Simple on-site extraction and GC-MS analysis of rotenone and degradation products for monitoring invasive fish eradication treatments in fresh and brackish waters.

The introduction of invasive fish species to aquatic ecosystems has been demonstrated to cause disastrous ecological effects. Current conservation strategies regard rotenone-containing piscicide formulations, such as commercial product CFT Legumine, as a potentially viable alternative to the cumbersome traditional approaches to fish eradication. This consideration relies on the fast degradation of rotenone and its relatively rapid dissipation from the environment. Piscicide treatments in fragile aquatic ecosystems should thus monitor not only rotenone concentrations following application, but also other byproducts and degradation products. We present a methodology for the analysis of rotenoids in fresh and brackish waters that addresses two main challenges: the accurate determination of applied concentrations in different salinity concentrations by performing a simplified on-site solid-phase extraction, overcoming the fast degradation of rotenone in sample storage conditions, and the selective analysis of rotenoid byproducts and degradation products by gas chromatography coupled to mass spectrometry. Limits of quantification were below the ecological no-effect concentration of rotenone (2 µg/L) and average recoveries exceeded 80%. Accuracy (compared to expected values) and precision (deviation of replicates) ranged from 78 to 103% and 3 to 14%, respectively, across various rotenoid concentrations. These metrics are more than satisfactory for the intended application of this simplified procedure. The method was applied to piscicide-treated samples, revealing significant and fast degradation of parent rotenoids in storage conditions, as well as a non-negligible accumulation of rotenone in the particulate fraction of water that could impact the effectivity of eradication efforts.

Innovative analytical methodologies for characterizing chemical exposure with a view to next-generation risk assessment.

The chemical burden on the environment and human population is increasing. Consequently, regulatory risk assessment must keep pace to manage, reduce, and prevent adverse impacts on human and environmental health associated with hazardous chemicals. Surveillance of chemicals of known, emerging, or potential future concern, entering the environment-food-human continuum is needed to document the reality of risks posed by chemicals on ecosystem and human health from a one health perspective, feed into early warning systems and support public policies for exposure mitigation provisions and safe and sustainable by design strategies. The use of less-conventional sampling strategies and integration of full-scan, high-resolution mass spectrometry and effect-directed analysis in environmental and human monitoring programmes have the potential to enhance the screening and identification of a wider range of chemicals of known, emerging or potential future concern. Here, we outline the key needs and recommendations identified within the European Partnership for Assessment of Risks from Chemicals (PARC) project for leveraging these innovative methodologies to support the development of next-generation chemical risk assessment.

Conflicts of Interest in the Assessment of Chemicals, Waste, and Pollution.

Pollution by chemicals and waste impacts human and ecosystem health on regional, national, and global scales, resulting, together with climate change and biodiversity loss, in a triple planetary crisis. Consequently, in 2022, countries agreed to establish an intergovernmental science-policy panel (SPP) on chemicals, waste, and pollution prevention, complementary to the existing intergovernmental science-policy bodies on climate change and biodiversity. To ensure the SPP's success, it is imperative to protect it from conflicts of interest (COI). Here, we (i) define and review the implications of COI, and its relevance for the management of chemicals, waste, and pollution; (ii) summarize established tactics to manufacture doubt in favor of vested interests, i.e., to counter scientific evidence and/or to promote misleading narratives favorable to financial interests; and (iii) illustrate these with selected examples. This analysis leads to a review of arguments for and against chemical industry representation in the SPP's work. We further (iv) rebut an assertion voiced by some that the chemical industry should be directly involved in the panel's work because it possesses data on chemicals essential for the panel's activities. Finally, (v) we present steps that should be taken to prevent the detrimental impacts of COI in the work of the SPP. In particular, we propose to include an independent auditor's role in the SPP to ensure that participation and processes follow clear COI rules. Among others, the auditor should evaluate the content of the assessments produced to ensure unbiased representation of information that underpins the SPP's activities.

Investigating the relationship between non-occupational pesticide exposure and metabolomic biomarkers.

