Toxicity Reference Values Research Articles

Toxicity reference values for force health protection: Provisional occupational exposure guidelines

Force Health Protection programs in the U.S. Air Force endeavor to sustain the operational readiness of the warfighters. We have previously identified hundreds of chemical substances of interest and toxicity reference value (TRV) knowledge gaps that constrain risk based-decision-making for potential exposures. Multiple approaches to occupational TRV estimation were used to generate possible guideline values for 84 compounds (18% of the substances of interest). These candidate TRVs included values from international databases, chemical similarity (nearest neighbor) approaches, empirical adjustments to account for duration differences, quantitative activity relationships, and thresholds of toxicological concern. This present work describes derivation of provisional TRVs from these candidate values. Rodent bioassay-derived long-term worker Derived No-Effect Levels (DNELs) were deemed presumptively the most reliable, but only 19 such DNELs were available for the 84 substances with TRV gaps. In the absence of DNELs, the quality of the approaches and consistency among candidate values were key elements of the weight of evidence used to select the most suitable guideline values. The use of novel nearest-neighbor approaches, empirical adjustment of short term TRVs, and occupational exposure bands were found to be options that would allow occupational TRV estimation with reasonable confidence for nearly all substances evaluated.

Toxicity reference values (TRVs) for force health protection: Gap identification and TRV prediction

The mission of the Force Health Protection (FHP) program of the U.S. Air Force (USAF), sustaining the readiness of warfighters, relies on determinations of acceptable levels of exposure to a wide array of substances that USAF personnel may encounter. In many cases, exposure details are limited or authoritative toxicity reference values (TRVs) are unavailable. To address some of the TRV gaps, we are integrating several approaches to generate health protective exposure guidelines. Descriptions are provided for identification of chemicals of interest for USAF FHP (467 to date), synthesis of multiple TRVs to derive Operational Exposure Limits (OpELs), and strategies for identifying and developing candidate values for provisional OpELs when authoritative TRVs are lacking. Rodent bioassay-derived long-term Derived No Effect Levels (DNELs) for workers were available only for a minority of the substances with occupational TRV gaps (19 of 84). Additional occupational TRV estimation approaches were found to be straightforward to implement: Tier 1 Occupational Exposure Bands, cheminformatics approaches (multiple linear regression and novel nearest-neighbor approaches), and empirical adjustment of short term TRVs. Risk assessors working in similar contexts may benefit from application of the resources referenced and developed in this work.

Do dietary exposures to multi-class endocrine disrupting chemicals translate into health risks for Gangetic dolphins? An assessment and way forward

Dietary exposure risks of 39 multi-class Endocrine Disrupting Chemicals (EDCs) to the threatened Gangetic dolphins (Platanista gangetica) were investigated in a conservation-priority segment of the Ganga River. Elevated EDCs bioaccumulation was observed across prey fish species, with di(2-ethylhexyl) phthalate (DEHP) and di-n-butyl phthalate (DnBP) significantly contributing to the EDC burden. The concentrations of persistent organochlorines in prey revealed a shift from dioxin-like polychlorinated biphenyls (PCBs) to non-dioxin-like PCBs. The prevalence of regulated p,p' DDT (Dichlorodiphenyltrichloroethane) and γ-HCH (Lindane) residues suggests regional non-compliance with regulatory standards. The concentration of some EDCs is dependent on the habitat, foraging behavior, trophic level and fish growth. The potential drivers of EDCs contamination in catchment includes agriculture, vehicular emissions, poor solid waste management, textile industry, and high tourist influx. Risk quotients (RQs) based on toxicity reference value were generally below 1, while the RQ derived from the reference dose highlighted a high risk to Gangetic dolphins from DEHP, DDT, DnBP, arsenic, PCBs, mercury, and cadmium, emphasizing the need for their prioritization within monitoring programs. The study also proposes a monitoring framework to provide guidance on monitoring and assessment of chemical contamination in Gangetic dolphin and habitats.

