International audience | The study was prompted to characterize the B-type esterase activities in the terrestrial snail <em>Xeropicta derbentina</em> and to evaluate its sensitivity to organophosphorus and carbamate pesticides. Specific cholinesterase and carboxylesterase activities were mainly obtained with acetylthiocholine (Km =77.2 mM; Vmax= 38.2 mU/mg protein) and 1-naphthyl acetate (Km= 222 mM, Vmax= 1095 mU/mg protein) substrates, respectively. Acetylcholinesterase activity was concentration-dependently inhibited by chlorpyrifos-oxon, dichlorvos, carbaryl and carbofuran (IC50 =1.35 x 105–3.80 x 108 M). The organophosphate-inhibited acetylcholinesterase activity was reactivated in the presence of pyridine-2- aldoxime methochloride. Carboxylesterase activity was inhibited by organophosphorus insecticides (IC50 =1.20 x 105–2.98 x 108 M) but not by carbamates. B-esterase-specific differences in the inhibition by organophosphates and carbamates are discussed with respect to the buffering capacity of the carboxylesterase to reduce pesticide toxicity. These results suggest that B-type esterases in<em> X. derbentina</em> are suitable biomarkers of pesticide exposure and that this snail could be used as sentinel species in field monitoring of Mediterranean climate regions

Pesticides used in agriculture are some of the most common pollutants in the world. This study aimed to investigate the effects of Organophosphorus Pesticides (OPPs) and Organochlorine Pesticides (OCPs) on the families of farmworkers in the southeast of Iran.In the present case-control study, 141 family members of farmworkers (as the case group) and 59 family members of non-farmworkers (as the controls) were recruited. Serum levels of OCPs such as α-HCH, β-HCH, γ-HCH, 2,4-DDE, 4,4-DDE, 2,4-DDT, and 4,4-DDT were determined. In addition, erythrocyte acetylcholinesterase (AChE) activity, malondialdehyde (MDA), total antioxidant capacity (TAC), protein carbonyl (PC), nitric oxide (NO) serum levels, arylesterase activity of paraoxonase 1 (PON-1), superoxide dismutase (SOD), catalase (CAT), and glutathione peroxidase (GPx) activity were determined in all participants. Furthermore, distance to farmlands, education, crops, type, and the number of consumed fruits were evaluated for each individual separately.The erythrocyte AChE activity and serum activities of GPx, SOD, and PON-1 and TAC levels were significantly decreased, whereas the concentration of MDA, PC, NO, and seven OCPs were significantly increased in the farmworkers’ families as compared to the controls. Spearman correlation and linear regression suggest that OCPs increase the oxidative stress in farmworkers’ family members. Moreover, distance, education, farming precedence, products, and ventilation had significant effects on the OCP levels and increased the odds ratio of OCP levels in farmworkers’ families.With regards to the data obtained in this study, it was revealed that OCPs as illegal pesticides and OPPs were higher than expected in the farmworkers’ family members. Furthermore, exposure to OCPs and OPPs, apart from the other effects on the body, leads to oxidative stress (OS) that may cause serious diseases in the exposed populations.

However the physiological stress in aquatic organisms associated with hydropower plants (HPP) ecosystems has been previously investigated, no studies have so far assessed it on biochemical level. Therefore this study evaluated an oxidative stress and toxicity in the gibel carp Carassius auratus gibelio associated with a small-scale HPP in the West Ukraine. A battery of liver, brain and blood markers was evaluated individuals inhabiting upstream and downstream of the dam of the small-scale Kasperivtci HPP (KHPP; an installed capacity of 7.5 MW), and from a reference site. Number of alterations were noted in fish from the KHPP impoundment facility including signs of oxidative stress (a decrease in superoxide dismutase (SOD) activity and an increase in protein carbonyls) and cytotoxicity (an increase in micronucleated erythrocytes and caspase-3 activity). No changes in DNA fragmentation in hepatocytes or brain cholinesterase activity were detected. As demonstrated by the integral stress index, fish associated with downstream of the dam revealed the greatest alterations reflected by the combined oppression of antioxidant system (SOD, catalase) and pro-oxidants (thiobarbituric acid reactive substances and oxyradicals), low concentration of metallothioneins, but high cathepsin D activity (as markers of lysosomal dysfunction and autophagy) and increased vitellogenin concentration in males (indicating an endocrine disruption). The study highlights that fish inhabiting ecosystems associated with HPP, particularly downstream of the dam, may face additional stresses with long-term effects yet to be evaluated.

