PCB Congeners Research Articles

Organochlorine contaminants in cetaceans: how to facilitate interpretation and avoid errors when comparing datasets

This paper reviews current scientific literature to provide information for avoiding errors commonly made in comparing and interpreting datasets from laboratories measuring organochlorine contaminants in cetaceans. Before making comparisons and interpretations using heterogeneous datasets (e.g. those from different laboratories or those from different methods in the same laboratory), it is essential to consider specific information about the animals sampled (e.g. age, sex, reproductive status, body condition and health status), sampling procedures (e.g. necropsy of subsistence, stranded or bycaught individuals; remote or surgical biopsy), methods for measuring and conventions for expressing analytical results for lipids and contaminants (e.g. percent lipid, percent dry weight, contaminant concentration units, totals of contaminant groups such as PCB congeners) and quality assurance performance. Reformatting should be carried out, as necessary, to unify the datasets (e.g. into like units and weight basis) and allow a critical evaluation of the data to be made. As part of the data interpretation, caveats or limits in the comparability of the datasets (based on quality assurance results) should be provided. In addition, the biological relevance of the data must be considered in interpreting the datasets.

Formation and distribution of dioxins in agglomerated products and emitted dust during iron ore sintering

This study investigated the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in sintered products and emitted dust samples. Four types of iron ores were used in this study and tested in a sinter pot grate. The PCDD/F analysis showed that the PCDD concentrations (0.175–1.415, pg/g, 0.028–0.087 pg WHO-TEQ/g) were higher than the PCDFs (0.105–0.327 pg/g, 0.006–0.032 pg WHO-TEQ/g) in sinter. In dust samples, three of the four test experiments showed PCDDs < PCDFs in their measured concentrations. Although PCDD/F concentrations were different in sinter and dust samples, the PCBs presented similar behavior in both solid samples. The PCB analysis (pg WHO-TEQ/g) showed that non-ortho PCBs were higher in concentration than the mono-ortho PCBs. The statistical analysis showed significant correlations between low chlorinated PCDD/F congeners and high chlorinated PCDD/F congeners, as well as strong correlations between non-ortho PCBs and mono-ortho PCBs in both sinter and dust samples. However, the dust samples presented stronger and more positive correlations among the PCDD/F and PCB congeners in comparison to corresponding data in sinter samples. The differences in PCDD/F profiles and correlation matrix in sinter and dust samples suggest the dioxin formation during sintering undergos different mechanisms in the sinter and dust samples.

Use of DDTs and PCBs as chemical tracers in assessing the foraging locations and habits of northern elephant seals from Guadalupe Island (Mexico)

AbstractOrganochlorine contaminants (OCs) accumulate in top predators, reaching high levels associated with negative physiological effects. Measuring OCs is key for assessing the accumulation of their loads and evaluating the efficiency of contaminant regulations. Some OCs generate specific signatures in certain areas, which allow us to track potential movements and feeding habits of species. Thirty‐five blubber biopsies were taken from northern elephant seals (NES) during fall at Guadalupe Island (GI), Mexico, an important site for hauling‐out, molting, and breeding. Biopsies were analyzed for dichlorodiphenyltrichloroethane and its metabolites (tDDTs), hexachlorobenzene, chlordanes, and total PCB congeners (tPCBs). tDDTs were higher in adults than in juveniles, suggesting age class‐based bioaccumulation, related to time and differences in foraging and habitat use between age groups. Females had higher variability of OCs than males, attributed to multiple causes, including variation in the use of foraging grounds and niche segregation. The DDT:PCB ratios were the highest, showing similarity with the Palos Verdes (California) contaminant signature, suggesting the use of similar feeding areas in relation to juvenile NES from Southern California.Our baseline of OC levels for NES at GI, allows future monitoring of changes in legacy contaminants over time, and the evaluation of the efficiency of their regulations.

