Trace elements and heavy metal(loid)s triggering ecological risks in a heavily polluted river-reservoir system of central Mexico: Probabilistic approaches.

The contamination of trace elements and heavy metal(loid)s in water bodies has emerged as a global environmental concern due to their high toxicity at low concentrations to both biota and humans. This study aimed to evaluate the ecological risk associated with the occurrence and spatial distribution of Mn, Fe, Co, Cd, Ni, Zn, Sb, As, Tl, Cu, Pb, U, and V in the heavily polluted waters of an important river-reservoir system (Atoyac River Basin) in central Mexico, using two-level tired probabilistic approaches: Risk Quotient based on Species Sensitivity Distribution (RQSSD) and Joint Probability Curves (JPCs). The concentrations of these elements varied widely, ranging from 0.055 µg L-1 to 9200 µg L-1 and from 0.056 µg L-1 to 660 µg L-1, in both total and dissolved fractions, respectively. Although geogenic and anthropogenic sources contribute to the presence of these elements in waters, the discharge of untreated or poorly treated industrial wastewater is the main source of contamination. In this regard, the RQSSD results indicated high ecological risk for Mn, Fe, Co, Ni, Zn, and Sb, and medium or low ecological risk for As, Tl, U, and V at almost all sampling sites. The highest RQSSD values were found downstream of a large industrial corridor for Co, Zn, Tl, Pb, and V, with Tl, Pb, and V escalating to higher risk levels, highlighting the negative impact of industrial contamination on biota. The JPC results for these elements are consistent with the RQSSD approach, indicating an ecological risk to species from Mn, Fe, Co, Ni, Zn, and Sb in waters of the Atoyac River Basin. Therefore, the results of this study offer a thorough assessment of pollution risk, providing valuable insights for legislators on managing and mitigating exposure.

Arsenic and fluoride in groundwater triggering a high risk: Probabilistic results using Monte Carlo simulation and species sensitivity distribution.

The widespread presence of arsenic (As) and fluoride (F-) in groundwater poses substantial risks to human health on a global scale. These elements have been identified as the most prevalent geogenic contaminants in groundwater in northern Mexico. Consequently, this study aimed to evaluate the human health and ecological risks associated with the content of As and F- in the Meoqui-Delicias aquifer, which is in one of Mexico's most emblematic irrigation districts. Concentrations of As and F- were measured in 38 groundwater samples using ICP-MS and ion chromatography, respectively. Overall, these elements showed a similar trend across the aquifer, revealing a positive correlation between them and pH. The concentration of As and F- in the groundwater ranged from 5.3 µg/L to 303 µg/L and from 0.5 mg/L to 8.8 mg/L, respectively. Additionally, the levels of As and F- surpassed the established national standards for safe drinking water in 92% and 97% of samples, respectively. Given that groundwater is used for both agricultural purposes and human activities, this study also assessed the associated human health and ecological risks posed by these elements using Monte Carlo simulation and Species Sensitivity Distribution. The findings disclosed a significant noncarcinogenic health risk associated with exposure to As and F-, as well as an unacceptable carcinogenic health risk to As through water consumption for both adults and children. Furthermore, a high ecological risk to aquatic species was identified for F- and high to medium risks for As in the sampling sites. Therefore, the findings in this study provide valuable information for Mexican authorities and international organizations (e.g., WHO) about the adverse effects that any exposure without treatment to groundwater from this region represents for human health.

Integrative ecotoxicity evaluation of Cd, Cu, Zn and Ni in aquatic animals reveals high tolerance of Artemia franciscana.