The relationship between pesticide exposures and metabolomics biomarkers is not well understood. We examined the changes in the serum metabolome (early biomarkers) and the metabolic pathways associated with various pesticide exposure scenarios (OPE: overall exposure, PEM: exposure in months, PEY: exposure in years, and PEU: reported specific pesticides use) using data from the Northern Finland Birth Cohort 1966 31-year cross-sectional examination. We utilized questionnaire data on pesticide exposures and serum samples for nuclear magnetic resonance (NMR)-based metabolomics analyses. For exposures and metabolites associations, participants size varied between 2,361 and 5,035. To investigate associations between metabolomics biomarkers and exposure to pesticide scenarios compared to those who reported no exposures multivariable regression analyses stratified by sex and adjustment with covariates (season of pesticide use, socioeconomic position (SEP), alcohol consumption, BMI, and latitude of residence) were performed. Multiple testing by Benjamini-Hochberg false discovery rate (FDR) correction applied. Pesticide exposures differed by sex, season of pesticide use, alcohol, SEP, latitude of residence. Our results showed that all pesticide exposure scenarios were negatively associated with decreased HDL concentrations across all lipoprotein subclasses in women. OPE, PEY, and PEU were associated with decreased branched-chain amino acid concentrations in men and decreased albumin concentrations in women. OPE, PEY and PEU were also associated with changes in glycolysis metabolites and ketone bodies in both sexes. Specific pesticides exposure was negatively associated with sphingolipids and inflammatory biomarkers in men. In women, OPE, PEM, and PEU were associated with decreased apolipoprotein A1 and increased apolipoprotein B/apolipoprotein A1 ratio. Our findings suggest that identification of early biomarkers of disease risk related to pesticide exposures can inform strategies to reduce exposure and investigate causal pathways. Women may be more susceptible to non-occupational pesticide exposures when compared to men, and future sex-specific studies are warranted.

Diurnal source apportionment of organic and inorganic atmospheric particulate matter at a high-altitude mountain site under summer conditions (Sierra Nevada; Spain).

High-altitude mountain areas are sentinel ecosystems for global environmental changes such as anthropogenic pollution. In this study, we report a source apportionment of particulate material with an aerodynamic diameter smaller than 10 µm (PM10) in a high-altitude site in southern Europe (Sierra Nevada Station; SNS (2500 m a.s.l.)) during summer 2021. The emission sources and atmospheric secondary processes that determine the composition of aerosol particles in Sierra Nevada National Park (Spain) are identified from the concentrations of organic carbon (OC), elemental carbon (EC), 12 major inorganic compounds, 18 trace elements and 44 organic molecular tracer compounds in PM10 filter samples collected during day- and nighttime. The multivariate analysis of the joint dataset resolved five main PM10 sources: 1) Saharan dust, 2) advection from the urbanized valley, 3) local combustion, 4) smoke from a fire-event, and 5) aerosol from regional recirculation with high contribution of particles from secondary inorganic and organic aerosol formation processes. PM sources were clearly associated with synoptic meteorological conditions, and day- and nighttime circulation patterns typical of mountainous areas. Although a local pollution source was identified, the contribution of this source to PM10, OC and EC was small. Our results evidence the strong influence of middle- and long-range transport of aerosols, mainly from anthropogenic origin, on the aerosol chemical composition at this remote site.

Extreme glacial cooling likely led to hominin depopulation of Europe in the Early Pleistocene.

The oldest known hominin remains in Europe [~1.5 to ~1.1 million years ago (Ma)] have been recovered from Iberia, where paleoenvironmental reconstructions have indicated warm and wet interglacials and mild glacials, supporting the view that once established, hominin populations persisted continuously. We report analyses of marine and terrestrial proxies from a deep-sea core on the Portugese margin that show the presence of pronounced millennial-scale climate variability during a glacial period ~1.154 to ~1.123 Ma, culminating in a terminal stadial cooling comparable to the most extreme events of the last 400,000 years. Climate envelope-model simulations reveal a drastic decrease in early hominin habitat suitability around the Mediterranean during the terminal stadial. We suggest that these extreme conditions led to the depopulation of Europe, perhaps lasting for several successive glacial-interglacial cycles.

