The identification of readily bioavailable pollutants in lake shkodra/skadar using semipermeable membrane devices (SPMDs), bioassays and chemical analysis

GOAL, SCOPE AND BACKGROUND: Lake Shkodra/Skadar is the largest lake in the Balkans region and located on the border between Albania to the south and Montenegro to the north. Because of the wide range of endemic, rare or endangered plant and animal species it supports, Lake Shkodra/Skadar and its extensive associated wetlands are internationally recognised as a site of significance and importance (Ramsar site). In recent years, social and economic changes in both Albania and Montenegro have lead to unprecedented levels of urban and industrial effluent entering the lake. Of particular concern is the increasing input of toxic hydrophobic organic pollutants (HOPs) into the lake and the degree to which these compounds are available for uptake by aquatic biota. Semipermeable membrane devices (SPMDs) have been shown to sample the readily bioavailable fraction (dissolved phase) of waterborne HOPs and in doing so provide relevant data for exposure assessment. The aim of the current study was to use SPMD-based sampling in conjunction with appropriate bioassays and chemical analysis to identify readily bioavailable HOPs in the lake. METHODS: SPMDs were constructed and deployed at three sites in the Albanian sector and three sites in the Montenegrin sector of Lake Skadar/Shkodra for 21 days. Following the dialytic recovery of target analytes and size exclusion chromatographic clean-up, aliquots of SPMD samples were subjected to GC-MS scan analysis for major components, GC-MS SIM analysis for 16 priority pollutant polycyclic aromatic hydrocarbons (PP-PAHs) and assayed for EROD-inducing, estrogenic and mutagenic potential using rainbow trout liver cells (RTL-W1), the yeast estrogen screen (YES) and the Ames Test, respectively. RESULTS AND DISCUSSION: A total of 39 compounds were tentatively identified in SPMD samples from the six sampling sites. Alkylated PAHs were the most abundant and ubiquitous compounds present along with various sterols and sterol derivatives. Numerous other compounds remain unidentified. 15 of the 16 targeted PP-PAHs were present in samples from one or more of the sampling sites indicating these compounds are both readily bioavailable and widely distributed in Lake Shkodra/Skadar. Total PP-PAH concentrations ranged between 3991 ng/SPMD and 10695 ng/SPMD. Bioassays carried out on SPMD samples revealed significant EROD-inducing and estrogenic potential at five of the six sampling sites indicating toxicologically relevant compounds are readily available for uptake by resident aquatic biota. EROD-inducing potential was positively correlated with targeted PP-PAH concentration (r2 = 0.74). However, comparison of bioassay- and analytically-derived toxicity equivalents revealed targeted PP-PAHs were responsible for less than 0.06% of the total EROD-inducing potential. CONCLUSIONS AND OUTLOOK: The combination of SPMD-based sampling with appropriate bioassays and chemical analysis provided an effective tool for the identification of environmentally relevant waterborne pollutants in Lake Shkodra/Skadar. Our results show that toxicologically relevant HOPs including EROD-inducing and potentially estrogenic compounds are widely distributed in the lake and readily available for uptake by aquatic biota. Our results also suggest that alkylated PAHs rather than parent compounds may be of greater toxicological relevance in the lake. As anthropogenic influences continue to increase, SPMD-based sampling is expected to play a central role in future research concerned with the identification, monitoring and assessment of the risk posed by HOPs to Lake Shkodra/Skadar's aquatic biota.     

A comparison of mussels (Perna viridis) and semi-permeable membrane devices (SPMDs) for monitoring chlorinated trace organic contaminants in Hong Kong coastal waters.

A comparison of mussels (Perna viridis) and semi-permeable membrane devices (SPMDs) was carried out at five sites, representing a gradient of contaminant concentrations, in Hong Kong coastal waters. Mussels, originally collected from a “clean” location, were deployed along with SPMDs at each site for 30 days. Analyses for chlorinated pesticides and polychlorinated biphenyls (PCBs) indicated that SPMDs have potential as monitoring tools, and to some extent can overcome the problems associated with mussels, such as natural variability, differing age, sex, and physical condition. However, in most cases, SPMDs failed to rank the sites in the same order as mussels in terms of contaminant concentrations. Nonetheless, in localities where mussels cannot survive – as shown at Kwun Tong in the present experiment – SPMDs may be valuable in providing an indication of potentially bio-available lipophilic pollutants.     