Heavy Metals In Bivalves From Coastal Municipalities Of C apiz,P hilippines

This research study is based on the current status of heavy metal contamination in bivalves within the coastal areas of Capiz, Philippines, drawing insights from accessible data. The findings shed light on the contamination’s extent, potential threats to human health, and the pollution’s origins. The researchers acknowledge the study’s limitations. As per the findings, elevated levels of heavy metals, such as lead, mercury, cadmium, arsenic, and chromium, in bivalves collected from Capiz’s coastal regions. Variations in metal concentrations are observed among different bivalve species and sampling sites, with identified geographical distribution patterns and potential contamination hotspots. An assessment of conformity to regulatory limits and guidance for heavy metal levels in shellfish consumption is conducted, identifying any exceedances or areas of concern. The research aims to establish the extent to which bivalves from Capiz aligns with legal requirements. Potential health risks allied to the bivalve consumption are evaluated based on the detected heavy metal levels, considering various exposure routes, population characteristics, and toxicity reference values. The research scrutinizes the impact of human activities, including industrial discharges, agricultural practices, and urban runoff, on heavy metal contamination in coastal ecosystems. The ongoing discussion underscores the need for further investigation and underscores the importance of addressing the issue to ensure the environmental sustainability and safety of coastal resources in Capiz.

Feeding Ration Impacts Larval Pimephales Promelas 7-Day Subchronic Growth Endpoint: Case Study with Perfluorooctanesulfonic Acid

The larval fathead minnow, Pimephales promelas, 7-day subchronic survival and growth standard toxicity test method is commonly used for research and regulatory testing of effluents and compounds, including emerging contaminants such as Perfluorooctanesulfonic Acid (PFOS). Existing feeding guidelines for testing are described in multiple methods but are open to interpretation. The current study sought to determine the impact of feeding ration on P. promelas survival and biomass during a subchronic exposure to PFOS. The study was conducted in two phases: (1) a control experiment to determine the most significant feeding ration factors that maximize biomass, with consideration to laboratory logistics, and (2) application of down-selected feeding rations in a PFOS exposure to determine toxicity reference values. The control optimization study supported that feeding ration and feeding frequency were significant factors in fish biomass. In the subsequent PFOS study, fish were fed a high or low ration of Artemia twice daily, while exposed to 0.3 to 3.4 mg/L PFOS. Fish fed a high ration of Artemia had significantly (p < 0.05) greater biomass than fish fed a low ration in all exposure concentrations except 3.4 mg/L, where survival was low in both treatments. The feeding ration was not a significant factor on the survival endpoint for either treatment, but the PFOS concentration was (p < 0.0001) (high ration LC50 = 2.44 mg/L; low ration LC50 = 2.25 mg/L). These findings contribute to a better understanding of the impact feeding ration has in toxicity assessments and downstream regulatory decisions.

Methylmercury Effects on Birds: A Review, Meta-Analysis, and Development of Toxicity Reference Values for Injury Assessment Based on Tissue Residues and Diet.

