Legacy Contaminants Research Articles

Multi-omics eco-surveillance of bacterial community function in legacy contaminated estuary sediments

Complex legacy contamination is a major issue for many estuaries, with toxicity affecting change in bacterial communities, and their provision of associated goods and services. Sequencing surveys of bacterial community composition provide inferred function; however, additional insights may be generated by measurement of realised metabolic phenotypes. We apply multi-omics (genomics, lipidomics, and metabolomics), with traditional sediment quality analyses, to characterise sediment-associated bacterial communities in an estuary subject to legacy metal contamination (Zn, Hg, As, Cd, Cu and Pb). Analyses of bacterial composition and inferred function (genomics) are coupled with measurements of realised bacterial phenotype (metabolomics and lipidomics) at multiple industrialised and reference sites. At sites with the highest sediment metal concentrations (NTB), we also observed increased abundances of hydrocarbon and sulphuric acid metabolites, indicating additional sediment contamination. Bacterial phyla across sampled sites were dominated by Proteobacteria and Desulfobacteria. NTB sites were enriched with metabolically versatile, cooperative and biofilm forming phyla including, Zixibacteria, Spirochaetota, SAR324 clade, Proteobacteria, Latescibacterota, Desulfobacterota, Deferrisomtota and Acidobateriota; with inferred functions characterised by sulphur metabolism, pathways associated with the degradation of complex organic molecules, and fermentation. Reference sites were characterised by enhanced vitamin biosynthesis, cell wall, cofactor and carbohydrate biosynthesis, and CO2 fixation. Measured metabolic phenotypes at NTB sites supported predicted functions, with most consistent change observed to naphthalene and aminobenzoate degradation pathways and carbohydrate metabolism (galactose, amino and nucleotide sugar). Change in NTB metabolite profiles was most highly correlated with sediment Hg concentrations, indicative of toxic exposure and potential for Hg methylation. Lipid profiles generated further insight into potential functional (hydroxy fatty acids) and community level change (ceramide phosphoethanolamines, unsaturated glycerides). Multi-omics outputs provided insights into bacterial community functions, modes of contaminant toxicity and expressed mechanisms of adaptation, necessary to better inform management decisions and predictive models in increasingly human-influenced environments.

Lake management under severe drought: Lake Mead, Nevada/Arizona

AbstractDrought can affect both the quantity and quality of water in lakes and reservoirs, yet larger, highly managed waterbodies, such as Lake Mead, may be somewhat buffered from drought effects. From 2000 to present, Lake Mead has experienced a 71% decline in volume; however, influent water quality has remained high and consistent outflow volumes through Hoover Dam have been maintained. Furthermore, management activities, such as increased removal of phosphorus by wastewater dischargers and legacy contamination cleanup efforts, have been initiated since the drought began. These efforts have led to small improvements in values of water quality parameters, such as phosphorus, nitrogen, and perchlorate, despite loss of volume for dilution of constituents, and consequently, decreased residence time. As the drought continues, Lake Mead is projected to continue declining in volume, inflows are projected to become warmer, and the population of Las Vegas is projected to grow, potentially adding additional stress to the hydrologic system. Maintenance of outflow may mitigate some potentially negative consequences, and understanding the drivers behind continued high water quality despite prolonged drought is important to continue to maintain the health and vitality of the entire Lower Colorado River Basin.

Spatial patterns and seasonal timing of increasing riverine specific conductance from 1998 to 2018 suggest legacy contamination in the Delaware River Basin

Increasing salinization of freshwater threatens water supplies that support a range of human and ecological uses. The latest assessments of Delaware River Basin (DRB) surface-water-quality changes indicate widespread salinization has occurred in recent decades, which may lead to meaningful degradation in water quality. To better understand how and when salinity transport occurs and implications for DRB streams, this study: 1) explores the variability of specific conductance (SC) trends spatially and seasonally from 1998 to 2018, and 2) investigates how trends relate to streamflow, land disturbance, and impervious surface area to better understand regional salinization drivers. We find widespread increases in SC across the DRB, with several sites in the lower basin exceeding thresholds for aquatic life and experiencing increasing frequencies of exceedance over time. In general, the greatest basin wide increases in SC occurred during low flow conditions, indicating that a legacy component resulting from subsurface retention and transport processes has driven observed changes in riverine SC. For a subset of sites in the lower basin, where impervious area and cumulative land disturbance are higher, the greatest SC increases occurred during high flow conditions in winter months. Given the patterns of SC and watershed changes across the basin, as well as strong relationships between SC trends and sodium and chloride trends, deicing salt appears to be a likely driver of observed SC change. Even if deicing salt application plateaus or declines in coming years, the continued release and transport of the legacy subsurface component may still contribute to elevated DRB riverine SC.

