Pesticides and PPCPs in aquatic ecosystems of the andean central region: Occurrence and ecological risk assessment in the Uco valley.

Uco valley (Mendoza, Argentina) suffers the concomitant effect of climate change, anthropic pressure and water scarcity. Moreover chemical pollution to aquatic ecosystems could be another pressuring factor, but it was not studied enough to the present. In this sense, the aim of this study was to assess the occurrence of pesticides, pharmaceuticals and personal care products (PPCPs) in aquatic ecosystems of the Uco Valley and to perform an ecological risk assessment (ERA). The presence of several insecticides (mainly neonicotinoids), herbicides (atrazine, diuron, metolachlor, terbutryn) and fungicides (strobilurins, triazolic and benzimidazolic compounds) in water samples in two seasons, related to crops like vineyards, garlic or fruit trees was associated to medium and high-risk probabilities for aquatic biota. Moreover, PPCPs of the group of non-steroidal anti-inflammatory drugs, parabens and bisphenol A were detected in all the samples and their calculated risk quotients also indicated a high risk. This is the first record of pesticides and PPCPs with an ERA in this growing agricultural oasis. Despite the importance of these findings in Uco Valley for decision makers in the region, this multilevel approach could bring a wide variety of tools for similar regions in with similar productive and environmental conditions, in order to afford actions to reach Sustainable Development Goals. SYNOPSIS: Aquatic ecosystems in arid mountain regions are threatened worldwide. This study reports relevant data about chemical pollution in Central Andes, which could be a useful tool to enhance SDGs' accomplishment.

Evaluation of hematological parameters, oxidative stress and DNA damage in the cichlid Australoheros facetus exposed to the fungicide azoxystrobin.

Azoxystrobin (AZX) is a broad-spectrum systemic fungicide massively used worldwide. Its mode of action consists in the inhibition of mitochondrial respiration decreasing the synthesis of ATP and leading to oxidative stress in the target fungus. However, whether this effect occurs in non target organisms has been scarcely studied. The objectives of this work were (1) to evaluate biomarkers of oxidative stress, hematological, physiological and of genotoxicity in the native cichlid fish Australoheros facetus exposed to environmentally relevant concentrations of AZX and (2) to compare these biomarkers in different developmental stages using juvenile and adult fish (n = 6) exposed during 48 h. The exposure concentrations were 0 (negative control, C (-)), 0.05, 0.5, 5 and 50 µg/L AZX of the commercial formulation AMISTAR®. Blood was drawn to evaluate hematology, and DNA damage through the comet assay (CA) and micronucleus test (MN). Genotoxicity was observed by mean of both biomarkers in juvenile and adult fish at 50 µg/L AZX. Samples of liver and gills were used to determine antioxidant enzymes activity, hydrogen peroxide (H2O2) and malondialdehyde (MDA) contents. In juvenile fish inhibition of superoxide dismutase (SOD) was observed in liver at 0.05, 5 and 50 µg/L AZX and in gills at 5 and 50 µg/L AZX. Glutathione- S- transferases (GST) activity increased in gills at all AZX concentrations tested. In adult fish, increase of hepatic catalase (CAT) activity at 0.5 and 50 µg/L AZX and MDA content at 50 µg/L AZX were observed. In gills only H2O2 content showed changes at 50 µg/L AZX. The sensitivity showed by gills constitutes the first report about AZX toxicity in this organ. All these negative effects were observed in the range of realistic AZX concentrations, which warns of the possible consequences that it may have on the health of aquatic biota. Differences between juvenile and adult fish demonstrate the relevance of considering the developmental stage on the evaluation of biomarkers.

Ecological risk assessment of current-use pesticides and biocides in soils, sediments and surface water of a mixed land-use basin of the Pampas region, Argentina.

