Serum concentrations of persistent organic pollutants (POPs) in the inhabitants of a Sicilian city

Background

Polychlorinated biphenyls (PCBs) and organochlorine pesticides are common environmental contaminants that have been associated with human health problems.

Objectives

To assess serum concentrations of several organochlorine contaminants in general population living in a city with an ancient agricultural tradition and to identify possible exposure sources in Sicily.

Methods

A cross-sectional study was conducted on 101 individuals. Each participant answered a face-to-face questionnaire submitted by well-trained personnel and provided a serum sample which was analyzed for the concentrations of PCBs, HCB, HCHs and DDTs by using gas-chromatography coupled with mass spectrometry.

Results

HCB, p,p′-DDE, PCB 138, PCB 153 and PCB 180 were detected in more than 80% of the study participants. The ng g⁻¹ lipid median concentrations were: 18.6 for HCB; 175.1 for p,p′-DDE; 22. for PCB 138; 32.5 for PCB 153 and 23.0 for PCB 180. PCB 153 and PCB 138, PCB 138 and PCB 180, PCB 153 and PCB 180, and p,p′-DDE and HCB showed a high correlation each other (p < 0.05). HCB and p,p′-DDE concentrations were significantly higher in subjects >49 years old (adj-p = 0.03 in 50-69 years old and adj-p < 0.001 in >69 years old, respectively) whereas PCB 138, PCB 153 and PCB 180 concentrations were higher in males (adj-p = 0.03), in subjects >69 years old (adj-p = 0.04) and in current smokers (adj-p = 0.04).

Conclusions

The present study shows that serum concentrations of organochlorine compounds detected in subjects living in a small Sicilian city with ancient agricultural tradition are similar to those found in subjects living in urban areas of other countries. However, further investigations are needed to compare data from rural/urban areas in the same country, assessing correlations between serum concentrations of several chemical compounds and potential health effects in general population.     

Aphanizomenon gracile (Nostocales), a cylindrospermopsin-producing cyanobacterium in Polish lakes

The cyanobacterial cytotoxin cylindrospermopsin (CYN) has become increasingly common in fresh waters worldwide. It was originally isolated from Cylindrospermopsis raciborskii in Australia; however, in European waters, its occurrence is associated with other cyanobacterial species belonging to the genera Aphanizomenon and Anabaena. Moreover, cylindrospermopsin-producing strains of widely distributed C. raciborskii have not yet been observed in European waters. The aims of this work were to assess the occurrence of CYN in lakes of western Poland and to identify the CYN producers. The ELISA tests, high-performance liquid chromatography (HPLC)-DAD, and HPLC-mass spectrometry (MS)/MS were conducted to assess the occurrence of CYN in 36 lakes. The cyrJ, cyrA, and pks genes were amplified to identify toxigenic genotypes of cyanobacteria that are capable of producing CYN. The toxicity and toxigenicity of the C. raciborskii and Aphanizomenon gracile strains isolated from the studied lakes were examined. Overall, CYN was detected in 13 lakes using HPLC-MS/MS, and its concentrations varied from trace levels to 3.0 μg?L^?1. CYN was widely observed in lakes of western Poland during the whole summer under different environmental conditions. Mineral forms of nutrients and temperature were related to CYN production. The molecular studies confirmed the presence of toxigenic cyanobacterial populations in all of the samples where CYN was detected. The toxicity and toxigenicity analyses of isolated cyanobacteria strains revealed that A. gracile was the major producer of CYN.     