Seasonal Patterns of Mixing and Arsenic Distribution in a Shallow Urban Lake

AbstractArsenic, a neurotoxin and carcinogen, is a legacy contaminant in the sediments of many urban lakes and poses health risks to aquatic ecosystems and lake users. Arsenic uptake into the aquatic food web is enhanced in shallow, polymictic lakes compared to deep, seasonally stratified lakes. We present the results of a 17‐month field study in Lake Killarney, a shallow, urban lake in Federal Way, Washington, USA, which examines the physical and biogeochemical mechanisms controlling arsenic mobilization and transport from sediment into lake waters, a prerequisite for arsenic uptake into the food web. In Lake Killarney, arsenic mobilization and transport into bottom waters occurred only when stratified conditions and elevated temperatures facilitated deoxygenation of bottom waters. Frequency of lake mixing varied seasonally and controlled the vertical distribution of arsenic in the water column. Convective mixing was the main contributor to elevated vertical turbulent intensity in the water column during periods of high arsenic mobilization, and thus to the upwards transport of arsenic from bottom waters. Maximum near‐surface arsenic occurred when the lakebed sediment temperature was elevated and the water column was overturning frequently. This work clarifies the mechanisms that contribute to vertical arsenic transport in shallow lakes and provides a basis for identifying contaminated systems with the physical and biogeochemical conditions that promote transport of arsenic into near‐surface water.

Legacy of contamination with metal(loid)s and their potential mobilization in soils at a carbonate-hosted lead-zinc mine area

Chemical weathering of carbonate-hosted Pb–Zn mines via acid-promoted or oxidative dissolution generates metal-bearing colloids at neutral mine drainage sites. However, the mobility and bioavailability of the colloids associated with metals in nearby soils are unknown. Here, we monitored the mobility of metal(loid)s in soils affected by aeolian deposition and river transport in the vicinity of a carbonate-hosted Pb–Zn mine. Using chemical extraction, ultrafiltration, and microscopic and spectroscopic analysis of metals we find that contamination levels of the soil metals cadmium (Cd), lead (Pb) and zinc (Zn) were negatively correlated with metal extractability. However, nano-scale characterization indicates that colloid-metal(loid) interactions induced potential mobilization and increased risk from metal(loid)s. Dynamic light scattering (DLS) and HRTEM-EDX-SAED analysis further indicate that organic matter (OM)-rich nano-colloids associated with calcium (Ca), silicon (Si) and iron (Fe) precipitates accounted for the majority of the dissolved metal fractions in carbonate-hosted Pb–Zn mine soils. More stable nano-crystals (ZnS, ZnCO3, Zn-bearing sulfates, hematite and Al–Si–Fe compounds) were present in the pore water of aeolian-impacted upland soils rather than in river water-impacted soils. Our results suggest that future work should consider the possibility that potential mobilization of metal(loid)s induced by the weathering and transformation of these metal-bearing nano-crystals to metal-bearing amorphous colloids, potentially elevating metal mobility and/or bioavailability in river water-impacted agricultural soils.

Feeding and contaminant patterns of sub-arctic and arctic ringed seals: Potential insight into climate change-contaminant interactions

