Calibration and Application of PUF Disk Passive Air Samplers To Assess Chlorinated Paraffins in Ambient Air in Australia, China, and Vietnam.

Ambient air samples were collected in Brisbane (Australia), Dalian (China), and Hanoi (Vietnam) during Mar 2013-Feb 2018 using polyurethane foam based passive air samplers. A sampling rate calibration experiment was conducted for chlorinated paraffins (CPs, i.e., short-chain, medium-chain, and long-chain CPs), where the sampling rates were 4.5 ± 0.7, 4.8 ± 0.3, and 4.8 ± 2.1 m3 day-1 for SCCPs, MCCPs, and LCCPs, respectively. The atmospheric concentration of CPs was then calculated and the medians of ∑CPs were 0.079, 1.0, and 0.89 ng m-3 in Brisbane, Dalian, and Hanoi, respectively. The concentration of CPs in Brisbane's air remained at low levels, with no significant differences observed between the city background site and the city center site, indicating limited usage and production of CPs in this city. The highest concentration of MCCPs was detected in Dalian, while the highest concentration of SCCPs was detected in Hanoi. A decrease of SCCP concentration and an increase of MCCPs' were found in Brisbane's air from 2016 to 2018, while increasing trends for both SCCPs and MCCPs were observed in Dalian. These results indicated impacts from different sources of CPs in the investigated cities.

Oxidative stress response induced by atrazine in Palaemonetes argentinus: the protective effect of vitamin E.

The widespread contamination and persistence of the herbicide atrazine residues in the environment resulted in the exposure of non-target organisms. The present study was undertaken to investigate the effect of atrazine in the response of oxidative stress biomarkers in the freshwater shrimp Palaemonetes argentinus and the protective effect of vitamin-E against atrazine-induced toxicity. Therefore, two batches of P. argentinus were fed for 21 days with a commercial food enriched in proteins (D1) or with D2, composed of D1 enriched with vitamin-E (6.8 and 16.0mg% of vitamin-E, respectively). Subsequently, half of the individuals of each group were exposed to atrazine (0.4mgL(-1)) for 24h and the others remained as controls. Atrazine promoted oxidative stress response in P. argentinus fed with D1 as indicated by enhanced H2O2 content and induction of superoxide dismutase, glutathione-S-transferases and glutathione reductase. This antioxidant activity would prevent the increment of thiobarbituric acid reactive substances in the shrimp tissues. P. argentinus fed with D2 reversed the response of the biomarkers measured. However, the activation of antioxidants response had an energetic cost, which was revealed by a decrease in lipids storage in shrimps. These results show the modulatory effect of vit-E on oxidative stress and its potential use as an effective antioxidant to be applied in chemoprotection strategies during aquaculture.

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.

Pesticides bioassays using neotropical aquatic species: Trends during the last twenty years and future challenges in Argentina.

The presence of pesticides in aquatic ecosystems is one of the most relevant stressors which biota usually face. Laboratory tests using model organisms for pesticides toxicity assessment are employed worldwide. The use of these species has been encouraged in the scientific community due to their advantageous features and their acceptation by regulatory and standardization organizations. However, non-model species as well as those belonging particular ecosystems could contribute in the laboratory-field toxicity extrapolation. In this context, this work aims on exploring the state of the ecotoxicological studies of pesticides in neotropical aquatic species, focusing on bioassays performed in Argentina over the last 20 years as a case of study. Furthermore, we analyzed the possible advantages and disadvantages of these studies, possible differential sensitivities among native and model species, and future challenges to be faced. The analysis of more than 150 publications allowed identify the chemical identity of tested compounds, organisms used for the bioassays, characteristics of the experimental designs, and the toxicity endpoints. Particularly, the studied cases showed that the tested chemicals are related to those most used in the agricultural activity in Argentina, the predilection for particular species in some taxonomic groups (e.g. amphibians), and the wide election of biochemical biomarkers in the studies. Regarding the sensitivity comparison between native and non-native species, the amount of data available indicates that there is not a clear difference beyond some particular cases. However, deeper understanding of toxic effects of pesticides on non-model species could help in a more comprehensive ecological risk assessment in different ecosystems.

