Suspect screening of pharmaceuticals, illicit drugs, pesticides, and other emerging contaminants in Argentinean Piaractus mesopotamicus, a fish species used for local consumption and export.

The widespread distribution of contaminants of emerging concern (CECs) is a major concern due to their potential effects on human health and the environment. The insufficient sewage treatment plant infrastructures is a global problem most accentuated in less developed countries and results in the discharge of CECs to water bodies. Pacu (Piaractus mesopotamicus) is a ray-finned freshwater fish species native to the Paraná basin. It is also the most produced aquaculture fish species in Argentina since 2012. Though uninvestigated to date, the occurrence of CECs in pacu may be of high relevance due to production volumes and relevance to human exposure through fish consumption. In this study, we applied a high-resolution mass spectrometry screening method to qualitatively analyze over 100 CECs in pacu. Four extraction/cleanup methods were tested on pooled pacu fillet, including solid-phase extraction and QuEChERS. The method that produced the highest number of detections was selected for further analysis of pacu purchased in supermarkets and fish markets in Argentina between 2017 and 2020. Residues of pesticides, antibiotics, pharmaceuticals, personal care products, plasticizers, sweeteners, drug metabolites, stimulants, and illegal drugs were detected in the samples. A total of 38 CECs were detected, ranging between 24 and 35 CECs per individual sample. 100% of the samples had positive detections of caffeine, 1,7-dimethylxanthine, xanthine, benzoylecgonine, methylparaben, ethylparaben, bis(2-ethylhexyl) phthalate (DEHP), metolachlor, carbendazim, salicylic acid, 2,4-D, saccharin, cyclamate, and dodecanedioic acid. Mappings generated with correspondence analysis were used to explore similarities/dissimilarities among the detected compounds. To our knowledge this is the first report of saccharin, cyclamate, 2,4 - D, carbendazim, metolachlor, ethylparaben, propylparben, bisphenol A, DEHP, and benzotriazole in fish from Argentina, and the first report on the presence of lisinopril, metropolol acid and dodecanedioic acid in fish worldwide.

Pesticides in Surface Waters in Argentina Monitored Using Polar Organic Chemical Integrative Samplers.

Polar Organic Chemical Integrative Samplers (POCIS) were deployed in two watersheds in Córdoba province and one watershed in Buenos Aires province in Argentina. The fungicides, tebuconazole, carbendazim and azoxystrobin, and the herbicides, atrazine, dicamba and 2,4-D were detected in POCIS deployed in each of the three watersheds. Estimated time weighted average concentrations of atrazine were greater than 2 µg/L at the outflow of Brava Lake in Buenos Aires province, and this concentration exceeds the Canadian water quality guideline for protection of aquatic life. The concentrations of all other pesticides were less than 400 ng/L. The distribution of pesticides detected in surface waters indicated that the sources were runoff from agricultural and urban lands and discharges from wastewater treatment plants.

Ecological Risk Assessment (ERA) of pesticides from freshwater ecosystems in the Pampas region of Argentina: Legacy and current use chemicals contribution.

Agricultural production in the Pampas region is one of the most important economic activities in Argentina. However, the possible environmental effects related to the growth of this activity in the last years have not been studied enough. Particularly, the effects of pesticides mixtures are a topic of great concern both for society and regulatory authorities worldwide, given the possible additive and synergistic relationships between these chemicals and their possible effects on aquatic biota. Based on a concentration addition model, this study developed an Ecological Risk Assessment (ERA) of pesticides from freshwater ecosystems in the Pampas region. For this purpose, reported pesticides concentrations available in public bibliography and a Risk Quotients (RQs) approach were used. A cumulative risk map was established to display RQs for current use pesticides (CUPs) and legacy chemicals. The ΣRQs were calculated for 66 sites, using available reported measured environmental concentrations (MECs) and predicted no effect concentrations (PNECs) of pesticides. While ΣRQ for only CUPs resulted in a high and very high risk (ΣRQ > 1) for 29% of the sites, when legacy pesticides were incorporated this percentage reached the 41% of the sites, increasing significantly the absolute values of RQ. Herbicides like glyphosate and atrazine contributed considerably to the ΣRQCUPs while organochlorines were the major contributors for ΣRQs when legacy pesticides were incorporated. Moreover, some active ingredients (acetochlor, carbendazim and fenitrothion) which are approved for their use in Argentina but banned in EU showed high contribution to ΣRQCUPs. The present study is the first attempt to develop an ERA in surface water of the Pampas region of Argentina and it provides a starting point for a more comprehensive pesticides monitoring and a further risk assessment program.

Determination of priority pesticides in water samples combining SPE and SPME coupled to GC-MS. A case study: Suquía River basin (Argentina).

This study reports a combined method using solid phase extraction (SPE), followed by solid phase microextraction (SPME) to concentrate different pesticides, including chlorinated, organophosphorus, triazines, pyretroids and chloroacetamides, present at trace levels in water samples. Identification and quantification was carried out by gas chromatography coupled to Mass Spectrometry (GC-MS). The optimized methodology showed LOQs at ng L(-1) levels (ranging 0.2-3.5 ng L(-1)) in addition to acceptable precision and robustness (recoveries ranged 63-104%, RSD from 4% to 23%), presenting a novel method to reach trace levels, similar to that obtainable using EC detector, with structural confirmation by MS during the analysis of a wide range of environmental pollutants. This method was applied to the study of temporal and spatial distribution of pesticides in the Suquía River basin (Córdoba-Argentina). As expected, highest levels of agrochemicals were observed in areas with intensive agricultural practices, being atrazine (max.=433.9 ng L(-1)), alpha-cypermetrine (max.=121.7 ng L(-1)) and endosulfan sulfate (max.=106.7 ng L(-1)) predominant. In urban areas, the prevalent pesticide was alpha-cypermethrine. These results draw attention to the need of pesticide monitoring programs in rivers, considering both urban and rural sections.