Methanol promotes the biodegradation of 2,2′,3,4,4′,5,5′-heptachlorobiphenyl (PCB 180) by the microbial consortium QY2: Metabolic pathways, toxicity evaluation and community response

As one of the most frequently detected PCB congeners in human adipose tissue, 2,2′,3,4,4′,5,5′-heptachlorobiphenyl (PCB 180) has attracted much attention. However, PCB 180 is difficult to be directly utilized by microorganisms due to its hydrophobicity and obstinacy. Herein, methanol (5 mM) as a co-metabolic carbon source significantly stimulated the degradation performance of microbial consortium QY2 for PCB 180 (51.9% higher than that without methanol addition). Six metabolic products including low-chlorinated PCBs and chlorobenzoic acid were identified during co-metabolic degradation, denoting that PCB 180 was metabolized via dechlorination, hydroxylation and ring-opening pathways. The oxidative stress and apoptosis induced by PCB 180 were dose-dependent, but the addition of methanol effectively promoted the tolerance of consortium QY2 to resist unfavorable environmental stress. Additionally, the significant reduction of intracellular reactive oxygen species (ROS) and enhancement of cell viability during methanol co-metabolic degradation proved that the degradation was a detoxification process. The microbial community and network analyses suggested that the potential PCB 180 degrading bacteria in the community (e.g., Achromobacter, Cupriavidus, Methylobacterium and Sphingomonas) and functional abundance of metabolic pathways were selectively enriched by methanol, and the synergies among species whose richness increased after methanol addition might dominate the degradation process. These findings provide new insights into the biodegradation of PCB 180 by microbial consortium.

Combined tracers reveal the multi‐dimensionality of resource partitioning among sympatric forage fish

Abstract Quantifying the multi‐dimensional nature of resource partitioning in‐situ represents a fundamental challenge for understanding how environmental conditions contribute to the co‐existence of sympatric species. For aquatic poikilotherms, the availability of temperatures at or near optima generally define the ranges and limitations of species biology and ecology. Specifically, how poikilotherms partition this abiotic resource remains a broader unknown in aquatic ecology. Alewife (Alosa pseudoharengus), deepwater sculpin (Myoxocephalus thompsonii), rainbow smelt (Osmerus mordax), and round goby (Neogobius melanostomus) co‐occur throughout Lake Ontario and are known to share common prey resources. Here, we used a combination of trophic tracers (stable isotopes), pollutants (polychlorinated biphenyls, PCBs), and bioenergetic modelling to illustrate resource partitioning of diet items and thermal habitat among Lake Ontario prey fish species. We predicted that the combined use of δ13C, δ15N, and PCBs will capture the multi‐dimensional nature of resource partitioning among coexisting species inhabiting similar compartments within this ecosystem. The δ13C and δ15N values confirmed our understanding of trophic relationships among these species. A bioenergetic model predicted temperature occupancies for each species and for individuals during the open water growing season when prey consumption rates are likely to be maximised and the PCB congener profiles were highly correlated with these predictions. Three‐dimensional niche modelling demonstrated that ecological tracer assimilation is probably a direct result of species behavioural thermoregulation during the open water growing season when temperatures are at or near physiological optima. These results demonstrate that the ability of aquatic poikilotherms to track optimal temperatures and exploit habitat and food resources is captured by their PCB congener profiles. Consumer PCB congener profiles integrate not only the specific prey resources consumed, but also the predominant thermal conditions under which those resources were acquired and assimilated and that subsequently regulate individual and species growth. Given their global ubiquity and capacity for interpretation under the assumptions applied to ecological tracers, consumer PCB profiles could greatly advance our understanding of the mechanisms regulating resource partitioning, especially among aquatic poikilotherms.

