Risk evaluation and prioritization of contaminants of emerging concern and other organic micropollutants in two river basins of central Argentina.

A research gap exists in baseline concentrations of organic micropollutants in South American rivers. Identification of areas with different degrees of contamination and risk to the inhabitant biota is needed to improve management of freshwater resources. Here we inform the incidence and ecological risk assessment (ERA) of current used pesticides (CUPs), pharmaceutical and personal care products (PPCPs) and cyanotoxins (CTX) measured in two river basins from central Argentina (South America). Risk Quotients approach was used for ERA differentiating wet and dry seasons. High risk was associated to CUPs in both basins (45 % and 30 % of sites from Suquía and Ctalamochita rivers, respectively), mostly in the basins extremes. Main contributors to risk in water were insecticides and herbicides in Suquía river and insecticides and fungicides in Ctalamochita river. In Suquía river sediments, a very high risk was observed in the lower basin, mainly from AMPA contribution. Additionally, 36 % of the sites showed very high risk of PCPPs in Suquía river water, with the highest risk downstream the wastewater treatment plant of Córdoba city. Main contribution was from a psychiatric drug and analgesics. In sediments medium risk was observed at the same places with antibiotics and psychiatrics as main contributors. Few data of PPCPs are available in the Ctalamochita river. The risk in water was low, with one site (downstream Santa Rosa de Calamuchita town) presenting moderated risk caused by an antibiotic. CTX represented in general medium risk in San Roque reservoir, with San Antonio river mouth and the dam exit showing high risk during the wet season. The main contributor was microcystin-LR. Priority chemicals for monitoring or further management include two CUPs, two PPCPs, and one CTX, demonstrating a significant input of pollutants to water ecosystems from different sources and the need to include organic micropollutants in current and future monitoring.

Whole-body bioconcentration and biochemical and morphological responses of gills of the neotropical fish Prochilodus lineatus exposed to 2,4-dichlorophenoxyacetic acid or fipronil individually or in a mixture.

The herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) and the insecticide fipronil have been used widely in agriculture and detected in aquatic ecosystems, where they threaten wildlife. This study evaluated the whole-body bioconcentration and the biochemical and morphological changes in the gills of the neotropical fish Prochilodus lineatus exposed for 96 h to 2,4-D or fipronil as single compounds or as a mixture (2,4-D + fipronil). Fish exposed to either compound alone bioconcentrated 2,4-D (77 ± 23 ng g - 1 fish dry mass) and fipronil (789 ± 178 ng g - 1 fish dry mass). Fish exposed to 2,4-D + fipronil bioconcentrated fipronil (683 ± 73 ng g - 1 fish dry mass) but not 2,4-D. In the gills, catalase (CAT) and glutathione-S-transferase (GST) activities and the lipid peroxidation (LPO) level increased after exposure to 2,4-D. GST activity increased after exposure to fipronil. Conversely, no changes occurred in CAT and GST activities and LPO upon exposure to 2,4-D + fipronil. Histopathological changes such as hyperplasia, cellular hypertrophy, epithelial lifting, and vascular congestion were frequent in the gills of fish exposed to 2,4-D or fipronil individually or 2,4-D + fipronil. The mitochondria-rich cell (MRC) density increased on gill surface in fish exposed to fipronil or 2,4-D + fipronil. Only exposure to 2,4-D alone induced oxidative stress in the gills. Most morphological changes showed defense responses against the pesticides; however, hypertrophy and the change in MRC indicated compensatory responses to maintain the gill osmoregulatory function. The 2,4-D + fipronil mixture showed antagonistic interaction, except for the MRC fractional area at gill surface, which showed synergistic interaction. This is the first report showing antagonistic interaction of 2,4-D and fipronil in the gills after exposing fish to the mixture of both pesticides. The biochemical and morphological changes in gills endanger the gill functions, a phenomenon that implies an energy cost for fish.

Different antibiotic profiles in wild and farmed Chilean salmonids. Which is the main source for antibiotic in fish?

Fish from both aquaculture and wild capture are exposed to veterinary and medicinal antibiotics (ABs). This study explored the occurrence and probable source of 46 antibiotic residues in muscle of farmed salmon and wild trout from Chile. Results showed that at least one AB was detected in all studied samples. Diverse patterns were observed between farmed and wild specimens, with higher ABs concentrations in wild fish. Considering antimicrobial resistance, detected ABs corresponded to the categories B (Restrict), C (Caution) and D (Prudence) established by Antimicrobial Advice Ad Hoc Expert Group (European Medicines Agency). Multivariate statistic was used to verify differences between farmed and wild populations, looking for the probable source of ABs as well. Principal components analysis (PCA) revealed that ciprofloxacin, moxifloxacin, enrofloxacin, amoxicillin, penicillin G, oxolinic acid, sulfamethoxazole, trimethoprim and clarithromycin were associated with wild samples, collected during the cold season. Conversely, norfloxacin, sulfaquinoxaline, sulfadimethoxine, nitrofurantoin, nalidixic acid, penicillin V, doxycycline, flumequine, oxacillin, pipemidic acid and sulfamethizole were associated with wild samples collected during the warm season. All farmed salmon samples were associated with ofloxacin, tetracycline, cephalexin, erythromycin, azithromycin, roxithromycin, sulfabenzamide, sulfamethazine, sulfapyridine, sulfisomidin, and sulfaguanidine. In addition, linear discriminant analysis showed that the AB profile in wild fish differ from farmed ones. Most samples showed ABs levels below the EU regulatory limit for edible fish, except for sulfaquinoxaline in one sample. Additionally, nitrofurantoin (banned in EU) was detected in one aquaculture sample. The differences observed between farmed and wild fish raise questions on the probable source of ABs, either aquaculture or urban anthropic activities. Further research is necessary for linking the ABs profile in wild fish with the anthropic source. However, to our knowledge, this is the first report showing differences in the ABs profile between wild and aquaculture salmonids, which could have both environmental and health consequences.