Prenatal exposure to multiple persistent organic pollutants in association with adiposity markers and blood pressure in preadolescents.

BACKGROUND: Several studies have reported that prenatal exposure to some persistent organic pollutants (POPs) is associated with higher adiposity in childhood. Few studies have assessed whether this finding persists into adolescence, and few have considered exposure to POPs as a mixture. This study aims to assess the association between prenatal exposure to multiple POPs and adiposity markers and blood pressure in preadolescents. METHODS: This study included 1667 mother-child pairs enrolled in the PELAGIE (France) and the INMA (Spain) mother-child cohorts. Three polychlorobiphenyls (PCB 138, 153 and 180, treated as a sum of PCBs) and three organochlorine pesticides (p,p'-Dichlorodiphenyldichloroethylene [p,p'-DDE], ß-hexachlorocyclohexane [ß-HCH], and hexachlorobenzene [HCB]) were assessed in maternal or cord serum. Body mass index z-score (zBMI), abdominal obesity (waist-to-height ratio > 0.5), percentage of fat mass, and blood pressure (mmHg) were measured at around 12 years of age. Single-exposure associations were studied using linear or logistic regressions, and the POP mixture effect was evaluated using quantile G-computation (qgComp) and Bayesian Kernel Machine Regression (BKMR). All models were adjusted for potential confounders and performed for boys and girls together and separately. RESULTS: Prenatal exposure to the POP mixture was associated with higher zBMI (beta [95 % CI] of the qgComp = 0.15 [0.07; 0.24]) and percentage of fat mass (0.83 [0.31; 1.35]), with no evidence of sex-specific association. These mixture effects were also statistically significant using BKMR. These associations were driven mainly by exposure to HCB and, to a lesser extent, to ß-HCH. In addition, the single-exposure models showed an association between ß-HCH and p,p'-DDE and higher systolic blood pressure, especially in girls (p,p'-DDE for girls = 1.00 [0.15; 1.86]). No significant associations were found for PCBs. CONCLUSION: This study suggests that prenatal exposure to POPs, particularly organochlorine pesticides, remains associated with unfavorable cardiometabolic health up to the age of 12.

Determination of subpicogram levels of airborne polycyclic aromatic hydrocarbons for personal exposure monitoring assessment.

A method based on the use of GC coupled to Q-exactive Orbitrap mass spectrometry (GC-Orbitrap-MS) has been developed for the analysis of polycyclic aromatic hydrocarbons (PAHs) at sub-picogram levels. Outdoor ambient air particulate matter (PM2.5) and standard reference materials (SRM2260a) were analyzed in full scan mode showing low instrumental uncertainties (1-22%) and high linearity over a wide concentration range (0.5 pg and 500 pg/µL). Good reproducibility was obtained compared to the use of conventional single quadrupole GC-MS of PM samples. The quantification limit of the GC-Orbitrap-MS method for full scan analysis of PAHs in outdoor ambient air PM samples was 0.5 pg/µL. This low limit allowed the analysis of PAHs in samples collected with low volumes (< 0.5 m3), such as punch samples from whole filters or filter strips from personal exposure monitoring equipment. PAHs were successfully analyzed in filter strips from real-time Aethalometer AE51 equivalent black carbon (eBC) analyzers used in urban and rural sites, and in personal exposure monitors of firefighters during prescribed burns. The correlations between PAHs and eBC in these analyses were very strong (r2 ≥ 0.93). However, the equations obtained reflected the dominance of different emission sources, such as traffic in urban areas, wood burning for domestic heating, or wildfires. The method reported here affords the analyses of PAHs in high precision studies of atmospheric PM samples, e.g., high frequency sampling of low volumes, affording personal exposure monitoring assessments.

Passive water sampling and air-water diffusive exchange of long-range transported semi-volatile organic pollutants in high-mountain lakes.