Evidence of microplastic-mediated transfer of PCB-153 to sea urchin tissues using radiotracers

The present study reports the first experimental microplastic-mediated transfer of a key PCB congener into adult specimens of the sea urchin Paracentrotus lividus. Three experiments were conducted to assess whether 14C-PCB-153 adsorbed onto negatively buoyant microplastics (MPs) (500–600 μm) is bioavailable to the sea urchin: (1) exposure to a low concentration of 14C-PCB-153 sorbed onto a high number of virgin MPs (“lowPCB highMP” experiment), (2) exposure to a high concentration of 14C-PCB-153 sorbed onto a relatively low number of virgin MPs (“highPCB lowMP” experiment), and (3) exposure to a low concentration of 14C-PCB-153 sorbed onto a relatively low number of aged MP (“lowPCB lowMP” experiment). Results showed that the transfer of 14C-PCB-153 from MPs to sea urchin tissues occurred in each of the three 15-day experiments, suggesting that MPs located on the seafloor may act as vectors of PCB-153 to sea urchins even during short-term exposure events.

Changes in Polychlorinated Biphenyl Residues in Milk during Lactation: Levels of Contamination, Influencing Factors, and Infant Risk Assessment.

Given the importance of breastfeeding infants, the contamination of human milk is a significant public concern. The aim of this study was to assess the contamination of human milk with dioxin-like PCBs (dl-PCBs) and non-dioxin-like PCBs (ndl-PCBs) in relation to the duration of lactation and other influencing factors, especially the frequency of the consumption of selected foods during pregnancy. Based on this, the health risk to infants was assessed and compared to the tolerable daily intake (TDI). PCB determinations were performed using gas chromatography/mass spectrometry. The ∑ndl-PCB content ranged from 0.008 to 0.897 ng/g w.w., at an average of 0.552 ng/g wet weight, which was 55% of the maximum level according to the EU guidelines for foods for infants and young children. The toxic equivalent (TEQ) was in the range of 0.033-5.67 pg-TEQ/g w.w. The content of non-ortho, mono-ortho, and ndl-PCBs in human milk decreased the longer lactation continued. Moreover, when pregnant women smoked tobacco, this correlated significantly with increases in the concentrations of PCB congeners 156, 118, and 189 in human milk. The human milk contents of PCB congeners 77, 81, 186, 118, and 189 were strongly positively correlated with the amount of fish consumed. The content of stable congeners PCB 135 and PCB 153 increased with age.

Bioaccumulation of PCDD/Fs and PCBs in free-range hens: Congener fingerprints and biotransfer factors

The bioaccumulation of lipophilic environmental contaminants in farm animals is an important issue to control and prevent human exposure to toxic pollutants. Free-range hens were used as a model to assess the transfer and the bioaccumulation of PCDD/Fs, DL-PCBs and NDL-PCBs from the soil to eggs in an area in the Campania region particularly affected by pollution, the “Land of Fires”. We determined the following ranges of concentrations in eggs: 0.90–5.51 pg WHO-TEQ g−1 fat for PCDD/Fs; 1.63–4.24 pg WHO-TEQ g−1 fat for DL-PCBs; 2.77–9.75 pg WHO-TEQ g−1 fat for the sum of PCDD/Fs and DL-PCBs and 12.53–30.94 ng g−1 fat for NDL-PCBs. Higher contamination levels were observed in the eggs from free-range hens, compared to those of the control group, that is hens raised indoors; this indicates that soil remains a major source of contamination. Livers showed low levels of contamination for both outdoor and indoor reared hens. Biotransfer factors (BTFs) were calculated for each of the 35 PCDD/F and PCB congeners analysed. The BTFs highlighted that the transfer and bioaccumulation depend on chlorination degree and substitution pattern, in particular they increase with increasing chlorination degree up to the hexa-chlorinated congeners and then decrease. An exception to these finding was observed for 2,3,7,8 TCDD and 2,3,7,8 TCDF, which showed very high BTFs. These results demonstrate the importance of promoting studies on the environmental contaminants bioaccumulation as they provide an effective support for the risk assessment and management of exposure to toxic chemicals.