Multiantibiotic residues in commercial fish from Argentina. The presence of mixtures of antibiotics in edible fish, a challenge to health risk assessment.

The occurrence of 46 antibiotics (amphenicols, cephalosporins, dihydrofolate reductase inhibitors, fluroquinolones, macrolides, nitrofurans, penicillins, quinolones, sulfamides and tetracyclines) in Argentinean market fish were investigated by UPLC-MS/MS. Veterinary and human antimicrobials enrofloxacin, clarithromycin, roxithromycin, doxycycline and oxytetracycline were detected in 100% of the samples, being to our knowledge the first report of clarithromycin in edible fish muscle. Maximum Residual Limits were exceeded for at least one antibiotic in 82% of pacú, 57% of shad, 57% of trout and 50% of salmon samples. Chloramphenicol, furazolidone and nitrofurantoin (banned compounds in food items) were detected in 41%, 22% and 4% of the samples, respectively. Based on the estimated daily intake calculation, samples do not pose a serious risk to public health. Further investigation on the chronic impact and risk calculation of the mixture of antibiotics on the aquatic environment and human health is urgently needed.

Presence of pharmaceutical compounds, levels of biochemical biomarkers in seafood tissues and risk assessment for human health: Results from a case study in North-Western Spain.

This study assessed the presence of 27 pharmaceutically active compounds belonging to common therapeutic groups (cardiovascular, antiashmatic, psychoactive, diuretic, analgesic/anti-inflammatory, and antibiotic drugs) in the tissues of representative seafood species of bivalves, cephalopods, arthropods, and fish of high economic importance and consumption rates in North-Western Spain. Four pharmaceutical compounds, out of the 27 analyzed, were detected in the collected samples. The benzodiazepine citalopram was detected in the tissues of common octopus (14.1 ng g-1 dry weight) and pod razor (9.4 ng g-1 dw). The anxiolytic venlafaxine was detected in the tissues of common cockle (2.9 ng g-1 dw). The veterinary antiparasitic ronidazole was found in pod razor (2.3 ng g-1 dw) and, finally, the psychoactive compound alprazolam was also measured in common octopus (0.3 ng g-1 dw). Hazard quotients were calculated to assess the hazard posed by the consumption of the sampled seafoods. Octopus and pod razor tissues containing citalopram and alprazolam exceeded our chosen hazard limits (HQ > 0.1) for toddlers who are high consumers of seafood (HQ values between 0.18 and 0.27). A battery of biochemical biomarkers of effects (acetylcholinesterase, glutathione S-transferase; catalase, glutathione peroxidase and glutathione reductase enzymes activities and reduced/oxidized glutathione and malondialdehyde levels) was applied to samples of the study species with the aim of characterizing their basal levels and evaluating their suitability as a tool in the monitoring chronic exposure to environmental contaminants such as those analyzed in this study. According to the measured biomarkers, pod razor and cockles have the potential to be good bioindicator species, based on the observed among-site differences detected on acetylcholinesterase, glutathione S-transferase, catalase, glutathione peroxidase activities; reduced/oxidized glutathione and malondialdehyde levels.

Screening concentration of E1, E2 and EE2 in sewage effluents and surface waters of the "Pampas" region and the "Río de la Plata" estuary (Argentina).

Concentrations of estrone (E1), 17ß-estradiol (E2) and 17α-ethinylestradiol (EE2) were investigated for the first time in sewage effluents and receiving waters of the "Río de la Plata" estuary and neighboring areas by means of LC-MS/MS. E2 and EE2 were ubiquitous in the evaluated sewage effluent samples showing concentrations ranging between 122-631 and 65-187 ng/L, respectively. In surface waters, these estrogens were only detected in the "Girado" stream (Chascomús) at 369 and 43 ng/L, respectively. No significant relationship was found among the size of the served population and the concentration of the estrogens in the sewage effluent. The detection of these estrogens in receiving waters was dependent on the dilution capacity of the system. The studied estrogens were undetectable at the La Plata City water supply station. Conversely, concentrations found at the "Girado" stream indicate a potential ecotoxicological risk of these estrogens to the local aquatic biota.

Occurrence and bioaccumulation of pharmaceuticals in a fish species inhabiting the Suquía River basin (Córdoba, Argentina).

In South America, there is a lack of data concerning the occurrence and levels of pharmaceuticals in main rivers as well as their negative effects on the biota. Here we report the occurrence as well as the spatial and temporal variations of some common prescribed pharmaceuticals in the Suquía River basin (Córdoba, Argentina). We also report the bioconcentration of two of them in Gambusia affinis, a widely distributed fish species inhabiting the river basin. The influence of the wastewater treatment plant of Córdoba City was critical (up to 70 km downstream). Among 15 compounds analyzed, atenolol, carbamazepine and diclofenac were the most frequently detected (reaching sub µg L(-1) levels), showing different distribution patterns. Bioconcentration of atenolol and carbamazepine was studied under laboratory controlled conditions. Estimated bioconcentration factors (BCFs) were: 0.13 and 0.08 L kg(-1) upon exposure to 100 and 1,000 µg L(-1) atenolol in water, respectively; while BCFs were 0.7 and 0.9 L kg(-1) when exposed to 10 and 100 µg L(-1) carbamazepine, respectively. To the extent of our knowledge, this is the first report on pharmaceuticals in superficial waters of Argentina as well as the first report on the bioaccumulation of atenolol in whole body fish.