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.

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.

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.

Atmospheric Concentrations of New Persistent Organic Pollutants and Emerging Chemicals of Concern in the Group of Latin America and Caribbean (GRULAC) Region.

A special initiative was run by the Global Atmospheric Passive Sampling (GAPS) Network to provide atmospheric data on a range of emerging chemicals of concern and candidate and new persistent organic pollutants in the Group of Latin America and Caribbean (GRULAC) region. Regional-scale data for a range of flame retardants (FRs) including polybrominated diphenyl ethers (PBDEs), organophosphate esters (OPEs), and a range of alternative FRs (novel FRs) are reported over 2 years of sampling with low detection frequencies of the novel FRs. Atmospheric concentrations of the OPEs were an order of magnitude higher than all other FRs, with similar profiles at all sites. Regional-scale background concentrations of the poly- and perfluoroalkyl substances (PFAS), including the neutral PFAS (n-PFAS) and perfluoroalkyl acids (PFAAs), and the volatile methyl siloxanes (VMS) are also reported. Ethyl perfluorooctane sulfonamide (EtFOSA) was detected at highly elevated concentrations in Brazil and Colombia, in line with the use of the pesticide sulfluramid in this region. Similar concentrations of the perfluoroalkyl sulfonates (PFAS) were detected throughout the GRULAC region regardless of location type, and the VMS concentrations in air increased with the population density of sampling locations. This is the first report of atmospheric concentrations of the PFAAs and VMS from this region.

DDTs-induced antioxidant responses in plants and their influence on phytoremediation process.

Phytoremediation is a low cost technology based on the use of plants to remove a wide range of pollutants from the environment, including the insecticide DDT. However, some pollutants are known to enhance generation of reactive oxygen species (ROS), which can generate toxic effects on plants affecting the phytoremediation efficiency. This study aims to analyze the potential use of antioxidant responses as a measure of tolerance to select plants for phytoremediation purposes. Tomato and zucchini plants were grown for 15 days in soils contaminated with DDTs (DDT + DDE + DDD). Protein content, glutathione-S-transferase (GST), glutathione reductase (GR), glutathione peroxidase (GPx) and catalase (CAT) activities were measured in plant tissues. Exposure to DDTs did not affect protein content or CAT activity in any of the species. GST, GR and GPx activity showed different responses in exposed and control tomato plants. After DDTs exposure, tomato showed increased GR and GPX activity in stems and leaves, respectively, and a decrease in the GST activity in roots. As no effects were observed in zucchini, results suggest different susceptibility and/or defense mechanisms involved after pesticide exposure. Finally, both species differed also in terms of DDTs uptake and translocation. The knowledge about antioxidant responses induced by pesticides exposure could be helpful for planning phytoremediation strategies and for the selection of tolerant species according to particular scenarios.

Antioxidant responses in soybean and alfalfa plants grown in DDTs contaminated soils: Useful variables for selecting plants for soil phytoremediation?

Phytoremediation is a low-cost alternative technology based on the use of plants to remove pollutants from the environment. Persistent organic pollutants such as DDTs with a long half-life in soils are attractive candidates for remediation. This study aimed to determine the potential of antioxidant response use in the evaluation of plants' tolerance for selecting species in phytoremediation purposes. Alfalfa and soybean plants were grown in DDT contaminated soils. After 60days, growth, protein content, antioxidant capacity, GST activity, concentration of proteic and non-proteic thiol groups, chlorophyll content and carotenoid content were measured in plant tissues. Results showed no effect on alfalfa or soybean photosynthetic pigments but different responses in the protein content, antioxidant capacity, GST activity and thiol groups on roots, stems and leaves, indicating that DDTs affected both species. Soybean showed higher susceptibility than alfalfa plants due to the lower antioxidant capacity and GST activity in leaves, in spite of having the lowest DDT accumulation. This study provides new insights into the role of oxidative stress as an important component of the plant's response to DDT exposure.

Assessing polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in air across Latin American countries using polyurethane foam disk passive air samplers.

A passive air sampling network has been established to investigate polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) at Global Atmospheric Passive Sampling (GAPS) sites and six additional sites in the Group of Latin American and Caribbean Countries (GRULAC) region. The air sampling network covers background, agricultural, rural, and urban sites. Samples have been collected over four consecutive periods of 6 months, which started in January 2011 [period 1 (January to June 2011), period 2 (July to December 2011), period 3 (January to June 2012), and period 4 (July 2012 to January 2013)]. Results show that (i) the GAPS passive samplers (PUF disk type) and analytical methodology are adequate for measuring PCDD/F burdens in air and (ii) PCDD/F concentrations in air across the GRULAC region are widely variable by almost 2 orders of magnitude. The highest concentrations in air of Σ4-8PCDD/Fs were found at the urban site São Luis (Brazil, UR) (i.e., 2560 fg/m3) followed by the sites in São Paulo (Brazil, UR), Mendoza (Argentina, RU), and Sonora (Mexico, AG) with values of 1690, 1660, and 1610 fg/m3, respectively. Very low concentrations of PCDD/Fs in air were observed at the background site Tapanti (Costa Rica, BA), 10.8 fg/m3. This variability is attributed to differences in site characteristics and potential local/regional sources as well as meteorological influences. The measurements of PCDD/Fs in air agree well with model-predicted concentrations performed using the Global EMEP Multimedia Modeling System (GLEMOS) and emission scenario constructed on the basis of the UNEP Stockholm Convention inventory of dioxin and furan emissions.

Assessment of persistent organic pollutants accumulation and lipid peroxidation in two reproductive stages of wild silverside (Odontesthes bonariensis).

Persistent organic pollutants (POPs) in streamwater can sometimes exceed the guidelines values reported for biota and human protection in watersheds with intensive agriculture. Oxidative stress and cytotoxicity are some of the markers of exposure to POPs in fish. Accumulation of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) as well as lipid peroxidation (LPO) was assessed in wild silverside (Odontesthes bonariensis) from maturation and pre-spawning stages sampled in a typical soybean growing area. Pollutants were quantified by gas chromatography with electron capture detection and LPO by the method of thiobarbituric acid reactive substances. Concentrations of POPs were in the following order: OCPs>PCBs>PBDEs in all organs and stages. Liver, gills and gonads had the highest OCP concentrations in both sexes and stages with a predominance of endosulfan in all samples. Matured individuals, sampled after endosulfan application period, showed higher endosulfan concentrations than pre-spawning individuals. The predominance of endosulfan sulfate could be due to direct uptake from diet and water column, as well as to the metabolism of the parent compounds in fish. The prevalence of p,p'-DDE in liver would also reflect both the direct uptake and the metabolic transformation of p,p'-DDT to p,p'-DDE by fish. The highest levels of PBDEs and PCBs were found in gills and brain of both stages of growth. The pattern BDE-47>BDE-100 in all samples corresponds to pentaBDE exposure. In the case of PCBs, penta (#101 and 110) and hexa-CB congeners (#153 and 138) dominated in the maturation stages and tri (#18) and tetra-CB (#44 and 52) in pre-spawning stages, suggesting biotransformation or preferential accumulation of heavier congeners during gonadal development. Differences in LPO levels in ovaries were associated with growth dilution and reproductive stage. Differences in LPO levels in gills were related with pesticide application periods. As a whole, endosulfan, a current-use pesticide, constituted the main pollutant found in wild silverside reflecting the intense agriculture activity in the study area. Moreover endosulfan was positively correlated with LPO.

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.

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.

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.

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.

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.

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.

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.

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.