Contamination of food crops by unintentionally released PCB 47, PCB 51 and PCB 68 in the vicinity of silicone production sites and their relevance for human health assessment

Since it was shown that silicone rubber production can unintentionally release PCBs, these production sites have become a focus of investigation. The use of the cross-linking agent bis(2,4)-dichlorobenzoylperoxide (2,4-DCBP) can lead to emissions of the PCB congeners PCB 47, PCB 51 and PCB 68 into the environment and cause their accumulation e. g. in food crops. To determine the presence and extent of this uptake, we used the newly developed method dandelion screening. Samples were taken from wild dandelion plants near nine production sites in North Rhine-Westphalia, Germany, and analysed for PCBs. In some cases, the regional orientation values for the maximum background level (OMB) were exceeded by up to nine times. Overall, background levels were exceeded at seven of the nine sites investigated and mitigation measures were initiated at the production sites. In order to validate the dandelion screening results, kale was exposed, which allowed for a health assessment. A wide-ranging consumption recommendation was then issued in four out of nine study areas. At this point in the investigations, risk reduction measures had already been implemented at all production sites investigated, so it can be assumed that the exposures at sites not yet in focus are significantly greater. This is a globally relevant problem, as 2,4-DCBP is used in many countries.

Environmental release of non-Aroclor polychlorinated biphenyls by a silicone rubber production site did not lead to elevated plasma levels in the nearby population.

In 2019, high concentrations of the non-Aroclor PCB congeners 47, 51, and 68 were released by a silicone rubber production site in North-Rhine Westphalia, Germany. Local authorities announced a consumption alert for home-grown fruits and vegetables for the affected area which led to a great level of insecurity among the population regarding potential health effects. The aim of study was to determine the plasma levels of the non-Aroclor congeners and the six ndl-indicator congeners (PCB 28, 52, 101, 138, 153, 180) in children and women with child-bearing potential living close to the production site. Altogether n=111 participants, with n=73 female adults and n=38 children were included in this analysis. For the non-Aroclor-PCBs as well as the lower-clorinated ndl-indicator PCBs 28, 52, and 101, the median plasma concentrations were below the LOQ. Only one adult showed an elevated PCB 47 value. In conclusion, no elevated plasma levels could be detected for PCB 47, 51, or 68 in the nearby population of the silicone-rubber production site. However, our study was highly important for risk characterisation as well as risk communication.

Characterization, source and risk assessments of sediment contaminants (PCDD/Fs, DL-PCBs, PAHs, PCBs, OCPs, metals) in the urban water supply area

Water resources are becoming more valuable day by day. They need to evaluate the pollution and risk situations of the sources that supply water in detail. It is aimed to determine the level of POPs (PCDD/Fs, DL-PCBs, PAHs, PCBs, and OCPs) and metals, which are persistent pollutants, in the surface sediments taken from Yuvacık lake to reveal their possible sources, and to make toxicological and ecological risk assessments of sediment quality. It is one of the most comprehensive studies on the sediment scale for a drinking water source and is a first for the study area. Seventeen 2,3,7,8-substituted PCDD/Fs were analyzed with US EPA method (M.1613). The concentrations of all POPs were determined by GC-MS/MS. The range of ∑PCDD/F is 3.171 (Y8) to 28.42 (Y10) pg/g, with the highest concentrations of OCDD and 1234678-HpCDF compounds. Total DL-PCB concentrations 6.369 (Y8) to 37.41 (Y9) pg/g Total PAH concentrations in the samples ranged from 36.97 ng/g (Y1) to 81.38 ng/g (Y10). The PAH compounds with the highest concentrations at all sampled points were Phenanthrene 3141 (Y7) - 21,636 (Y10) and Naphthalene (11.40–19.41) ng/g. Total OCP concentrations ranged from 1.045 ng/g (Y8) to 4.179 ng/g (Y2), while total PCB concentrations ranged from 0.308 (Y1) to 1.55029 (Y9) ng/g. DDT p,p (0.4078–3.2544 ng/g) has the highest concentration among OCPs. PCB 101, 153, 138, and 180 are the highest detected PCB congeners. As a result of the source analysis, three different main sources were determined for all pollutant groups. They show accumulation in the sediment as a result of long-distance atmospheric transport. Toxicological values were found below acceptable limits. The main metals posing ecological risk were Ag, Cu, and Cd. Monitoring of POPs and assessing their toxicological and ecological risks are important for planning water resources and should be applied especially for critical basins.