To provide insight into how climate-driven diet shifts may impact contaminant exposures of Arctic species, we compared feeding ecology and contaminant concentrations in ringed seals (Pusa hispida) from two Canadian sub-Arctic (Nain at 56.5°N, Arviat at 61.1°N) and two Arctic sites (Sachs Harbour at 72.0 °N, Resolute Bay at 74.7 °N). In the sub-Arctic, empirical evidence of changing prey fish communities has been documented, while less community change has been reported in the Arctic to date, suggesting current sub-Arctic conditions may be a harbinger of future Arctic conditions. Here, Indigenous partners collected tissues from subsistence-harvested ringed seals in 2018. Blubber fatty acids (FAs) and muscle stable isotopes (δ15N, δ13C) indicated dietary patterns, while measured contaminants included heavy metals (e.g., total mercury (THg)), legacy persistent organic pollutants (e.g., dichlorodiphenyltrichloroethanes (DDTs)), polybrominated diphenyl ethers (PBDEs), and per-/polyfluoroalkyl substances (PFASs). FA signatures are distinct between sub-Arctic and Resolute Bay seals, likely related to higher consumption of southern prey species including capelin (Mallotus villosus) in the sub-Arctic but on-going feeding on Arctic species in Resolute Bay. Sachs Harbour ringed seals show FA overlap with all locations, possibly consuming both southern and endemic Arctic species. Negative δ13C estimates for PFAS models suggest that more pelagic, sub-Arctic type prey (e.g., capelin) increases PFAS concentrations, whereas the reverse occurs for, e.g., THg, ΣPBDE, and ΣDDT. Inconsistent directionality of δ15N estimates in the models likely reflects baseline isotopic variation not trophic position differences. Adjusting for the influence of diet suggests that if Arctic ringed seal diets become more like sub-Arctic seals due to climate change, diet-driven increases may occur for newer contaminants like PFASs, but not for more legacy contaminants. Nonetheless, temporal trends studies are still needed, as are investigations into the potential confounding influence of baseline isotope variation in spatial studies of contaminants in Arctic biota.

Bioaccumulation of Mercury and Radiocesium in Waterfowl Introduced to a Site with Legacy Contamination.

Despite the propensity of waterfowl species to readily accumulate anthropogenic contaminants within polluted environments, few studies have examined bioaccumulation rates over time when entering such a contaminated site. We examined mercury (Hg) and radiocesium (137 Cs) bioaccumulation over time in two waterfowl species released into a wetland system containing legacy contamination on the US Department of Energy's Savannah River Site in South Carolina. Released birds were collected at select time intervals over an exposure period of 94 days. We quantified total Hg concentrations in blood, muscle, and liver tissues, and 137 Cs activity in whole-body and muscle tissues. The relationship between the contaminant burdens of different body tissue types was examined over time. Likely a result of microhabitat selection, mallards in our study readily accumulated both Hg and 137 Cs at consistent rates over time within our study system, while ring-neck ducks did not. The findings demonstrated that whole blood can be used as a robust, nondestructive sampling alternative to estimate Hg burdens within muscle and liver, and whole-body 137 Cs activity is a good predictor of muscle burdens. Understanding such bioaccumulation information in waterfowl is useful for the assessment of the potential health risk in wildlife, as well as being important for human risk assessment toward the consumption of popular game species. Environ Toxicol Chem 2022;41:2479-2487. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Simulation of the Environmental Fate and Transformation of Nano Copper Oxide in a Freshwater Environment.

Production of engineered nanomaterials (ENMs) has rapidly increased, yet uncertainty exists regarding the full extent of their environmental implications. This study investigates the fate, transformation, and speciation of nano copper oxide (nanoCuO) released into Lake Waccamaw, North Carolina, over 101 years. Using the Advanced Toxicant module of the Water Quality Analysis Simulation Program (WASP8), we assessed the accumulation and mass proportions of nanoCuO and Cu2+ (the product of nanoCuO’s dissolution) in the water column and sediments. Our simulations suggest that when nanoCuO is released into Lake Waccamaw, the highest concentrations of both nanoCuO and Cu2+ are found in the surface sediments, followed by the subsurface sediments and the water column. Simulating different heteroaggregation attachment efficiencies of nanoCuO suggested that increases in attachment efficiency increased nanoCuO concentrations and mass proportions in the water column and sediments, while Cu2+ exhibited the opposite trends. After 101 years, most nanoCuO in the sediments was attached to particulate organic matter and clay particles at all attachment efficiencies, while low attachment efficiency slowed aggregate formation in the water column. Our results highlight the influence that heteroaggregation has on the behavior of nanoCuO inputs and suggest the potential for legacy contamination of nanoCuO and Cu2+ in sediments.

