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.

First Report of the Joint Exposure to Glyphosate and Glufosinate of a Male Population in the Province of Córdoba (Argentina).

Despite potential health implications, data on the presence of Glyphosate (GLY) and other non-GLY herbicides in human matrices remain scarce. This study aimed to develop a simple and cost-effective methodology for detecting and quantifying GLY, its primary biodegradation product; aminomethylphosphonic acid (AMPA); and glufosinate (GLU) in plasma and urine of environmentally and occupationally exposed populations from the province of Córdoba (Argentina). Different alternatives of pre-treatment, derivatization with FMOC-Cl, solid phase extraction, and final sample conditioning steps were evaluated to improve the quantification of the herbicides by a high-performance liquid chromatography system coupled to a triple-quadrupole mass spectrometer. Recoveries ranged from 39 to 84% in both matrices, while limits of quantification were 3, 1, and 0.3 ng/mL and 3.6, 5.1, and 0.3 ng/mL for AMPA, GLY, and GLU in plasma and urine, respectively. In plasma samples, GLY was the most frequently detected analyte (32%), followed by GLU (10%). In urine samples, GLU was the most frequently detected herbicide (13%), followed by GLY (6%). No differences between group or matrix correlations were found. This study is the first report of GLU in human biological matrices and should be used to establish baseline values for future surveillance systems.

Genetic Structure of a Native Neotropical Fish Species: New Insights about a South American Bioindicator.

The biodiversity of Neotropical region is affected by anthropogenic disturbance. Throughout Brazil, Argentina and Uruguay, the native fish, Cnesterodon decemmaculatus, is well distributed and widely used as an excellent bioindicator of environmental quality. We investigated the diversity and genetic structure of its populations along a water pollution gradient to answer the following questions: 1- Does the genetic diversity decrease under the stressful conditions of a severe water quality gradient? and 2- Is there any relationship between the haplotypes registered along the studied basin and those recorded in other distant basins? Two mitochondrial DNA markers, Cytochrome b and D-loop, were analyzed and four haplotypes were registered for both markers along the basin. H1 was present throughout all the river sections in high frequencies leading to a low genetic diversity. We suggest that only a few haplotypes tolerate the stressful conditions of mountain rivers. On the other hand, the presence of H4 at the site located downstream suggests a history of recent colonization from the southeast to the northwest of the biome. These results, together with the abundance decrease along the pollution gradient, and the non-migratory characteristic of C. decemmaculatus suggest that its populations may be at risk of local extinction.

Validation of exposure indexes to pesticides through the analysis of exposure and effect biomarkers in ground pesticide applicators from Argentina.

The characterization of the population exposed to pesticides and the use of effective biomarkers to evaluate potential health effects are determinant to identify vulnerable groups, understanding the causality of diverse pathologies and propose prevention policies. This is particularly important in countries where intensive agricultural practices had an explosive expansion in last decades. The aim of this study was assessing the usefulness of two exposure indexes questionnaire-based: Intensity Level of the pesticide Exposure (ILE) and Cumulative Exposure Index (CEI) and their scales, in terrestrial applicators of pesticide from the Province of Córdoba (Argentina). The analysis was performed contrasting ILE and CEI results with perceived symptomatology, in addition to effect and exposure biomarkers. A cross-sectional study was designed to compare pesticides body burdens and effect biomarkers between subjects occupationally (OE) and non-occupationally exposed (NOE) to pesticides. Prevalence of perceived symptomatology and genotoxicity damage was higher in the OE group. The exposure condition was the only variable explaining these differences. Significant associations were found between CEI and neurologic symptomatology (p < 0.05) and between ILE and plasmatic cholinesterase (p < 0.1). However, residues of HCB, ß-HCH, α-endosulfan, pp'DDE, endrin, ß-endosulfan, pp'DDT, endosulfan sulfate and mirex were found in blood samples from both groups. To our knowledge, this is the first report on pesticides body burdens in occupational exposure settings in Argentina. So far, our current results indicate that the occupational condition affects the health of the workers. Significant associations found between symptomatology and biomarkers with scales of CEI and ILE suggest their usefulness to verify different levels of exposure. Further research is necessary to propose these indexes as an affordable tool for occupational health surveillance in areas with difficult access to health care centres.

Pilot study of exposure of the male population to organophosphate and pyrethroid pesticides in a region of high agricultural activity (Córdoba, Argentina).