Evaluation and Distribution of Selected Polychlorinated Biphenyl Congeners and Triclosan in Soil, Sediment and Surface Water System: A Case Study of Ojutu River, Osun State, Nigeria

ABSTRACT This study evaluated the presence of seven-selected polychlorinated biphenyls and triclosan in the Ojutu River, Osun State Nigeria. The soil, sediment and surface water at five different sampling sites were investigated following the standard analytical procedure. The maximum concentration of targeted PCBs in soil, sediment and water are; 1.02 µg/g, 0.6490 µg/g and 0.02981 µg/mL respectively. While triclosan has 0.0562 ng/g, 0.0457 ng/g and 0.001070 ng/mL in sediment, soil and water samples respectively. The concentrations of some of the selected PCB congeners and triclosan were significant in sediment and soil samples across the sites while the majority analytes showed no significant differences in water samples across the sites. The parameters investigated were found within the WHO maximum permissible limit therefore the water could be considered less susceptible to these pollutants. Other contaminants such as personal care products, pharmaceuticals, heavy metals and micro-pollutants as well as pollution levels associated with microbial load are worthy of investigation to know the actual state of the river for the safety of aquatic lives and the health of humans who depends on this river.

Ecotoxicological Characterization of Type C Killer Whales From Terra Nova Bay (Ross Sea, Antarctica): Molecular Biomarkers, Legacy, and Emerging Persistent Organic Contaminants

Among killer whale forms, type C is a fish-eating form and is the most common in the Ross Sea. In the austral summer 2015, a study was conducted to evaluate the toxicological hazard these marine mammals face in the Antarctic ecosystem. Seven biopsy samples were collected from adult individuals (five males and two females) in the surroundings of the Italian Research Station Mario Zucchelli, Terra Nova Bay, by remote dart sampling from the pack ice. The accumulation levels of persistent organic pollutants (POPs) such as legacy (DDTs, PCBs, and HCB) and emerging (PBDEs and DP) were measured. Moreover, the protein expression of cytochrome P450 (CYP1A1 and 2B) and the mRNA level variations of the peroxisome proliferator-activated receptors α and γ (PPARα-γ) and the estrogen receptor α (ERα), aryl hydrocarbon receptor (AhR), andCyp1awere evaluated. Twenty PCB congeners, six DDTs, HCB, three HCHs, and fourteen brominated BDEs and DP-syn and anti-isomers were analyzed on freeze-dried blubber biopsy samples by GC-MS. The protein expression was evaluated by Western Blot and the mRNA levels were quantified by quantitative real-time PCR. The average abundance pattern for the contaminants was DDTs &amp;gt; PCBs &amp;gt; HCB &amp;gt; HCHs ≈ PBDEs &amp;gt;&amp;gt; DP. Contaminant levels resulted to be lower when compared to the existing data from the Antarctic type C killer whales from the McMurdo Sound (Ross Sea) and those reported for fish-eating killer whales worldwide. The mRNA levels of the five target genes were successfully quantified, but no statistical correlation was found with POP levels, suggesting that either the low levels of quantified POPs in blubber may not significantly affect the biological responses investigated, or that other stressors could contribute to the alterations of the molecular biomarkers. Although the results showed a lower risk related to contamination compared to more impacted areas, this study provides baseline data for the conservation of this species in an area with high ecological value, recently declared as the largest Marine Protected Area in Antarctica, where pollutants should remain at minimum levels despite increasing multiple stresses existing in the region.