Understanding the Evolution of Groundwater‐Contaminant Plume Chemistry Emanating from Legacy Contaminant Sources: An Example from a Long‐Term Crude Oil Spill

AbstractUnderstanding the evolution of plumes emanating from residual hydrocarbon contaminant sources requires evaluating how changes in source compositions over time cause changes in dissolved plume chemistry as residual sources age. This study investigates such changes at the site of a 1979 crude‐oil pipeline spill and is the first comprehensive look at groundwater chemistry associated with a residual hydrocarbon source zones in different stages of aging. The data show a direct relationship between concentrations of benzene and naphthalene in the residual oil and those measured in water samples collected below the oil. Groundwater associated with oil near the spill site had different chemical composition compared with water associated with oil that had spread downgradient from the spill zone, indicating a shift in biodegradation reactions. These results emphasize that source zone processes are spatially and temporally heterogeneous and should be accounted for in natural attenuation studies where residual source zones persist.

Maternal transfer of pharmaceuticals and personal care products in the Brazilian guitarfish Pseudobatos horkelii

Maternal transfer is a notable contaminant source for elasmobranchs during the embryonic development. The maternal offloading of several compounds has been evaluated, especially concerning legacy contaminants. However, information on pharmaceuticals and personal care products (PPCPs) offload and, consequently, embryonic exposure in elasmobranchs is still unknown. Despite this, previous detection of PPCPs in pregnant females suggested the maternal offloading of these compounds in the Brazilian guitarfish Pseudobatos horkelii, yet progeny levels were not investigated. For this reason, our goal was to estimate and describe the maternal transfer of four PPCPs in P. horkelii. Diclofenac, methylparaben, octocrylene and triclosan were determined in liver and uterine content samples of five pregnant females using gas chromatography coupled to mass spectrometry. Diclofenac and methylparaben were detected in maternal and uterine content samples, whereas octocrylene and triclosan were only detected in maternal livers. This suggests that diclofenac and methylparaben are transferred to the offspring, at maximum transfer capacities of 27% and 6%, respectively. The lack of detection of other analytes in uterine content suggests that these contaminants might not be transferred. The concentrations observed for diclofenac and methylparaben are similar to those reported in adult elasmobranchs and teleosts, showing that embryos are exposed to considerable levels during their development. In addition, maternal diclofenac concentrations were not influenced by maternal size, suggesting that this species is continuously exposed in the studied area. These results are important for understanding the maternal offloading process and predicting PPCPs impacts throughout this species life cycle.

Urban soils in a historically industrial city: patterns of trace metals in Pittsburgh, Pennsylvania

The distribution of legacy heavy metals in industrial city soils is not well documented. Therefore, fundamental details such as the ‘background’ (i.e., non-road/non-dripline) concentration of trace metals in urban soils are uncertain. While there has been a strong focus on mapping lead contamination near roads and residences, these studies are generally not placed in the context of the urban background. In this study, ‘background’ distributions of urban relevant trace metals: arsenic, cadmium, copper, lead, and zinc were mapped based on soil samples collected throughout Pittsburgh. Distinct spatial patterns were revealed: contamination is elevated in the eastern portion of the study area, driven by dominant wind patterns and historical coking activities in low-lying areas (paleochannels), areas subject to atmospheric temperature inversions that focus air contamination. The mixing analysis revealed spatial structures in contributions of industrial activities to metal soil contamination. In particular, regions enriched in cadmium relative to zinc (i.e., Zn:Cd<317) were located near historical coking operations, and areas enriched in lead relative to zinc (Pb:Zn>1) were located in areas with historical secondary lead smelters. These results suggest a comprehensive accounting of the trace metals concentrations in background soils has important implications for the assessment of exposure risk in populations residing in historically industrial areas. Relatively sparse sampling of background conditions in urban systems can indicate patterns of legacy contamination and attribute this contamination to historical sources.