Heavy metals pose a significant threat to animals in aquatic environments due to the adverse effects they exert. Species of the genus Artemia have been described as heavy metal tolerant, but the sensitivity/tolerance range for these species has not been established. In the present study, the toxicity of Cd, Cu, Zn and Ni as reported in the ECOTOX and Web of Science databases was examined for Artemia franciscana and compared with other species and taxonomic groups using an integrative ecotoxicity evaluation. The hazard concentration for 5% of the species (HC5) of acute toxicity tests (24-96 h), obtained through a species sensitivity distribution (SSD) indicated that Cu (0.02 mg/L) and Cd (0.03 mg/L) were the metals with the highest toxicity to aquatic animals followed by Zn (0.15 mg/L) and Ni (0.23 mg/L). In addition to the higher hazard of Cu and Cd to aquatic animals, the comparison of acute LC50 values for A. franciscana indicates lower toxicity of Cd followed by Cu, Zn, and Ni (200.0, 14.5, 9.5, and 0.6 mg/L, respectively). Using the SSD and physiological sensitivity (S) approaches, it was demonstrated that A. franciscana is relatively tolerant to Cd (SSD= HC99; S = 2.21), Cu (SSD= HC97; S = 2.00), Zn (SSD= HC90; S = 1.29) and Ni (SSD= HC83; S = 0.96) compared with other species and taxonomic groups. It appears that tolerance to the metals Cd, Cu, Zn and Ni is unique to the family Artemiidae within the order Anostraca, as the families Streptocephalidae and Thamnocephalidae are not tolerant (have negative S values). Our study confirmed that as expected, A. franciscana presents higher tolerance to Cd, Cu, Zn, and Ni than other aquatic animals. Our findings confirm that A. franciscana can be used as a model organism to understand mechanisms involved in tolerance to heavy metals, mainly Cd and Cu, which are considered highly toxic to other animals.

Sensitivity of the Neotropical Solitary Bee Centris analis F. (Hymenoptera, Apidae) to the Reference Insecticide Dimethoate for Pesticide Risk Assessment.

Currently, only Apis mellifera is used in environmental regulation to evaluate the hazard of pesticides to pollinators. The low representativeness of pollinators and bee diversity in this approach may result in insufficient protection for the wild species. This scenario is intensified in tropical environments, where little is known about the effects of pesticides on solitary bees. We aimed to calculate the medium lethal dose (LD50) and medium lethal concentration (LC50) of the insecticide dimethoate in the Neotropical solitary bee Centris analis, a cavity-nesting, oil-collecting bee distributed from Brazil to Mexico. Males and females of C. analis were exposed orally to dimethoate for 48 h under laboratory conditions. Lethality was assessed every 24 h until 144 h after the beginning of the test. After the LD50 calculation, we compared the value with available LD50 values in the literature of other bee species using the species sensitivity distribution curve. In 48 h of exposure, males showed an LD50 value 1.33 times lower than females (32.78 and 43.84 ng active ingredient/bee, respectively). Centris analis was more sensitive to dimethoate than the model species A. mellifera and the solitary bee from temperate zones, Osmia lignaria. However, on a body weight basis, C. analis and A. mellifera had similar LD50 values. Ours is the first study that calculated an LD50 for a Neotropical solitary bee. Besides, the results are of crucial importance for a better understanding of the effects of pesticides on the tropical bee fauna and will help to improve the risk assessment of pesticides to bees under tropical conditions, giving attention to wild species, which are commonly neglected. Environ Toxicol Chem 2023;42:2758-2767. © 2023 SETAC.

Individual and Combined Effects of Manganese and Chromium on a Freshwater Chlorophyceae.

Manganese (Mn), an essential metal in trace amounts, and chromium (Cr), a nonessential metal to algae, are often found in effluent discharges and may co-occur in contaminated aquatic environments. Therefore, we investigated the effects of Mn and Cr, and their mixtures, on a freshwater Chlorophyceae, Raphidocelis subcapitata, using a multiple endpoint approach. Regarding the single exposure of metals, Mn was 4 times more toxic (median inhibitory concentration at 72 h [IC5072 h ] = 4.02 ± 0.45 µM Mn) than Cr (IC5072 h = 16.42 ± 4.94 µM Cr) for microalgae, considering the effects on the relative growth rate. Moreover, this species was the most sensitive to Mn, according to the species sensitivity distribution curve. Overall, the tested metals did not lead to significant changes in reactive oxygen species production, cellular complexity, and cell relative size but significantly decreased the algal growth and the mean cell chlorophyll a (Chl a) fluorescence at the highest concentrations (3.64-14.56 µM of Mn and 15.36-19.2 µM of Cr). The decreased mean cell Chl a fluorescence indicates an impact on pigment synthesis, which may be related to the observed growth inhibition. In the mixture tests, the reference models concentration addition and independent action were used to analyze the data, and the independent action model was the best fit to describe our results. Therefore, the Mn and Cr mixture was noninteractive, showing additive effects. This is the first study to address the combined toxicity of Mn and Cr regarding freshwater Chlorophyceae. Environ Toxicol Chem 2022;41:1004-1015. © 2022 SETAC.