Toxic risk associated with sporadic occurrences of Microcystis aeruginosa blooms from tidal rivers in marine and estuarine ecosystems and its impact on Artemia franciscana nauplii populations

Microcystis aeruginosa is a species of freshwater cyanobacteria which can form harmful algal blooms in freshwater water bodies worldwide. However, in spite its sporadic occurrences for short periods of time in estuarine waters, their influence on zooplankton populations present in these ecosystems has not been extensively studied. In this work, Artemia franciscana was used as test organism model, studying mortality against several strains of M. aeruginosa with different degrees of toxigenicity, measuring whole-live cells and homogenate extracts. Results were compared with microcystin-LR equivalent content, measured by immunoassay. The results show that there were no significant differences between both exposure models (whole cells and extracts), and there are significant differences respect to the toxigenicity of cyanobacterial blooms depending of the M. aerugionosa strain involved in the process. Analysis of microcystin-LR equivalent concentration test immediately below the lowest significant concentration in all M. aerugionosa strains was used to determine the potential risk associated with the cell densities during a bloom. Comparison among the selected M. aerugionsa strains show that these factors have influence in the results obtained, and thus, several differences have been evidenced depending of the microcystin-LR equivalent production and the strain type involved.     

Fish consumption reduces transfer of BDE47 from dam to murine offspring

Fish and seafood are important contributions to a healthy diet, but also contain persistent organic pollutants (POPs) like polybrominated diphenylethers (PBDEs) and polychlorinated biphenyls (PCBs). Discrepancies have been found between intake and accumulated levels of POPs, where fish consumers have had similar levels of POPs to the general population. Similarly fish oil consumption has been found to reduce accumulation of POPs. This study examined the accumulation of BDE47 or PCB153 in mice fed diets with different nutritional composition, using female mice with pre-weanling pups exposed through gestation and lactation. A fish-based diet was compared to a standard casein-based rodent diet. All diets had low background levels of environmental contaminants and were spiked with BDE47 or PCB153 to levels representing a realistic (∼0.004 μmol kgbw⁻¹ d) or a high dietary exposure (∼1.3 μmol kgbw⁻¹ d). Accumulation of BDE47 or PCB153 in offspring tissues after 18 d lactation reflected the maternal exposure levels. However, the pups of dams fed a fish-based diet had consistently lower BDE47 accumulation in liver, fat and stomach than pups from casein-fed dams. Similarly the pups of dams fed a high dose of PCB153 in a fish diet also accumulated less PCB153 than pups of the dams fed a casein diet, although not significant. In conclusion, the fish based diets seemed to reduce transfer of BDE47 and PCB153 from dams to pups. The study highlights that in-depth knowledge about nutritional impact on toxicokinetics is of great interest to vulnerable consumers.     

Biodegradation of multiple cyanobacterial metabolites in drinking water supplies

The fate of multiple cyanobacterial metabolites was assessed in two Australian source waters. The saxitoxins were the only metabolites shown to be non-biodegradable in Myponga Reservoir water, while microcystin-LR (MCLR) and geosmin were biodegradable in this water source. Likewise, cylindrospermopsin (CYN) was shown to be biodegradable in River Murray water. The order of ease of biodegradability followed the trend: MCLR > CYN > geosmin > saxitoxins. Biodegradation of the metabolites was affected by temperature and seasonal variations with more rapid degradation at 24 °C and during autumn compared with 14 °C and during winter. A microcystin-degrading bacterium was isolated and shown to degrade four microcystin variants within 4 h. This bacterium, designated as TT25, was shown to be 99% similar to a Sphingopyxis sp. based on a 16S rRNA gene fragment. Isolate TT25 was shown to contain a homologue of the mlrA gene; the sequence of which was 99% similar to that of a previously reported microcystin-degrader. Furthermore, isolate TT25 could degrade the microcystins in the presence of copper sulphate (0.5 mg L⁻¹ as Cu²⁺) which is advantageous for water authorities dosing such algicides into water bodies to control cyanobacterial blooms.     