Urinary metabolites of organophosphate (OP) and pyrethroid (PYR) pesticides and biomarkers of effects were studied in a population (n=40) residing in an important agricultural area of the province of Córdoba (Argentina). Detection frequencies (DF) higher than 85% were observed for the metabolites of pirimiphos (2-diethylamino-6-methylpyrimidin-4-ol -DEAMPY-, median 7.5 µg/g creatinine, DF: 100%), parathion (p-nitrophenol, 0.99 µg/g creatinine, 100%), and chlorpyrifos (3,5,6-trichloro-2-pyridinol, 0.25 µg/g creatinine, 85%). The DEAMPY concentrations doubled the levels found in other studies and were negatively associated with Er-AChE activity, suggesting the appearance of health effects already in environmental exposure levels below established acceptable daily intakes (ADIs). 3-Phenoxybenzoic acid, the metabolite of several PYR pesticides, was also found in all samples. This metabolite was also significantly negatively correlated with Er-AChE, indicating effects of pyrethroid pesticides on the acetylcholine system even at concentrations below the ADI.

Peanut Seed Cultivars with Contrasting Resistance to Aspergillus parasiticus Colonization Display Differential Temporal Response of Protease Inhibitors.

Significant efforts are being made to minimize aflatoxin contamination in peanut seeds and one possible strategy is to understand and exploit the mechanisms of plant defense against fungal infection. In this study we have identified and characterized, at biochemical and molecular levels, plant protease inhibitors (PPIs) produced in peanut seeds of the resistant PI 337394 and the susceptible Forman cultivar during Aspergillus parasiticus colonization. With chromatographic methods and 2D-electrophoresis-mass spectrometry we have isolated and identified four variants of Bowman-Birk trypsin inhibitor (BBTI) and a novel Kunitz-type protease inhibitor (KPI) produced in response to A. parasiticus colonization. KPI was detected only in the resistant cultivar, while BBTI was produced in the resistant cultivar in a higher concentration than susceptible cultivar and with different isoforms. The kinetic expression of KPI and BBTI genes along with trypsin inhibitory activity was analyzed in both cultivars during infection. In the susceptible cultivar an early PPI activity response was associated with BBTI occurrence. Meanwhile, in the resistant cultivar a later response with a larger increase in PPI activity was associated with BBTI and KPI occurrence. The biological significance of PPI in seed defense against fungal infection was analyzed and linked to inhibitory properties on enzymes released by the fungus during infection, and to the antifungal effect of KPI.

Impairments in aromatase expression, reproductive behavior, and sperm quality of male fish exposed to 17ß-estradiol.

Growing evidence shows that environmental estrogen can reach levels that are high enough to exert adverse reproductive effects on wild fish populations. The authors report different parameters of male reproductive behavior, brain, and gonadal aromatase expression, as well as sperm quality in an internally fertilizing fish species (Jenynsia multidentata, Jenyns) exposed to environmentally relevant concentrations of 17ß-estradiol (E(2) ). Adult males were exposed to 0, 50, 100, and 250 ng/L E(2) over 28 d. The authors' findings demonstrate that E(2) exposure resulted in a very clear increase in brain aromatase transcript abundance at all assayed concentrations compared with control; however, no effects on gonadal aromatase expression were observed. Behavioral measures revealed increased sexual activity at 50 ng/L but not 100 or 250 ng/L E(2) . In contrast to the molecular and behavioral responses, the condition factor, gonadosomatic index, and sperm quality were unaltered by E(2) exposure. The results from the present work suggest that E(2) affects some aspects of the reproductive biology of J. multidentata. These modifications in the reproductive biology caused by exposure to E(2) could potentially lead to long-term effects at population levels that may not always be immediately evident. To the best of the authors' knowledge, this is the first report on the combined effect of E(2) on aromatase expression, sexual behavior, and sperm parameters in fish.

Biotransformation and antioxidant enzymes of Limnoperna fortunei detect site impact in watercourses of Córdoba, Argentina.

The golden mussel Limnoperna fortunei was used as a biomonitor of environmental pollution in the Suquía River basin around Córdoba City (Argentina). The sampling sites along the river were chosen according to their increasing levels of pollutants (e.g. heavy metals) as well as biological oxygen demand (BOD) and chemical oxygen demand (COD). A water quality index (WQI) was constructed from the interaction of several normalized factors that affect the aquatic environment, such as the mentioned pollutants and physico-chemical characteristics of the sampling sites. Activity changes of biotransformation enzyme glutathione S-transferase (GST) and the antioxidant enzymes glutathione peroxidase (GPx), glutathione reductase (GR) and catalase (CAT), after exposure to pollutants, served as biomarkers. Membrane bound GST and antioxidant enzymes responded at the most polluted sampling site within 1 day showing increased activities lasting for 4 days. Further sampling was restricted due to no survival of the animals. Antioxidant enzymes GPx, GR and CAT were sensitive responding to the different pollution scenarios, showing good correlation to the chemical characterization.