A comparison of mussels (Perna viridis) and semi-permeable membrane devices (SPMDs) for monitoring chlorinated trace organic contaminants in Hong Kong coastal waters

A comparison of mussels (Perna viridis) and semi-permeable membrane devices (SPMDs) was carried out at five sites, representing a gradient of contaminant concentrations, in Hong Kong coastal waters. Mussels, originally collected from a “clean” location, were deployed along with SPMDs at each site for 30 days. Analyses for chlorinated pesticides and polychlorinated biphenyls (PCBs) indicated that SPMDs have potential as monitoring tools, and to some extent can overcome the problems associated with mussels, such as natural variability, differing age, sex, and physical condition. However, in most cases, SPMDs failed to rank the sites in the same order as mussels in terms of contaminant concentrations. Nonetheless, in localities where mussels cannot survive – as shown at Kwun Tong in the present experiment – SPMDs may be valuable in providing an indication of potentially bio-available lipophilic pollutants.     

Prediction of PCB content in sportfish using semipermeable membrane devices (SPMDs)

Triolein-filled semipermeable membrane devices (SPMDs) were immersed at three locations along the St. Joseph River in northern Indiana for 30 days to see if the PCB content of fish from the same location could be predicted with this model device. Triolein from the SPMD's was analyzed for PCB using enzyme-linked immunosorbent assay (ELISA) and compared to residues detected in fish collected from the same locations. There was a significant difference (p < 0.05) in total PCB concentrations between SPMD samples. However, due to variability in PCB residues between species and low PCB residues in SPMDs, a direct correlation between PCBs in sportfish and SPMDs could not be determined.     

Assessing seasonal and spatial trends of persistent organic pollutants (POPs) in Indian agricultural regions using PUF disk passive air samplers

The first survey of persistent organic pollutant (POP) concentrations in air across several Indian agricultural regions was conducted in 2006-2007. Passive samplers comprising polyurethane foam (PUF) disks were deployed on a quarterly basis at seven stations in agricultural regions, one urban site and one background site. The project was conducted as a sub-project of the Global Atmospheric Passive Sampling (GAPS) Network. In addition to revealing new information on air concentrations of several organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs), the study has demonstrated the feasibility of conducting regional-scale monitoring for POPs in India using PUF disk samplers. The following analytes were detected with relatively high concentrations in air (mean for 2006 and 2007, pg/m³): α- and γ-hexachlorocyclohexane (HCH) (292 and 812, respectively); endosulfan I and II (2770 and 902, respectively); p,p′-DDE and p,p′-DDT (247 and 931, respectively); and for the sum of 48 PCBs, 12,100 (including a site with extremely high air concentrations in 2007) and 972 (when excluding data for this site).     

An approach for assessment of water quality using semipermeable membrane devices (SPMDs) and bioindicator tests

As an integral part of our continued development of water quality assessment approaches, we combined integrative sampling, instrumental analysis of widely occurring anthropogenic contaminants, and the application of a suite of bioindicator tests as a specific part of a broader survey of ecological conditions, species diversity, and habitat quality in the Santa Cruz River in Arizona, USA. Lipid-containing semipermeable membrane devices (SPMDs) were employed to sequester waterborne hydrophobic chemicals. Instrumental analysis and a suite of bioindicator tests were used to determine the presence and potential toxicological relevance of mixtures of bioavailable chemicals in two major water sources of the Santa Cruz River. The SPMDs were deployed at two sites; the effluent weir of the International Wastewater Treatment Plant (IWWTP) and the Nogales Wash. Both of these systems empty into the Santa Cruz River and the IWWTP effluent is a potential source of water for a constructed wetland complex. Analysis of the SPMD sample extracts revealed the presence of organochlorine pesticides (OCs), polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs). The bioindicator tests demonstrated increased liver enzyme activity, perturbation of neurotransmitter systems and potential endocrine disrupting effects (vitellogenin induction) in fish exposed to the extracts. With increasing global demands on limited water resources, the approach described herein provides an assessment paradigm applicable to determining the quality of water in a broad range of aquatic systems.     

