Persistent organic pollutants and chlorpyrifos in tissues of a histotrophic viviparous species, the Southern Eagle Ray Myliobatis goodei.

Elasmobranchs are good indicators of marine pollution as they accumulate pollutants from water and food, and occupy different trophic levels. Concentrations of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and chlorpyrifos were quantified in muscle, liver, gonads, gills, and brain in both sexes and maturity stages of the Southern Eagle Ray, Myliobatis goodei, captured in Argentine coastal waters. Moreover, possible histological alterations in the liver and gonads were analyzed. Pollutant concentrations were pervasive across all tissues, with PCBs > OCPs > chlorpyrifos. Elevated pollutant levels were notably found in the liver and gills. We identified thirty-six PCB congeners in tissues, with low-chlorine congeners prevailing. Among OCPs, ∑DDT and ∑endosulfan were predominant. Females exhibited higher pollutant levels in most tissues compared to males, except in the gonads, and adults generally displayed elevated pollutant levels. Histological analysis revealed the presence of atretic follicles and melanomacrophages (MM). Continuous monitoring of pollutant levels, alongside their effects on physiological and ecological traits, is imperative for effective management and conservation efforts.

Integrated biomarker responses in wild populations of the intertidal sea anemone Bunodosoma zamponii living under different anthropogenic pressures.

Bunodosoma zamponii is the most abundant anemone in Mar del Plata (Buenos Aires, Argentina). Given that the presence of persistent organic pollutants (organochlorine pesticides and PCBs) and the organophosphate pesticide chlorpyrifos has recently been reported in this species, two wild populations living under different anthropogenic pressures were studied and compared regarding basic aspects of their ecology and physiological response to oxidative stress. A population from an impacted site (Las Delicias, LD) and another from a reference site (Punta Cantera, PC) were monitored seasonally (spring, summer, autumn, and winter), for one year. Anemones from PC were larger and more abundant than those from LD for most sampling periods. During winter, glutathione-S-transferase and catalase activities were higher in LD. Moreover, protein content and antioxidant defenses were higher in anemones from PC during winter as well. Taking into account their ecology (size and abundance) and biomarker responses, the population from PC was comparatively healthier. Furthermore, such differences are in agreement with recent studies indicating a higher concentration of pollutants in anemones from LD (specially during the winter sampling). In this sense, considering that B. zamponii can bioaccumulate the aforementioned pollutants, its resilience to their presence, and the fact that biomarker response differed between sites, this species can be regarded as a proper sentinel species of environmental pollution. Overall, this anemone seems to be a good bioindicator to be considered in future biomonitoring and ecotoxicological studies.

Contaminant dynamics in honey bees and hive products of apiaries from environmentally contrasting Argentinean regions.

Argentina is a leading honey producer and honey bees are also critical for pollination services and wild plants. At the same time, it is a major crop producer with significant use of insecticides, posing risks to bees. Therefore, the presence of the highly toxic insecticide chlorpyrifos, and forbidden contaminants (organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs)) was investigated in honey bee, beebread, wax and honey samples in apiaries from three contrasting regions of Argentina. Chlorpyrifos was detected in all samples with higher levels during period 1 (spring) in contrast to period 2 (fall), agreeing with its season-wise use in different crops, reaching 3.05 ng/g in honey bees. A subsequent first-tier pesticide hazard analysis revealed that it was relevant to honey bee health, mainly due to the high concentrations found in wax samples from two sites, reaching 132.4 ng/g. In addition, wax was found to be the most contaminated matrix with a prevalence of OCPs (∑OCPs 58.23-172.99 ng/g). Beebread samples showed the highest concentrations and diversity of pesticide residues during period 1 (higher temperatures). A predominance of the endosulfan group was registered in most samples, consistent with its intensive past use, especially in Central Patagonia before its prohibition. Among the industrial compounds, lighter PCB congeners dominated, suggesting the importance of atmospheric transport. The spatio-temporal distribution of pesticides shows a congruence with the environmental characteristics of the areas where the fields are located (i.e., land use, type of productive activities and climatic conditions). Sustained monitoring of different pollutants in beekeeping matrices is recommended to characterize chemical risks, assess the health status of honey bee hives and the pollution levels of different agroecosystems. This knowledge will set a precedent for South America and be helpful for actions focused on the conservation of pollination services, apiculture and ecosystems in Argentina.