Heavy metals in moss guide environmental justice investigation: A case study using community science in Seattle, WA, USA

AbstractHeavy metal concentrations often vary at small spatial scales not captured by air monitoring networks, with implications for environmental justice in industrial‐adjacent communities. Pollutants measured in moss tissues are commonly used as a screening tool to guide use of more expensive resources, like air monitors. Such studies, however, rarely address environmental justice issues or involve the residents and other decision makers expected to utilize results. Here, we piloted a community science approach, engaging over 55 people from nine institutions, to map heavy metals using moss in two industrial‐adjacent neighborhoods. This area, long known for disproportionately poor air quality, health outcomes, and racial inequities, has only one monitor for heavy metals. Thus, an initial understanding of spatial patterns is critical for gauging whether, where, and how to invest further resources toward investigating heavy metals. Local youth‐led sampling of the moss Orthotrichum lyellii from trees across a 250 × 250 m sampling grid (n = 79) and generated data comparable to expert‐collected samples (n = 19). We mapped 21 chemical elements measured in moss, including 6 toxic “priority” metals: arsenic, cadmium, chromium, cobalt, lead, and nickel. Compared to other urban O. lyellii studies, local moss had substantially higher priority metals, especially arsenic and chromium, encouraging community members to investigate further. Potential hotspots of priority metals varied somewhat but tended to peak near the central industrial core where many possible emission sources, including legacy contamination and converge. Informed by these findings, community members successfully advocated regulators for a second study phase—a community‐directed air monitoring campaign to evaluate residents' exposure to heavy metals—as is needed to connect moss results back to the partnership's core goal of understanding drivers of health disparities. This follow‐up campaign will measure metals in the PM10 fraction owing to clues in the current study that airborne soil and dust may be locally important carriers of priority metals. Future work will address how our approach combining bioindicators and community science ultimately affects success addressing longstanding environmental justice concerns. For now, we illustrate the potential to co‐create new knowledge, to help catalyze and strategize next steps, in a complex air quality investigation.

Landscapes of Inequity: Environmental Justice in the Andes-Amazon Region ed. by Nicholas A. Robins and Barbara J. Fraser

Reviewed by: Landscapes of Inequity: Environmental Justice in the Andes-Amazon Region ed. by Nicholas A. Robins and Barbara J. Fraser Aaron Groth Nicholas A. Robins and Barbara J. Fraser (Eds.) Landscapes of Inequity: Environmental Justice in the Andes-Amazon Region. Lincoln, NE: University of Nebraska Press, 2020. xxxi + 347 pp. Maps, tables, notes, references, and index. $65.00 cloth (ISBN 978-1-4962-0802-6); $65.00 eBook (PDF) (ISBN 978-1-4962-2141-4); $65.00 eBook (ISBN 978-1-4962-2139-1). For those captivated by the andes-Amazon region’s biological and cultural diversity and are alarmed by multiple threats posed by extractive activities and infrastructure projects to its people and landscapes, this venerable volume constitutes an essential addition. Since Francisco Pizzaro’s conquest of Peru and Francisco de Orellana’s first descent of the Amazon from Quito, the region has endured successive waves of boom-and-bust cycles. Colonial governments and modern states attracted capital and promoted extraction of natural resources and production of commodities, while wealth generated was (and is) removed from the places of extraction and production to regional elites, far away capitals, and financial centers such as London and New York. These legacies of uneven development, persistence of inequality and land concentration, environmental contamination, usurpation of Indigenous territory, infrastructure projects, and extractive industries, directly impact the health, land uses, and livelihoods of communities across the region, as well as cultural identity. The editors and contributors offer evolving definitions of environmental justice, provide political context for the region, and frame environmental justice in multiple, site-specific contexts. Despite Andean-Amazon region countries’ status as signatories of International Labor Agreement 169, Indigenous (and other) communities are not systematically included in infrastructure and resource extraction planning. From Andean summits to lowland tropical forests, a variety of actors, confront and contest government agencies, large and powerful economic interests, and respond to development projects that have failed to include their input or consent. In addition, states, private industries, and organized crime syndicates target environmental defenders with physical threats, assault, targeted assassinations, criminalization of protest, extra-judicial killings, and judicial harassment. Hundreds of years of violence, disease, exploitation, repeated encroachment upon and attempts at privatization of community lands have not succeeded in eliminating community property. Governments across the region, as modern authoritarian, neoliberal, or pluri-national states have sought to make Indigenous and rural communities invisible (by legal instrument or cartographic omission) in order to facilitate [End Page 198] extraction. Richard Chase Smith, in We Are Here: The State of Community-Based Landscapes in Peru, showcases the efforts of the Common Good Institute (IBC), partners, and communities in the mapping and titling of community lands. While about one half of Peru is titled as peasant or native communities, the government controls and regulates rights to the subsoil, timber resources, and carbon. Planned mining, oil, gas, and timber concessions are superimposed on existing communities or communities still in the process of titling their land claims. Across the region, communities play a key role in forest protection and biodiversity conservation. However, employment opportunities are often concentrated in the exact extractive activities and commodities production that threaten community health, land uses, and livelihoods. Processes unleashed by the colonization of the Andes include demographic collapse of Indigenous populations, their forced resettlement into reducciones, and the dreaded mita–including corvée labor for mining centers. Nicholas Robins’ chapter, A Toxic Reckoning: Legacy Contamination in Huancavelica, Peru highlights colonial and modern Peru’s extraction of cinnabar and processing of mercury. Huancavelica produced mercury for the amalgamation processing of silver deposits in Potosí, Cerro de Pasco, and other mining centers. Cumulatively, successive mining and smelting, since the colonial period, has resulted in contamination of air, soil, and water, causing acute impacts on human health for the residents of several Andean cities (e.g., Huancavelica, Cerro de Pasco, La Oroya, Oruro, and Potosí). According to Robins, the Peruvian state, in failing to recognize and remediate sites contaminated during the colonial period in Huancavelica, practices a process of “invisibilization” of an entire city (p. 23). If the contamination does not legally exist, the Peruvian state bears no responsibility for cleanup. In addition to national and...