Levels of persistent organic pollutants in the Neretva River (Bosnia and Herzegovina) determined by deployment of semipermeable membrane devices (SPMD)

The main objective of this study was to determine levels of certain persistent organic pollutants (POPs) in Neretva River, Bosnia and Herzegovina (BiH), which is currently facing implementation of the Stockholm Convention on persistent organic pollutants (POPs) and environmental protection strategies. This is the very first report on the deployment of semipermeable membrane devices (SPMDs) in BiH. SPMDs were used for continuous 3-weeks sampling of POPs at three locations, covering 220 km long stream of the Neretva River. Water concentrations of polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs) and polybrominated diphenylethers (PBDEs) were calculated using performance reference compounds (PRCs). The total OCP concentrations ranged from 40 to 140 pg L^?1 and most of compounds were detected only in lower course of the river. Total PAH ranged from 160 to 4000 pg L^?1 and show a clear spatial variation. Dominant PAHs were phenanthrene, fluoranthene, fluorene and acenaphthene. Total PCB ranged from undetectable to 120 pg L^?1. From the group of 15 PBDE congeners investigated, only PBDE-47 and PBDE-99 were detected. Since the concentrations of broad spectrum of POPs found in the Neretva River are quite low, future actions should be focused on preservation rather than on sanitation measures. Regular monitoring should anyhow be established.     

Uptake rates of semipermeable membrane devices (SPMDs) for PCDDs, PCDFs and PCBs in water and sediment

Uptake rates of several PCDDs, PCDFs and PCBs were measured for semipermeable membrane devices (SPMDs) under controlled conditions in bulk water and sediment. The study was performed at 19 degrees C and 11 degrees C, and water and sediment concentrations were measured during the exposure. Linear uptake rates for specific PCDD/Fs and PCBs in 19 degrees C water varied from 34 to 111 l/m2 day and in 11 degrees C water from 8.8 to 96 l/m2 day for the whole SPMD. Uptake rates at 19 degrees C sediment ranged from 9.0 to 80 mgOC/m2 day and in 11 degrees C sediment, from 3.0 to 31, mgOC/m2 day. Partitioning of the compounds between membrane and lipid was also measured during the linear uptake phase. The membrane-lipid concentration ratios ranged from 0.02 to 1.11 depending on the compound, temperature, and bulk medium.     

Measurement and modeling of urban atmospheric PCB concentrations on a small (8 km) spatial scale

Atmospheric transport and deposition of polychlorinated biphenyls (PCBs) is an important problem for ecosystems around the world. Data from several monitoring networks demonstrate that atmospheric PCB concentrations are dramatically elevated in urban areas compared to rural or background regions, such that these urban emissions of PCBs support the regional and global transport and deposition of PCBs to more remote areas. Identifying and controlling the sources of urban atmospheric PCBs is thus essential in minimizing the regional and global transport and deposition of these compounds. From December 1999 to November 2000, gas-phase PCB concentrations were measured at two monitoring locations, 8 km apart, within the New York City metropolitan area, at Jersey City and Bayonne, NJ. Concentrations, congener patterns, and temporal patterns of PCBs differ dramatically at the two sites, suggesting that a significant source of atmospheric PCBs exists within 8 km of the Bayonne site, resulting in spikes in gas-phase PCB concentration at Bayonne that are not observed at Jersey City. The Regional Atmospheric Model System (RAMS) coupled with the Hybrid Particle and Concentration Transport model (HYPACT) was used to estimate that the PCB source near Bayonne emits a flux of ΣPCBs on the order of 100 g d⁻¹. Extrapolation of this source magnitude to the area of New York City suggests that this urban area emits at least 300 kg yr⁻¹ ΣPCBs to the regional atmosphere, similar in magnitude to the flow of ΣPCB out of the Upper Hudson River into the New York/New Jersey Harbor.     

Persistent organic pollutants (PCB, DDT, HCH, HCB & BDE) in eels (Anguilla anguilla) in Scotland: Current levels and temporal trends

Eels are an ideal biomonitor for persistent organic pollutants (POPs) because of their high lipid content, longevity and tendency to remain within a defined range during their freshwater life phase. This study investigated concentrations of POPs in eels (Anguilla anguilla) from 30 sites across Scotland, including polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (BDEs), DDT (and metabolites), hexachlorocyclohexanes (α, β, γ-HCH), hexachlorobenzene (HCB), hexachlorobutadiene (HCBD) and pentachlorobenzene. Despite its EU-wide ban ∼30 years ago, DDT and its derivatives were detected in almost all samples. PCB 153 and 138 were the most widely detected PCB congeners, while BDE 47 was the dominant BDE. Pentachlorobenzene was not detected, while HCBD was detected once only. α-HCH, β-HCH and HCB concentrations were very low (generally <3 μg/kg or below detection). When compared with 1986 and 1995 data, the results revealed considerable decreases in p,p′-DDE concentrations. More drastic reductions were evident for γ-HCH, reflecting the tightening restrictions on pesticide use imposed over the previous decades.     

