,3,7,8-TCDD from other tetra isomers. There are several advantages of the newly developed GC capillary column.     

Sediment pollution and dynamic in the Mar Piccolo of Taranto (southern Italy): insights from bottom sediment traps and surficial sediments

Major and trace element, PAH, and PCB concentrations were measured in surface sediments and particles from sediment traps collected in the First and Second Basin of the Mar Piccolo (Gulf of Taranto) in two periods (June–July and August–September, 2013). The aim of the study was to evaluate pollution degree, sediment transport and particle redistribution dynamic within the area. Results confirm the higher contamination of sediments from the First Basin observed by previous researches, particularly for Cu, Hg, Pb, total PAHs, and total PCBs. Advective transport from the First to the Second Basin appears to be the leading transfer mechanism of particles and adsorbed contaminants, as evidenced by measured fluxes and statistical analyses of contaminant concentrations in surficial sediments and particles from sediment traps. Long-range selective transports of PAHs and microbial anaerobic degradation processes for PCBs have been also observed. These results are limited to a restricted time window but are consistent with the presence of transport fluxes at the bottom of the water column. This mechanism deserves further investigation and monitoring activities, potentially being the main responsible of pollutant delivering to the less contaminated sectors of the Mar Piccolo.     

Sampling and analysis of polycyclic aromatic hydrocarbons (PAH) from two-stroke chain-saw engines

A sampling and analysis method for PAH from two-stroke engines is described. The method, which uses a standard glass fiber filter with a back-up section of Amberlite XAD-2 for sampling and GC or GC-MS for analysis, is suitable for both emission studies and occupational studies during logging. Filters and XAD-2 are desorbed with cyclohexane in an ultrasonic bath. After separation on a silica-gel micro column, the samples are submitted to analyses by capillary GC. The method is simple and covers both gaseous and particulate PAH. Naphthalene and alkyl substituted naphthalenes are also quantified.     

Separation of PCBs and PAHs in sediment samples using silica gel fractionation chromatography

The aim of this research is to develop a silica gel fractionation procedure for sediment sample extracts, which separates polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) into two groups, while simultaneously eliminating most interfering substances for subsequent instrumental analysis. This is achieved by optimizing the fraction cut-off volume of eluting solvent and the deactivation level of the silica gel. Using fully activated silica gel and cutting off PCB collection after passing 60-65 ml eluting solvent (pentane or hexane) through the column resulted in satisfactory separation of PCBs and PAHs. This procedure tends to have a higher reliability for PCBs and PAHs with higher molecular mass. This approach deviates only slightly from the standard methods of the USEPA, and it is less expensive due to reduced sample pre-treatment time and solvent consumption.     

Fate of PCBs, PAHs and their source characteristic ratios during composting and digestion of source-separated organic waste in full-scale plants

Composting and digestion are important waste management strategies. However, the resulting products can contain significant amounts of organic pollutants such as polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs). In this study we followed the concentration changes of PCBs and PAHs during composting and digestion on field-scale for the first time. Concentrations of low-chlorinated PCBs increased during composting (about 30%), whereas a slight decrease was observed for the higher chlorinated congeners (about 10%). Enantiomeric fractions of atropisomeric PCBs were essentially racemic and stable over time. Levels of low-molecular-weight PAHs declined during composting (50-90% reduction), whereas high-molecular-weight compounds were stable. The PCBs and PAHs concentrations did not seem to vary during digestion. Source apportionment by applying characteristic PAH ratios and molecular markers in input material did not give any clear results. Some of these parameters changed considerably during composting. Hence, their diagnostic potential for finished compost must be questioned.     

Minimization of blank values of the miniature silica gel column

Several methods involving silica gel separations of polychlorinated biphenyls from chlorinated insecticides are already described in literature. Our intention was to find a system of solvent and silica gel of the lowest blank values. The first step was to find a solvent mixture which will keep the homogenity of a silica gel column. PCBs elution was performed with pentane, while the chlorinated insecticides eluated with diethylether, acetone, methanol, and benzene. The elution of pesticides gave the best results for the following solvent systems: diethylether + hexane (1:1), acetone + hexane (1:4), methanole + pentane (1:8) and benzene.Separation of pesticides from polychlorinated biphenyls found in a synthetic mixture was also examined. It was found that all solvent systems used gave similar results of separation. However, only if benzene is used as eluant, the silica gel column can be used for four successive separations after the “on column” regeneration. In order to obtain the lowest blank values silica gel was cleaned with several solvents. The eluates after the silica gel separation were also cleaned up by means of deactivation alumina and concentrated sulphuric acid.     