Multivariate toxicity profiles and QSAR modeling of non-dioxin-like PCBs--an investigation of in vitro screening data from ultra-pure congeners

The non-dioxin-like PCBs (NDL-PCBs) found in food and human samples have a complex spectrum of adverse effects, but lack a detailed risk assessment. The toxicity profiles of 21 carefully selected PCBs (19 NDL-PCBs) were identified by in vitro screening in 17 different assays on specific endpoints related to neurotoxicity, endocrine disruption and tumor promotion. To ensure that the test results were not affected by polychlorinated dioxins, dibenzofurans or DL-PCB contaminants, the NDL-PCB congeners were thoroughly purified before testing. Principal component analysis (PCA) was used to derive general toxicity profiles from the in vitro screening data. The toxicity profiles indicated different structure-activity relationships (SAR) and distinct mechanisms of action. The analysis also indicated that the NDL-PCBs could be divided into two groups. The first group included generally smaller, ortho-substituted congeners, comprising PCB 28, 47, 51, 52, 53, 95, 100, 101, 104 and 136, with PCB 95, 101 and 136 as generally being most active. The second group comprising PCB 19, 74, 118, 122, 128, 138, 153, 170, 180 and 190 had lower biological activity in many of the assays, except for three endocrine-related assays. The most abundant congeners, PCB 138, 153, 170, 180 and 190, cluster in the second group, and thereby show similar SAR. Two quantitative structure-activity relationship (QSAR) models could be developed that added information to the SAR and could aid in risk assessments of NDL-PCBs. The QSAR models predicted a number of congeners as active and among these e.g., PCB 18, 25, 45 and 49 have been found in food or human samples.     

Assessment of exposure to PCB 153 from breast feeding and normal food intake in individual children using a system approach model

Investigators have typically relied on a single or few discrete time points as measures of polychlorinated biphenyl (PCB) body burden, however health effects are more likely to be the result of integrative exposure in time, optionally expressed as an area under the time curve (AUC) of PCB serum concentration. Using data from a subgroup of 93 infants from a birth cohort in eastern Slovakia—a region highly polluted by PCBs—we fit a system type model, customized to our longitudinal measures of serum PCB concentrations in cord, 6, 16, and 45 month blood specimens. The most abundant congener, PCB 153, was chosen for modeling purposes. In addition to currently used methods of exposure assessment, our approach estimates a concentration time profile for each subject, taking into account mean residence time of PCB 153 molecules in the body, duration of breast feeding, hypothetical PCB 153 concentration in steady-state without breast feeding and alternately without normal food intake. Hypothetical PCB 153 concentration in steady-state without normal food intake correlates with AUC (r = 0.84, p < 0.001) as well as with duration of breast feeding (r = 0.64, p < 0.001). It makes possible to determine each subject’s exposure profile expressed as AUC of PCBs serum concentration with a minimum model parameters. PCB body burden in most infants was strongly associated with duration of breast feeding in most, but not all children, was apparent from model output.     

Effects of polychlorinated biphenyls on whole animal energy mobilization and hepatic cellular respiration in rainbow trout, Oncorhynchus mykiss

The production of polychlorinated biphenyls (PCBs) was banned in 1977 but these chemicals persist in the environment and threaten aquatic organisms. PCB exposure often results in activation of the aryl hydrocarbon receptor (AhR) and increases in hepatic detoxification mechanisms. Activation of these detoxification mechanisms is believed to be associated with energetic demands that may come at the expense of other physiological processes such as growth, activity and reproduction. We tested the hypothesis that exposure to sub-lethal levels of PCBs results in increased energy demand and energy mobilization using both an in vivo and in vitro approach. Rainbow trout (Oncorhynchus mykiss) received a single intraperitoneal sub-lethal dose (50 μg kg⁻¹) of 3,3’,4,4’,5-pentachlorobiphenyl (PCB 126) and left for 10 d after which standard oxygen consumption and plasma and liver metabolites were assessed. PCB 126 exposed trout did not alter standard oxygen consumption but did increase plasma glucose concentration implying the mobilization of glucose to cope with this exposure regime. Cellular respiration was assessed in trout hepatocytes exposed to PCB 126 or PCB 77 (3,3′4,4′-tetrachlorobiphenyl) two AhR activators but with different potencies (PCB 126 ? PCB 77). Mitochondrial respiration was assessed by stimulating complex II with succinate and although no increases in respiration were associated with PCB exposure in non-stimulated cells, PCB 77 impaired mitochondrial respiration by preventing stimulation of complex II respiration and potentially masking any actual energetic costs of PCB exposure. These studies suggest that energy is mobilized upon exposure to PCBs, however, actual increases in energy demand may be overshadowed by impaired mitochondrial respiration.     