Is Glacial Meltwater a Secondary Source of Legacy Contaminants to Arctic Coastal Food Webs?

Climate change-driven increases in air and sea temperatures are rapidly thawing the Arctic cryosphere with potential for remobilization and accumulation of legacy persistent organic pollutants (POPs) in adjacent coastal food webs. Here, we present concentrations of selected POPs in zooplankton (spatially and seasonally), as well as zoobenthos and sculpin (spatially) from Isfjorden, Svalbard. Herbivorous zooplankton contaminant concentrations were highest in May [e.g., ∑polychlorinated biphenyls (8PCB); 4.43, 95% CI: 2.72–6.3 ng/g lipid weight], coinciding with the final stages of the spring phytoplankton bloom, and lowest in August (∑8PCB; 1.6, 95% CI: 1.29–1.92 ng/g lipid weight) when zooplankton lipid content was highest, and the fjord was heavily impacted by sediment-laden terrestrial inputs. Slightly increasing concentrations of α-hexachlorocyclohexane (α-HCH) in zooplankton from June (1.18, 95% CI: 1.06–1.29 ng/g lipid weight) to August (1.57, 95% CI: 1.44–1.71 ng/g lipid weight), alongside a higher percentage of α-HCH enantiomeric fractions closer to racemic ranges, indicate that glacial meltwater is a secondary source of α-HCH to fjord zooplankton in late summer. Except for α-HCH, terrestrial inputs were generally associated with reduced POP concentrations in zooplankton, suggesting that increased glacial melt is not likely to significantly increase exposure of legacy POPs in coastal fauna.

Concentration dynamics of polychlorinated biphenyls and organochlorine pesticides in blood of growing Grey heron (Ardea cinerea) chicks in the wild

Organochlorine contaminants (OCs) – organochlorine pesticides (OCPs) and industrial products and byproducts – are included in different monitoring programmes and surveys, involving various animal species. Fish-eating birds are suitable indicator species for OCs. Adult birds may be difficult to capture, but chicks can be sampled more easily. Blood of birds is a potentially suitable non-destructive matrix for analysis, as OC levels in blood reflect their concentrations in the body. The study was aimed at investigating how age of fast-growing Grey heron (Ardea cinerea) chicks affects contaminant levels in their blood and thus how important is sampling at exact age for biomonitoring purposes. In 1999 on Lake Engure in Latvia whole blood samples of heron chicks were collected at three different time points, with seven and nine days in between the first and second and second and third sampling points, respectively. Twenty-two chicks were sampled at all three times. In total, 102 samples were analysed for 19 polychlorinated biphenyl (PCB) congeners, DDT metabolites – DDE and DDD, hexachlorobenzene (HCB), α-, β-, γ-hexachlorocyclohexane (HCH), and trans-nonachlor. Total PCB concentrations averaged around 2000 ng/g dry extracted matter (EM). DDE was the dominant individual contaminant (ca. 800 ng/g EM), followed by CB-153, -138, and −118. Most of the other analysed OCs were below 100 ng/g EM. No significant (p > 0.05) differences in OC concentrations were found between the three sampling occasions, except for trans-nonachlor. This means that blood can safely be sampled for biomonitoring purposes during the 17 days’ time window. The analysed legacy contaminants may serve as model substances for other persistent organic pollutants.