Augmentation of an Engineered Bacterial Strain Potentially Improves the Cleanup of PCB Water Pollution.

ABSTRACTPolychlorinated biphenyls (PCBs) are recalcitrant organohalide pollutants, consisting of 209 congeners. PCB cleanup in natural landscapes is expected to be achieved by the metabolic activity of microorganisms, but aerobic PCB-degrading bacteria that inhabit sites polluted by PCBs cannot degrade all PCB congeners due to the specificity of their enzymes. In this study, we investigated the degradability of PCBs when a genetically modified PCB-degrading bacterium was compounded with wild-type PCB-degrading bacteria. We used two bacterial strains, Comamonas testosteroni YAZ2 isolated from a PCB-uncontaminated natural landscape and Escherichia coli BL21(DE3) transformed with a biphenyl dioxygenase (BphA) gene from a well-known PCB degrader, Burkholderia xenovorans LB400. The enzymatic specificities of BphA were 2,3-dioxygenation in the YAZ2 and 2,3- and 3,4-dioxygenations in the recombinant E. coli. For the PCB-degrading experiment, a dedicated bioreactor capable of generating oxygen microbubbles was prototyped and used. The combined cells of the recombinant and the wild-type strains with an appropriate composite ratio degraded 40 mg/L of Kaneclor KC-300 to 0.3 ± 0.1 mg/L within 24 h. All of the health-toxic coplanar PCB congeners in KC-300 were degraded. This study suggested that the augmentation of an engineered bacterial strain could improve the cleanup of PCB water pollution. It also revealed the importance of the ratio of the strains with different PCB-degrading profiles to efficient degradation and that the application of oxygen microbubbles could rapidly accelerate the cleanup.IMPORTANCE PCB cleanup technique in a natural environment relies on the use of enzymes from microorganisms, primarily biphenyl dioxygenase and dehalogenase. Herein, we focused on biphenyl dioxygenase and created a recombinant PCB-degrading E. coli strain. Despite the development of environments for the field use of transgenic microbial strains around the world, verification of the applicability of transgenic microbial strains for PCB cleanup in the field has not yet been reported. We tentatively verified the extent to which degradability could be obtained by an augmentation model of a transgenic strain, the enzyme expression of which is easily regulated in rivers and lakes with PCB pollution. Our experiments used a dedicated bioreactor to model the natural landscape and produced results superior to those of bioremediation or biostimulation methods. The application of micro-nano bubbles, which has recently been discussed, to the cleanup of environmental pollution was also found to be useful in this study.

Passive-Sampler-Based Bioavailability Assessment of PCB Congeners Associated with Aroclor-Containing Paint Chips in the Presence of Sediment

This is the first investigation of the bioavailability of PCBs associated with paint chips (PC) dispersed in sediment. Bioavailability of PCB-containing PC in sediment was measured using ex situ polyethylene passive samplers (PS) and compared to that of PCBs from field-collected sediments. PC were mixed in freshwater sediment from a relatively uncontaminated site with no known PCB contamination sources and from a contaminated site with non-paint PCB sources. PC < 0.045 mm generated concentrations in the PS over one order of magnitude higher than coarser chips. The bioavailable fraction was represented by the polymer-sediment accumulation factor (PSAF), defined as the ratio of the PCB concentrations in the PS and organic carbon normalized sediment. The PSAF was similar for both field sediments. The PSAFs for the field sediments were ~ 50–60 and ~ 5 times higher than for the relatively uncontaminated sediment amended with PC for the size fractions 0.25–0.3 mm and < 0.045 mm, respectively. These results indicate much lower bioavailability for PCBs associated with PC compared to PCBs associated with field-collected sediment. Such information is essential for risk assessment and remediation decision-making for sites where contamination from non-paint PCBs sources is co-located with PCB PC.