The concentrations of legacy and currently emitted organic pollutants were determined in the freely dissolved phase of water from six high-mountain lakes in the Pyrenees (1619-2453 m) by passive water sampling. Low-density polyethylene (LDPE) and silicone rubber (SR) sheets were exposed for three consecutive periods lasting each one year between 2017 and 2020 for the study of polychlorinated biphenyls (PCBs), organophosphate esters (OPEs), polycyclic aromatic hydrocarbons (PAHs), and other organochlorine compounds (e.g., hexachlorobenzene, HCB). HCB concentrations (1.0-14 pg L-1) remained essentially the same as those measured with pumping systems over two decades ago in the same area. Æ©PAHs (35-920 pg L-1) were around half of those observed in the past, which agrees with reductions in European atmospheric emissions. Æ©PCB concentrations (1.2-2.2 pg L-1) were substantially lower, although unexpectedly large differences could be due to comparing yearly averages from the present study to seasonally variable (i.e., affected by snowmelt, stratification, and colloidal organic matter) episodic pumping measurements from previous studies. Æ©OPEs (139-2849 pg L-1) were measured for the first time in this area and were found at high concentrations in some sites. Concentrations of most compounds obtained with LDPE and SR samplers agreed with each other by ratios generally lower than three or four times, except for a few PAHs and OPEs. Diffusive exchange flux calculations between the atmospheric gas phase and the freely dissolved water phase revealed net deposition of pollutants from air to water, except for some OPEs and PCBs presenting equilibrium conditions, and HCB with volatilization fluxes. Atmospheric degradation fluxes of PAHs and OPEs pointed at competing removal mechanisms that support the air-to-water direction of their diffusive exchange, while PCBs and organochlorines were not affected by photodegradation. In their current state, these remote lakes accumulate many emerging and legacy pollutants subject to long-range atmospheric transport.

Phenotypic and Metabolomic Characterization of 3D Lung Cell Cultures Exposed to Airborne Particulate Matter from Three Air Quality Network Stations in Catalonia.

Air pollution constitutes an environmental problem that it is known to cause many serious adverse effects on the cardiovascular and respiratory systems. The chemical characterization of particulate matter (PM) is key for a better understanding of the associations between chemistry and toxicological effects. In this work, the chemical composition and biological effects of fifteen PM10 air filter samples from three air quality stations in Catalonia with contrasting air quality backgrounds were investigated. Three-dimensional (3D) lung cancer cell cultures were exposed to these sample extracts, and cytotoxicity, reactive oxygen species (ROS) induction, metabolomics, and lipidomics were explored. The factor analysis method Multivariate Curve Resolution-Alternating Least-Squares (MCR-ALS) was employed for an integrated interpretation of the associations between chemical composition and biological effects, which could be related to urban traffic emission, biomass burning smoke, and secondary aerosols. In this pilot study, a novel strategy combining new approach methodologies and chemometrics provided new insights into the biomolecular changes in lung cells associated with different sources of air pollution. This approach can be applied in further research on air pollution toxicity to improve our understanding of the causality between chemistry and its effects.

Wild fish and seafood species in the western Mediterranean Sea with low safe mercury concentrations.

A total of 1345 specimens belonging to 58 different species of wild fish and seafood from the western Mediterranean Sea were analyzed to assess total mercury levels and to estimate which species meet the EU recommendations for human consumption (0.5 µg g-1 ww) in all cases. All fish species were caught off the Mediterranean coasts and intended for human consumption. All specimens were collected from local markets located in Spain, Italy and France that sell fish caught by local fishermen (Eivissa, Menorca, Mallorca, Alacant, L'Ampolla, Ametlla de Mar, Marseille, Genoa, Civitavecchia, Alghero) at different time periods. Mercury concentrations were measured by thermal decomposition-gold amalgamator-atomic absorption spectrometry. Only thirteen species were found that did not exceed 0.5 µg g-1 ww in any specimen analyzed. These safe species were sardines (Sardina pilchardus), anchovies (Engraulis encrasicolus), blue whiting (Micromesistius poutassou), picarel (Spicara smaris), blackspot seabream (Pagellus bogaraveo), gilthead seabream (Sparus aurata), pearly razorfish (Xyrichtys novacula), surmullet (Mullus surmuletus), painted comber (Serranus scriba), brown meagre (Sciaena umbra), salema (Sarpa salpa), common dolphinfish (Coryphaena hippurus) and squid (Loligo vulgaris). These species occupy different trophic levels, have different lengths and average weights, but show a low mercury concentration than others living in the same environments. Potential human consumption of these species as sole source of fish would imply estimated weekly intakes representing between 49% and 70% of the recommended provisional tolerable weekly intake of methylmercury in the worst case. Health authorities should pay specific attention to species that do not meet EU thresholds and make appropriate precautionary health recommendations, especially for pregnant women and children.