Birds are used as bioindicators of environmental mercury (Hg) contamination, and toxicity reference values are needed for injury assessments. We conducted a comprehensive review, summarized data from 168 studies, performed a series of Bayesian hierarchical meta-analyses, and developed new toxicity reference values for the effects of methylmercury (MeHg) on birds using a benchmark dose analysis framework. Lethal and sublethal effects of MeHg on birds were categorized into nine biologically relevant endpoint categories and three age classes. Effective Hg concentrations where there was a 10% reduction (EC10) in the production of juvenile offspring (0.55 µg/g wet wt adult blood-equivalent Hg concentrations, 80% credible interval: [0.33, 0.85]), histology endpoints (0.49 [0.15, 0.96] and 0.61 [0.09, 2.48]), and biochemical markers (0.77 [<0.25, 2.12] and 0.57 [0.35, 0.92]) were substantially lower than those for survival (2.97 [2.10, 4.73] and 5.24 [3.30, 9.55]) and behavior (6.23 [1.84, >13.42] and 3.11 [2.10, 4.64]) of juveniles and adults, respectively. Within the egg age class, survival was the most sensitive endpoint (EC10 = 2.02 µg/g wet wt adult blood-equivalent Hg concentrations [1.39, 2.94] or 1.17 µg/g fresh wet wt egg-equivalent Hg concentrations [0.80, 1.70]). Body morphology was not particularly sensitive to Hg. We developed toxicity reference values using a combined survival and reproduction endpoints category for juveniles, because juveniles were more sensitive to Hg toxicity than eggs or adults. Adult blood-equivalent Hg concentrations (µg/g wet wt) and egg-equivalent Hg concentrations (µg/g fresh wet wt) caused low injury to birds (EC1) at 0.09 [0.04, 0.17] and 0.04 [0.01, 0.08], moderate injury (EC5) at 0.6 [0.37, 0.84] and 0.3 [0.17, 0.44], high injury (EC10) at 1.3 [0.94, 1.89] and 0.7 [0.49, 1.02], and severe injury (EC20) at 3.2 [2.24, 4.78] and 1.8 [1.28, 2.79], respectively. Maternal dietary Hg (µg/g dry wt) caused low injury to juveniles at 0.16 [0.05, 0.38], moderate injury at 0.6 [0.29, 1.03], high injury at 1.1 [0.63, 1.87], and severe injury at 2.4 [1.42, 4.13]. We found few substantial differences in Hg toxicity among avian taxonomic orders, including for controlled laboratory studies that injected Hg into eggs. Our results can be used to quantify injury to birds caused by Hg pollution. Environ Toxicol Chem 2024;43:1195-1241. Published 2024. This article is a U.S. Government work and is in the public domain in the USA. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Dietary exposure of potentially toxic elements to freshwater mammals in the Ganga river basin, India

The threatened Gangetic dolphin (Platanista gangetica) and smooth-coated otter (Lutrogale perspicillata) occuring in the Ganga River Basin (GRB), are experiencing a decline in their population and distribution range owing to multiple anthropogenic pressures, including pollution by Potentially Toxic Elements (PTEs). Apex predators primarily encounter contaminants through dietary exposure. Yet, notable gaps persist in our understanding of the risks associated with the ingestion of PTE-contaminated prey for Gangetic dolphins and smooth-coated otters. In this study, we examined the occurrence and spatial variation of PTEs in the prey (fish) of both these riverine mammals across three major rivers of the Basin, while also evaluating the associated risk of ingesting contaminated prey. Our assessment revealed no statistical variation in bioaccumulation profiles of PTEs across the three rivers, attributable to comparable land use patterns and PTE consumption within the catchment. Zn and Cu were the most dominant PTEs in the prey species. The major potential sources of pollution identified in the catchment include agricultural settlements, vehicular emissions, and the presence of metal-based additives in plastics. Zn, As and Hg accumulation vary with the trophic level whereas some PTEs show concentration (Hg) and dilution (As, Cr, Pb and Zn) with fish growth. The Risk Quotient (RQ), based on the dietary intake of contaminated prey calculated using Toxicity Reference Value was consistently below 1 indicating no significant risk to these riverine mammals. Conversely, with the exception of Co and Ni, the Reference Dose-based RQs for all other PTEs indicated a substantial risk for Gangetic dolphins and smooth-coated otters through dietary exposure. This study serves as a pivotal first step in assessing the risk of PTEs for two threatened riverine mammals in a densely populated river basin, highlighting the importance of their prioritization in regular monitoring to reinforce the ongoing conservation efforts.

Concentrations of 45 Per- and Polyfluoroalkyl Substances in North American River Otters (Lontra canadensis) from West Virginia, USA.