Pesticides in soil, groundwater and food in Latin America as part of one health.

We here report of a conference about "Pesticides in Soil, Groundwater and Food in Latin America as part of One Health" that took place at the "IV Seminario Internacional de Sanidad Agropecuaria (SISA)" in Varadero, Cuba, 8-12 May 2023. Researchers of Latin America (Argentina, Brazil, Chile, Costa Rica, Colombia, Cuba, Mexico) and Switzerland (workshop initiator) held presentations about occurrence and effects of pesticides on the environment, human health, the replacement of highly hazardous pesticides (HHP) by agroecological alternatives and the agri-food value chain. In a subsequent round table discussion, the presenters identified deficits, needs, interests and opportunities. According to them, the lack of awareness of pesticide use affects the health and safety of workers applying the chemicals. Despite Latin America representing the main agricultural area in the world with a very intense pesticide use, monitoring data of pesticides in soil, surface and groundwaters, food, as well as in humans are missing. Risks of pesticides to humans should be assessed so that authorities can withdraw or limit within "short time" the access to corresponding formulations on the market. Also, communication is not state of the art and should be improved as, e.g. the teaching of workers and farmers, how to correctly use and apply pesticides or the briefing of decision makers. Pollinators suffer from multiple stressors not the least due to pesticides, and alternatives are badly needed. On the technical side, the different analytical methods to determine residues of active ingredients and transformation products in matrices of concern should be harmonized among laboratories.Seven future actions and goals were identified to overcome the above deficits. Next steps after the publishing of this conference report are to harmonize and complete the information status of the presenters by exchanging the results/data already present. Therefore, a platform of interaction to address issues described above and to enhance collaboration shall be created. Samples of different matrices shall be exchanged to harmonize the chemical analysis and establish interlaboratory comparisons. Such activities might be facilitated by joining international associations or organizations, where researchers can offer their expertise, or by forming a new pesticide network for Central and South America that could present tailored projects to national and international organizations and funding agencies.

Occurrence of chlorpyrifos and organochlorine pesticides in a native bumblebee (Bombus pauloensis) living under different land uses in the southeastern Pampas, Argentina.

Pollinators such as Apidae bees are vital for ecosystems and food security. Unfortunately, their populations have declined due to several factors including pesticide use. Among them, the organophosphate insecticide chlorpyrifos, poses a global threat, while legacy compounds like organochlorine pesticides (OCPs) easily bioaccumulate, increasing the concern. Bombus pauloensis, a widely distributed native bee in Argentina, is used for commercial pollination; however, information regarding their health status is scarce. This study assessed chlorpyrifos and OCP levels in B. pauloensis (workers and males) and related environmental matrices living from three different land uses schemes, by means of GC-ECD and GC-MS. The ornamental horticulture field (OP) showed the highest total pesticide concentrations in workers (13.1 ng/g), flowers and soils, whereas the organic agriculture field (OA) exhibited the lowest. Chlorpyrifos was the most abundant compound, accounting for at least 20 % of pesticide load across all matrices. The food production horticulture field (FH) had the highest chlorpyrifos concentration in workers, males and soils (5.0, 4.4 and 3.3 ng/g, respectively), suggesting a local greater usage, whereas OA showed the lowest. Regarding OCPs groups, Drins and DDTs were predominant in most matrices, with FH males registering the highest levels (4.0 and 2.5 ng/g, respectively), closely followed by OP. However, metabolites' contribution indicated historical use and atmospheric inputs in all sites. Multivariate analyses confirmed the significance of site and bumblebee sex to explain pesticide composition. Males from all sites exhibited higher chlorpyrifos levels than workers and this trend was similar for some OCP groups. Overall, OA differed from FH and OP, indicating a correlation between production modes and pesticide profiles. This study demonstrates the value of B. pauloensis as a pesticide biomonitor but also offers insights into its populations' health in the area. In this sense, this information could be useful towards the preservation of this crucial pollinator.