Chlorpyrifos, permethrin and cyfluthrin effect on cell survival, permeability, and tight junction in an in-vitro model of the human blood-brain barrier (BBB).

The blood-brain barrier (BBB) is a structural and functional interface between the plasma and the human brain. Predictive BBB in-vitro models like immortalized human capillary microvascular endothelial cells (HCMEC/D3) can be used to explore the BBB disruption potential of daily exposed chemicals. The present study was focused on investigating the human BBB permeation potential of one organophosphate pesticide, chlorpyrifos (CPF), and two pyrethroids, permethrin (PMT) and cyfluthrin (CFT). HCMEC/D3 cells were exposed to the chemical and the time-dependent pass across BBB along with permeation coefficient (Papp) was calculated. Transendothelial electrical resistance (TEER) was measured for the cells to check the monolayer formation and later to check the reduction in integrity after chemical exposure. Real time PCR was conducted to investigate the effect of chemicals on the expression BBB´s tight and adherens junction proteins. Calculated Papp value for three chemicals was in the following order: CPF>CFT>PMT, where CPF showed the highest permeation coefficient. TEER calculation showed that the integrity decreased after CPF exposure which was in concordance with Papp value whereas for other chemicals, no change in TEER after exposure was observed. In addition, the transwell study showed a higher efflux ratio (ER) (>2) of CFT indicating that CFT could be a substrate for active transport. For CPF and PMT, ER was less than 2, so no active transport seems to be involved. The evaluation of the mRNA expression analysis revealed a statistically significant decrease in Occludin (OCLN) gene expression for CPF, VE-Cadherin (CDH5) for PMT and Zonula Occludens (ZO1) expression for CFT. Our study showed that CPF has the highest potential for inducing cell death, higher permeation, and capability to induce BBB dysfunction than among the above-mentioned chemicals. Additionally, the results of the permeation study could be useful to build a human PBPK model using in vitro-to-in vivo extrapolation approach.

Occupational and residential exposures to organophosphate and pyrethroid pesticides in a rural setting.

Organophosphate (OP) and pyrethroid pesticides (PYR) are extensively used in agriculture, resulting in higher exposures among farmworkers. The present study reports the occurrence of 8 urinary OP and PYR metabolites in a sample of farmworkers and residents from Sucs (n = 87), a rural township in North West Catalonia (Spain). The aim of the present study was to examine differences in urinary pesticide metabolite concentrations between occupationally-exposed (farmworkers; n = 45) and environmentally-exposed subjects (n = 42) and to assess the relationship between pesticide's exposures and occupational activities in a real-case scenario. Six OP and two PYR metabolites have been investigated, urine samples were extracted using SPE extraction and analyzed by UPLC-MS/MS. Three OP metabolites were commonly detectable in urine, namely TCPY (metabolite of chlorpyrifos), PNP (parathion) and DEAMPY (pirimiphos). Regarding pyrethroids, the two analyzed metabolites, 3-PBA and 4F-3-PBA, were detected in a high proportion of urine samples. Differences in concentrations between both groups were statistically significant for TCPY and 4F-3-PBA (Mann-Whitney U Test for independent groups, p < 0.05). In the case of TCPY, the concentrations were higher among the farmworkers, which is consistent with their occupational activity. The small differences found in DEAMPY, PNP, 3-PBA or even the significant higher concentrations of 4F-3-PBA among rural population suggest a general exposure to these compounds, even in those who do not carry an occupational activity. Specific personal protective equipment (PPE) among farmworkers, such as the use of gloves and mask during mixing, showed a decrease in the exposure levels, although the differences were not statistically significant. However, a positive association was found between the use of a cap during mixing (for PNP and 3-PBA) and during application (only for 3-PBA). However, this piece of cloth is mainly used for sun protection, and when not cleaned after the handling of pesticides, it might represent a continuous source of exposure through dermal contact. Farmworkers using tractors with cabin had statistically significant lower concentrations of DEAMPY than those using a tractor without cabin. The previous results suggest that occupational protections should be encouraged among farmworkers and other potential workers handling with pesticides.