North American river otters (Lontra canadensis) are top predators in riverine ecosystems and are vulnerable to per- and polyfluoroalkyl substance (PFAS) exposure. Little is known about the magnitude of exposure and tissue distribution of PFAS in river otters. We measured 45 PFAS in various tissues of 42 river otters collected from several watersheds in the state of West Virginia, USA. The median concentrations of ∑All (sum concentration of 45 PFAS) varied among tissues in the following decreasing order: liver (931 ng/g wet weight) > bile > pancreas > lung > kidney > blood > brain > muscle. Perfluoroalkylsulfonates (PFSAs) were the predominant compounds accounting for 58-75% of the total concentrations, followed by perfluoroalkyl carboxylates (PFCAs; 21-35%). 8:2 fluorotelomer sulfonate (8:2 FTS), 10:2 FTS, and 6:2 chlorinated polyfluoroalkyl ether sulfonate were frequently found in the liver (50-90%) and bile (96-100%), whereas hexafluoropropylene oxide dimer acid (HFPO-DA) was rarely found. The hepatic concentrations of ∑All in river otters collected downstream of a fluoropolymer production facility located along the Ohio River were 2-fold higher than those in other watersheds. The median whole body burden of ∑All was calculated to be 1580 μg. PFOS and perfluorooctanoic acid (PFOA) concentrations in whole blood of some river otters exceeded the human toxicity reference values, which warrant further studies.

Country-Wide Ecological Health Assessment Methodology for Air Toxics: Bridging Gaps in Ecosystem Impact Understanding and Policy Foundations.

Amid the growing concerns about air toxics from pollution sources, much emphasis has been placed on their impacts on human health. However, there has been limited research conducted to assess the cumulative country-wide impact of air toxics on both terrestrial and aquatic ecosystems, as well as the complex interactions within food webs. Traditional approaches, including those of the United States Environmental Protection Agency (US EPA), lack versatility in addressing diverse emission sources and their distinct ecological repercussions. This study addresses these gaps by introducing the Ecological Health Assessment Methodology (EHAM), a novel approach that transcends traditional methods by enabling both comprehensive country-wide and detailed regional ecological risk assessments across terrestrial and aquatic ecosystems. EHAM also advances the field by developing new food-chain multipliers (magnification factors) for localized ecosystem food web models. Employing traditional ecological multimedia risk assessment of toxics' fate and transport techniques as its foundation, this study extends US EPA methodologies to a broader range of emission sources. The quantification of risk estimation employs the quotient method, which yields an ecological screening quotient (ESQ). Utilizing Kuwait as a case study for the application of this methodology, this study's findings for data from 2017 indicate a substantial ecological risk in Kuwait's coastal zone, with cumulative ESQ values reaching as high as 3.12 × 103 for carnivorous shorebirds, contrasted by negligible risks in the inland and production zones, where ESQ values for all groups are consistently below 1.0. By analyzing the toxicity reference value (TRV) against the expected daily exposure of receptors to air toxics, the proposed methodology provides valuable insights into the potential ecological risks and their subsequent impacts on ecological populations. The present contribution aims to deepen the understanding of the ecological health implications of air toxics and lay the foundation for informed, ecology-driven policymaking, underscoring the need for measures to mitigate these impacts.

Interspecies scaling of toxicity reference values in human health versus ecological risk assessments: A critical review.

Risk assessments that focus on anthropogenic chemicals in environmental media-whether considering human health or ecological effects-often rely on toxicity data from experimentally studied species to estimate safe exposures for species that lack similar data. Current default extrapolation approaches used in both human health risk assessments and ecological risk assessments (ERAs) account for differences in body weight between the test organisms and the species of interest, but the two default approaches differ in important ways. Human health risk assessments currently employ a default based on body weight raised to the three-quarters power. Ecological risk assessments for wildlife (i.e., mammals and birds) are typically based directly on body weight, as measured in the test organism and receptor species. This review describes differences in the experimental data underlying these default practices and discusses the many factors that affect interspecies variability in chemical exposures. The interplay of these different factors can lead to substantial departures from default expectations. Alternative methodologies for conducting more accurate interspecies extrapolations in ERAs for wildlife are discussed, including tissue-based toxicity reference values, physiologically based toxicokinetic and/or toxicodynamic modeling, chemical read-across, and a system of categorical defaults based on route of exposure and toxic mode of action. Integr Environ Assess Manag 2024;20:749-764. © 2023 SETAC.

