Traces of the past: assessing the impact of potentially toxic elements from an abandoned mine on groundwater and agricultural soil in San Luis Potosí, México.

The study was conducted in Cerritos, San Luis Potosí, México, near the Guaxcama mine, focused on environmental contamination (groundwater and agricultural soil) from antimony (Sb), arsenic (As), lead (Pb), cadmium (Cd), and mercury (Hg). In March 2022, 20 agricultural soil and 16 groundwater samples were collected near the historically cinnabar (HgS)- and arsenopyrite (FeAsS)-rich Guaxcama mine. Hydride generation atomic fluorescence spectrometry (HG-AFS) for As, cold vapor atomic fluorescence spectrometry (CV-AFS) for Hg, and inductively coupled plasma optical emission spectrometry (ICP-OES) for Cd, Pb, and Sb were used for the determinations of potentially toxic elements (PTEs). While concentrations of Cd, Hg, Pb, and Sb in groundwater were below detection limits, As levels exhibited a range from 40.9 ± 1.4 to 576.0 ± 1.0 µg/L, exceeding permissible limits for drinking water (10 µg/L). In agricultural soil, As was between 7.67 ± 0.16 and 24.1 ± 0.4 µg/g, Hg ranged from 0.203 ± 0.018 to 2.33 ± 0.19 µg/g, Cd from 2.53 ± 0.90 to 2.78 ± 0.01 µg/g, and Pb from 11.7 ± 1.2 to 34.3 ± 4.1 µg/g. Only one study area surpassed the Mexican As soil limit of 22 µg/g. Sequential extraction (four-step BCR procedure) indicated significant As bioavailability in soil (fractions 1 and 2) ranging from 3.66 to 10.36%, heightening the risk of crop transfer, in contrast to the low bioavailability of Hg, showing that fractions 1, 2, and 3 were below the limit of quantification (LOQ). Crucial physicochemical parameters in soil, including nitrate levels, pH, and organic matter, were pivotal in understanding contamination dynamics. Principal component analysis highlighted the influence of elements like Fe and Ca on phytoavailable As, while Pb and Cd likely originated from a common source. Ecological risk assessments underscored the significant impact of pollution, primarily due to the concentrations of Cd and Hg. Non-cancer and cancer risks to residents through As poisoning via contaminated water ingestion also were found. The hazard index (HI) values varied between 4.0 and 82.2 for adults and children. The total incremental lifetime cancer risk (TILCAR) values for adults ranged from 7.75E - 04 to 1.06E - 02, whereas for children, the values were from 2.47E - 04 to 3.17E - 03.

Unlocking Biological Activity and Metabolomics Insights: Primary Screening of Cyanobacterial Biomass from a Tropical Reservoir.

Cyanobacterial harmful algal blooms can pose risks to ecosystems and human health worldwide due to their capacity to produce natural toxins. The potential dangers associated with numerous metabolites produced by cyanobacteria remain unknown. Only select classes of cyanopeptides have been extensively studied with the aim of yielding substantial evidence regarding their toxicity, resulting in their inclusion in risk management and water quality regulations. Information about exposure concentrations, co-occurrence, and toxic impacts of several cyanopeptides remains largely unexplored. We used liquid chromatography-mass spectrometry (LC-MS)-based metabolomic methods associated with chemometric tools (NP Analyst and Data Fusion-based Discovery), as well as an acute toxicity essay, in an innovative approach to evaluate the association of spectral signatures and biological activity from natural cyanobacterial biomass collected in a eutrophic reservoir in southeastern Brazil. Four classes of cyanopeptides were revealed through metabolomics: microcystins, microginins, aeruginosins, and cyanopeptolins. The bioinformatics tools showed high bioactivity correlation scores for compounds of the cyanopeptolin class (0.54), in addition to microcystins (0.54-0.58). These results emphasize the pressing need for a comprehensive evaluation of the (eco)toxicological risks associated with different cyanopeptides, considering their potential for exposure. Our study also demonstrated that the combined use of LC-MS/MS-based metabolomics and chemometric techniques for ecotoxicological research can offer a time-efficient strategy for mapping compounds with potential toxicological risk. Environ Toxicol Chem 2024;43:2222-2231. © 2024 SETAC.