The present study aimed to assess the ecological risk of 30 current-use agricultural pesticides and biocides in the soil, sediments and aquatic organisms of a mixed land-use basin located in the Depressed Pampas Region of Argentina. Risk Quotients (RQs) were used to evaluate the chronic risk in soil and aquatic organisms, while Toxic Units (TUs) were used to assess the acute risk in sediment-dwelling organisms and aquatic biota. Acetochlor, hydroxy-atrazine, glyphosate, AMPA, metolachlor, imidacloprid and tebuconazole were the only pesticide residues detected (>30%) and quantified in all the matrices evaluated. Glyphosate and AMPA showed the highest concentrations, being their mean and maximum levels 27.90-176.00 µg kg-1 and 270-712.50 µg kg-1 in soils, 8.28-32.0 µg kg-1 and 6.85-17.50 µg kg-1 in sediments, and 1.88-4.36 µg L-1 and 0.66-1.03 µg L-1 in surface water. The RQs in soils showed high chronic risk, mainly due to AMPA and imidacloprid. The TUs in sediments showed acute risk in dwelling organisms, mainly due to glyphosate and imidacloprid. RQs assessment showed a range of chronic risk levels according to the site/sampling event, with higher contribution of atrazine and its metabolites, and acetochlor, whereas TUs assessment showed no acute risk in aquatic biota. In contrast to Europe, in Argentina, there are no restrictions regarding the use of atrazine, acetochlor, imidacloprid and glyphosate to protect aquatic life. Thus, it is recommended that the current Argentine pesticide regulations should be modified to prevent ecological risk and protect ecosystems.

Imidacloprid modifies the mitotic kinetics and causes both aneugenic and clastogenic effects in the macrophyte Bidens laevis L.

Imidacloprid (IMI) is a neonicotinoid insecticide widely used in agricultural activities all around the world. This compound is transported from croplands to surrounding freshwater ecosystems, producing adverse effects on non-target organisms. Because of the relevance of aquatic macrophytes in the above-mentioned environments and the lack of studies of potential effects of IMI on them, this work aimed to assess the mitotic process and potential genotoxicity in the aquatic macrophyte Bidens laevis L. Although the analysis of the Mitotic Index (MI) showed that IMI was not cytotoxic, the Cell Proliferation Kinetics (CPK) frequencies evidenced modifications in the kinetics of the mitotic process. Indeed, the anaphases ratio decreased at 10 and 100 µg/L IMI, while at 1000 µg/L an increase of prophases ratio and a decrease of metaphases ratio were observed. Regarding genotoxicity, IMI produced an increase of the abnormal metaphases frequency from 10 µg/L to 1000 µg/L as well as an increase in clastogenic anaphases-telophases frequency at 100 and 1000 µg/L. In addition, aneugenic anaphases-telophases and C-mitosis frequencies also increased at 1000 µg/L, confirming the effects on the mitotic spindle. Considering the genotoxic effects on B. laevis through two different mechanisms (aneugenic and clastogenic) and the wide spread use of IMI in agriculture, these mechanisms of toxicity on macrophytes should be considered among other recognized effects of this insecticide on aquatic biota.

Imidacloprid Causes DNA Damage in Fish: Clastogenesis as a Mechanism of Genotoxicity.

Neonicotinoids are one of the most widely used insecticides in the world. DNA damage is considered an early biological effect which could lead to reproductive and carcinogenic effects. The present study aimed to evaluate DNA damage and bases oxidation as a mechanism of genotoxicity, on the freshwater fish Australoheros facetus acutely exposed to imidacloprid (IMI). The Comet assay with the nuclease ENDO III enzyme was performed for detecting pyrimidine bases oxidation using blood samples. Micronucleus and other nuclear abnormalities frequencies were also quantified. A significant increase of damage index at 100 and 1000 µg/L IMI was detected; while ENDO III score increased from 1 to 1000 µg/L IMI; varying both in a linear concentration-response manner. MN frequency increased in fish exposed to 1000 µg/L IMI. These results show that short-term exposures to environmentally relevant concentrations of IMI could affect the genetic integrity of fishes through oxidative damage.