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.

Assessment of phytotoxic effects, uptake and translocation of diclofenac in chicory (Cichorium intybus).

Pharmaceuticals in the environment have been an increasing research topic over the past decade, since they can be found in both natural and drinking water, including irrigation of crops and edible plants with contaminated water. Our main goal was to evaluate the phytotoxic effect of diclofenac (DCF), a widely used pharmaceutical, on chicory (Cichorium intybus) seedlings. Additionally, we verified the uptake, bioconcentration and translocation of DCF from soil to chicory tissues. Results show that DCF induces different physiological changes in chicory seedlings. On the other hand, the soil-chicory experiment showed the activation of the detoxification system in plants treated with DCF (1 mg L-1). Finally, we found the migration of DCF from the irrigation water to the soil, followed by its uptake through the root, and its translocation to the aerial part of the chicory. However, DCF does not bioaccumulate in chicory leaves, being scarcely translocated from roots to aerial parts. This last result, along with the estimation of a daily intake of chicory, show that irrigation with water containing DCF (≤1 mg L-1) does not represent a threat to human health. To our knowledge, this is the first report on the effect of DCF on chicory seedlings, including the evaluation of its uptake and translocation.

Native crustacean species as a bioindicator of freshwater ecosystem pollution: A multivariate and integrative study of multi-biomarker response in active river monitoring.

The aim of this study was to evaluate the ability of Palaemonetes argentinus to evidence the environmental degradation due to pollutants mixture in a freshwater aquatic ecosystem. For this purpose, an active monitoring (96 h exposure) was carried out in seven sites along the Ctalamochita River basin (Córdoba, Argentina), as a case of study. Our results evidenced sewage discharges impact in the water quality index, as well as metal pollution in water (Ag, Al, B, Pb, Hg) and sediments (Hg) with a potential effect on aquatic biota. The accumulation of total metals measured in exposed P. argentinus showed significant correlation with metals in water. Also, metallothioneins in cephalothorax showed significant changes along the basin, correlating with soluble concentrations of Cr, Zn, Cd, Hg, and V measured in shrimp tissues, which would be reflecting their bioavailability in the environment. In addition, the increase in antioxidant and detoxifying enzymes suggests the occurrence of oxidative stress in exposed shrimps. The integrative biomarker response index (IBR) pointed out the effect of metals on P. argentinus but also the occurrence of others pollutants. Finally, a high consensus was observed for water, sediments, and shrimps through the multivariate analysis (90%), indicating that P. argentinus can reflect changes in the abiotic matrixes. Moreover, studied sites were grouped according to their environmental quality. The use of active biomonitoring and the integration of biological responses through an IBR confirm that native biota could be a useful monitoring tool for bioavailable pollutants in aquatic ecosystems constituting a highly valuable approach.

Tissue-specific bioconcentration and biotransformation of cypermethrin and chlorpyrifos in a native fish (Jenynsia multidentata) exposed to these insecticides singly and in mixtures.

