The use of reclaimed water in agriculture represents a promising alternative to relieve pressure on freshwater supplies, especially in arid or semiarid regions facing water scarcity. However, this implies introducing micropollutants such as pharmaceutical residues into the environment. The fate and the ecotoxicological impact of valsartan, an antihypertensive drug frequently detected in wastewater effluents, were evaluated in soil-earthworm microcosms. Valsartan dissipation in the soil was concomitant with valsartan acid formation. Although both valsartan and valsartan acid accumulated in earthworms, no effect was observed on biomarkers of exposure (acetylcholinesterase, glutathione S-transferase and carboxylesterase activities). The geometric mean index of soil enzyme activity increased in the soils containing earthworms, regardless of the presence of valsartan. Therefore, earthworms increased soil carboxylesterase, dehydrogenase, alkaline phosphatase, β-glucosidase, urease and protease activities. Although bacterial richness significantly decreased following valsartan exposure, this trend was enhanced in the presence of earthworms with a significant impact on both alpha and beta microbial diversity. The operational taxonomic units involved in these changes were related to four (Proteobacteria, Bacteroidetes, Actinobacteria and Firmicutes) of the eight most abundant phyla. Their relative abundances significantly increased in the valsartan-treated soils containing earthworms, suggesting the presence of potential valsartan degraders. The ecotoxicological effect of valsartan on microbes was strongly altered in the earthworm-added soils, hence the importance of considering synergistic effects of different soil organisms in the environmental risk assessment of pharmaceutical active compounds.

Toluene is a highly flammable and commonly used industrial chemical with severe health consequences on humans upon exposure and ingestion. In this study, multispecies bioassays were conducted using a species sensitivity distribution approach to determine acute and chronic hazardous concentrations of toluene in soil. Acute and chronic toluene toxicity tests were conducted with seven soil species from four taxonomic groups. The results from the toxicity tests were used to estimate the acute and chronic HC₅ (hazardous concentration for 5 % of species) of toluene in the terrestrial environment at 58.9 (5.4–639.6) mg kg⁻¹ and 2.2 (0.2–19.8) mg kg⁻¹, respectively. To the best of our knowledge, this is the first study to estimate the hazardous concentration of toluene in soil by conducting a battery of bioassays. These values can be used as references for the environmental risk assessment of chemical accidents involving toluene and estimating its impact on soil to protect the terrestrial environment.

Evaluation of the toxicity of pesticide residues on non-target organisms in the ecosystem is an important part of pesticide environmental risk assessment. Flupyradifurone is a new type of butenolide insecticide produced by Bayer, who claims it to be “low toxic” to non-target organisms in the environment. However, there is little evidence in the literature to show how flupyradifurone affects aquatic organism development. In the current study, zebrafish embryos were treated with 0.1, 0.15, and 0.2 mg/mL of flupyradifurone within 6.0–72 h past fertilization (hpf). We found that the half-lethal concentration (LC₅₀) of flupyradifurone for zebrafish embryos at 96 hpf was 0.21 mg/mL. Flupyradifurone decreases the heart rate, survival rate, and body length of zebrafish embryos. The flupyradifurone treatment also led to the failure of heart looping, and pericardial edema. Moreover, flupyradifurone increased the level of reactive oxygen species (ROS) and decreased the enzymatic catalysis of catalase (CAT) and superoxide dismutase (SOD). Alterations were induced in the transcription of apoptosis-related genes (bcl-2, bax, bax/bcl-2, p53 and caspase-9) and the heart development-related genes (gata4, myh6, nkx2.5, nppa, tbx2b, tbx5 and vmhc). In the current study, new evidences have been provided regarding the toxic effects of flupyradifurone and the risk of its residues in agricultural products and the environment.

In many countries, including Morocco, groundwater contamination with pesticides such as globally banned organochlorides (e.g., dichlorodiphenyltrichloroethane (DDT)) and some accredited organophosphates and pyrethroids poses ecological and human health risks. To assess these risks, we herein monitored pesticides in Saïss plain groundwater (Morocco) during the summer of 2017 and the winter of 2018 using polar organic chemical integrative samplers. The two types of passive samplers were deployed in 22 traditional wells for 14–20 days and subjected to solid-phase extraction. The extracts were analyzed by gas chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry using a multiresidue method, and 27 pesticides were detected in total. In the summer campaign, 22 pesticides with individual concentrations ranging from <limit of quantitation (LOQ) to 243.1 ng L⁻¹ were identified, whereas 17 compounds with concentrations ranging from <LOQ to 53.8 ng L⁻¹ were detected in the winter campaign. In the summer period, the maximum individual concentrations of chlorothalonil, DDT, and α-hexachlorocyclohexane (α-HCH) equaled 111.7, 36.1, and 22.3 ng L⁻¹, respectively, with the respective values for the winter period equaling 18.14, 16.62, and 22.2 ng L⁻¹. Health risk assessment indicated that the carcinogenic α-HCH, β-HCH, DDT, and dichlorodiphenyldichloroethylene present in groundwater may also contaminate drinking water and thus pose a threat to human health, particularly to that of infants and children. Further analysis revealed that the Saïss aquifer presents a high ecological risk. Thus, the monitoring of pesticides in groundwater by passive sampling was effective and could be combined with human health and ecological risk assessment to develop ways of reducing human and environmental exposure to pesticides.