Is BDE-175 an important enough component of commercial octabromodiphenyl ether mixtures to be listed in Annex A of the Stockholm Convention?

Commercial octabromodiphenyl ether mixtures, containing hexabromodiphenyl ethers and heptabromodiphenyl ethers were listed in Annex A of the Stockholm Convention on May 2009 (Fourth Conference of the Parties) (UNEP, 2009a). Four compounds are specifically mentioned: 2,2′,4,4′,5,5′-hexabromodiphenyl ether (BDE-153), 2,2′,4,4′,5,6′-hexabromodiphenyl ether (BDE-154), 2,2′,3,3′,4,5′,6-heptabromodiphenyl ether (BDE-175), and 2,2′,3,4,4′,5′,6-heptabromodiphenyl ether (BDE-183). Presumably they were identified as key components of commercial mixtures and found to be present in environmental samples. However, since BDE-175 and BDE-183 co-elute on common HRGC columns, the presence of BDE-175 as an important component in technical octa-BDE mixtures has not been illustrated. The successful HRGC/LRMS separation of a 1:1 mixture of BDE-175 and BDE-183, as well as ¹H NMR analysis of technical material, has allowed us to confirm that this congener is not present in technical products (e.g. Great Lakes DE-79™) in quantifiable amounts.     

Assessment of exposure to PCB 153 from breast feeding and normal food intake in individual children using a system approach model

Investigators have typically relied on a single or few discrete time points as measures of polychlorinated biphenyl (PCB) body burden, however health effects are more likely to be the result of integrative exposure in time, optionally expressed as an area under the time curve (AUC) of PCB serum concentration. Using data from a subgroup of 93 infants from a birth cohort in eastern Slovakia—a region highly polluted by PCBs—we fit a system type model, customized to our longitudinal measures of serum PCB concentrations in cord, 6, 16, and 45 month blood specimens. The most abundant congener, PCB 153, was chosen for modeling purposes. In addition to currently used methods of exposure assessment, our approach estimates a concentration time profile for each subject, taking into account mean residence time of PCB 153 molecules in the body, duration of breast feeding, hypothetical PCB 153 concentration in steady-state without breast feeding and alternately without normal food intake. Hypothetical PCB 153 concentration in steady-state without normal food intake correlates with AUC (r = 0.84, p < 0.001) as well as with duration of breast feeding (r = 0.64, p < 0.001). It makes possible to determine each subject’s exposure profile expressed as AUC of PCBs serum concentration with a minimum model parameters. PCB body burden in most infants was strongly associated with duration of breast feeding in most, but not all children, was apparent from model output.     

PBDE flame retardants and PCBs in migrating Steller sea lions (Eumetopias jubatus) in the Strait of Georgia, British Columbia, Canada

Polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) were measured in blubber biopsy samples from 22 live-captured Steller sea lions (Eumetopias jubatus) that had just entered the Strait of Georgia, British Columbia, Canada, for their overwintering feeding season. ∑PBDE ranged from 50 μg kg⁻¹ (lipid weight) in adult females to 3780 μg kg⁻¹ in subadult individuals. ∑PCBs ranged from 272 μg kg⁻¹ in adult females to 14 280 μg kg⁻¹ in subadult individuals. While most PBDE and PCB congeners were transferred through milk to pups, PCBs with log K_OW > 7.0 (PCBs 206, 207, 208 and 209) appeared constrained, resulting in a lighter mixture in pups compared to adult females. The ratio of individual PCB congeners by metabolic group (Groups I, II, III, IV and V) to PCB-153 regressed against length of males suggested poor biotransformation of these compounds (slopes did not differ from zero, p > 0.05). PBDE congeners 49, 99, 153 and 183 appeared bioaccumulative (slopes of ratio BDE/PCB 153 versus length were higher than zero, p < 0.05), but the dominance of the single congener, BDE-47 (64% of total PBDEs), likely due in part to debromination pathways, reduced our ability to explore congener-specific dynamics of PBDEs in these pinnipeds. With 80% of our Steller sea lions exceeding a recent toxicity reference value for PCBs, the fasting-associated mobilization of these contaminants raises concerns about a heightened vulnerability to adverse effects during annual migrations.     