Uptake rates of alkylphenols, PAHs and carbazoles in semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCIS)

Passive sampling devices provide a useful contribution to the monitoring of contaminants in the aquatic environment. However, calibration data needed for the calculation of water concentrations from sampler accumulations are restricted to a limited number of compound classes. Thus uptake of a range of alkylated phenols (AP), polycyclic aromatic hydrocarbons (PAH) and carbazoles was determined for semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCIS) using a flow through exposure system. Sampling rates ranged from 0.02 to 0.26 l d(-1) for POCIS and 0.02 to 13.83 l d(-1) for SPMDs. Observed SPMD uptake was also compared to that predicted by an empirical model including the use of performance reference compounds (PRCs). Predicted sampling rates did not differ by more than a factor of 1.3 from experimental values for PAH, providing further evidence that the PRC approach can be successfully used to determine in situ sampling rates for these compounds. Experimental sampling rates for AP in SPMDs were, however, much lower than predicted. This discrepancy was too large to be explained by small uncertainties in the calibration system or in the calculations. Based on these data we conclude that while hydrophobic AP are accumulated by SPMDs their partitioning cannot be predicted from their logK(ow) using current methods. Due to this lower than expected uptake, sampling rates were only higher in SPMDs than POCIS in the range of logK(ow)>5.0. Simultaneous deployment of both sampler types allows the study of compounds with a broad range of physicochemical properties.     

Persistent organic pollutants in soils and sediments from James Ross Island, Antarctica

Soil and sediment samples from James Ross Island were analyzed for their PCB, OCP and PAH contents. Soil concentrations ranged between 0.51 and 1.82 ng g(-1) for seven indicator PCB congeners, between 0.49 and 1.34 ng g(-1) for HCH congeners, between 0.51 and 3.68 ng g(-1) for the sum of p,p'-DDT, DDE, and DDD, and between 34.9 and 171 ng g(-1) for the sum of 16 EPA PAHs. Sediment levels from 0.32 to 0.83 ng g(-1) were found for PCBs, from 0.14 to 0.76 ng g(-1) for HCHs, from 0.19 to 1.15 ng g(-1) for DDTs, and from 1.4 to 205 ng g(-1) for PAHs. A prevalence of low-mass PAHs, less chlorinated PCBs, and more volatile chemicals indicates that the long-range atmospheric transport from populated areas of Africa, South America, and Australia is the most probable contamination source for the solid matrices in James Ross Island.     

Altitude dependence of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in surface soil from Tibetan Plateau, China

Remote mountain areas besides high latitude regions are beginning to receive increased attention in studying the transport and behavior of persistent organic pollutants (POPs). In the present work, surface soil samples were collected from the Tibetan Plateau, the highest plateau in the world which includes the northern slope of Mt. Qomolangma, to investigate the levels and trends of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) along the altitudinal gradient. The average PCB and PBDE concentrations were 185.6 ng kg⁻¹ dry weight (dw) (range 47.1–422.6 ng kg⁻¹ dw) and 11.1 ng kg⁻¹ dw (range 4.3–34.9 ng kg⁻¹ dw), respectively. Regression analysis between the log-transformed TOC-normalized concentrations and the altitudes of the sampling sites showed two opposite trends with regard to altitude dependence: negative relationship with altitude below about 4500 m followed by a positive altitude dependence above this point. Considering minimum anthropogenic activities and very sparse precipitation in the north of Himalayas, the trends above 4500 m imply that the significant altitude dependence of these two groups of POPs were irrespective of pollution sources, but could be predicted by the global distillation effect involving cold condensation in high altitude mountain areas. Increasing levels of heavier congeners were found in higher altitude sites, although the lighter congeners were the main contributors to the total amount, suggesting that less volatile congeners seem to become enriched easier than those more volatile at higher altitudes in this region.     