Vulnerability of Eastern Tropical Pacific chondrichthyan fish to climate change.

Climate change is an environmental emergency threatening species and ecosystems globally. Oceans have absorbed about 90% of anthropogenic heat and 20%-30% of the carbon emissions, resulting in ocean warming, acidification, deoxygenation, changes in ocean stratification and nutrient availability, and more severe extreme events. Given predictions of further changes, there is a critical need to understand how marine species will be affected. Here, we used an integrated risk assessment framework to evaluate the vulnerability of 132 chondrichthyans in the Eastern Tropical Pacific (ETP) to the impacts of climate change. Taking a precautionary view, we found that almost a quarter (23%) of the ETP chondrichthyan species evaluated were highly vulnerable to climate change, and much of the rest (76%) were moderately vulnerable. Most of the highly vulnerable species are batoids (77%), and a large proportion (90%) are coastal or pelagic species that use coastal habitats as nurseries. Six species of batoids were highly vulnerable in all three components of the assessment (exposure, sensitivity and adaptive capacity). This assessment indicates that coastal species, particularly those relying on inshore nursery areas are the most vulnerable to climate change. Ocean warming, in combination with acidification and potential deoxygenation, will likely have widespread effects on ETP chondrichthyan species, but coastal species may also contend with changes in freshwater inputs, salinity, and sea level rise. This climate-related vulnerability is compounded by other anthropogenic factors, such as overfishing and habitat degradation already occurring in the region. Mitigating the impacts of climate change on ETP chondrichthyans involves a range of approaches that include addressing habitat degradation, sustainability of exploitation, and species-specific actions may be required for species at higher risk. The assessment also highlighted the need to further understand climate change's impacts on key ETP habitats and processes and identified knowledge gaps on ETP chondrichthyan species.

El cambio climático es una emergencia medioambiental que amenaza a especies y ecosistemas en todo el mundo. Los océanos han absorbido alrededor del 90% del calor antropogénico y entre el 20% y el 30% de las emisiones de carbono, lo que ha provocado su calentamiento, acidificación, desoxigenación, cambios en la estratificación de los océanos y en la disponibilidad de nutrientes, así como fenómenos extremos más pronunciados. Dadas las predicciones de cambios, hay una importante necesidad de entender cómo las especies marinas se verán afectadas. En este estudio utilizamos una Evaluación Integrada de Riesgos para evaluar la vulnerabilidad de 132 condrictios del Pacífico Tropical Oriental (PTO) a los impactos del cambio climático. Adoptando un enfoque preventivo, estimamos que la vulnerabilidad general al cambio climático es Alta para casi una cuarta parte (23%) de las especies de condrictios del PTO evaluadas y Moderada para gran parte del resto (76%). La mayoría de las especies altamente vulnerables son batoideos (77%), y una gran proporción de éstas (90%) son especies costeras o especies pelágicas que utilizan los hábitats costeros como áreas de crianza. Seis especies de batoideos tuvieron una vulnerabilidad Alta en los tres componentes de la evaluación. Esta evaluación indica que las especies costeras, en particular las que dependen de áreas de crianza costeras, son las más vulnerables al cambio climático. Es probable que el calentamiento de los océanos, junto con la acidificación y la posible desoxigenación, tenga efectos generalizados sobre las especies de condrictios del PTO, pero las especies costeras se verán también afectadas por los cambios en los aportes de agua dulce, la salinidad y el aumento del nivel del mar. Esta vulnerabilidad relacionada con el clima se ve agravada por otros factores antropogénicos que ya se están produciendo en la región, como la sobrepesca y la degradación del hábitat. La mitigación de los impactos del cambio climático sobre los condrictios del PTO implica medidas que incluyan abordar la degradación del hábitat y la sostenibilidad de la explotación pesquera, y acciones para las especies de mayor riesgo son necesarias. Esta evaluación también destaca la necesidad de comprender mejor los impactos del cambio climático en los hábitats y procesos clave del PTO y las lagunas de conocimiento identificadas en relación con las especies de condrictios del PTO.

Ecological risk of metals in Andean water resources: A framework for early environmental assessment of mining projects in Peru.