Assessment of environmental and carcinogenic health hazards from heavy metal contamination in sediments of wetlands

Sediment contamination jeopardizes wetlands by harming aquatic organisms, disrupting food webs, and reducing biodiversity. Carcinogenic substances like heavy metals bioaccumulate in sediments and expose consumers to a greater risk of cancer. This study reports Pb, Cr, Cu, and Zn levels in sediments from eight wetlands in India. The Pb (51.25 ± 4.46 µg/g) and Cr (266 ± 6.95 µg/g) concentrations were highest in Hirakud, Cu (34.27 ± 2.2 µg/g) in Bhadrak, and Zn (55.45 ± 2.93 µg/g) in Koraput. The mean Pb, Cr, and Cu values in sediments exceeded the toxicity reference value. The contamination factor for Cr was the highest of the four metals studied at Hirakud (CF = 7.60) and Talcher (CF = 6.97). Furthermore, high and moderate positive correlations were observed between Cu and Zn (r = 0.77) and Pb and Cr (r = 0.36), respectively, across all sites. Cancer patients were found to be more concentrated in areas with higher concentrations of Pb and Cr, which are more carcinogenic. The link between heavy metals in wetland sediments and human cancer could be used to make policies that limit people's exposure to heavy metals and protect their health.

Distribution, Site-Specific Water Quality Criteria, and Ecological Risk Assessment of Heavy Metals in Surface Water in Fen River, China.

Due to a lack of toxicity reference values that match the regional environmental characteristics, the ecological risk of metals in water bodies cannot be accurately assessed. The Fen River is the second-largest tributary of the Yellow River in China, and the sustainability of this area is threatened by heavy metal pollution caused by intensive industrial and agricultural activities. In this study, site-specific water quality criteria (WQCs) for heavy metals in the Fen River were derived considering toxicity data from native aquatic organisms and regional water quality factors (e.g., water hardness). Short-term WQCs for Mn, Cu, Cd, Zn, Cr, Pb, and Ni were 2026.15, 98.62, 10.02, 63.07, 6.06, 166.74, and 132.73 μg/L, respectively, and long-term WQCs were 166.53, 29.71, 2.18, 19.29, 4.15, 6.38, and 14.76 μg/L, respectively. The distribution characteristics of these metals during the wet season in 2020 were explored, and their average concentrations in the river water did not exceed the environmental quality standards for surface water in China but were higher than the world average levels. Cr was the main pollutant in the sampling sites of Yaodu region, Hongdong Shitan, Xiao River, and Duanchun River, as was Pb in Duanchun River. Based on the site-specific WQCs, using hazardous quotient (HQ) and margin of safety (MOS10) approaches, a high risk of Pb was identified in the Duanchun River, and a medium risk of Cr might occur at midstream and downstream of Yaodu and Xiaodian. The results will provide a reference basis for heavy metal pollution control and water quality management in the Fen River.

Large-scale assessment of exposure to legacy and emerging per- and polyfluoroalkyl substances in China's shorebirds

