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.

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.

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.

Persistent organic pollutants in sediments, intertidal crabs, and the threatened Olrog's gull in a northern Patagonia salt marsh, Argentina.

Persistent organic pollutants (POPs) are of great concern for the environment. In this study we (a) determine levels and distribution of OCPs, PCBs, and PBDEs in sediments and two crab species (Neohelice granulata and Cyrtograpsus altimanus), (b) assess bioaccumulation in crabs, and (c) explore the occurrence of POPs in the Near Threatened Olrog's gull (Larus atlanticus) chicks and eggs in one of the most important salt marsh environments in the South West Atlantic. Sediments, crabs, and gull chicks and eggs showed POPs presence at low levels; being α-endosulfan, PCB-153, and BDE-47 the most represented compounds. In sediments, pollutant concentrations were lower than those reported in Canadian guidelines for the protection of the aquatic life. POP bioaccumulation was recorded in crabs, suggesting a risk to upper trophic level predators. Further studies are needed to understand the trophic effects of POPs in San Blas bay, particularly on the threatened Olrog's gull.

Reproductive biology of the cockfish, Callorhinchus callorynchus (Chondrichthyes: Callorhinchidae), in coastal waters of the northern Argentinean Sea

The cockfish, Callorhinchus callorynchus, is a widely distributed holocephalan in the south-western Atlantic and an important resource for Argentinean fisheries. The reproductive characteristics of this species were studied in northern Argentinean coastal waters, where specimens arrive seasonally (winter-spring). Sexual dimorphism in maximum precaudal length (PCL) and total body mass (TM) was found, being females (PCL=630 mm; TM=3330 g; n=167) larger and heavier than males (PCL=482 mm; TM=1630 g; n=19). Maturity size for females was 466.22 mm PCL, representing 74% PCL of the largest female sampled. The mean number of ovarian follicles was 8.37 (± 4.84). The highest values of ovarian follicles diameter, gonadosomatic and oviducalsomatic indices were found in spring. A high proportion of mature females (44%) had atretic ovarian follicles, suggesting that they were in the resting stage of their reproductive cycle. The low number of mature males recorded and the absence of mature females with spermatophore masses or egg cases indicate that the study area would not be a reproductive zone. The seasonal presence of C. callorynchus in this region could be related to trophic movements. These results, obtained in an area with high fishing pressure on chondrichthyans, will be useful for implementing conservation and management measures.(AU)

El pez gallo, Callorhinchus callorynchus, es un holocéfalo con amplia distribución en el Atlántico Sudoccidental y un recurso importante para las pesquerías en Argentina. Las características reproductivas de esta especie fueron estudiadas en aguas costeras al norte del Mar Argentino, adonde se acercan estacionalmente (invierno-primavera). Se observó dimorfismo sexual en los valores máximos de longitud precaudal (LPC) y masa corporal total (MT), siendo las hembras (LPC=630 mm; MT=3330 g; n=167) más grandes y pesadas que los machos (LPC=482 mm; MT=1630 g; n=19). La talla de maduración para las hembras fue de 466,22 mm LPC, representando el 74% de la LPC máxima observada. El número promedio de folículos ováricos fue 8,37 (± 4,84). Los valores más altos del diámetro de los folículos ováricos, índice de la glándula oviductal e índice gonadosomático fueron hallados durante primavera. Una gran proporción de hembras maduras (44%) presentaron folículos ováricos atrésicos, sugiriendo que se encontraban en la etapa de reposo de su ciclo reproductivo. El bajo número de machos maduros registrados y la ausencia de hembras maduras con espermatóforos o cápsulas de huevos indican que las aguas costeras del norte de Argentina no serían una zona reproductiva. La presencia de C. callorynchus en el área de estudio podría estar relacionada con movimientos tróficos. Los resultados, obtenidos en un área con una gran presión pesquera sobre los condrictios, serán útiles para implementar adecuados planes de manejo y conservación de esta especie.(AU)

Persistent organic pollutants (POPs) in fish with different feeding habits inhabiting a shallow lake ecosystem.

The occurrence of persistent organic pollutants (POPs) in the environment can affect organisms inhabiting aquatic systems, in particular shallow lakes that are vulnerable to environmental stressors. This study aimed to assess POPs accumulation and changes at histological and physiological levels in tissues of three fish species with different trophic habits. Gills, brain, muscle, liver and gonads of Odontesthes bonariensis, Oligosarcus jenynsii and Cyphocharax voga were collected from the shallow lake La Peregrina, located in an agricultural area from Argentina. In addition, contaminant levels in surface water (SW), suspended particulate matter (SPM) and bottom sediments (BS) were assessed. Histological lesions were evaluated in fish tissues and levels of vitellogenin (VTG) were assessed in plasma of male fish in order to correlate these alterations with the presence of POPs in the environment. Organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were determined by GC-ECD. Biotic and abiotic samples showed the same POPs distribution pattern: OCPs>PCBs>PBDEs. Although tissue distribution of OCPs was species-specific, muscle showed the lowest levels in all species. The most abundant contaminants were endosulfans, suggesting their widespread use in the area. O. bonariensis showed the highest endosulfans levels in liver (184.2-219ngg(-1)wet w), which was associated with the high SPM levels considering this species is a filter feeder. The occurrence of PCBs and PBDEs shows the ubiquity of these pollutants in the area. Histological lesions in gills and liver of O. bonariensis and O. jenynsii, might be related with the high levels of endosulfans in these organs. The detection of VTG in males warns about a possible exposure to estrogenic compounds in the environment. In conclusion, the simultaneous exposure of fish to multiple environmental pollutants leads to different alterations, so measures should be taken in order to prevent their occurrence and toxic effects.