Metallic contaminants in Andean water resources influenced by mining activities poses risks to aquatic ecosystems and a challenge to regulatory agencies responsible for environmental compliance. In this study, the Ecological Risk Assessment (ERA) framework was adapted to assess dissolved heavy metal concentrations at 283 surface water monitoring stations near to six mining projects during the dry and wet seasons. Reports from OEFA-Peru on Early Environmental Assessment (EEA) were used to apply various criteria and non-parametric statistical tests. They included ecological, ecotoxicological, chemical, and regulatory factors. The main goal of this research was to identify, analyze, characterize, and compare the risks present at different trophic levels. These levels were categorized as T1 (Microalgae), T2 (Zooplankton and Benthic invertebrates), and T3 (Fish). Individual risk (IR) was estimated using the quotient model, while total risk (TR) was assessed using the additive probability rule. Rainbow trout (Oncorhynchus mykiss), representing trophic level T3, showed the highest sensitivity to Fe and Cu. Statistical tests ranked the IR as Fe > Cu > Zn > Mn > Pb (p < 0.01). The TR was more prevalent during the wet season compared to the dry season (p < 0.01). Notably, around 50 % of the monitoring stations (n = 142) were classified as high risk, and 9 % (n = 13) showed extremely high-risk values for Cu and Fe. The adapted ERA framework demonstrated great effectiveness in identifying critical points of metal contamination in high Andean aquatic ecosystems under mining influence. However, specialized studies are suggested that allow the sources of pollution to be associated with specific regulatory actions.

Effects of acute toxicity of the pesticide Chlorpyrifos and the metal Cadmium, both individually and in mixtures, on two species of native neotropical cladocerans.

The excessive use of pesticides in agriculture and the widespread use of metals in industrial activities and or technological applications has significantly increased the concentrations of these pollutants in both aquatic and terrestrial ecosystems worldwide, making aquatic biota increasingly vulnerable and putting many species at risk of extinction. Most aquatic habitats receive pollutants from various anthropogenic actions, leading to interactions between compounds that make them even more toxic. The aim of this study was to assess the effects of the compounds Chlorpyrifos (insecticide) and Cadmium (metal), both individually and in mixtures, on the cladocerans Ceriodaphnia rigaudi and Ceriodaphnia silvestrii. Acute toxicity tests were conducted for the compounds individually and in mixture, and an ecological risk assessment (ERA) was performed for both compounds. Acute toxicity tests with Cadmium resulted in EC50-48 h of 0.020 mg L-1 for C. rigaudi and 0.026 mg L-1 for C. silvestrii, while tests with Chlorpyrifos resulted in EC50-48 h of 0.047 µg L-1 and 0.062 µg L-1, respectively. The mixture test for C. rigaudi showed the occurrence of additive effects, while for C. silvestrii, antagonistic effects occurred depending on the dose level. The species sensitivity distribution curve for crustaceans, rotifers, amphibians, and fishes resulted in an HC5 of 3.13 and an HC50 of 124.7 mg L-1 for Cadmium; an HC5 of 9.96 and an HC50 of 5.71 µg L-1 for Chlorpyrifos. Regarding the ERA values, Cadmium represented a high risk, while Chlorpyrifos represented an insignificant to a high risk.

Assessing the environmental pesticides impact of river sediments from a basin in western Mexico: Spatiotemporal distribution, risk assessment of aquatic invertebrates and pesticides prioritization.

The intensive use of pesticides in Mexican agriculture has contributed significantly to the increase in food production, but at the same time represents potential risk to biota. This situation creates a dilemma between the need to increase food production and the preservation of the environment and human health. Aquatic invertebrates play a vital role in the balance of aquatic ecosystems but are sensitive to pesticides contamination. The sensitivity of aquatic invertebrates to pesticides contamination has led them to be used to assess the potential impact of this contamination on aquatic ecosystems. In the present study, conducted in the Ayuquila-Armería basin, the following aims were achieved: 1) quantifying the presence of 20 pesticides in river sediments, 2) assessing the spatiotemporal distribution of pesticides in river sediments, 3) determining the potential risk to aquatic invertebrates, and 4) prioritizing pesticides based on their potential risk. Twelve pesticides were consistently quantified in 192 river sediments samples. The pesticides with the highest concentrations were ametrine, malathion and picloram. The temporal analysis showed seasonality in pesticide concentrations, with higher detection frequencies during the wet season. The risk assessment showed that aquatic invertebrates may be affected by the concentrations of carbofuran, malathion, diazinon and ametrine. Pesticides prioritization identified ametrine, carbofuran, and diazinon as major concerns based on the methodology that considers the Frequency and Extent of Exceedance. This study provides valuable insights into the current pesticides scenario in the Ayuquila-Armería River sediments. The findings underscore the need for sustainable alternatives to mitigate the ecological risks associated with pesticides contamination in this aquatic ecosystem.