Environmental and dietary determinants of metal exposure in four-year-old children from a cohort located in an industrial area (Asturias, Northern Spain).

Urine samples from four-year-old children located in a heavily industrialized zone in Asturias (Spain) were collected between 2009 and 2012 (n = 334). Vanadium (V; median 54 µg/g creatinine), cobalt (Co; 1.0 µg/g c.), nickel (Ni; 3.8 µg/g c.), copper (Cu; 22 µg/g c.), zinc (Zn; 590 µg/g c.), arsenic (As; 64 µg/g c.), selenium (Se; 49 µg/g c.), molybdenum (Mo; 110 µg/g c.), cadmium (Cd; 0.27 µg/g c.), antimony (Sb; 1.0 µg/g c.), cesium (Cs; 14 µg/g c.), barium (Ba; 2.6 µg/g c.), thallium (Tl; 0.55 µg/g c.) and lead (Pb; 1.9 µg/g c.) were analysed. Comparison with children from other sites showed that this Asturias cohort was characterized by high levels of V, As, Sb, Cs and Tl. The concentrations of Co, Ni, Zn, Cu, Mo, Se, Cd, Ba and Pb were within the range of other cohorts. Terrestrial dietary items were most strongly related to increased urinary concentrations of metals in children, e.g., red meat with Ba and Ni, pasta/cereal with Ni and Zn, sweets with Zn, Co, and Cu, eggs with Mo, Cd, and Cs, and dairy products with Co and Sb. Seafood was the second group of dietary items significantly related to increased metals, e.g., shellfish with Ba, Cs, Pb, and V, fatty fish with As, and lean fish with As and Se. In contrast, higher fruit intake was significantly associated with decreased Cu and Sb, and higher legume intake with decreased Cu, Se and Cs. Higher intakes of other dietary items also led to significant decreases in some metals, such as vegetables and lower concentrations of Se and Mo, and dairy products with decreases in Cu and As. These negative correlations implied very low concentrations of the mentioned metals in these foods. Higher exposure to traffic was associated with higher concentrations of Ba, present in brake components. Children living outside urban areas had higher concentrations of Se. No association of metals with smoking in the family was found.

Serum concentrations of persistent organic pollutants mixture during pregnancy and anogenital distance in 8-year-old children from the INMA-Asturias cohort.

BACKGROUND: During pregnancy, women are commonly exposed to several endocrine-disrupting chemicals, including persistent organic pollutants (POPs). These compounds can transfer to the fetus through the placenta. Prenatal POP exposure is related to altered fetal genital and reproductive tract development. However, the relationship between exposure to POP mixtures and anogenital distance (AGD) is poorly investigated. This study investigated the association between prenatal exposure to POP mixtures and AGD in 8-year-old children. METHODS: Data were collected from the INMA-Asturias cohort. Maternal serum POP concentrations were measured during the first trimester of pregnancy. Anoscrotal distance (AGDAS) and anopenile distance (AGDAP) in males and anofourchetal distance (AGDAF) and anoclitoral distance (AGDAC) in females were recorded in 362 8-years-olds. Conventional linear regression, and the novel weighted quantile sum regression (WQSR) and Bayesian kernel machine regression (BKMR) models were applied to assess the relationships between AGD and POPs exposure stratified by sex. RESULTS: Among males, in the linear regression, b-hexachlorocyclohexane, PCB138, PCB153, and PCB180 were inversely associated with the anogenital index (AGI)AS (-0.06 mm/kg (95% confidence interval [CI]: -0.11, -0.02), -0.07 mm/kg (95% CI: -0.14, -0.01), -0.07 mm/kg (95% CI: -0.13, -0.01), and -0.08 mm/kg (95% CI: -0.14, -0.02), respectively). Among females, polybrominated diphenyl ether (PBDE)47 and PBDE154 were positively associated with increased AGIAF (0.02 mm/kg (95% CI: 0.00, 0.03) and 0.09 mm/kg (95% CI: 0.01, 0.17), respectively). BKMR confirmed these associations. WQSR found a negative combined effect of the POP mixture on AGD, and PCB138, PCB153, and PCB180 (weighted 0.18, 0.13, and 0.09, respectively) were identified as the most impacting chemicals. In females, WQSR found a positive combined effect and determined PBDE47 (weighted 0.35) as the most impacting. CONCLUSIONS: Maternal exposure to a POP mixture was negatively associated with AGD in male children and positively associated with AGD in female children, thus providing evidence of the adverse effects of POPs on genital development.