A large number of toxicity studies report abnormalities in early life-stage (ELS) fish that are described here as a sublethal toxicity syndrome (TxSnFELS) and generally include a reduced heart rate, edemas (yolk sac and cardiac), and a variety of morphological abnormalities. The TxSnFELS is very common and not diagnostic for any chemical or class of chemicals. This sublethal toxicity syndrome is mostly observed at high exposure concentrations and appears to be a baseline, non-specific toxicity response; however, it can also occur at low doses by specific action. Toxicity metrics for this syndrome generally occur at concentrations just below those causing mortality and have been reported for a large number of diverse chemicals. Predictions based on tissue concentrations or quantitative-structure activity relationship (QSAR) models support the designation of baseline toxicity for many of the tested chemicals, which is confirmed by observed values. Given the sheer number of disparate chemicals causing the TxSnFELS and correlation with QSAR derived partitioning; the only logical conclusion for these high-dose responses is baseline toxicity by nonspecific action and not a lock and key type receptor response. It is important to recognize that many chemicals can act both as baseline toxicants and specific acting toxicants likely via receptor interaction and it is not possible to predict those threshold doses from baseline toxicity. We should search out these specific low-dose responses for ecological risk assessment and not rely on high-concentration toxicity responses to guide environmental protection. The goal for toxicity assessment should not be to characterize toxic responses at baseline toxicity concentrations, but to evaluate chemicals for their most toxic potential. Additional aspects of this review evaluated the fish ELS teratogenic responses in relation to mammalian oral LD50s and explored potential key events responsible for baseline toxicity.

A monitoring network was established in streams within a catchment near the Costa Rican Pacific coast (2008–2011) to estimate the impact of pesticides in surface water (84 samples) and sediments (84 samples) in areas under the influence of melon and watermelon production. A total of 66 (water) and 47 (sediment) pesticides were analyzed, and an environmental risk assessment (ERA) was performed for four taxa (algae, Daphnia magna, fish and Chironomus riparius). One fungicide and seven insecticides were detected in water and/or sediment; the fungicide azoxystrobin (water) and the insecticide cypermethrin (sediments) were the most frequently detected pesticides. The insecticides endosulfan (5.76 μg/L) and cypermethrin (301 μg/kg) presented the highest concentrations in water and sediment, respectively. The ERA revealed acute risk in half of the sampling points of the melon-influenced area and in every sampling point from the watermelon-influenced area. Safety levels were exceeded within and around the crop fields, suggesting that agrochemical contamination was distributed along the catchment, with potential influence of nearby crops. Acute risk was caused by the insecticides chlorpyrifos, cypermethrin and endosulfan to D. magna, fish and C. riparius; the latter was the organism with the overall highest/continuous risk. High chronic risk was determined in all but one sampling point, and revealed a higher number of pesticides of concern. Cypermethrin was the only pesticide to pose chronic risk for all benchmark organisms. The results provide new information on the risk that tropical crops pose to aquatic ecosystems, and highlight the importance of including the analysis of sediment concentrations and chronic exposure in ERA.

As emerging pollutants, microplastics (MPs) have been found globally in various freshwater and marine matrices. This study recompiled 270 endpoints of 3765 individuals from 43 publications, reporting the onset of enhanced biological performance and reduced oxidative stress biomarkers induced by MPs in aquatic organisms at environmentally relevant concentrations (≤1 mg/L, median = 0.1 mg/L). The stimulatory responses of consumption, growth, reproduction and survival ranged from 131% to 144% of the control, with a combined response of 136%. The overall inhibitory response of 9 oxidative stress biomarkers was 71% of the control, and commonly below 75%. The random-effects meta-regression indicated that the extents of MPs-induced responses were independent of habitat, MP composition, morphology, particle size and exposure duration. The results implied that the exposure to MPs at low and high concentrations might induce opposite/non-monotonic responses in aquatic biota. Correspondingly, the hormetic dose response relationships were found at various endpoints, such as reproduction, genotoxicity, immunotoxicity, neurotoxicity and behavioral alteration. Hormesis offers a novel perspective for understanding the dose response mode of aquatic organisms exposed to low and high concentrations of MPs, highlighting the necessity to incorporate the hormetic dose response model into the ecological/environmental risk assessment of MPs.