Limited contribution of photoenzymatic DNA repair in mitigating carry-over effects from larval UVB exposure: Implications for frog recruitment.

Solar ultraviolet-B (UVB) radiation has increased due to stratospheric ozone depletion, climate and ecosystem changes and is a driver of amphibian population declines. Photoenzymatic repair (PER) is a critical mechanism for limiting UVB lethality in amphibian larvae. However, the link between PER and the UVB-induced effects remains understudied through long-term investigations in vivo. Here, we assessed how larval PER determines the lethal and sublethal effects induced by environmentally relevant acute UVB exposure until the juvenile phase in the Neotropical frog Odontophrynus americanus. We conducted laboratory-based controlled experiments in which tadpoles were or were not exposed to UVB and subsequently were exposed to light (for PER activation) or dark treatments. Results showed that the rates of mortality and apoptosis observed in post-UVB dark treatment are effectively limited in post-UVB light treatment, indicating PER (and not dark repair, i.e. nucleotide excision repair) is critical to limit the immediate genotoxic impact of UVB-induced pyrimidine dimers. Nonetheless, even tadpoles that survived UVB exposure using PER showed sublethal complications that extended to the juvenile phase. Tadpole responses included alterations in morphology, chromosomal instability, increased skin susceptibility to fungal proliferation, as well as increased generation of reactive oxygen species. The short-term effects were carried over to later stages of life because metamorphosis time increased and juveniles were smaller. No body abnormalities were visualized in tadpoles, metamorphs, and juveniles, suggesting that O. americanus is UVB-resistant concerning these responses. This study reveals that even frog species equipped with an effective PER are not immune to carry-over effects from early UVB exposure, which are of great ecological relevance as late metamorphosis and smaller juveniles may impact individual performance and adult recruitment to breeding. Future ecological risk assessments and conservation and management efforts for amphibian species should exercise caution when linking PER effectiveness to UVB resistance.

Occurrence and toxicological relevance of pesticides and trace metals in agricultural soils, sediments, and water of the Sogamoso River basin, Colombia.

Historical pesticide use in agriculture and trace metal accumulation have long term impact on soil, sediment, and water quality. This research quantifies legacy and current-use pesticides and trace metals, assessing their occurrence and toxicological implications on a watershed scale in the Sogamoso River basin, tributary of the Magdalena River in Colombia. Organochlorine pesticides (22), organophosphates (7), and azole fungicides (5), as well as trace metals cadmium (Cd), chromium (Cr), copper (Cu), mercury (Hg), nickel (Ni), lead (Pb), and zinc (Zn) were analyzed in croplands and along the river. Toxic units (TU) and hazard quotients (HQ) were calculated to assess the mixture toxicity. Organochlorines were detected in 84% of soils, 100% of sediments, and 80% of water samples. Organophosphates were found in 100% of soil and sediment samples, as well as in 70% of water samples. Azole fungicides were present in 79% of soils, 60% of sediments, and in 10% of water samples. Total pesticide concentrations ranged from 214.2 to 8497.7 µg/kg in soils, 569.6-12768.2 µg/kg in sediments, and 0.2-4.1 µg/L in water. In addition, the use of partition coefficient (Kd) and organic carbon fraction (foc) allowed the distribution analysis for most of the pesticides in sediments, suspended particulate matter (SPM), and water systems, but not for soils. Concentrations of trace metals Cu, Zn, Pb, and Zn exceeded international quality guidelines for agricultural soils in 16% of the samples. Furthermore, Cu and Zn concentrations exceeded sediment quality guidelines in 50 and 90% of the samples, respectively. These findings demonstrate the broad distribution of complex mixtures of trace metals, legacy organochlorines, and current-use pesticides across the basin, indicating that conventional agriculture is a significant source of diffuse pollution. Sustainable agricultural practices are needed to mitigate adverse impacts on ecosystems and human health.