The aim of the present study was to evaluate the accumulation of cypermethrin and chlorpyrifos when the fish Jenynsia multidentata was exposed to these pesticides singly and in technical and commercial mixtures. Adult female fish were exposed over 96 h to 0.04 µg/L of cypermethrin; 0.4 µg/L of chlorpyrifos; 0.04 µg/L of cypermethrin + 0.4 µg/L of chlorpyrifos in a technical mixture; and 0.04 µg/L of cypermethrin + 0.4 µg/L of chlorpyrifos in a mixture of commercial products. Fish exposed to cypermethrin accumulated this compound only in muscle, probably because of the low biotransformation capacity of this organ and the induction of cytochrome P4501A1 (CYP1A1) expression in the liver. The accumulation of chlorpyrifos occurred in fish exposed to the insecticide (intestine > liver > gills) even when these fish had higher gluthatione-S-transferase (GST) activity in gills and P-glycoprotein (P-gp) expression in the liver, compared with the control. Fish exposed to the technical mixture showed cypermethrin accumulation (liver > intestine > gills) with higher levels than those measured in fish after only cypermethrin exposure. Higher expression levels of CYP1A1 in the liver were also observed compared with the Control. Fish exposed to the commercial mixture accumulated both insecticides (cypermethrin: intestine > gills and chlorpyrifos: liver > intestine > gills > muscle). In the organs where accumulation occurred, biotransformation enzymes were inhibited. Consequently, the commercial formulation exposure provoked the highest accumulation of cypermethrin and chlorpyrifos in J. multidentata, possibly associated with the biotransformation system inhibition. Environ Toxicol Chem 2017;36:1764-1774. © 2016 SETAC.

Sensitive biomarker responses of the shrimp Palaemonetes argentinus exposed to chlorpyrifos at environmental concentrations: Roles of alpha-tocopherol and metallothioneins.

The aim of this study was to evaluate the toxic effects of chlorpyrifos (CPF) at environmental concentrations on the shrimp Palaemonetes argentinus, a South American native species. Organisms were exposed to environmentally relevant concentrations of CPF (from 3.5 to 94.5ngCPFL(-1)) at laboratory conditions for 96h. A wide battery of biochemical responses including bioaccumulation, damage and defense biomarkers were measured in cephalothorax and abdomen of shrimp. The concentration of CPF was below the detection limit of the method in both body sectors (8ngCPFg(-1)ww), probably indicating fast biotransformation of the parental compound. Our results showed that CPF exposure inhibits acetylcholinesterase activity from 3.5ngCPFL(-1), a concentration below the suggested Argentinean guidelines for the protection of aquatic biota. Moreover, oxidative stress was evidenced by increased H2O2 content and increased levels of TBARs and carbonyl groups in proteins. The induction of antioxidant enzymes like catalase, glutathione S-transferase and glutathione peroxidase seems not be sufficient to prevent oxidative damages. In addition, the mobilization of α-tocopherol from abdomen to cephalothorax was observed and reported for the first time in non-reproductive condition. Likewise, a strong diminution of metallothioneins occurred in cephalothorax from the lowest CPF concentration while induction occurred from the same treatment in abdomen as an oxidative stress response. Finally, significant correlation between Integrated Biomarker Response values and exposure concentrations suggest the usefulness of P. argentinus as bioindicator of CPF exposure at concentrations as low as environmental ones.

Matching in Vitro Bioaccessibility of Polyphenols and Antioxidant Capacity of Soluble Coffee by Boosted Regression Trees.

The aim of this study was to evaluate changes in polyphenol profile and antioxidant capacity of five soluble coffees throughout a simulated gastro-intestinal digestion, including absorption through a dialysis membrane. Our results demonstrate that both polyphenol content and antioxidant capacity were characteristic for each type of studied coffee, showing a drop after dialysis. Twenty-seven compounds were identified in coffee by HPLC-MS, while only 14 of them were found after dialysis. Green+roasted coffee blend and chicory+coffee blend showed the highest and lowest content of polyphenols and antioxidant capacity before in vitro digestion and after dialysis, respectively. Canonical correlation analysis showed significant correlation between the antioxidant capacity and the polyphenol profile before digestion and after dialysis. Furthermore, boosted regression trees analysis (BRT) showed that only four polyphenol compounds (5-p-coumaroylquinic acid, quinic acid, coumaroyl tryptophan conjugated, and 5-O-caffeoylquinic acid) appear to be the most relevant to explain the antioxidant capacity after dialysis, these compounds being the most bioaccessible after dialysis. To our knowledge, this is the first report matching the antioxidant capacity of foods with the polyphenol profile by BRT, which opens an interesting method of analysis for future reports on the antioxidant capacity of foods.