A numerical study on the seasonal variability of polychlorinated biphenyls from the atmosphere in the East China Sea

A three-dimensional/high-resolution transport model for persistent organic pollutants (POPs) has been developed for the East China Sea (ECS). The POPs model has four compartments (gaseous, dissolved, phytoplankton-bound, and detritus-bound phases) and includes processes for diffusive air-water exchange, phytoplankton uptake/depuration to POPs, decomposition of dissolved phase, vertical sinking of phytoplankton, detritus production by phytoplankton mortality, and vertical sinking and decomposition of detritus. The POPs model is coupled with an ocean circulation model that can reproduce the seasonal variation in physical variables to represent the advection and diffusion of POPs. We applied the POPs model to the polychlorinated biphenyl congener 153 (PCB 153) from the atmosphere and examined the behavior of PCB 153 in the ocean. The model showed a remarkable seasonal variability of PCB 153. Concentrations in the dissolved and particulate phases are high in winter (January-March) and low in summer (July-September). In coastal regions, where chlorophyll a concentration is high, horizontal and vertical distributions in the dissolved and particulate PCB 153 concentrations are strongly affected by phytoplankton uptake. The sensitivity experiments on the dynamics of PCB 153 suggested that a change of Henry’s law constant associated with water temperature is the major factor controlling the seasonal variability of PCB 153. The model-based yearly mass balance of PCB 153 in the ECS indicated that most of the atmospheric input (35.5 kg year⁻¹) is removed by the horizontal advection outside the ECS (19.0 kg year⁻¹) and accumulates to the sea bottom by vertical sinking (15.7 kg year⁻¹). For comparison with PCB 153, we also conducted simulations for PCB 52, 101, and 180. The seasonal variations are similar to that of PCB 153. The mass balance of PCB 52 that has short half-life time and less hydrophobic property shows the different results compared with PCB 101, 153, and 180.     

A model compound study: the ecotoxicological evaluation of five organic contaminants employing a battery of marine bioassays

This paper describes the ecotoxicological evaluation of five organic contaminants frequently detected in marine sediments (tributyltin, triphenyltin, benzo[a]pyrene, fluoranthene, and PCB 153) using three marine species (Vibrio fischeri, Tetraselmis suecica, and Tisbe battagliai). The sensitivity of each species varied for all compounds. The triorganotins were consistently the most toxic to all species. The applicability of each test system to assess the acute toxicity of environmental contaminants and their use in Toxicity Identification Evaluation (TIE) is discussed. Suitability of the Microtox and T. battagliai tests for employment in TIE studies were further assessed through spiking experiments with tributyltin. Results demonstrated that the most effective treatment to remove organotin toxicity from the sample was the C18 resin. The results of this study have important implications for risk assessment in estuarine and coastal waters in Ireland, where, at present the monitoring of sediment and water quality is predominantly reliant on chemical analysis alone.     