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.

Computational modeling (in silico) methods combined with ecotoxicological experiments (in vivo) to predict the environmental risks of an antihistamine drug (loratadine).

This study employed computational modeling (in silico) methods, combined with ecotoxicological experiments (in vivo) to predict the persistence/biodegradability, bioaccumulation, mobility, and ecological risks of an antihistamine drug (Loratadine: LOR) in the aquatic compartment. To achieve these goals, four endpoints of the LOR were obtained from different open-source computational tools, namely: (i) "STP total removal"; (ii) Predicted ready biodegradability; (iii) Octanol-water partition coefficient (KOW); and (iv) Soil organic adsorption coefficient (KOC). Moreover, acute and chronic, ecotoxicological assays using non-target freshwater organisms of different trophic levels (namely, algae Pseudokirchneriella subcapitata; microcrustaceans Daphnia similis and Ceriodaphnia dubia; and fish Danio rerio), were used to predict the ecological risks of LOR. The main results showed that LOR: (i) is considered persistent (after a weight-of-evidence assessment) and highly resistant to biodegradation; (ii) is hydrophobic (LOG KOW = 5.20), immobile (LOG KOC = 5.63), and thus, it can potentially bioaccumulate and/or can cause numerous deleterious effects in aquatic species; and (iii) after ecotoxicological evaluation is considered "toxic" and/or "highly toxic" to the three trophic levels tested. Moreover, both the ecotoxicological assays and risk assessment (RQ), showed that LOR is more harmful for the crustaceans (RQcrustaceans = moderate to high risks) than for algae and fish. Ultimately, this study reinforces the ecological concern due to the indiscriminate disposal of this antihistamine drug in worldwide aquatic ecosystems.

Occurrence of mercury in polychaete species (Annelida) and their associated sediments from an important Southern Atlantic Ocean Bay.

In the present study, the Hg levels in freshly collected polychaete species and their associated sediments were evaluated from Todos os Santos Bay, Northeastern Brazil. Additionally, it was also measured the Hg distribution along the annelids' body parts (anterior region, abdomen, and posterior region). Total Hg concentration was as follows: 13.6-144 µg kg-1 (Scolelepis chilensis, deposit feeder), 8.2-122 µg kg-1 (Laeonereis acuta, deposit feeder), 95-612 µg kg-1 (Armandia agilis, deposit feeder); 96.6-206 µg kg-1 (Lumbrineris sp., carnivorous), 75.3-112 µg kg-1 (Goniada echinulate, carnivorous), and 115-198 µg kg-1 (Branchiomma sp., suspension feeder). In turn, Hg levels in sediments ranged from 2.77 ± 0.24 to 6.38 ± 0.15 µg kg-1. Hg concentrations found in polychaete soft tissues were higher than those found in the sediments. Specific habits, feeding behavior, trophic level, and stressful environmental conditions are the main factors affecting the Hg levels in the species studied. The bioaccumulation factor (BAF), contamination factor (CF), and ecological risk assessment (Er) were calculated. The BAF values were higher than 1 for all studied species, indicating Hg bioaccumulation in the annelids, but the low levels of CF e Er showed those Hg levels present low to no significant ecological risk for the biota and benthonic organisms living in the sediments. Finally, no statistically significant difference was observed for Hg concentration levels along the polychaete body parts.

Environmental analysis of the eutrophication and spread of aquatic macrophytes in a tropical reservoir: a case study in Brazil.