Pesticides exposure in pregnant Argentinian women: Potential relations with the residence areas and the anthropometric neonate parameters.

Intrauterine environment is the first chemical exposure scenario in life, through transplacental transfer. In this study, the aim was to determine concentrations of organochlorine pesticides (OCPs) and selected current use pesticides in the placentas of pregnant women from Argentina. Socio-demographic information, the mother's lifestyle and neonatal characteristics were also analysed and related to pesticides residue concentrations. Thus, 85 placentas were collected at birth, from an area of intensive fruit production for the international market, in Patagonia Argentina. Concentrations of 23 pesticides including, trifluralin (herbicide), the fungicides chlorothalonil and HCB, and the insecticides chlorpyrifos, HCHs, endosulfans, DDTs, chlordanes, heptachlors, drins and metoxichlor, were determined by GC-ECD and GC-MS. Results were first analysed all together and then grouped by their residential settings, in urban and rural groups. Total mean pesticide concentration was 582.6 ± 1034.4 ng/g lw, where DDTs (325.9 ± 950.3 ng/g lw) and chlorpyrifos (188.4 ± 365.4 ng/g lw) showed a high contribution. Pesticide levels found exceeded those reported in low, middle and high income countries from Europe, Asia and Africa. In general, pesticides concentrations were not associated with neonatal anthropometric parameters. When the results were analysed by residence place, significantly higher concentrations of total pesticides and chlorpyrifos (Mann Whitney test p = 0.0003 and p = 0.032, respectively) were observed in placentas collected from mothers living in rural settings compared to urban areas. Rural pregnant women presented the highest pesticide burden (5.9 µg), where DDTs and chlorpyrifos were the major constituents. These results suggested that all pregnant women are highly exposed to complex pesticide mixtures, including banned OCPs and the widely used chlorpyrifos. Based on the pesticide concentrations found, our results warn of possible health impacts from prenatal exposure through transplacental transfer. This is one of the first reports of both chlorpyrifos and chlorothalonil concentrations in placental tissue, and contributes to the knowledge of current pesticide exposure in Argentina.

Distribution of PAHs and trace elements in Spartina densiflora and associated sediments from low to highly contaminated South American estuarine saltmarshes.

Estuarine saltmarshes from South America are exposed to several anthropogenic impacts due to diverse human activities that occur in both Atlantic/Pacific coastal environments. Primarily, chemical and petrochemical industries negatively impact saltmarshes generating inputs/deposition of non-essential trace elements (NTEs) and polycyclic aromatic hydrocarbons (PAHs) in sediments. The native cordgrass Spartina densiflora inhabits a wide range of environments, from non-impacted to highly impacted areas. It is important to know its performance towards pollution in different environmental settings in South America. The content of Cd, Hg, Pb, and PAHs was determined in the roots and leaves of S. densiflora, bulk sediments (Bs), and rhizosediments (Rs) of estuaries from Argentina, Brazil, and Chile. Differences in NTEs and PAHs levels were observed between Bs, Rs, and Spartina tissues from different saltmarsh areas. Differences in Rs/Bs (RHICF; rhizosediments concentration factors), roots/Bs (RCF; roots concentration factors) and leaves/roots (TF; translocation factors) factors were also found. In terms of NTEs, S. densiflora showed a high capability to increase levels in their Rs (RHICF>1) and bioconcentrate Cd in roots (RCF > 1), while no general translocation (TF < 1) was observed. Conversely, in cordgrass tissues, Bs and Rs, PAHs contents showed RCF and TF > 1, which was in line with lower levels in Rs related to Bs (RHICF<1) in most sites. These findings showed the S. densiflora capacity to retain, remove and/or translocate priority contaminants depending on intrinsic chemical characteristics and the level of contamination. The present study enables future considerations regarding the biomonitoring and phytoremediation/stabilization capabilities of Spartina in coastal environments.