Seabird-mediated transport of organohalogen compounds to remote sites (North West Greenland polynya).

The role of sea birds as carriers of pollutants over long distances was evaluated by analyzing organochlorine and organobromine compounds in lake sediment cores from three remote sites around the North Water polynya (North West Greenland). One lake, NOW5, was in the vicinity of a little auk (Alle alle L.) bird colony, whereas the other two lakes, NOW14 and Q5, were undisturbed by seabirds. The former was strongly acidic (pH = 3.4) but the latter had a pH close to 8. Due to the guano loading, NOW5 exhibited higher chlorophyll concentrations (74 µg/L) than the other two lakes (1.6-3.4 µg/L), higher content of total phosphorous (0.34 mg/L vs. 0.007-0.01 mg/L) and total nitrogen (3.75 mg/L vs. 0.21-0.75 mg/L). The concentrations of all organohalogen compounds were substantially greater in NOW5 than in the other lakes, indicating the strong influence of these seabirds in the transport and deposition of these compounds to remote sites. However, not all compounds showed the same increases. Hexachlorocyclohexanes and endosulfans were more than 18 times higher in NOW5, the drin pesticides and hexachlorobenzene (HCB), between 9.5 and 18 times and DDTs, polybromodiphenyl ethers (PBDEs), polychlorobiphenyls (PCBs) and chlordanes about 2.7-6 times. These differences demonstrated that the bird-mediated deposition has preservation effects of the less stable and more volatile compounds, e.g. those with log Kaw < -2.4, log Koa < 9 and/or log Kow < 6.8. The sedimentary fluxes of PCBs, HCHs, drins, chlordanes, PBDEs, HCB and endosulfans were highest in the upper sediment layer of the polynya lake (year 2014). In contrast, the highest DDT fluxes were found in 1980. These trends indicate that despite restrictions and regulations, bird transport continues to introduce considerable amounts of organohalogen pollutants to the Arctic regions with the exception of DDTs, which show successful decline, even when mediated by bird metabolism.

Pilot study on the concentrations of organochlorine compounds and potentially toxic elements in pregnant women and local food items from the Finnish Lapland.

In the Arctic, main sources of persistent organic pollutants and potentially toxic elements are industry and agriculture in the lower latitudes. However, there are also local sources of pollution. Our study was focused on possible pollution in the Finnish Lapland, transferred from the Pechenganikel industrial complex located in the borders of Russia, Finland and Norway. Local food items and blood samples of pregnant women from the Inari municipality were collected and organochlorine compounds (OCs) and metal(oid)s analyzed. Most of the examined food samples showed detectable levels of these compounds. The mean concentrations of DDTs and polychlorobiphenyls (PCBs) were higher in fish (0.18-0.32 ng/g and 0.34-0.64 ng/g, respectively), than in the other food groups (0.027-0.047 ng/g and 0.11-0.20 ng/g, respectively). PCBs were found at the highest concentrations in blood samples of the pregnant women, and congeners 153 and 118 were dominant. The mean concentration of PCB153, 0.29 µg/kg serum lipid, was lower than those described in many other studies. Concerning DDTs, the 4,4'-DDT/4,4'-DDE ratio, 0.092, in the blood samples was lower than that observed in the food items, 0.25-0.71, reflecting old uses of the DDT pesticide. None of the observed levels of selected potentially toxic elements in blood samples and in food items exceeded the known safe limits. Higher concentrations of PCB52 and γ-HCH were observed in the serum of pregnant women who consumed greater amounts of meat, and berries and mushrooms, respectively. The OC concentrations from the pregnant women currently studied were lower than those observed fourteen years ago with pregnant women from the same municipality. Compounds whose occurrence is likely related to a long-distance transport showed clear decreases, e.g., 63% for PCBs, and for those from pesticides, decreases were 93% and 97% for 4,4'-DDE and ß-HCH, respectively. No obvious influence from the Pechenganikel complex is observed from the results.