Land use changes threaten the maintenance of water quality and challenge the management of tropical reservoirs. In particular, eutrophication alters several ecosystem functions and services, compromising multiple uses of water. For example, in the Lajeado Reservoir (Araraquara, São Paulo, Brazil), aquatic macrophytes rapidly spread and occupied more than 90% of the system's surface area (from 2016 to 2019). In such a scenario, this research aimed to evaluate the eutrophication causes and impacts to provide technical and scientific support to public agencies and propose remediation alternatives. First, a diagnosis of the study area was performed, using available data on land use, water quality, and climate (between 2010 and 2018). Second, water and sediment samples were collected for physical, chemical, and ecotoxicological analyses. The Ecological Risk Assessment consisted of a triad of Lines of Evidence, including physical-chemical, chemical, and ecotoxicological results. The expansion of agricultural activities (e.g., sugarcane cultivation) and diffuse pollution were highlighted among possible causes, and water quality was affected by increases in the concentration of nutrients (e.g., nitrogen and phosphorus), metals (e.g., iron), and emerging contaminants (e.g., pesticides and caffeine). As a result, the Lajeado Reservoir presented a high ecological risk, and alternatives for macrophyte removal are needed. This research involved several stakeholders (i.e., community, government agencies, and universities) who participated more effectively in environmental monitoring and recovery.

Temporal distribution patterns of metals in water, sediment, and components of the trophic structure in a tropical coastal lagoon of the Gulf of Mexico.

Trophic transfer and bioaccumulation of trace metals have a profound impact on the structure and function of coastal areas; however, the metal accumulation patterns in detritus-based food webs and the influence of climatic variability have not been thoroughly investigated. The Tampamachoco Lagoon (Gulf of Mexico) is a coastal system impacted by emissions from a thermoelectric plant. We evaluated the spatial-temporal distribution patterns of Al, Cd, Hg, Cr, Cu, and Pb in water, sediments, and in organisms categorized by trophic levels (TLs), trophic guilds, and habitat preferences. The sediments had the highest concentrations of metals with no significant differences between seasons. The indices of geo-accumulation and potential ecological risk classified sediments as "moderately contaminated", evidencing a threat to human health through consumption of detritivores and filter-feeders. The lowest TLs (filter-feeders and detritivorous) reached the maximum Metal Pollution Index in the rainy season. According to discriminant analyses of metals and species, omnivorous and zoobentivorous organisms were associated with Hg during the rainy and dry seasons; while Al, Cd, and Cu were related to low TLs, and seston was associated with Pb. Food web magnification factor analysis showed that: (a) Pb, Cu, and Cr were biodiluted as trophic levels increased; (b) Cd and Hg showed temporal biomagnification trends; (c) Al, Pb, Cu, and Cd showed significant biodilution from the lowest TL to intermediate TLs; and (d) Hg was transferred from the lowest to intermediate TLs with clear biomagnification effects.

Ecological risk assessment of pesticides in urban streams of the Brazilian Amazon.

The use of pesticides in households and peri-urban areas of the Amazon has increased notably during the last years. Yet, the presence of these contaminants in Amazonian freshwater ecosystems remains unexplored. Here, we assessed the exposure to 18 pesticides and 5 transformation products in the Amazon River and in the urban streams of Manaus, Santarém, Macapá, and Belém (Brazil). Pesticide concentrations were analyzed by liquid and gas chromatography methods. Ecological risks were assessed following a two-tiered approach. First, hazard quotients and an overall hazard index were calculated using toxicity data for standard test species of primary producers, invertebrates, and fish. Second, the pesticides showing moderate-to-high ecological risks in the first tier were evaluated using Species Sensitivity Distributions (SSDs). Our study shows that pesticides are widespread in urban and peri-urban areas of the Brazilian Amazon. The frequency of detection was higher in urban streams than in the Amazon River, with some samples taken in Manaus, Santarém, and Belém containing up to 8 compounds. Most pesticides were measured at relatively low concentrations (ng L-1), except for malathion, carbendazim and the bulk concentration of chlorpyrifos, which were monitored at concentrations above 100 ng L-1. Based on the first-tier assessment, we found moderate-to-high risks for freshwater invertebrates for malathion, chlorpyrifos, and chlorpyrifos-methyl, and moderate risks for malathion to fish. The risk assessment performed with SSDs indicated high risks of malathion and chlorpyrifos-methyl in urban areas, with up to 15% and 5% of invertebrate species potentially affected, respectively. The bulk concentrations of chlorpyrifos resulted in high risks in some urban areas (14-22% of species affected) and in areas of the main river (32-44%) impacted by agriculture. We conclude that pesticide residues may contribute to a biodiversity impact in the Amazon and should be further monitored in urban and peri-urban areas, particularly after heavy rainfall events.