Copper ecological risk assessment using DGT technique and PNEC: A case study in the Brazilian coast.

Estuarine systems are vulnerable to metals stress, such as copper (Cu). Thus, the development of applicable tools to improve routine monitoring programs is increasingly necessary. In the present work a comprehensive Ecological Risk Assessment (ERA) was implemented by coupling the Measured Environmental Concentration (MEC), based on labile Cu (DGT) and the total dissolved Cu concentration. Additionally, toxicity data related to site-specific Predicted No Effect Concentration (PNEC) were used. As case study, estuarine areas were selected on Brazilian coast, previously reported as Cu release in shipyard areas. The results indicated an increase in concentrations of dissolved and labile Cu during the application of antifouling paints. In locations where more vessels in maintenance were found, the concentration of Cu-DGT exceeded the PNEC value (0.16 µg.L-1) and represented an important part of the total dissolved fraction (>93 %). The MEC/PNEC quotients, showed that shipyard areas represent a high ecological risk. Thus, it is highlighted the need for site-specific environmental assessments to manage complex ecosystems and set in environmental legislation. Consequently, the novel coupling of DGT technique and the derivation of a site-specific PNEC represent an easily applicable tool as an alternative to classical ERAs.

Ecological risk assessment of Piper aduncum essential oil in non-target organisms / Avaliação de risco ecológico do óleo essencial de Piper aduncum em organismos não alvo

One possible alternative to chemotherapeutic agents in the treatment and prevention of diseases in fish farms is the use of Piper aduncum essential oil. However, ecotoxicological data are required to ensure its proper use and to prevent adverse effects on non-target organisms. These data are relevant since this essential oil is described as having insecticidal, molluscicidal and cytotoxic activitiy that may be associated with its chemical composition. Thus, the aim of this study was to evaluate the ecotoxicity of P. aduncum essential oil to five test organisms using the species sensitivity distribution (SSD) statistical approach. The chemical composition of the essential oil was characterized by means of gas chromatography coupled to mass spectrometry (GC-MS) and gas chromatography-flame ionization detection (GC-FID) for identification and quantitation purposes, respectively. The main component (75.5%) of the essential oil was dillapiole. The hazardous concentration for 5% of biological species (HC5) was calculated to determine the 95% protection level, resulting in a value of 0.47 mg L-1 (with a confidence interval of 0.028 - 1.19 mg L-1. ). A concentration range related to the level of protection for aquatic communities (the predicted no-effect concentration, PNEC) was determined through the application of safety factors to the HC5 value. The ecotoxicity parameters showed that P. aduncum essential oil can be used safely in water bodies at a concentration equal to or below 0.09 mg L-1.(AU)

Uma possível alternativa ao uso de fármacos veterinários no tratamento e prevenção de doenças na piscicultura é o uso do óleo essencial de Piper aduncum. No entanto, são necessários dados ecotoxicológicos para garantir seu uso apropriado sem causar efeitos adversos a organismos não alvo. Esta informação é relevante, pois esse óleo essencial é descrito como tendo atividades inseticidas, moluscicidas e citotóxicas, possivelmente associadas à sua composição química. Assim, o objetivo deste estudo foi avaliar a ecotoxicidade do óleo essencial de P. aduncum para cinco organismos-teste, usando o método estatístico da Distribuição da Sensibilidade das Espécies (SSD). A composição química do óleo essencial foi caracterizada por cromatografia gasosa acoplada a espectrometria de massa (GC-MS) e cromatografia gasosa com detector de ionização de chama (GC-FID), para fins de identificação e quantificação, respectivamente. O principal componente (75,5%) do óleo essencial foi o dilapiol. A concentração perigosa para 5% de espécies biológicas (HC5) foi calculada com um nível de proteção de 95%, resultando em um valor de 0,47 mg L-1 (com intervalo de confiança de 50% = 0,028 - 1,19 mg L-1). A faixa de concentração relacionada aos níveis de proteção para comunidades aquáticas (concentração sem efeito previsto - PNEC) foi calculada através da aplicação de fatores de segurança ao valor de HC5. Os parâmetros de ecotoxicidade indicaram que o óleo essencial de P. aduncum pode ser usado com segurança em corpos dágua se a concentração for igual ou inferior a 0,09 mg L-1.(AU)

Toxicity of methylparaben to green microalgae species and derivation of a predicted no effect concentration (PNEC) in freshwater ecosystems.