Trends of banned pesticides and PCBs in different tissues of striped dolphins (Stenella coeruleoalba) stranded in the Northwestern Mediterranean reflect changing contamination patterns

Although banned for years, organochlorine pesticides and PCBs continue to affect aquatic life, dolphins being particularly exposed. The concentrations of 31 PCB congeners, and 15 banned pesticides or metabolites were measured in 5 tissues of 68 striped dolphins stranded in the Northwestern Mediterranean coast in 2010–16. The results were compared to historical data (1988–2009) and, even though there is a slow decreasing trend, the levels in the 2010–2016 samples were still elevated based on common cetacean toxicological thresholds. A transition period in 2007–08, probably caused by a morbillivirus epizootic amplified the stranding, espacially of highly contaminated specimens. From 2010, higher proportions in parent compounds towards metabolites were observed yet again. These changing patterns were likely reflect the exposure of dolphins to the remobilization of pollutants from contaminated soils and sediments, with a prominent role of rivers. This should lead to an even slower decline of these contaminants that could last for decades, requiring new efforts to reduce their dispersal to aquatic ecosystems.

Ortho-substituted PCB 153: effects in CHO-K1 cells.

Non-planar di-ortho-substituted PCB 153 (2,2’,4,4’,5,5’-hexachlorobiphenyl), one of the most abundant PCB congeners in the environment and in biological and human tissues, has been identified as potential endocrine disruptor affecting the reproductive and endocrine systems in rodents, wildlife, and humans. The aim of this study was to gain a deeper insight into its mode/mechanism of action in Chinese hamster ovary K1 cells (CHO-K1). PCB 153 (10–100 μmol/L) inhibited CHO-K1 cell proliferation, which was confirmed with four bioassays (Trypan Blue, Neutral Red, Kenacid Blue, and MTT), of which the MTT assay proved the most sensitive. PCB 153 also induced ROS formation in a dose-dependent manner. Apoptosis was seen after 6 h of exposure to PCB 153 doses ≥50 μmol/L, while prolonged exposure resulted in the activation of the necrotic pathway. PCB 153-induced disturbances in normal cell cycle progression were time-dependent, with the most significant effects occurring after 72 h.

Spatial distribution, source identification and ecological risk assessment of POPs and heavy metals in lake sediments of Istanbul, Turkey

Istanbul needs to be protected and constantly monitored water resources due to its increasing population and the decrease in precipitation. This study aims to comprehensively reveal surface sediments collected from reservoirs that supply water to Istanbul concerning POPs (PAHs, PCBs, and OCPs) and heavy metals; to identify possible sources of PAHs, and conduct their ecological risk assessment. Pollution indices in this study were used as contamination degree (CD) contamination factor (CF), geoaccumulation index (Igeo), pollution load index (PLI) and Sediment Quality Guidelines (SQGs). Total PAH concentrations of surface sediments at the sampling points ranged from 46.29 ng/g (A7) to 403.9 ng/g (A15). Benzo(b)fluoranthene (5.647–59.42 ng/g), Pyrene (3.625–83.10 ng/g), Fluoranthene (3.363–66.48 ng/g), Phenanthrene (3.115–52.48 ng/g), Chrysene (3.532–43.98 ng/g), Naphthalene (6.606–36.20 ng/g), Benzo(g,h,i)perylene (3.316–41.73 ng/g) and Indeno(1,2,3-c,d)pyrene (3.453–38.84 ng/g) are the dominant PAH compounds. PAH pollution may be caused by the village-town settlements near the dam and the O7-D020 highway. Total OCP concentration ranged from 2.233 ng/g (A12) to 7.337 ng/g (A1), while total PCB concentration ranged from 0.246 ng/g (A13) to 3.708 ng/g (A1). The lowest total OCP and PCB concentrations were found in surface sediments taken from Kazandere, Papuçdere and Alibey Dam lakes. DDT p,p (0.072–5.177 ng/g) has the highest concentration among all sediment samples. While the most dominant OCP compounds in the samples were DDT p,p, DDE p,p and DDD p,p, HCH alpha, HCH beta, respectively, PCB 153, 138 and 180 were the highest detected PCB congeners in the same samples. Total heavy metal concentration varied from 77,812 mg/kg to 267,072 mg/kg. According to PAH diagnostic analysis, the surface sediments of Terkos, Büyükçekmece, Elmalı, Darlık, Sazlıdere, Alibey and Ömerli Dams were polluted by petrogenic sources, while the surface sediments of Kazandere and Papuçdere Dams were affected by pyrogenic sources. None of the levels of POPs in the samples exceeded the ERM values. Slight and moderate contamination of heavy metals, such as Pb and Zn, were present in most of the sampling points according to CD, CF, PLI and Igeo values. The quality criteria of heavy metals showed that almost all of the sampling points had Cd, Pb and Hg concentrations below the ERL values. The Ni concentrations at most of the sampling points significantly exceeded the ERM values. The concentrations of As, Cr, Cu and especially Ni and Zn exhibit a significant toxic risk to aquatic organisms to sediment quality criteria.