Occurrence of polychlorinated biphenyls (PCBs) in the sea anemone Bunodosoma zamponii, sediments and seawater from the southwestern Atlantic.

Polychlorinated biphenyls (PCBs) are persistent and bioaccumulable organic compounds. The occurrence of PCBs was assessed in two populations of the intertidal sea anemone Bunodosoma zamponii living under different anthropogenic strains. One location was in vicinity to a wastewater plant (Las Delicias, LD), and the other was a preserved location chosen as a reference site (Punta Cantera, PC). Anemone populations were sampled 4 times (spring, summer, autumn and winter) throughout a year, in addition to seawater and sediment from those areas. PCB loadings ranged from 2.89 to 79.41 ng L-1 in seawater samples and from 0.07 to 6.61 ng g-1 dry weight in sediment samples. Total PCB levels ranged from 0.22 to 14.94 and 2.79 to 24.69 ng g-1 wet weight in anemones from PC and LD, respectively. PCBs concentrations in anemones from LD were significantly greater than PC during spring, summer and winter. The congeners 18 and 44 prevailed in seawater samples, 44 and 52 in sediment and 18 and 132+153 in anemones. Redundancy analysis integrated PCB levels from all matrixes and bolstered contrast between sampling sites. Seasonality was also a relevant factor since during winter PCB loading was greater in sediment and anemone samples, coincident with the rainiest season. Disparity between sites could be due to LD's proximity to the wastewater plant, effect of littoral drift direction and/or asymmetries in anemones physiological condition.

Organochlorine pesticides and chlorpyrifos in the sea anemone Bunodosoma zamponii (Actiniaria: Actiniidae) from Argentina's southeastern coast.

Temporal and spatial distribution of organochlorine pesticides (OCPs) and the organophosphate pesticide chlorpyrifos, one of the main insecticides used in Argentina, was evaluated in two populations of the sea anemone Bunodosoma zamponii living under different anthropological stressors: Las Delicias (LD) adjacent to a wastewater plant, and Punta Cantera (PC) a reference site. Pesticides were analyzed throughout the year in water, sediments and whole organisms. Chlorpyrifos represented 50% of the total pesticide found in water samples during winter. HCHs and drins were predominant in sediment samples, mainly in LD. Total pesticide concentration in anemones from LD was higher than those from PC during winter (mainly associated with HCHs, endosulfans, DDTs and chlorpyrifos levels), coincident with the main period of effluent discharge to the coast after pesticide applications and also the rainiest season. Dissimilarities among anemones populations could stem from a differential input of pesticides in each site and/or a contrasting physiological status of the populations.

Multibiomarker responses and bioaccumulation of fipronil in Prochilodus lineatus exposed to spiked sediments: Oxidative stress and antioxidant defenses.

Fipronil is a current use pesticide, widely used in many crops, commonly adsorbed to sediments of aquatic environments. The purpose of this study was to evaluate the biomarker responses and fipronil distribution pattern in different matrixes (fish, sediment and water) after juveniles P. lineatus exposure at two environmental concentrations (5.5 and 82 µg kg--1) of fipronil-spiked sediments. The levels of oxidized proteins (PO), lipid peroxidation (LPO), and enzymatic activity of superoxide dismutase (SOD), reduced glutathione content (GSH), antioxidant capacity against peroxyls (ACAP) and acetylcholinesterase (AChE) were evaluated in liver, gills and brain. Concentrations of fipronil and its metabolites (f. desulfinyl, f sulphpHide and f. sulfone) were quantified by GC-ECD. F. desulfinyl was the major metabolite found in all matrixes, followed by f. sulphide in sediments, while f. sulfone was mainly accumulated in fish. Fipronil promoted oxidative stress in P. lineatus, as evidenced by the increases in LPO and PO levels and the decrease brain AChE activity. Fish exposed at both concentrations showed significant decrease in antioxidant capacity. Alterations in the antioxidant defenses system was evidenced in all organs. These results suggest that the occurrence of fipronil in aquatic environments can generate oxidative stress at different levels in P. lineatus, showing that this species is highly sensitive to the deleterious effects of fipronil and metabolites.