Emerging per- and polyfluoroalkyl substances (PFAS) have become more widely applied, whereas legacy PFAS such as PFOS continue to distribute ubiquitously in the environment. Large-scale assessment of wildlife exposure to both emerging and legacy PFAS plays a key role in effective biomonitoring to better discriminate regional contamination patterns and provide early warnings. Using eggs of two closely-related shorebird species collected across China during the breeding season in 2021, we constructed contrasting PFAS levels and profiles in coastal versus inland populations. The highest ∑PFAS concentrations were found in two Kentish plover (Charadrius alexandrinus) populations from the Bohai Sea, a semi-enclosed shallow bay located in northeast China. These two populations showed exceptionally high PFOA concentrations (mean: 94 and 121 ng/g wet weight; West and North Bohai Sea, respectively) dominating the overall PFAS profile (66% for both). This pattern is characteristic, compared to that of other seabird eggs worldwide. By comparison, PFAS profile in the white-faced plover (Charadrius dealbatus) population at the South China Sea coast was dominated by PFOS (46%), which showed similar levels to those at the North Bohai Sea coast (mean: 29 and 20 ng/g, respectively). PFAS concentrations of Kentish plovers from the remote Qinghai Lake were lower compared to the three coastal populations, and were dominated by PFNA (mean: 2.6 ng/g, 29%) and PFOS (mean: 2.5 ng/g, 27%). None of the eggs analyzed in the present study exceeded estimated toxicity reference values for PFOS or PFOA. Additionally, the emerging 6:2 Cl-PFESA was detected in eggs from all regions, while its concentrations were highest in the Bohai Sea populations, and short-chain PFBS was only detected in the North Bohai Sea population. Our results indicate intensive local emissions of PFOA and emerging PFAS at the Bohai Sea region, and warrant further investigation and monitoring.

Grain size analysis and ecological risk assessment of metals in the sediments of Konsin River and Igboho dam reservoir, Oyo State, Nigeria, under agricultural disturbances.

A large amount of agrochemicals and organic manures are applied on agricultural lands which is one of the major pathways of metal contamination in sediments. The present study was an attempt to appraise the grain-size of sediments and metal status of the Konsin River and Igboho dam reservoir sediments using several indexes as contamination factor (CF), degree of contamination (DC), geo-accumulation index (Igeo), enrichment factor (EF), potential ecological risk index (PERI), pollution load index (PLI), and statistical analysis. A total of seven sampling sites were chosen based on prevalent anthropogenic features and analyzed for the concentration of metals, viz., Cd, Cr, Pb, Mn, Fe, Cu, and Zn. The finding from this study showed high presence of very rough grains at the upstream and sand particles at the downstream. The average values of Cd, Cr, Pb, Mn, Fe, Cu, and Zn range from 0.00 - 2.00, 19.50 - 49.90, 20.80 - 65.30, 593.90 - 2532.90, 22,133.60 - 46,058.60, 19.60 - 66.10, and 81.60 - 191.30mg/kg, respectively. The concentrations of metals in the sediments followed the increasing order of Cd < Cu < Cr < Pb < Zn < Mn < Fe. The observation from this study showed higher affinity of metals to less particle size. The mean concentrations of Cd, Cr, Pb, Mn, Fe, Cu, and Zn were above the toxicity reference value. The Igeo and EF indicated that most of the sites were moderately to strongly polluted due to Cd while the calculated PLI showed progressive deterioration of the environment in most sites. The Pearson's correlation analysis revealed that the presence of metals in the sediments were from anthropogenic and unidentified sources. The status of metals in the study area portends a serious ecological threat to the sediment biota and occupants of the agrarian communities that depend on the water and its produce for survival.

Comparison of migration and cumulative risk assessment of antioxidants, antioxidant degradation products, and other non-intentionally added substances from plastic food contact materials

Antioxidants are used in the production of synthetic resins to prevent oxidative degradation. However, non-intentionally added substances (NIAS) and the degradation products of antioxidants may contaminate food contact materials (FCM) and migrate into food. Herein, NIAS and antioxidant degradation products in synthetic resins and their migration into food simulants under various conditions were evaluated. Risk assessment was performed based on the toxicity reference values or with threshold of toxicological concern (TTC) approach. The antioxidant degradation products migrated mainly to fatty-food simulants, with the highest migration in isooctane, followed by n-heptane (similar to or lower than isooctane) and 95 % ethanol. Especially, the migration of 2,4-di-tert-butylphenol was high when the FCM was used for the first time under daily use conditions such as ultraviolet sterilization or heating in a pot, oven, or microwave. In addition, 36 target substances were monitored in 142 products of 18 synthetic resins. Of these, 2,4-di-tert-butylphenol was most sensitively detected. Risk assessment demonstrated that all the investigated substances were below the toxicity reference values. However, the risk associated with polyethylene was relatively high compared to other synthetic resins. The cumulative risks of oxidizing Irgafos 168, (z)−9-octadecenamide, tri-o-tolyl phosphite, tri-p-tolyl phosphite, and 7,9-di-tert-butyl-1-oxaspiro(4,5)deca-6,9-diene-2,8-dione using the TTC approach were calculated to range from 34.81 % to 73.74 %, suggesting that the TTC is a more conservative risk assessment.