Pollutants and the health of green sea turtles resident to an urbanized estuary in San Diego, CA

Rapid expansion of coastal anthropogenic development means that critical foraging and developmental habitats often occur near highly polluted and urbanized environments. Although coastal contamination is widespread, the impact this has on long-lived vertebrates like the green turtle (Chelonia mydas) is unclear because traditional experimental methods cannot be applied. We coupled minimally invasive sampling techniques with health assessments to quantify contaminant patterns in a population of green turtles resident to San Diego Bay, CA, a highly urbanized and contaminated estuary. Several chemicals were correlated with turtle size, suggesting possible differences in physiological processes or habitat utilization between life stages. With the exception of mercury, higher concentrations of carapace metals as well as 4,4′-dichlorodiphenyldichloroethylene (DDE) and γ chlordane in blood plasma relative to other sea turtle studies raises important questions about the chemical risks to turtles resident to San Diego Bay. Mercury concentrations exceeded immune function no-effects thresholds and increased carapace metal loads were correlated with higher levels of multiple health markers. These results indicate immunological and physiological effects studies are needed in this population. Our results give insight into the potential conservation risk contaminants pose to sea turtles inhabiting this contaminated coastal habitat, and highlight the need to better manage and mitigate contaminant exposure in San Diego Bay.     

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.     

Influence factors of multicomponent mixtures containing reactive chemicals and their joint effects

Organic chemicals usually coexist as a mixture in the environment, and the mixture toxicity of organic chemicals has received increased attention. However, research regarding the joint effects of reactive chemicals is lacking. In this study, we examined two kinds of reactive chemicals, cyanogenic toxicants and aldehydes and determined their joint effects on Photobacterium phosphoreum. Three factors were found to influence the joint effects of multicomponent mixtures containing reactive chemicals, including the number of components, the dominating components and the toxic ratios. With an increased number of components, the synergistic or antagonistic effects (interactions) will weaken to the additive effects (non-interactions) if the added component cannot yield a much stronger joint effect with an existing component. Contrarily, the joint effect of the mixture may become stronger instead of weaker if the added components can yield a much stronger joint effect than the existing joint effect of the multicomponent mixture. The components that yield the strongest interactions in their binary mixture can be considered the dominating components. These components contribute more to the interactions of multicomponent mixtures than other components. Moreover, the toxic ratios also influence the joint effects of the mixtures. This study provides an insight into what are the main factors and how they influence the joint effects of multicomponent mixtures containing reactive chemicals, and thus, the findings are beneficial to the study of mixture toxicology.     

Metabolites of 2,2'-dichlorobiphenyl and 2,6-dichlorobiphenyl in hairy root culture of black nightshade Solanum nigrum SNC-9O

The hairy root culture of black nightshade (Solanum nigrum) SNC-9O was exposed to 2,2′-dichlorobiphenyl (PCB 4) and 2,6-dichlorobiphenyl (PCB 10) to follow the metabolites produced. The analytical standards of 4-hydroxy-2,2′-dichlorobiphenyl, 5′-hydroxy-2,2′-dichlorobiphenyl, 4-hydroxy-2,6-dichlorobiphenyl, 2-hydroxy-2′,6′-dichlorobiphenyl, 3-hydroxy-2′,6′-dichlorobiphenyl and 4-hydroxy-2′,6′-dichlorobiphenyl have been synthesized. Hydroxy-metabolites of both PCB 4 and PCB 10 were present in the biomass. These appeared mainly as conjugates rather than as free hydroxy-PCBs, both maintained in plant cells. The concentrations of non-conjugated hydroxy-PCBs ranged between 0.9 and 35.2 μg kg⁻¹ of biomass fresh weight and the concentration of the conjugated ones ranged between 2.0 and 113.0 μg kg⁻¹ depending on the position of hydroxyl. The para- position of biphenyl (4 or 4′) seems to be preferred for hydroxylation. Methoxy-PCBs and hydroxy-methoxy-PCBs have also been identified in plant cells. Hydroxyl in the meta-position (3, 3′, 5 or 5′) appears to be preferred for methylation in hydroxy-PCBs. Hydroxy-methoxy-PCBs have occurred in the conjugated form as well.     