Persistent organic pollutants and chlorpyrifos in the cockfish Callorhinchus callorynchus (Holocephali: Callorhynchidae) from Argentine coastal waters: Influence of sex and maturity.

Organic contaminants are of great environmental concern due to their negative impacts on coastal ecosystems, especially on highly vulnerable species as chondrichthyans. Accumulation of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and chlorpyrifos was assessed in muscle, gonads, and liver of the cockfish Callorhinchus callorynchus for both sexes and maturity stages. This species has a wide distribution in South Atlantic Ocean and it is an important resource for coastal Argentine fisheries. Pollutants were quantified by gas chromatography with electron capture detector and the distribution pattern found in C. callorynchus was the following: (∑OCPs+chlorpyrifos) > ∑PCBs>∑PBDEs. Endosulfan was predominant among OCP groups, penta-CBs and hexaCBs among PCBs and BDE 47, 66, 99, and 100 in PBDE group. The highest levels were found in liver followed by muscle and gonads. The highest percentage of lipids was also observed in the liver. Moreover, the concentrations of ∑OCPs and ∑PCBs in C. callorynchus liver varied with maturity stage, and ∑OCPs also with sexes. Females presented higher values than males, and mature individuals showed higher concentrations than immature ones, according with biological parameters such as age, sex, maturity stage, metabolic and redistribution processes and habitat use influence. These results indicate that C. callorynchus reflects a historical and recent contamination in their tissues, and therefore, especially females, becomes as a good biomonitor of these pollutants in the marine environment. To our knowledge, this work represents one of the few investigations on the occurrence of POPs and chlorpyrifos in chondrichtyans from South Atlantic Ocean; therefore more research is mandatory for an adequate management and conservation of existing fisheries and aquatic resources.

Exposure to environmental concentrations of fipronil induces biochemical changes on a neotropical freshwater fish.

Fipronil is a broad-use insecticide with severe toxicity to fish. Biomarkers responses and bioaccumulation were evaluated on Prochilodus lineatus after exposure to environmentally relevant concentrations of fipronil (0.5 µg L-1, 9 µg L-1, and 100 µg L-1) in a prolonged flow-through assay and ex vivo gills short-term exposition. Lipid peroxidation (LPO), oxidatively modified proteins (PO), the activity of superoxide dismutase (SOD), the content of reduced glutathione (GSH), antioxidant capacity against peroxyles (ACAP), and acetylcholinesterase (AChE) were evaluated. Besides, levels of fipronil and metabolites were analyzed by GC-ECD. At the end of the flow-through assay, fipronil, Fp. sulfone and Fp. desulfinyl were detected in fish, being liver the target organ. Fipronil prolonged exposition promoted oxidative damage in lipids and proteins, alterations in the defense system and low-antioxidant capacity in organs of P. lineatus. The brain AChE activity was affected after prolonged exposition. Ex vivo gills exposition to fipronil promoted changes in antioxidant capacity and damage to lipids, providing a fast and suitable test to assess the pesticide exposure in fish. The results revealed that fipronil at environmental concentrations would be an inducer of oxidative stress in this fish, becoming a vulnerable species to the effects of fipronil in aquatic environments.

Multi-matrix approach reveals the distribution of pesticides in a multipurpose protected area from the Atlantic Rainforest: potential risk for aquatic biota and human health?