Changes and distribution of gas-phase polycyclic aromatic hydrocarbons and organochlorine compounds in a high-mountain gradient over a three-year period (Pyrenees, 2017-2020).

The atmospheric gas-phase concentrations of several polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), hexachlorobenzene (HCB), and pentachlorobenzene (PeCB) were measured in six high-mountain sites in the Pyrenees (1619-2453 m). Polyurethane foam passive air samplers were used for this purpose, providing continuous records spanning over three years (2017-2020). The mean concentrations of ∑PCBs, HCB, and PeCB, 13 ± 4 pg m-3, 44 ± 18 pg m-3, and 23 ± 20 pg m-3, respectively, were of the order of those reported in other mountain sites and similar to those measured 20 years ago in the same area, evidencing the persistence of these compounds despite the international regulatory actions. The mean concentration of ∑PAHs was 631 ± 238 pg m-3, representing between two- and three-times lower values than 20 years ago in the same area, but still in the range of other mountain regions. Statistically significant increases in gas-phase concentrations at higher temperatures were observed for most compounds. The experimental phase-change pseudo-enthalpies calculated from the slopes of the regressions between the natural logarithm of the concentrations and the reciprocal of temperature were lower than the reference values for nearly all compounds. This difference suggested a main contribution of long-range atmospheric transport of the gas-phase PAH and organochlorine concentrations in this mountain area. However, the less volatile compounds such as benz[a]anthracene, PCB138, and PCB180 showed a closer similarity between experimental and laboratory enthalpies, indicating that a significant portion of the variations in concentration of these compounds originated from temperature-dependent diffusive exchange by re-volatilization from local surfaces. The concentrations found in these sentinel ecosystems demonstrate that long-range transport of organic pollutants remains a risk in remote continental environments.

Influence of gestational weight gain on the organochlorine pollution content of breast milk.

BACKGROUND: Transplacental transfer and breastfeeding are the main transport routes of organic pollutants into children at the beginning of life. Although pollutant transmission through these mechanisms primarily depends on the maternal pollution burden, its impact may be modulated by physiological effects. OBJECTIVES: We have examined whether gestational weight gain (GWG) exerts an influence on the content of lipophilic low volatile pollutants in breast milk. RESULTS: Colostrum from mothers from the INMA cohorts of Sabadell and Gipuzkoa (n = 256 and 119, respectively) with low GWG as defined by the Institute of Medicine (IOM) from the US National Academies of Sciences, Engineering and Medicine had significantly higher concentrations of polychlorobiphenyls (PCBs) and 4,4'-DDE than colostrum in mothers who gained weight within IOM recommendations or in those who exceeded this threshold. Statistically significant differences were also found in the colostrum:maternal serum ratios of these compounds. Women with low GWG retained higher pollutant amounts in colostrum. These observations are consistent with previously described higher concentrations of these pollutants in infant cord blood from mothers with low GWG by IOM standards. They indicate that mobilization of lipophilic organic pollutants by metabolic pregnant changes not only leads to higher fetal transfer but to higher accumulation into the mammary system upon low GWG. CONCLUSIONS: The present results show that insufficient GWG, besides increasing in utero exposure, also enhances pollutant transfer to infants during breastfeeding which considerably extends the significance of this physiological change for the pollutant children intake in early life.