The joint effects of sulfonamides and their potentiator on Photobacterium phosphoreum: differences between the acute and chronic mixture toxicity mechanisms

Organisms are typically exposed to mixtures of chemicals over long periods of time; thus, chronic mixture toxicity analysis is the best way to perform risk assessment in regards to organisms. However, most studies focus on the acute mixture toxicity. To investigate the difference between chronic mixture toxicity and acute mixture toxicity, Photobacterium phosphoreum were exposed to chronic (24 h exposure) and acute (15 min exposure) toxicity of single sulfonamide (SA) and their potentiator (trimethoprim, TMP), both individually and mixtures (SA with TMP). A comparison of chronic vs. acute mixture toxicity revealed the presence of an interesting phenomenon, that is, that the joint effects vary with the duration of exposure; the acute mixture toxicity was antagonistic, whereas the chronic mixture toxicity was synergistic. Based on the approach of Quantitative Structure Activity Relationships (QSARs) and molecular docking, this phenomenon was proved to be caused by the presence of two points of dissimilarity between the acute and chronic mixture toxicity mechanism: (1) the receptor protein of SAs in acute toxicity was Luc, while in chronic toxicity it was Dhps, and (2) there is a difference between actual concentration of binding-Luc in acute toxicity and individual binding-Dhps in chronic toxicity. This deep insight into the difference between chronic and acute mixture toxicity will benefit environmental science, medical science, and other disciplines. The existence of these differences poses a challenge for the assessment of routine combinations in medicine, risk assessment, and mixture pollutant control, in which, previously, only a synergistic effect has been observed between SA and their potentiator.     

Characterization of endocrine disruptors from a complex matrix using estrogen receptor affinity columns and high performance liquid chromatography–high resolution mass spectrometry

Complex mixtures of contaminants with potential adverse effects on human health and wildlife are found in the environment and in the food chain. These mixtures include numerous anthropogenic compounds of various origins and structures, which may behave as endocrine disruptors. Mixture’s complexity is further enhanced by biotic and abiotic transformations. It is therefore necessary to develop new strategies allowing the identification of the structure of known, as well as unknown, nuclear receptor (NR) ligands present in complex matrices. We explored the possibility to use NR-based affinity columns to characterize the presence of bioactive molecules in environmental complex mixtures. Estrogen receptor α (ERα)-based affinity columns were used to trap and purify estrogenic substances present in surface sediment samples collected in a French river under mixed anthropogenic pressure. We combined biological, biochemical and analytical approaches to characterize the structure of ligands retained on columns and demonstrate the presence of known active molecules such as bisphenol A and octylphenol, but also of unexpected ERα ligands (n-butylparaben, hydroxyl-methyl-benzofuranone). High resolution mass spectrometry results demonstrate that ERα affinity columns can be used for the isolation, purification and identification of known as well as unknown estrogenic contaminants present in complex matrices.     

Effects of black carbon on bioturbation-induced benthic fluxes of polychlorinated biphenyls

It is unknown whether carbonaceous geosorbents, such as black carbon (BC) affect bioturbation by benthic invertebrates, thereby possibly affecting sediment-water exchange of sediment-bound contaminants. Here, we assess the effects of oil soot on polychlorinated biphenyl (PCB) mass transfer from sediment to overlying water, for sediments with and without tubificid oligochaeta as bioturbators. PCB levels were so low that toxicity to the oligochaeta played no role, whereas soot levels and binding affinity of PCBs to soot were so low that pore water PCB concentrations were not significantly affected by binding of PCBs to soot. This setup left direct effects of BC on bioturbation activity as the only explanation for any observed effects on mass transfer. Mass transfer coefficients (K_L) for benthic boundary layer transport were measured by a novel flux method using Empore™ disks as a sink for PCBs in the overlying water. For the PCBs studied (logK_ow 5.2-8.2), K_L values ranged from 0.2 to 2 cm × d⁻¹ in systems without tubificids. Systems with tubificids showed K_L values that were a factor of 10-25 higher. However, in the presence of oil soot, tubificids did not cause an increase in mass transfer coefficients. This suggests that at BC levels as encountered under field conditions, the mechanism for reduction of sediment-water transfer of contaminants may be twofold: (a) reduced mass transfer due to strong binding of the contaminants to BC, and (b) reduced mass transfer of contaminants due to a decrease in bioturbation activity.