The Atlantic Rainforest is among the main biodiversity hotspots in the world, the Yabotí Biosphere Reserve (YBR) being one of the most important remaining areas. Agriculture practices could lead to intensive usage of pesticides resulting in a risk to the environment and human health. Water, suspended particulate matter (SPM), sediment, and fish (Andromakhe paris and Andromakhe saguazu) samples were collected from four streams with different degrees of protection of the YBR in two periods in order to assess the distribution of 18 organochlorine pesticides. Legacy and current-use pesticides were found in the different environmental matrices of the stream headwaters in non-anthropized areas within the buffer zone that drains the intangible area. A similar occurrence pattern of pesticides was found in all matrices. Levels of DDTs (<3.63 ng/L) and endosulfans (<21.8 ng/L) in surface water were above international guidelines for the protection of aquatic life in several streams for both sampling periods. HCHs, DDTs, endosulfans, and chlorpyrifos were detected in SPM and sediments from three streams, while γ-HCH (<60.3 ng/g lipid weight), chlorpyrifos (<698 ng/g lw), p,p´-DDD (<367 ng/g lw), and α-endosulfans (<209 ng/g lw) were detected in fish muscle in several streams. Chlorpyrifos and endosulfans were associated with current use, while DDx/DDT ratios suggested an old use. The concentration of pesticides found would not represent a risk to human health; however, it highlights the need to establish better regulation and action guidelines to reduce the anthropogenic effect on natural reserves.

Spatial and temporal distribution of Persistent Organic Pollutants and current use pesticides in the atmosphere of Argentinean Patagonia.

XAD-based passive air samplers (PAS) were used to evaluate organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and some current use pesticides (chlorotalonil, trifluralin and dichlofluanid) in the atmosphere of Argentinian Patagonia. The PAS were deployed for 12 months during three consecutive years along a longitudinal (Rio Negro watershed) and a latitudinal (Patagonian coast) transect. Endosulfan, trifluralin and DDT-related substances were the most prevalent pesticides in the Rio Negro watershed, an intensive agricultural basin, consistent with ongoing use of endosulfan at the time of sampling. Concentrations of industrial contaminants were low (mean 25 pg/m3 and 1.9 pg/m3 for Σ38 PCBs, and Σ5PBDEs, respectively) and similar among sites. However, along the Patagonian coast, air concentrations of total contaminants were highly variable (14-400 pg/m3) with highest values recorded at Bahia Blanca, an important industrial area that is also downwind of the most intensively agriculturally used area of Argentina. Contaminant levels decreased toward the south, with the exception of the southernmost sampling site (Rio Gallegos) where a slight increase of total pollutant levels was observed, mainly due to the lower chlorinated PCB congeners. Interannual variability was small, although the last year tended to have slightly higher levels for different contaminant groups at most sampling sites. This large-scale spatial atmospheric monitoring of POPs and some CUPs in the South of Argentina highlights the important and continuing role of rural and urban areas as emission sources of these chemicals.

What types of enzyme activities are useful biomarkers of bifenthrin exposure on Chironomus sp. (Diptera, Chironomidae) larvae under laboratory and field-based microcosm conditions?

Bifenthrin is a second generation synthetic pyrethroid insecticide that is widely used in Australia and worldwide. It is frequently found in urban freshwater sediments at concentrations likely to impact biota as it is highly toxic to fish and macroinvertebrates, such as chironomids. Our main goal was to evaluate if oxidative stress and hydrolase enzymes are useful biomarkers of effect of synthetic pyrethroids exposure under different scenarios. Chironomus tepperi larvae (5 days old) were exposed to sub-lethal sediment concentrations of bifenthrin for 5 days under controlled laboratory conditions. A field-based microcosm exposure with bifenthrin-spiked sediments (using the same concentrations as the laboratory exposure) was carried out at a clean field site for four weeks to allow for colonization and development of resident chironomid larvae. At the end of both experiments, Chironomus larvae (C. tepperi in the laboratory exposures and C. oppositus in the microcosm exposures) were collected and oxidative stress enzymes (Glutathione-s-Transferase, Glutathione Reductase and Glutathione Peroxidase) and hydrolase enzymes (Acetylcholinesterase and Carboxylesterase) were measured. Only the Glutathione Peroxidase activity was significantly impacted in larvae from the laboratory exposure. On the contrary, significant changes were observed in all the measured enzymes from the field-based microcosm exposure. This is likely because exposure was throughout the whole life cycle, from egg mass to fourth instar, showing a more realistic exposure scenario. Furthermore, this is the first time that changes in oxidative stress and hydrolase enzymes have been shown to occur in Australian non-biting midges exposed under field-based microcosm conditions. Thus, this study demonstrated the usefulness of these enzymes as biomarkers of effect following bifenthrin exposure in microcosms. It also highlights the importance of using a range of different biochemical endpoints to get a more holistic understanding of pesticide effects and the pathways involved.