Boron originating from produced water discharged to Brazilian coastal waters: Ecological risk assessment with marine organisms.

Deterministic and probabilistic ecological risk assessments were performed for the boron present in coastal waters in the region of the São Sebastião channel (coast of São Paulo State, Brazil) surrounding the outfall of the São Sebastião waterway terminal (TEBAR) and in reference areas far from the outfall. A set of ecotoxicity tests with 9 marine organisms (Lytechinus variegatus, Arbacia lixula, Skeletonema costatum, Asterionellopsis glacialis, Parablenius pilicornis, Artemia salina, Megabalanus coccopoma, Mysidopsis juniae and Hypnea musciformes) was performed in the laboratory. Ecotoxicity tests confirmed that boron presents low ecotoxicity, with Lytechinus variegatus being the most sensitive species studied, with an EC50 of 14.6 mg L-1 and a no-observed effect concentration (NOEC) of 6.75 mg L-1. According to the deterministic ecological risk assessment, no significant environmental impact is expected if we consider the most sensitive of the organisms tested and the highest concentration of boron found in the coastal waters (5.82 mg L-1).

Antifouling paint particles in soils: toxic impact that goes beyond the aquatic environment.

Antifouling paint particles (APPs) originate from vessel maintenance and cleaning activities and their potentially toxic components are found at high concentrations in nearby soils, yet no studies have investigated their toxicity to soil organisms. We investigated the effects of exposure to soils containing APPs on the mortality, biomass, and reproductive performance of the earthworm Eisenia andrei. Earthworms were exposed to contaminated soil from a boatyard and non-contaminated soils treated with different concentrations of APPs (0.01, 0.14 and 1.50%, w/w) for 56 days. An ecological risk assessment using a Hazard Quotient (HQ) was also carried out. Exposure to contaminated soils reduced worm survival, biomass, and reproductive performance and these effects were concentration-dependent. The HQ was high in soil samples with APPs in both acute and chronic tests, and copper contributed the most to the HQ. Copper, zinc, and lead had the highest concentrations and exceeded the Brazilian legal limits. A principal component analysis (PCA) was performed and showed that biomass and number of juveniles parameters was associated with the metals Cu, Sn and Zn, while the mortality parameter had no association with any analyzed metal. These findings highlighted that the synergistic effects of compounds present in the APPs, such as the booster biocides DCOIT, and metal mixtures should not be overlooked. We conclude that soils contaminated with APPs are toxic to earthworms. This reveals that the ecological impact of APPs goes beyond effects on aquatic environments, compromising key organisms of edaphic ecological processes.

Ecological risk assessment of booster biocides in sediments of the Brazilian coastal areas.

Although booster biocides (Irgarol, diuron, chlorothalonil, dichlofluanid, and DCOIT) have been detected in sediments along the Brazilian coastal areas, the risk associated to their occurrence and levels is still unknown. Thus, the ecological risk of booster biocides to sediment-dwelling organisms from the Brazilian coast was assessed using a risk characterization approach through the Risk Quotient (Measured environmental concentration (MEC)/Predicted no effect concentrations (PNECs)). Sedimentary PNECs for Irgarol, diuron, chlorothalonil and DCOIT were derived based on published ecotoxicological data from both freshwater and marine studies, while a NORMAN methodology was used to derived it for dichlofluanid. Results showed that DCOIT, diuron, Irgarol, chlorothalonil, and dichlofluanid can pose high risk on 47%, 35%, 15%, 1% and 1%, respectively, of the 113 Brazilian sites appraised. Considering the trend of expansion of navigation/maritime activities, DCOIT may worsen its impact over the coastal areas of Brazil, especially ports, but also ship/boatyards, marinas, and maritime traffic zones. The present study is an important contribution to support advance on policy formulation concerning booster biocides worldwide, particularly considering the lack of regulation on the use of antifouling biocides in Brazil.

Assessing the ecological risk of active principles used currently by freshwater fish farms.