Fatty acid profile as an efficient bioindicator of PCB bioaccumulation in a freshwater lake food web: A stable isotope guided investigation

In past studies, the health and ecological risks of PCBs are well established. The impact of low-dose PCBs on aquatic ecosystems for an extended period is a matter of concern in the current era. The application of fatty acids (FAs) as bioindicators of pollution in the freshwater food web is almost unavailable. This study investigated concentrations of 209 PCB congeners, stable isotope levels, and FAs composition in ten freshwater species of Dongtinghu Lake, China. Total PCB congeners (∑PCBs) concentrations were ranged from 4.17 to 38.35 ng/g lipid weight. A total of 84 PCB congeners were detected out of 209 target PCB congeners, particularly PCB101, 118, 138, 153, and 155 found in all samples. The concentrations of 24 PCB congeners increased with trophic levels, but PCB 155 concentrations were consistent throughout trophic levels. The toxic equivalents (TEQ) of dl-PCBs (mostly PCB 126 and 169) also increased with trophic levels Out of total 35 FAs, 21 FAs were significantly positively correlated with 43 PCB congeners. Among FAs, C16:0 was the most abundant and positively correlated with most PCB compounds. Positive correlations between FAs and PCBs indicated that FAs can be used as efficient bioindicators of PCBs pollution in the aquatic food web.

Validation of an improved European standard method for the determination of PCBs in oil samples

Two European standard methods (EN 12766 and EN 61619) are currently used for the determination of PCBs in specific oil matrix. However, apolar matrix compounds (e.g. hydrocarbons) elute from the adsorbent together with the PCBs and are injected into the analytical system where their presence contaminates the inlet, detectors and columns; and decreases system performances. Insufficient cleanup causes delay of elution of PCBs from GC columns. By using new sulfoxide-bonded silica, PCBs are better separated from aliphatic hydrocarbons because the specificity of the stationary phase for these compounds is much higher that that used in both standard methods. A gas chromatograph AT6890 with two capillary columns of different polarities (HP-5MS and DB-1701) coupled to two μECDs is used. Oven temperature program is as followed: 90°C (1 min), 70°C/min to 180°C, 5°C/min to 230°C (0.1 min), 1.5°C/min to 280°C. Run time is 46 min. The procedure was validated through regular analysis of blanks, fortified samples (transformer oil, motor used and unused oil) and certified materials (BCR-449 and BCR-420, waste mineral oils, high and low PCB levels). Two internal standards were used (PCB 30 and PCB 209). An average recovery ± RSD of 82.8 ± 5.4 % was achieved for all six PCBs in different matrices. The LOQ per single PCB congener is 0.2 mg kg-1. The average recovery ± RSD for the BCR-420 is 92.0 ± 4.6 % and for the BCR-449 is 105 ± 2.5 % for all certified PCBs in waste oils.