Organophosphate flame retardants (OPFRs) have been detected at high concentrations in various environmental and biotic samples, but little is known about their toxicity. In this study, the potential neurotoxicity of three OPFRs (TCEP, TDCPP, and TPP) and Chlorpyrifos (CPF, an organophosphate pesticide) were compared in Chinese rare minnow using an acute toxicity test and a 21-day fish assay. The acute test demonstrated significant inhibition of acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) by CPF. Although significant AChE inhibition at high concentration of TPP was also observed, none of the OPFRs had effects similar to CPF on these enzymes, indicating that their acute toxicities to Chinese rare minnow may be unrelated to cholinesterase inhibition. In addition, the 21-day fish assay with TDCPP demonstrated no significant effects on cholinesterase activities or neurotransmitter levels. Nonetheless, this OPFR exhibited widespread effects on the neurotrophic factors and their receptors (e.g., ntf3, ntrk1, ntrk2, ngfr, and fgf2, fgf11, fgf22, fgfr4), indicating that TDCPP or other OPFRs may elicit neurological effects by targeting neurotrophic factors and their receptors in Chinese rare minnow.

Enzymatic conductometric biosensor, using immobilized Arthrospira platensis cells on gold interdigitated electrodes, for the detection of pesticides in water, was elaborated. Cholinesterase activity (AChE) was inhibited by pesticides and a variation of the local conductivity was measured after addition of the substrate acetylthiocholine chloride (AChCl). The Michaelis–Menten constant (Km) was evaluated to be 1.8 mM through a calibration curve of AChCl. Inhibition of AChE was observed with paraoxon-methyl, parathion-methyl, triazine and diuron with a detection limit of 10−18 M, 10−20 M, 10−20 M and 10−12 M, respectively and the half maximal inhibitory concentration (IC50) was determined at 10−16 M, 10−20 M, 10−18 M and 10−06 M, respectively. An important decrease of response time τ90% was recorded for AChE response towards AChCl after 30 min cell exposure to pesticides. Scanning electron microscopy images revealed a degradation of the cell surface in presence of pesticides at 10−06 M.

Next to imposing direct lethal effects, pollutants may also indirectly impose mortality by making prey organisms more vulnerable to predation. We report that four water boatmen species differed strongly in direct endosulfan-imposed mortality, and only the species that suffered highest mortality, Sigara iactans, also showed a reduction in escape swimming speed. While head AChE activity was inhibited in all four species, body ChE was only inhibited in S. iactans where it covaried with escape swimming speed, indicating a mechanistic link between body ChE and swimming speed. Our study underscores the need for risk assessment to consider sublethal pollutant effects, which may considerably affect survival rates under natural conditions, also when testing concentrations of a pesticide that cause direct mortality. Such sublethal effects may generate discrepancies between laboratory and field studies and should be considered when designing safety factors for toxicants where the risk assessment is solely based on LC50 values.

Assessment of wildlife exposure to organophosphorus (OP) pesticides generally involves the measurement of cholinesterase (ChE) inhibition, and complementary biomarkers (or related endpoints) are rarely included. Herein, we investigated the time course inhibition and recovery of ChE and carboxylesterase (CE) activities in the earthworm Lumbricus terrestris exposed to chlorpyrifos, and the ability of oximes to reactivate the phosphorylated ChE activity. Results indicated that these esterase activities are a suitable multibiomarker scheme for monitoring OP exposure due to their high sensitivity to OP inhibition and slow recovery to full activity levels following pesticide exposure. Moreover, oximes reactivated the inhibited ChE activity of the earthworms exposed to 12 and 48 mg kg-1 chlorpyrifos during the first week following pesticide exposure. This methodology is useful for providing evidence for OP-mediated ChE inhibition in individuals with a short history of OP exposure (≤1 week); resulting a valuable approach for assessing multiple OP exposure episodes in the field.