The global aquaculture industry has grown exponentially in recent years using to control of infections and diseases, a variety of veterinary drugs (VMP) are used, including antibiotics, antifungals and antiparasitics, which have different routes of emission, environmental persistence and side effects to aquatic organisms, becoming one of the main concerns in its use of veterinary drugs (VMP) and its potential toxicological impact on the environment, in this context, Chile is considered one of the main salmon producers. Ecological risk assessment of active principles used infreshwater fish farms worldwide and in Chile were investigated. We recollect a physical - chemical properties of active principles used by fish farms and we could estimate the relative hazard a priori. Later active principles grouped as antibiotics (n = 6), antiparasitics (n = 5), anesthetics (n = 3), and disinfectants (n = 7) were assessed using a mass balance model based on fugacity was developed for each active principle under treatments via immersion and food administration in fish, while a volumetric model for disinfectants and sodium chloride was used for estimating the predicted environmental concentration (PEC), under a real smolt farming scenario in fish farms. Ecotoxicological data were collected from open literature to predict the no-effect concentration (PNEC). The ecological risk assessment was characterized using a risk quotient (RQ = PEC/PNEC) based in two assessment tiers. Results revealed that 12 active ingredients showed a high risk (RQ ≥ 1), thus indicating that adverse effects could occur and further investigation with measured concentrations in the field are required to reduce exposure in surface waters.

Monensin occurrence in surface water and its impact on aquatic biota in a stream of the southeast Pampas, Argentina.

Monensin is an ionophore antibiotic used as a feed additive and growth promoter in cattle production worldwide. The occurrence of monensin in aquatic surficial ecosystems is of concern due to its possible detrimental effects on human health and native biota. Argentina is one of the most important cattle beef producers worldwide; however, there is little knowledge on the environmental occurrence of monensin and the associated risks to aquatic biota. In this study, we developed a method for the extraction and quantification of monensin in surface water; then, we evaluated the occurrence of monensin in a stream impacted by different animal husbandry's operations, and then, we analyzed the ecological implications of monensin residues on aquatic organisms using the risk quotient (RQ) method. Sampling was carried out on August 2017 from the headwaters to the floodplain of the El Pantanoso stream, Buenos Aires province, Argentina. Monensin detection frequency was 75% (n = 20). The median level was 0.40 µg/L and the maximum concentration was 4.70 µg/L. The main input of monensin was from a cattle slaughterhouse, an activity that has not been considered before in the literature as a source of emission of veterinary pharmaceuticals into the environment. The RQ assessment showed that monensin levels could have potential negative effects on aquatic biota in the sampling site closest to the cattle slaughterhouse. The data obtained in this study shows that monensin was present in El Pantanoso surface waters at levels of high ecotoxicological risk to aquatic biota.

Occurrence of organic micropollutants in an urbanized sub-basin and ecological risk assessment.

The João Mendes River - an important contributor to the Piratininga/Itaipu lagoon system in Rio de Janeiro State, Brazil - receives untreated sewage from the population occupying the drainage basin with no proper sanitation infrastructure. The present study assessed the ecological risk resulting from the presence of five organic micropollutants (17α-ethynylestradiol, ibuprofen, trimethoprim, sulfamethoxazole, bisphenol A) based on four monitoring campaigns which included three sampling points and one reference area. Chronic ecotoxicity assays were conducted with the bioindicators R. subcapitata, C. dubia and O. niloticus. Estrogenicity was assessed with genetically modified S. cerevisiae based on YES protocol. The Ecological Risk Assessment was conducted based on the Chemical and the Ecotoxicological Lines of Evidence (LoE). In order to analyse the results from different sampling points, principal component analysis (PCA) was performed using a correlation matrix. Micropollutants below limit of detection or in very low concentrations were detected in the reference area; no significant differences were observed when samples from the reference area were compared to the negative controls for the ecotoxicity assays. A PCA including selected variables revealed the latent relationships among the three sampling points (not verified for the reference area), which confirmed the analytical results. An extreme ecological risk index was estimated for all sampling points in all campaigns. The extreme ecological risk index was mostly associated to the high concentrations of 17α-ethynylestradiol and the antibiotic sulfamethoxazole.