Polychlorinated naphthalenes in urban soils: analysis,concentrations, and relation to other persistent organic pollutants

We determined the concentrations of 35 PCNs, 12 PCBs, and 20 PAHs in 49 urban topsoils under different land use (house garden, roadside grassland, alluvial grassland, park areas, industrial sites, agricultural sites) and in nine rural topsoils. The sums of concentrations of 35 PCNs (sigma35 PCNs) were <0.1-15.4 microg kg(-1) in urban soils and <0.1 to 0.82 microg kg(-1) in rural soils. The PCN, PCB, and PAH concentrations were highest at industrial sites and in house gardens. While rural soils receive PCNs, PCBs, and PAHs by common atmospheric deposition, there are site-specific sources of PCNs, PCBs, and PAHs for urban soils such as deposition of contaminated technogenic materials. The PCN, PCB, and PAH concentrations decreased from the central urban to the rural area. In the same order the contribution of lower chlorinated PCNs and PCBs increased because they are more volatile and subject to increased atmospheric transport. The PCNs 52+60, and 73 were more abundant in soil samples than in Halowax mixtures, indicating that combustion contributed to the PCN contamination of the soils.     

Measurements of selected PCBs in open urban ambient air of Madrid (Spain)

The focus of this study was to characterize the concentration levels of selected PCBs and compare them to compiled data in order to contribute to the international database. The sampling site is located in the outskirts of Madrid and can be considered an open urban area. 32 samples of air were taken from February 1998 to June 1998 by using a high volume air sampler. Glass fiber filters and polyurethane foam (PUF) were used to collect the paniculate and gas phase material, respectively. PUF plugs were Soxhlet extracted and filters were ultrasonically extracted by using pesticide-grade hexane and dichloromethane, respectively. The cleanup procedure was carried out on a florisil column with hexane and hexane/dichloromethane as elution solvents. GC/MS in a selected ion monitoring mode was used for quantification and 29 selected PCBs congeners were analyzed.     

PCBs,PCNs, PCDD/Fs,PAHs and Cl-PAHs in air and water particulate samples--patterns and variations

Methodology for the determination of biologically active polychlorinated biphenyls (PCBs), non-ortho PCBs, polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polycyclic aromatic hydrocarbons (PAHs) was used to investigate concentrations and patterns of certain chlorinated PAH (Cl-PAH) in source related samples using synthetic reference mixtures. Thus, in addition to the above mentioned compounds, mono-heptachlorosubstituted fluorenes, phenanthrenes/anthracenes and pyrenes/fluoranthenes (Cl-PAHs) were measured in vapour and particulate air samples from urban road tunnels, samples of settling particulate matter (SPM), and in bottom sediment samples from two point source locations (pulp and paper, and Mg-plant/Fe-Mn-smelter/chlor-alkali) and in the Baltic Sea. Concentrations in air samples followed: PAHs>PCBs>PCNs>non-ortho PCBs or Cl-PAHs>PCDD/Fs. SPM samples collected at increasing distance to the urban area of Stockholm showed: PAHs>PCBs>PCNs>PCDD/Fs>non-ortho PCBs or Cl-PAHs. For all compound groups there was a tenfold (Cl-PAHs fivefold) concentration decrease in SPM samples from highest levels in the urban water area to lowest levels at a distance of 26 km from city centre. PCB profiles of SPM showed similarities with combined profiles of Aroclor 1242 and 1254. PCN profiles of SPM showed similarities with combined profiles of Halowax 1099 and 1014. A correlation with concentration of all tested Cl-PAH and their corresponding parent PAH was found only for Cl-fluorene.     

Source apportionment and source/sink relationships of PAHs in the coastal atmosphere of Chicago and Lake Michigan

Multivariate statistical techniques were used to investigate source apportionment and source/sink relationships for polycyclic aromatic hydrocarbons (PAHs) in the urban and adjacent coastal atmosphere of Chicago/Lake Michigan in 1994–1995. The PAH signatures for the atmospheric particle phase, surface water particle phase and sediments indicate that atmospheric deposition is the major source of PAHs to the sediments and water column particulate phase of Lake Michigan. The PAH signature for the atmospheric gas phase and water dissolved phase indicate an intimate linkage between the lake and its overlying atmosphere. A modified factor analysis-multiple regression model was successfully applied to the source apportionment of atmospheric PAHs (gas+particle). Coal combustion accounted for 48±5% of the ΣPAH concentration in both the urban and adjacent coastal atmosphere, natural gas combustion accounted for 26±2%, coke ovens accounted for 14±3%, and vehicle emissions (gas+diesel) accounted for 9±4%. Each is an identified source category for the region. These results are consistent with the mix of fossil fuel combustion sources and ratios of indicator PAHs.     