DIFFERENCES IN THE ACUTE AMMONIA TOXICITY BETWEEN SEXES OF GUPPY &lt;i&gt;Poecilia reticulata&lt;/i&gt; (POECILIIDAE)

This study evaluated the sensitivity of male and female of guppies (Poecilia reticulata) to ammonia. LC50-96h for males, females and combined sexes of P. reticulata was 37.33, 48.34, and 42.45 mg/L of total ammonia or 1.03, 1.34, and 1.17 mg/L of un-ionized ammonia. The mortality at the concentration of 40 mg/L of total ammonia differed between the sexes with higher mortality in males. These results have implications for production systems, since recommendations of ammonia toxicity reference values that do not consider the difference between the sexes, can lead to the mortality of males, and cause economic losses because males have higher commercial value in the ornamental market.

Trace metal geochemistry of metalliferous black shales in the Mamfe basin (South West Cameroon): Implication for heavy metal assessment

This study is focused on assessing the contamination levels of heavy metal elements (Cu, Cd, Cr, Ni, and Zn) in black metalliferous shales of the Mamfe basin in South Western Cameroon and identifying the possible pollution sources. Forty (40) black shale samples collected from seven outcrops from different sites in the Mamfe basin were subjected to geochemical analysis by inductively coupled plasma-mass spectrometry (ICP-MS). The results obtained from these analyses were used to calculate the contamination factor (CF), geo-accumulation index (Igeo), and Pollution Load Index (PLI). Person's correlation coefficient was applied in this work to assess the metals origin. The values of heavy metals in the shales were compared with experimental values of TEL (Threshold Effects Level), PEL (Probable Effects Level), ERL (Effects Range Low), and ERM (Effects Range Medium) to assess the long-term adverse biota effect if the shales weathers and release the hosted heavy metals. The average heavy metal concentrations in the studied shales were 35 mg/kg, 89 mg/kg, 0.24 mg/kg, 82 mg/kg and 37.3 mg/kg for Cu, Zn, Cd, Cr and Ni respectively with some above the threshold values of United State Environment Protection Authority (USEPA), average shale (ASV), toxicity reference values (TRV) and Indian River system (IRS). The shales are poorly to moderately enriched in heavy metals which may cause a long-term effect on the surrounding soils and waters after degradation. The heavy metal values of the studied shales compared with the experimental results of TEL, PEL, ERL, and ERM indicate that a little adverse biota effect of Ni, Cu and Cr to the ecosystem after degradation of the studied shales. The geo-accumulation index ranged between 0 and 0.06 indicating that the black Mamfe shales are uncontaminated to moderately contaminated and may have adverse effects on the freshwater ecology and surrounding soils. The pollution load index (between 0.0 to 0.05) and contamination factor (0.18-1.84) indicate that the shales have a low level of contamination and their long-term degradation and weathering will have a limited effect on the soils and water ecosystems. The positive correlation between Cu, and Zn, suggest the same source of contamination input. The positive correlation between Zn, Cu, Cr, and Ni indicates a natural origin of these elements in the shales. A rapid weathering/degradation of large quantity of theses shales may increase the concentration of heavy metals in the surrounding rivers and soils in the near future.