Comprehensive screening of polar emerging organic contaminants including PFASs and evaluation of the trophic transfer behavior in a freshwater food web

Bioaccumulation and trophic transfer of persistent legacy contaminants have been intensively characterized, but little is known on the contaminants of emerging concern (CECs) in freshwater food webs. Herein, we comprehensively screened CECs with a focus on polar substances and further evaluated their trophic transfer behavior in selected items from the food web of Lake Templin, Germany. Weselected one plankton, two mussel, and nine fish samples covering three trophic levels. With an effective multi-residue sample preparation method and high-resolution mass spectrometry-based target, suspect, and non-target screening, we characterized 477 targets and further screened unknown features in complex biota matrices. Of the 477 targets, 145 were detected and quantified in at least one species (0.02–3640 ng/g, dry weight). Additionally, the suspect and non-target analysis with experimental mass spectra libraries and in silico techniques (MetFrag and SIRIUS4/CSI:FingerID) enabled further identification of 27 unknown compounds with 19 confirmed by reference standards. Overall, the detected compounds belong to a diverse group of chemicals, including 71 pharmaceuticals, 27 metabolites, 26 pesticides, 16 per- and polyfluoroalkyl substances (PFASs), 4 plasticizers, 3 flame retardants, 11 other industrial chemicals and 14 others. Moreover, we determined the trophic magnification factor (TMF) of 34 polar CECs with >80% detection frequency, among which 6 PFASs including perfluorooctane sulfonic acid (PFOS), perfluorodecanoic acid (PFDA), perfluorohexane sulfonic acid (PFHxS), perfluorotridecanoic acid (PFTrA), perfluorotetradecanoic acid (PFTeA), and perfluoroundecanoic acid (PFUnA), exhibited biomagnification potential (TMF =1.8 - 4.2, p < 0.05), whereas 5 pharmaceuticals (phenazone, progesterone, venlafaxine, levamisole, and lidocaine) and 1 personal care product metabolite (galaxolidone) showed biodilution potential (TMF = 0.4 - 0.6, p < 0.05).

A Novel Ex Vivo Approach Based on Proteomics and Biomarkers to Evaluate the Effects of Chrysene, MEHP, and PBDE-47 on Loggerhead Sea Turtles (Caretta caretta).

The principal aim of the present study was to develop and apply novel ex vivo tests as an alternative to cell cultures able to evaluate the possible effects of emerging and legacy contaminants in Caretta caretta. To this end, we performed ex vivo experiments on non-invasively collected whole-blood and skin-biopsy slices treated with chrysene, MEHP, or PBDE-47. Blood samples were tested by oxidative stress (TAS), immune system (respiratory burst, lysozyme, and complement system), and genotoxicity (ENA assay) biomarkers, and genotoxic and immune system effects were observed. Skin slices were analyzed by applying a 2D-PAGE/MS proteomic approach, and specific contaminant signatures were delineated on the skin proteomic profile. These reflect biochemical effects induced by each treatment and allowed to identify glutathione S-transferase P, peptidyl-prolyl cis-trans isomerase A, mimecan, and protein S100-A6 as potential biomarkers of the health-threatening impact the texted toxicants have on C. caretta. Obtained results confirm the suitability of the ex vivo system and indicate the potential risk the loggerhead sea turtle is undergoing in the natural environment. In conclusion, this work proved the relevance that the applied ex vivo models may have in testing the toxicity of other compounds and mixtures and in biomarker discovery.