Distribution and spatial trends of PAHs and PCBs in soils in the Seine River basin, France

Persistent organic pollutants (PAHs and PCBs) in soil samples from seven sites across the Seine basin were analysed. Samples were taken from industrialized, urban, suburban and remote sites. Results showed spatial differences, in terms of concentrations and congener profiles. PAH (Sigma14 PAHs) and PCB (Sigma 7 PCBs) concentrations ranged from 450 to 5650 microg kg(-1) and 0.09 to 150 microg kg(-1), respectively. A clear gradient from industrial to remote sites was highlighted, with a ratio of up to one order of magnitude for PAHs and two orders of magnitude for PCBs. Fluoranthene and pyrene were predominant, while the carcinogenic PAHs represented 15-46% of the total PAH content. Using hierarchical cluster analysis, soil samples profiles were compared and the influence of site location and potential sources were identified: automobile traffic, domestic heating, and industrial emissions were the prevalent PAHs sources in the Seine basin. PCB profiles suggested different transport patterns among congeners. For remote sites, the congener fingerprint showed a relatively higher proportion of the most volatile congeners, which were attributed to increased atmospheric residence times. Thus, PAH and PCB distributions in soils provided information on sources and evidence for short-range transport, and profiles of compounds reflected differences between regional and local emissions. This study demonstrates that soil sampling can be used to investigate spatial differences in atmospheric inputs of persistent organic pollutants based on differences in the mixtures of compounds, reflecting differences in regional and local atmospheric emissions.     

Microscale analytical methods for the quantitative detection of PCBs and PAHs in small tissue masses

Microscale methods (MM) were evaluated and compared to traditional methods (TM) for measuring polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) in spiked and standard reference fish and mussel tissues. MMs are advantageous because they use small tissue masses (ca. 100 mg), and maintain sensitivity through reducing final extract volume (traditionally 1 ml) by an order of magnitude or more (40 μl—PCBs; 100 μl—PAHs). Procedural losses occurred in the MMs’ combined cleanup/primary evaporation step (19% PAHs; 6% PCBs), and the final extract concentration (14% PAHs; 22% PCBs). The PAH MM performed comparably to the TM. Although most PCBs had recoveries >50%, the PCB MM generally yielded lower recoveries than the TM. Average method detection limits were 0.6 μg/kg (TM) and 1.0 μg/kg (MM) for PCBs and 25.7 μg/kg (TM) and 27.7 μg/kg (MM) for PAHs. MMs described for PCB and PAH tissue samples are potentially viable alternatives to TMs, and could lead to cost savings in bioaccumulation/toxicity tests.     

Polycyclic aromatic hydrocarbons and polychlorinated biphenyls in forest soils: depth distribution as indicator of different fate

We determined 20 polycyclic aromatic hydrocarbons (PAHs) and 12 polychlorinated biphenyls (PCBs) in Oi, Oe, and Oa horizons and at 0-5 and 15-20 cm mineral soil depth of 16 Norway spruce (Picea abies) stands in north Bavaria. The sum of PAH concentrations increased along the line Oi (mean+/-SD: 841+/-330 microg kg(-1))相似文献   

Persistent organic pollutants in soil density fractions: distribution and sorption strength

The sorption strength of persistent organic pollutants in soils may vary among different soil organic matter (SOM) pools. We hypothesized that polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were unevenly distributed and had different soil organic carbon (SOC)-water partition coefficients (K(OC)) among soil density fractions. We determined the concentrations and K(OC) values of 20 PAHs and 12 PCBs in bulk samples and three density fractions (light, <2.0, medium, 2.0-2.4, and heavy, >2.4 g cm(-3)) of 11 urban topsoils (0-5 cm) from Bayreuth, Germany. The K(OC) values were determined using sequential extraction with methanol-water mixtures (35% and 65% methanol) at 60 degrees C. The sum of 20 PAH concentrations in bulk soil ranged 0.4-186 mg kg(-1), and that of 12 PCB concentrations 1.2-158 microg kg(-1). The concentrations of all PAHs and PCBs decreased in the order light>medium>heavy fraction. When normalized to the SOC concentrations, PAH concentrations were significantly higher in the heavy than in the other density fractions. The K(OC) values of the PAHs in density fractions were 3-20 times higher than those of the PCBs with similar octanol-water partition coefficients (K(OW)). The K(OC) values of individual PAHs and PCBs varied up to a factor of 1000 among the studied soils and density fractions. The K(OC) values of 5- and 6-ring PAHs tended to be highest in the heavy fraction, coinciding with their enrichment in this fraction. For the other PAHs and all PCBs, the K(OC) values did not differ among the density fractions. Thus, there is no relationship between sorption strength and distribution among density fractions, indicating that density fractionation is not a suitable tool to distinguish among differently reactive PAH and PCB pools in soils.