GAPS-megacities: A new global platform for investigating persistent organic pollutants and chemicals of emerging concern in urban air.

A pilot study was initiated in 2018 under the Global Atmospheric Passive Sampling (GAPS) Network named GAPS-Megacities. This study included 20 megacities/major cities across the globe with the goal of better understanding and comparing ambient air levels of persistent organic pollutants and other chemicals of emerging concern, to which humans residing in large cities are exposed. The first results from the initial period of sampling are reported for 19 cities for several classes of flame retardants (FRs) including organophosphate esters (OPEs), polybrominated diphenyl ethers (PBDEs), and halogenated flame retardants (HFRs) including new flame retardants (NFRs), tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCDD). The two cities, New York (USA) and London (UK) stood out with ∼3.5 to 30 times higher total FR concentrations as compared to other major cities, with total concentrations of OPEs of 15,100 and 14,100 pg/m3, respectively. Atmospheric concentrations of OPEs significantly dominated the FR profile at all sites, with total concentrations in air that were 2-5 orders of magnitude higher compared to other targeted chemical classes. A moderately strong and significant correlation (r = 0.625, p < 0.001) was observed for Gross Domestic Product index of the cities with total OPEs levels. Although large differences in FR levels were observed between some cities, when averaged across the five United Nations regions, the FR classes were more evenly distributed and varied by less than a factor of five. Results for Toronto, which is a 'reference city' for this study, agreed well with a more in-depth investigation of the level of FRs over different seasons and across eight sites representing different urban source sectors (e.g. traffic, industrial, residential and background). Future sampling periods under this project will investigate trace metals and other contaminant classes, linkages to toxicology, non-targeted analysis, and eventually temporal trends. The study provides a unique urban platform for evaluating global exposome.

Indoor persistent organic pollutants in agricultural areas from Argentina.

Persistent Organic Pollutants (POPs) are anthropogenic chemicals extensively used in the past for industrial and agricultural purposes, characterized by their lipophilicity, ubiquity, volatility and environmental persistence. By other hand, chlorpyrifos is the most widely used current pesticide (CUPs) being the main insecticide used for crops in Argentina. The aim of this work was to assess levels of POPs and CUPs in different fractions of airborne particles collected indoor in agricultural areas from Argentina. Particles higher than 2.5 µm were trapped in polyurethane foams (PUF) while particles smaller than 1 µm and volatile compounds were adsorbed on activated charcoal. Compounds were analyzed by gas chromatograph with electron capture detector (GC-ECD). Endosulfans, chlordanes, PCBs, and HCHs were detected in all PUF samples, while endosulfans, chlorpyrifos, PCBs, and HCHs were the most abundant in smaller particles. Majority of pesticides showed higher concentrations during the summer season (1397.7 vs 832.5 pg/m3 ). Even adding up all measured organic compounds, no sample reaches the threshold limit value for indoor pesticides levels (0.1 pg/m3 ), neither in the large or small particle fraction. However, the fact that chronic exposure to POPs has been linked to several diseases raises concern for human health.

Pelagic seabirds as biomonitors of persistent organic pollutants in the Southwestern Atlantic.