Organochlorine,PCB, PAH,and metal concentrations in eggs of loggerhead sea turtles (Caretta caretta) from northwest Florida,USA

Abstract

Composite samples of unhatched and physically unaltered loggerhead sea turtle, Caretta caretta, eggs collected from 20 nests along northwest Florida were analyzed for organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and metals. Chemical analyses revealed that turtle eggs contained detectable amounts of metals, PAHs, and PCBs. Only one OCP, p, p'‐DDD, was detected, and its presence was restricted to eggs from two nesting sites. None of the PCB concentrations exceeded the Food and Drug Administration's (FDA) action limit. Concentrations of dioxin‐like PCB congeners, 105, 118, and 126, and total PCBs were also detected and are contributors to the toxic burden of loggerhead sea turtle eggs. Concentrations of PAHs, 1,2,5,6‐dibenzanthracene, 1‐methyl naphthalene, Cl‐naphthalene and naphthalene were variable at nesting sites. Comparison of mean metal burdens in eggs from different beaches suggested that no uniform geographic gradients exist. Presence of OCPs, PCBs, PAHs and metals and their additive or synergistic toxicity is a concern to loggerhead sea turtle eggs; however, additive or synergistic impacts for loggerhead sea turtles are largely undocumented.     

Regional dynamics of persistent organic pollutants (POPs) in the Pearl River Delta, China: implications and perspectives

The mass transport budgets of 1,1,1-trichloro-2,2-bis(chlorophenyl)ethane (p,p′-DDT) and decabromodiphenyl ether (BDE-209) in the Pearl River Delta, South China were calculated based on previously collected data. Residual p,p′-DDT, mostly related to historical use, has largely settled into soil (780,000 kg), while the soil BDE-209 inventory (44,000 kg) is considerably smaller. Conversely, large amounts of BDE-209 currently used in numerous commercial products have resulted in a much higher atmospheric depositional flux of BDE-209 (28,100 kg/yr) relative to p,p′-DDT (310 kg/yr). The soil inventory of p,p′-DDT is predicted to decrease to half of its current value after 22 years, and the percent area containing soil p,p′-DDT at levels exceeding the effects range-medium (27 ng/g) will decrease from 40% to 20%. Finally, soil BDE-209 inventory will reach an equilibrium value of 940 tons in ∼60 years, when BDE-209 levels in 50% of soil will be above an equivalent risk guideline value (125 ng/g).     

Comparison of semipermeable membrane device (SPMD) and large-volume solid-phase extraction techniques to measure water concentrations of 4,4'-DDT, 4,4'-DDE, and 4,4'-DDD in Lake Chelan, Washington

Semipermeable membrane devices (SPMDs) spiked with the performance reference compound PCB29 were deployed 6.1 m above the sediments of Lake Chelan, Washington, for a period of 27 d, to estimate the dissolved concentrations of 4,4'-DDT, 4,4'-DDE, and 4,4'-DDD. Water concentrations were estimated using methods proposed in 2002 and newer equations published in 2006 to determine how the application of the newer equations affects historical SPMD data that used the older method. The estimated concentrations of DDD, DDE, and DDD calculated using the older method were 1.5-2.9 times higher than the newer method. SPMD estimates from both methods were also compared to dissolved and particulate DDT concentrations measured directly by processing large volumes of water through a large-volume solid-phase extraction device (Infiltrex 300). SPMD estimates of DDD+DDE+DDT (SigmaDDT) using the older and newer methods were lower than Infiltrex concentrations by factors of 1.1 and 2.3, respectively. All measurements of DDT were below the Washington State water quality standards for the protection of human health (0.59 ng l(-1)) and aquatic life (1.0 ng l(-1)).     

Bioaccumulation of persistent organic pollutants in female common dolphins (Delphinus delphis) and harbour porpoises (Phocoena phocoena) from western European seas: geographical trends, causal factors and effects on reproduction and mortality

Concentrations of polychlorinated biphenyls (PCBs) in blubber of female common dolphins and harbour porpoises from the Atlantic coast of Europe were frequently above the threshold at which effects on reproduction could be expected, in 40% and 47% of cases respectively. This rose to 74% for porpoises from the southern North Sea. PCB concentrations were also high in southern North Sea fish. The average pregnancy rate recorded in porpoises (42%) in the study area was lower than in the western Atlantic but that in common dolphins (25%) was similar to that of the western Atlantic population. Porpoises that died from disease or parasitic infection had higher concentrations of persistent organic pollutants (POPs) than animals dying from other causes. Few of the common dolphins sampled had died from disease or parasitic infection. POP profiles in common dolphin blubber were related to individual feeding history while those in porpoises were more strongly related to condition.