Methylparaben (MeP) is one of the most used preservatives in the industry; however, the toxic effects on aquatic ecosystems are still poorly understood. Therefore, this study was conducted (1) to identify and compare the toxic effects of MeP on physiological parameters of different green microalgae species, using suitable mathematical models; and (2) to estimate a PNEC value for MeP in freshwater ecosystems, adopting either the deterministic or the probabilistic approaches. Toxicity tests were carried out with three green microalgae (Pseudopediastrum boryanum, Desmodesmus communis, Raphidocelis subcapitata), in which different endpoints such as growth rate, chlorophyll-a, and cell viability were measured and compared through the effective concentration which caused a response in x% of test organisms (ECx). ECx were obtained by adjusting different non-linear regression models for each microalgae dataset. Chlorophyll-a endpoint resulted in the lowest EC50 values, respectively 125, 81.2, 18.3 mg L-1 for D. communis, P. boryanum and R. subcapitata, showing R. subicapitata as the most sensitive, and D. communis as the most tolerant species to MeP (P < 0.05). PNEC was estimated from the present study and previous reports resulting in 5.7 and 65 µg L-1, respectively for the deterministic (PNECd) and the probabilistic (PNECp) approach. The development of chronic assays using test organisms from different ecological groups is encouraged to provide robust PNECp. In this meantime, we recommend the use of the estimated PNECd to support MeP risk assessments and policy formulation.

Freshwater neotropical oligochaetes as native test species for the toxicity evaluation of cadmium, mercury and their mixtures.

The toxicity of metals, whether isolated or in mixtures, involves changes in biochemical processes as well as in cell membranes, which may lead to deleterious short- and long-term effects on the affected organisms. Among metals, cadmium and mercury stand out due to their abundance in nature, frequent use for industrial activities and biological accumulation, with high levels of residence in trophic chains. Benthic communities are particularly prone to metal pollution since metals usually accumulate in sediments. The aim of this study was to evaluate the acute toxicity of mercury and cadmium, single and in mixture, to two native species of epibenthic oligochaetes: Allonais inaequalis and Dero furcatus. In order to assess the potential of these species as bioindicators, we compared their sensitivity with those of other internationally used species by applying the species sensitivity distribution approach. The 96h-LC50 of cadmium chloride was 627 and 364 µg L-1 for A. inaequalis and D. furcatus, respectively, evidencing that the latter species is almost twice as sensitive to this metal than A. inaequalis. For mercury chloride, the 96h-LC50 was 129 µg L-1 for A. inaequalis and 92 µg L-1 for D. furcatus. The sensitivities of these oligochaetes were superior or similar to that of other frequently used oligochaete test species such as Tubifex tubifex and Lumbriculus variegatus. The metal mixtures had synergism in general (D. furcatus) or at high doses only (A. inaequalis), implying a potentiation of their toxic effects when both metals co-occur in the environment. By comparing the derived toxicity values with concentrations of cadmium and mercury measured in the field, it can be concluded that aquatic organisms are likely to be at risk when exposed to the environmental relevant concentrations of cadmium and mercury here tested, especially when they are both present.

Chemical characterization and toxicity of water-accommodated fraction of oil on the South American native species Hyalella curvispina.

Chemical and toxicological crude oil analysis was performed on water-accommodated fraction of oil (WAF). This study characterized the chemical composition of WAF and its dissipation over a period of 192 h. Acute (96 h) and chronic (14 d) toxicity of WAF were evaluated on Hyalella curvispina from both reference (Los Barreales lake, LB) and hydrocarbon-contaminated (Durán stream, DS) sites. The total hydrocarbon (TPHs) concentration in WAF was 2.18 mg L-1. The dissipation rates of hydrocarbons in WAF showed a first-order kinetics, with half-lives ranging between 65 h-200 h. Amphipods from LB showed acute and chronic LC50 values of 0.33 and 0.018 mg L-1, respectively. Amphipods from DS exposed to pure WAF showed no mortality in either acute or chronic assays. Further biochemical and molecular research is required to determine the mechanisms underlying the resistance to WAF exposure on DS amphipods.