The study was prompted to characterize the B-type esterase activities in the terrestrial snail Xeropicta derbentina and to evaluate its sensitivity to organophosphorus and carbamate pesticides. Specific cholinesterase and carboxylesterase activities were mainly obtained with acetylthiocholine (Km = 77.2 mM; Vmax = 38.2 mU/mg protein) and 1-naphthyl acetate (Km = 222 mM, Vmax = 1095 mU/mg protein) substrates, respectively. Acetylcholinesterase activity was concentration-dependently inhibited by chlorpyrifos-oxon, dichlorvos, carbaryl and carbofuran (IC50 = 1.35 x 10-5-3.80 x 10-8 M). The organophosphate-inhibited acetylcholinesterase activity was reactivated in the presence of pyridine-2-aldoxime methochloride. Carboxylesterase activity was inhibited by organophosphorus insecticides (IC50 = 1.20 x 10-5-2.98 x 10-8 M) but not by carbamates. B-esterase-specific differences in the inhibition by organophosphates and carbamates are discussed with respect to the buffering capacity of the carboxylesterase to reduce pesticide toxicity. These results suggest that B-type esterases in X. derbentina are suitable biomarkers of pesticide exposure and that this snail could be used as sentinel species in field monitoring of Mediterranean climate regions. Characterization of the B-type esterases in the terrestrial snail Xeropicta derbentina in order to evaluate pesticide exposure.

Once in the aquatic ecosystems, nanoplastics (NPls) can interact with other contaminants acting as vectors of transport and altering their toxicological effects towards organisms. Thus, the present study aims to investigate how polystyrene NPls (44 nm) interact with the herbicide phenmedipham (PHE) and affect its toxicity to zebrafish embryos. Single exposures to 0, 0.015, 0.15, 1.5, 15 and 150 mg/L NPls and 0.02, 0.2, 2 and 20 mg/L PHE were performed. Embryos were also exposed to the binominal combinations: 0.015 mg/L NPls + 2 mg/L PHE, 0.015 mg/L NPls + 20 mg/L PHE, 1.5 mg/L NPls + 2 mg/L PHE and 1.5 mg/L NPls + 20 mg/L PHE. Due to the low solubility of PHE in water, a solvent control was performed (0.01% acetone). PHE was quantified. Mortality, heartbeat and hatching rate, malformations appearance, locomotor behavior and biomarkers related to oxidative stress, neurotransmission and energy budgets were analyzed. During 96 h, NPls and PHE single and combined exposures did not affect embryos development. After 120 h, NPls induced hyperactivity and PHE induced hypoactivity. After 96 h, NPls increased catalase activity and PHE increased glutathione S-transferases activity. On the combination 0.015 mg/L NPls + 20 mg/L PHE, hyperactivity behavior was found, similar to 0.015 mg/L NPls, and cholinesterase activity was inhibited. Additionally, the combination 1.5 mg/L NPls + 20 mg/L PHE increased both catalase and glutathione S-transferases activities. The combination NPls with PHE affected more biochemical endpoints than the single exposures, showing the higher effect of the binominal combinations. Dissimilar interactions effects – no interaction, synergism and antagonism – between NPls and PHE were found. The current study shows that the effects of NPls on bioavailability and toxicity of other contaminants (e.g. PHE) cannot be ignored during the assessment of NPls environmental behavior and risks.

A total of 164 blood samples from 16 clinically healthy bottlenose dolphins (Tursiops truncatus), were obtained from an aquarium in Spain between 2019 and 2020, as part of their preventive medicine protocol. In addition to conventional haematological and biochemical analyses, plasmatic B-esterase activities were characterised to determine the potential application of such analyses in wild counterparts. The hydrolysis rates for the substrates of acetylcholinesterase (AChE), butyrylcholinesterase (BuChE) and carboxylesterase (CE) activity in plasma were measured, the last using two commercial substrates, p-nitrophenyl acetate (pNPA) and p-nitrophenyl butyrate (pNPB). Activity rates (mean ± SEM in nmol/min/mL plasma) were (in descending order): AChE (125.6 ± 3.8), pNPB-CE (65.0 ± 2.2), pNPA-CE (49.7 ± 1.1) and BuChE (12.8 ± 1.3). These values for dolphins are reported in here for the first time in this species. Additionally, the in vitro sensitivity of two B-esterases (AChE and pNPB-CE) to chemicals of environmental concern was determined, and the protective role of plasmatic albumin assessed. Out of the B-esterases measured in plasma of dolphin, AChE activity was more responsive in vitro to pesticides, while CEs had a low response to plastic additives, likely due to the protective presence of albumin. However, the clear in vitro interaction of these environmental chemicals with purified AChE from electric eels and recombinant human hCEs (hCE1 and hCE2) and albumin, predicts their impact in other tissues that require in vivo validation. A relationship between esterase-like activities and health parameters in terrestrial mammals has already been established. Thus, B-esterase measures could be easily included in marine mammal health assessment protocols for dolphins as well, once the relationship between these measures and the animal's fitness has been established.