Temporal trends in PFAS concentrations in livers of a terrestrial raptor (common buzzard; Buteo buteo) collected in Belgium during the period 2000–2005 and in 2021

Per- and polyfluoroalkyl substances (PFAS) are anthropogenic chemicals that have been globally distributed. Biological time series data suggest variation in temporal PFAS concentrations due to regulations and the phase-out of multiple PFAS analytes. Nonetheless, biomonitoring temporal trends of PFAS concentrations in raptors has only been done sporadically in Europe at a national scale. In the present study, we examined the concentrations of 28 PFAS in livers of common buzzard (Buteo buteo) collected in Belgium in the period 2000–2005 and in 2021. Despite the regulations and phase-out, the ΣPFAS concentrations remained similar in the livers over the past 20 years. However, over time the abundance of perfluorooctane sulfonate (PFOS), dominant in livers collected in 2000–2005, to the ΣPFAS concentration decreased from 46% to 27%, whereas the abundance of perfluorotetradecanoic acid (PFTeDA), dominant in 2021, increased from 19% to 43%. The PFOS concentrations in the present study did not exceed the Toxicity Reference Values (TRVs), which were determined in liver on the characteristics of an avian top predator. The absence of temporal changes in PFAS concentrations is hypothesized to be due to a lagged response in environmental concentrations compared to atmospheric concentrations.

Heavy metal contamination and risk characterisation in sediment of an urban riverine system in Bangladesh

ABSTRACT Metal contamination in river sediment can cause environmental and human health hazards. The present study was conducted in sediments of Louhajong River, Bangladesh to determine the contents of six heavy metals, their spatial distribution, ecological risks, sources of metals and health hazards through several exposure pathways. The mean concentration of Ni, Cd, Cr, As, Pb and Cu in sediments were 12.35, 0.60, 14.14, 11.69, 8.91 and 25.28 mg/kg, respectively. The mean content of Cd and As was higher than the threshold effect level whereas As and Cu content was higher than the toxicity reference value indicating sediment pollution by these metals. Potential ecological risks (203.82) and Nemerow pollution index (5.68) showed moderate and the highest contamination in sediment. The mean PEL quotient (1.58) and mean ERM quotient (0.64) indicated medium-high contamination based on sediment quality guidelines. The PCA indicated that the Kaiser-Meyer-Olkin Measure of Sampling Adequacy value was 0.61 and Pb, As, Cu and Cr were derived from anthropogenic sources in sediment. The total hazard index and cancer risks values for adults (HI: 3.20E+00, CR: 1.26E-03) and children (HI: 2.08E+01, CR: 8.18E-03) were higher than the standard limit (HI > 1, CR> 1.0E-04) resulting potential health hazards.

Is Mixtures' Additivity Supported by Empirical Data? A Case Study of Developmental Toxicity of PFOS and 6:2 FTS in Wildtype Zebrafish Embryos.

Per- and polyfluoroalkyl substances (PFASs) are a major priority for many federal and state regulatory agencies charged with monitoring levels of emerging contaminants in environmental media and setting health-protective benchmarks to guide risk assessments. While screening levels and toxicity reference values have been developed for numerous individual PFAS compounds, there remain important data gaps regarding the mode of action for toxicity of PFAS mixtures. The present study aims to contribute whole-mixture toxicity data and advance the methods for evaluating mixtures of two key components of aqueous film-forming foams: perfluorooctanesulfonic acid (PFOS), and 6:2 fluorotelomer sulfonic acid (6:2 FTS). Wildtype (AB) zebrafish embryos were exposed to PFOS and 6:2 FTS, both as individual components and as binary mixtures, from 2 to 122 h post-fertilization. Five treatment levels were selected to encompass environmentally relevant exposure levels. Experimental endpoints consisted of mortality, hatching, and developmental endpoints, including swim bladder inflation, yolk sac area, and larval body length. Results from dose–response analysis indicate that the assumption of additivity using conventional points of departure (e.g., NOAEL, LOAEL) is not supported for critical effect endpoints with these PFAS mixtures, and that the interactions vary as a function of the dose range. Alternative methods for quantifying relative potency are proposed, and recommendations for additional investigations are provided to further advance assessments of the toxicity of PFAS mixtures to aquatic organisms.