Ecotoxicological effects of bisphenol A and nonylphenol on the freshwater cladocerans Ceriodaphnia silvestrii and Daphnia similis.

Toxicities of bisphenol A (BPA) and nonylphenol (NP) to the neotropical freshwater cladocerans Ceriodaphnia silvestrii and Daphnia similis were studied under laboratory conditions. Acute exposures to BPA generated mean 48-h EC50 values of 14.44 (6.02-22.85) mg L-1 for C. silvestrii and 12.05 (1.73-22.37) mg L-1 for D. similis. When the organisms were exposed to acute doses of NP, mean 48-h EC50 values were 0.055 (0.047-0.064) mg L-1 (C. silvestrii) and 0.133 (0.067-0.200) mg L-1 (D. similis). Ceriodaphnia silvestrii was also tested in chronic bioassays, which resulted in mean 8-d IC25 values of 2.43 (2.16-2.69) mg L-1 BPA [no observed effect concentration (NOEC): 1.38 mg L-1] and 0.020 (0.015-0.026) mg L-1 NP (NOEC: 0.015 mg L-1). These laboratory tests are valuable to broaden the understanding of the environmental threat posed by BPA and NP in aquatic ecosystems, and to increase the knowledge about the sensitivity of neotropical indigenous species to these contaminants. In addition to the laboratory bioassays, species sensitivity distributions were used to suggest protective concentrations of BPA and NP to prevent adverse effects on freshwater organisms. According to the obtained results, concentrations lower than 36.47 µg L-1 BPA and 1.39 µg L-1 NP are not expected to adversely impact aquatic organisms in natural ecosystems.

Acute and chronic toxicity of diuron and carbofuran to the neotropical cladoceran Ceriodaphnia silvestrii.

In order to contribute to the increase of the body of knowledge on the sensitivity of tropical indigenous species to pesticides, acute and chronic toxicity tests were conducted with the neotropical cladoceran Ceriodaphnia silvestrii. Tests were carried out with the active ingredients diuron and carbofuran and one of their commercial formulations, the Diuron Nortox® 500 SC and the Furadan® 350 SC, respectively. For carbofuran, the active ingredient was more toxic than the commercial product, whereas for diuron, the commercial product appeared more toxic. In addition, hormetic effects on fertility were recorded for intermediate diuron concentrations. Acute and chronic toxicity data indicated that C. silvestrii was among the most sensitive invertebrate species for both test compounds. Based on concentrations measured in Brazilian water bodies, these compounds represent ecological risks for causing direct and indirect toxic effects on C. silvestrii and other aquatic organisms. Our results support previous claims on the advantages of using native species to better tune ecological risk assessment of chemicals in tropical ecosystems.

Review: ecotoxicity of organic and organo-metallic antifouling co-biocides and implications for environmental hazard and risk assessments in aquatic ecosystems.

Hazard assessments of Irgarol 1051, diuron, 2-(thiocyanomethylthio)benzothiazole (TCMTB), dichloro-octylisothiazolin (DCOIT), chlorothalonil, dichlofluanid, thiram, zinc pyrithione, copper pyrithione, triphenylborane pyridine (TPBP), capsaicin, nonivamide, tralopyril and medetomidine were performed to establish robust environmental quality standards (EQS), based on predicted no effect concentrations (PNECs). Microalgae, zooplankton, fish and amphibians were the most sensitive ecological groups to all the antifoulants evaluated, especially in the early life stages. No differences were identified between freshwater and seawater species. The use of toxicity tests with non-standard species is encouraged because they increase the datasets, allowing EQS to be derived from probabilistic-based PNECs whilst reducing uncertainties. The global ban of tributyltin (TBT) has been heralded as a major environmental success; however, substitute antifoulants may also pose risks to aquatic ecosystems. Environmental risk assessments (ERAs) have driven decision-makings for regulating antifouling products, but in many countries there is still a lack of regulation of antifouling biocides which should be addressed.