As an emerging brominated flame retardant (BFR), tetrabromobisphenol S (TBBPS) has been frequently detected in the environmental media and organisms. Knowledges on the transformation and fate of TBBPS in both environment and engineering systems are essential to its ecological risk assessment. Herein, we reported the photochemical decomposition of TBBPS in aqueous solution upon 254 nm ultraviolet irradiation (UV₂₅₄). Results show that TBBPS was highly photoreactive, most likely due to the presence of four ortho-bromine substituents. The molar absorption coefficient and quantum yield of TBBPS were found to be pH-dependent, with the monoanionic form being most photoreactive. A series of photoproducts were identified by solid phase extraction (SPE) combined with liquid chromatography-electrospray ionization-triple quadrupole mass spectrometry (LC-ESI(+)-MS/MS. The photolysis of TBBPS likely proceeded through photonucleophilic substitution, photoreductive debromination, and β-scission reactions. A ketocarbene, possibly derived from the lower lying excited triplet state, was proposed to be involved in the photolysis of TBBPS. Ion chromatography analysis revealed that debromination occurred quickly, and the yield of bromide (Br⁻) approached 100% after 90 min irradiation. The presence of SRNOM and MRNOM inhibited the photodegradation rate of TBBPS, which is likely due to the light-screening and physical quenching effects of natural organic matter (NOM). Our results reveal that photolysis is an important process for the attenuation of TBBPS in aquatic system; however, naturally occurring species such as NOM can appreciably retard the decay of TBBPS.

Mecoprop-P (MCPP-P) is an auxin herbicide which has been used against dicotyledonous weed plants since the 1980s. While fate and monitoring data of MCPP-P in the aquatic environment revealing concentrations up to 103 μg/L in freshwaters are well documented, only very few toxicity data and no studies with dicotyledonous macrophytes have been published in open literature so far. To fill up this essential data gap, a microcosm study was conducted in order to test the sensitivity of nine dicotyledonous and one Ceratophyllales macrophyte species. The plant species were exposed to seven MCPP-P concentrations ranging from 8 to 512 μg/L for 21/22 days in one microcosm per concentration, and two further microcosms served as controls. Plant preparation was adapted to each species and endpoints were measured to calculate growth rates. Data were generated to obtain effect concentrations (ECX) which then were used to construct species sensitivity distribution curves (SSD). Eight species proved to be sensitive to MCPP-P in the tested concentration range with EC₅₀ values ranging from 46.9 μg/L for Ranunculus aquatilis to 656.4 μg/L MCPP-P for Ludwigia repens. Taking the EC₅₀ values of this study and published data for autotrophic organisms into account, a hazard concentration (HC₅) of 2.7 μg/L was derived from the SSD curve, while an SSD curve without dicotyledonous macrophytes resulted in an about 100 times higher HC₅ (360.8 μg/L MCCP-P). This confirms that a re-evaluation for old auxin herbicides by including dicotyledonous test species into the environmental risk assessment may be indicated. Furthermore, the use of MCPP-P in bitumen felts as protection against rooting by plants is not in the focus of any risk regulation so far. This application, however, can lead to high run-off concentrations that can enter surface waters easily, exceeding the new regulatory acceptable concentration values.

Microplastics (MPs) are widely found in coastal areas and oceans worldwide. The MPs are environmentally concerning due to their bioavailability and potential impacts on a wide range of marine biota, so assessing their impact on the biota has become an urgent research priority. In the present study, we exposed Crassostrea gigas oysters to irregular MPs of two polymer types (polyethylene (PE) and polyethylene terephthalate (PET)) at concentrations of 10 and 1000 μg L⁻¹ for 21 days. Accumulation of MPs, changes in metabolic enzyme activity, and histological damage were evaluated, and metabolomics analysis was conducted. Results demonstrated that PE and PET MPs were detected in the gills and digestive gland following exposure to both tested concentrations, confirming ingestion of MPs by the organisms. Moreover, both PE and PET MPs inhibited lipid metabolism, while energy metabolism enzyme activities were activated in the oysters. Histopathological damage of exposed oysters was also observed in this study. Integrated biomarker response (IBR) results showed that MPs toxicity increased with increasing MPs concentration, and the toxic effects of PET MPs on oysters was greater than PE MPs. In addition, metabolomics analysis suggested that MPs exposure induced alterations in metabolic profiles in oysters, with changes in energy metabolism and inflammatory responses. This study reports new insights into the consequences of MPs exposure in marine bivalves at environmentally relevant concentrations, providing valuable information for ecological risk assessment of MPs in a realistic conditions.