Myofibrilar functional dysregulation in fish: A new biomarker of damage to pesticides.

Endosulfan (ES) modifies the ultrastructure of skeletal muscle fibers and causes changes to the swimming behavior of fish. The objectives of the present work were to evaluate, in fishes of Australoheros facetus, 1) the integrity of myofibrils (Mf) by the analysis of SDS-PAGE profiles, and 2) the functionality of Mf through the microscopically monitoring of the contraction and changes in Mg2+ Ca2+- ATPase and Mg2+(EGTA) -ATPase activities. As expected, after the addition of the contraction buffer, control fish Mf contracted. On the contrary, Mf from fish exposed at 0.5 µg/L ES showed a partial contraction and none of the fish exposed at 10 µg/L ES contracted. As judged by its high Mg2+ Ca2+ ATPase activity and low Mg2+ (EGTA) ATPase activity, control Mf showed good functionality. In Mf from fish exposed to 0.5 and 10 µg/L ES the activities of these enzymes were similar, suggesting denaturation or degradation of some component of tropomyosin-troponin complex. SDS-PAGE patterns of Mf from fish exposed to ES showed degradation of the myosin heavy chain and of tropomyosin. Similar values of lipid peroxidation (TBARS) were found in both control and exposed Mf, suggesting that lipid oxidation was not be related to the above-mentioned changes. The observed effects expand the knowledge of ES action in muscles and could be used as biomarkers of damage in fishes exposed to organochlorine compounds like the insecticide endosulfan.

Uptake, distribution in different tissues, and genotoxicity of imidacloprid in the freshwater fish Australoheros facetus.

The neonicotinoid imidacloprid is under re-evaluation by regulatory agencies because of the poor current information available regarding its potential effects. One of the goals of the present study was to determine imidacloprid uptake and distribution in the freshwater fish Australoheros facetus experimentally exposed for 24 h and 48 h to 100 µg/L, 300 µg/L, and 2500 µg/L. The toxicity of imidacloprid to fish reported in the literature is in the milligrams per liter or gram per liter range, but sublethal effects at micrograms per liter in some groups other than fish have been described. Another goal of the present study was to evaluate imidacloprid's potential genotoxicity and to compare it between the individual compound and a commercial formulation. Concentrations of imidacloprid were measured in water, brain, muscle, gills, gut, liver, and blood by liquid chromatography-tandem mass spectrometry. Imidacloprid was detected in all the tissues tested. Concentrations were higher after 48 h than after 24 h in liver, gills, gut, and muscle, whereas in brain and blood they were similar at both exposure times. Although there was no accumulation, only uptake, of imidacloprid, genotoxicity was observed. In fish exposed to IMIDA NOVA 35® , increased micronucleus frequency at 100 µg/L and 1000 µg/L was detected, whereas in the imidacloprid active ingredient bioassay it increased only at 1000 µg/L imidacloprid. The present findings warn of the possible consequences that fish living in freshwater ecosystems can suffer. Environ Toxicol Chem 2017;36:699-708. © 2016 SETAC.

Survival, Reproduction, Avoidance Behavior and Oxidative Stress Biomarkers in the Earthworm Octolasion cyaneum Exposed to Glyphosate.

The massive use of glyphosate (GLY) in several countries has increased the interest in investigating its potential adverse effects in non-target organisms. The aim of the present study was to assess the potential effects in survival and reproduction; avoidance behavior and oxidative stress under short-term (48 h) and subchronic exposures (28 days) to GLY in the earthworm Octolasion cyaneum. After 48 h no significant changes in the behavior was observed. In addition, a lower catalase activity at 498 µg GLY kg(-1) dry soil section relative to earthworms from the control section was obtained. After 28 days of exposure inhibition of glutathione S-transferase activity was observed at 535 µg GLY kg(-1) dry soil while no changes in the other endpoints were detected. These results indicate that environmentally relevant concentrations of GLY (up to 996 µg GLY kg(-1) dry soil) did not exert a toxic effect to O. cyaneum.