Persistent Organic Pollutants (POPs) are accumulated through time and can exert different effect on ecosystems. POPs and Chlorpyrifos, a current use pesticide, were assessed in body feathers of males and females of Black-browed albatross (Thalassarche melanophris, BBA) and Cape petrels (Daption capense, CAP) during their non-breeding seasons at the Patagonian Shelf, Argentina. Chlorpyrifos showed the highest values among all pollutants in both species (49.56-84.88 ng g-1), resulting from current agricultural practices. The pattern OCPs > PCBs > PBDEs was observed in both species, and CAP showed higher concentrations than BBA probably as a consequence of higher lipid mobilization and pollutants availability during dispersion. Non-significant differences between sexes about POPs levels were found; however a slight tendency was observed, females>males in CAP, and males>females in BBA. More attention and further studies are needed to understand seabirds' physiology and its relationship with the pollutants distribution in their tissues and considering breeding season.

Critical review: Grand challenges in assessing the adverse effects of contaminants of emerging concern on aquatic food webs.

Much progress has been made in the past few decades in understanding the sources, transport, fate, and biological effects of contaminants of emerging concern (CECs) in aquatic ecosystems. Despite these advancements, significant obstacles still prevent comprehensive assessments of the environmental risks associated with the presence of CECs. Many of these obstacles center around the extrapolation of effects of single chemicals observed in the laboratory or effects found in individual organisms or species in the field to impacts of multiple stressors on aquatic food webs. In the present review, we identify 5 challenges that must be addressed to promote studies of CECs from singular exposure events to multispecies aquatic food web interactions. There needs to be: 1) more detailed information on the complexity of mixtures of CECs in the aquatic environment, 2) a greater understanding of the sublethal effects of CECs on a wide range of aquatic organisms, 3) an ascertaining of the biological consequences of variable duration CEC exposures within and across generations in aquatic species, 4) a linkage of multiple stressors with CEC exposure in aquatic systems, and 5) a documenting of the trophic consequences of CEC exposure across aquatic food webs. We examine the current literature to show how these challenges can be addressed to fill knowledge gaps. Environ Toxicol Chem 2019;38:46-60. © 2018 SETAC.

Pharmaceuticals, illicit drugs and their metabolites in fish from Argentina: Implications for protected areas influenced by urbanization.

Because an understanding of aquatic bioaccumulation of human pharmaceuticals in Latin America is limited, this area was recently identified as a priority environmental quality research need. We examined bioaccumulation of twenty-seven pharmaceuticals, illicit drugs and their metabolites in muscle, liver and gills of multiple fish species (Rhamdia quelen, Hypostomus commersoni, Hoplias lacerdae, Prochilodus lineatus) from an urban river receiving wastewater discharges (Paraná) and a lotic system (Acaraguá) without direct wastewater sources, which runs through a protected area. All samples were analyzed using isotope-dilution liquid chromatography-tandem mass spectrometry. Caffeine, which was detected up to 13 µg/kg, and antibiotics were consistently detected in all fish. Among antibiotics, erythromycin was ubiquitous (0.7-5.6 µg/kg) but its tissue concentrations were lower than levels of sulfamethoxazole, sulfathiazole and trimethoprim (0.9-5.5 µg/kg), which are used in human medicine, aquaculture and livestock. Erythromycin bioaccumulation in fish is reported here from Argentina for the first time, though levels of antibiotics in edible muscles of these species were lower than the maximum residue limits for human consumption. We observed norfluoxetine, the primary active metabolite of the antidepressant fluoxetine, ranging from 1.1-9.1 µg/kg in fish. We further identified benzoylecgonine, a primary metabolite of cocaine, in fish from both study systems, representing the first observation an illicit drug or associated metabolites bioaccumulation in aquatic life from Argentina. Interestingly, high pharmaceutical levels were observed in fish from the Acaraguá river suggesting their transport into the protected area, from the surrounding lands. Though fish from the Paraná river were sampled near WWTP discharges, pharmaceutical concentrations may have been reduced by hydrological and other environmental conditions, and biological differences among species. These findings, which observed bioaccumulation of select pharmaceuticals, their metabolites and illicit drugs in wild fish sampled inside a protected area, highlight the importance of developing an advanced understanding of urban influences on inland protected watersheds.