Small Arctic rivers transport legacy contaminants from thawing catchments to coastal areas in Kongsfjorden, Svalbard

Decades of atmospheric and oceanic long-range transport from lower latitudes have resulted in deposition and storage of persistent organic pollutants (POPs) in Arctic regions. With increased temperatures, melting glaciers and thawing permafrost may serve as a secondary source of these stored POPs to freshwater and marine ecosystems. Here, we present concentrations and composition of legacy POPs in glacier- and permafrost-influenced rivers and coastal waters in the high Arctic Svalbard fjord Kongsfjorden. Targeted contaminants include polychlorinated biphenyls (PCBs), hexachlorobenzene (HCB), dichlorodiphenyltrichloroethanes (DDTs), hexachlorocyclohexanes (HCHs) and chlordane pesticides. Dissolved (defined as fraction filtered through 0.7 μm GF/F filter) and particulate samples were collected from rivers and near-shore fjord stations along a gradient from the heavily glaciated inner fjord to the tundra-dominated catchments at the outer fjord. There were no differences in contaminant concentration or pattern between glacier and tundra-dominated catchments, and the general contaminant pattern reflected snow melt with some evidence of pesticides released with glacial meltwater. Rivers were a small source of chlordane pesticides, DDTs and particulate HCB to the marine system and the particle-rich glacial meltwater contained higher concentrations of particle associated contaminants compared to the fjord. This study provides rare insight into the role of small Arctic rivers in transporting legacy contaminants from thawing catchments to coastal areas. Results indicate that the spring thaw is a source of contaminants to Kongsfjorden, and that expected increases in runoff on Svalbard and elsewhere in the Arctic could have implications for the contamination of Arctic coastal food-webs.

Nano-remediation technologies for the sustainable mitigation of persistent organic pollutants

The absence of novel and efficient methods for the elimination of persistent organic pollutants (POPs) from the environment is a serious concern in the society. The pollutants release into the atmosphere by means of industrialization and urbanization is a massive global hazard. Although, the eco-toxicity associated with nanotechnology is still being debated, nano-remediation is a potentially developing tool for dealing with contamination of the environment, particularly POPs. Nano-remediation is a novel strategy to the safe and long-term removal of POPs. This detailed review article presents an important perspective on latest innovations and future views of nano-remediation methods used for environmental decontamination, like nano-photocatalysis and nanosensing. Different kinds of nanomaterials including nanoscale zero-valent iron (nZVI), carbon nanotubes (CNTs), magnetic and metallic nanoparticles, silica (SiO2) nanoparticles, graphene oxide, covalent organic frameworks (COFs), and metal organic frameworks (MOFs) have been summarized for the mitigation of POPs. Furthermore, the long-term viability of nano-remediation strategies for dealing with legacy contamination was considered, with a particular emphasis on environmental and health implications. The assessment goes on to discuss the environmental consequences of nanotechnology and offers consensual recommendations on how to employ nanotechnology for a greater present and a more prosperous future.

In Vitro Hepatotoxic and Neurotoxic Effects of Titanium and Cerium Dioxide Nanoparticles, Arsenic and Mercury Co-Exposure.

Considering the increasing emergence of new contaminants, such as nanomaterials, mixing with legacy contaminants, including metal(loid)s, it becomes imperative to understand the toxic profile resulting from these interactions. This work aimed at assessing and comparing the individual and combined hepatotoxic and neurotoxic potential of titanium dioxide nanoparticles (TiO2NPs 0.75–75 mg/L), cerium oxide nanoparticles (CeO2NPs 0.075–10 μg/L), arsenic (As 0.01–2.5 mg/L), and mercury (Hg 0.5–100 mg/L) on human hepatoma (HepG2) and neuroblastoma (SH-SY5Y) cells. Viability was assessed through WST-1 (24 h) and clonogenic (7 days) assays and it was affected in a dose-, time- and cell-dependent manner. Higher concentrations caused greater toxicity, while prolonged exposure caused inhibition of cell proliferation, even at low concentrations, for both cell lines. Cell cycle progression, explored by flow cytometry 24 h post-exposure, revealed that TiO2NPs, As and Hg but not CeO2NPs, changed the profiles of SH-SY5Y and HepG2 cells in a dose-dependent manner, and that the cell cycle was, overall, more affected by exposure to mixtures. Exposure to binary mixtures revealed either potentiation or antagonistic effects depending on the composition, cell type and time of exposure. These findings prove that joint toxicity of contaminants cannot be disregarded and must be further explored.