Assessment of Argentinean Patagonia pollution: PBDEs, OCPs and PCBs in different matrices from the Río Negro basin.

This work reports the occurrence and distribution of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in soil, sediment, suspended particle matter (SPM), streamwater and macrophytes, along the Río Negro basin, Argentinean Patagonia. The clear predominance of OCPs among all matrices indicates the impact of agriculture on the watershed. The highest levels were found for pp'-DDE which represented up to 95% in agricultural soils (42.0-1.27x10(3) ng/g d.w) from the Upper Valley (upstream), where long and historical intensive fruit cultures have been settled and represent a hot spot of legacy pesticides for the environment. The insecticide endosulfan, currently in use, was also found in all matrices. Levels ranged between 0.3 and 708.0 ng/g d.w, being the highest concentrations those of SPM from the Middle Valley, just before the delta area, where pesticides would be retained leading to lower concentrations as was observed downstream. PCB (#153, 138, 110, 101) and PBDE (BDE-47) levels were directly related with the presence of hydroelectric power plants, dams and dumping sites, mainly settled in the Upper Valley (0.8 ng/g and 15.1 ng/g d.w for PBDEs and PCBs, respectively). Although there was a decreasing gradient of these pollutant concentrations through the river flow, downstream urban areas enhanced PCB concentrations in the aquatic environment. More efforts and monitoring programs are highly required to control and reduce soil erosion in order to prevent the availability of forbidden pollutants in the environment.

Increasing levels of persistent organic pollutants in rainbow trout (Oncorhynchus mykiss) following a mega-flooding episode in the Negro River basin, Argentinean Patagonia.

In 2006, a severe flooding episode in the Negro River basin, Argentinean Patagonia, occurred and mainly affected the middle valley where lands are devoted to agriculture and soils known to be polluted with persistent organic pollutants. The aim of this study was to estimate the effects of this event on polybrominated diphenyl ethers (PBDEs), endosulfans (α-, ß-, sulfate), DDTs (p,p'-DDD, p,p'-DDE, p,p'-DDT) and polychlorinated biphenyls (PCBs) levels in rainbow trout (Oncorhynchus mykiss) tissues. Post-event fish showed higher contaminants levels than pre-event at expenses of all groups. DDTs presented the highest concentrations in all tissues followed by PCBs, endosulfans and PBDEs. The metabolite p,p'-DDE represented about 80% of total DDTs, while PCBs were dominated by penta- and hexa-chlorobiphenyls congeners. BDE-47 was the predominant congener among PBDEs. Endosulfan showed the maximum differences between post- and pre-flood fish (up to 43-fold) with a α-/ß- ratio >1, suggesting exposure to fresh technical mixture. Contaminant profiles observed in rainbow trout tissues from both periods (pre- and post-event) were consistent with previous results from water, suspended particle matter and soils, showing that this species is a good biomonitor of aquatic pollution of Negro River basin. The presence of the pesticides in the Negro River system resulted from past and current agricultural practices and it was modified and enhanced by the flooding. Additionally, PCBs and PBDEs occurrence in the aquatic environment deserve more attention, and monitoring programs are recommended in order to diminish their incorporation to aquatic ecosystem.

Polybrominated diphenyl ethers and organochlorine compound levels in brown trout (Salmo trutta) from Andean Patagonia, Argentina.

Polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), DDTs and endosulfan residues were analyzed in muscle, liver, gonads, gills and stomach content of brown trout (Salmo trutta) from the Andean Patagonia. PBDEs, PCBs and DDTs levels were positively correlated with lipid content, while less hydrophobic endosulfans showed a poor correlation. Endosulfan levels were about 99.9% of total contaminant (highest levels in liver 500×10(3)ng g(-1) lipid weight), with α-/ß-isomers ratio >1 in all organs. These results are in agreement to the current-use of the technical endosulfan and also suggest acute exposure to this insecticide. Conversely, DDT/DDE ratio reflects fish exposure to old DDT sources, showing a DDE predominance. Gills had the highest levels of DDTs, PCBs and PBDEs, indicating they represent the main uptake pathway for such hydrophobic compounds from water column. PCBs showed the lowest levels in all organs and the PBDEs/PCBs ratios >1 agree with worldwide trends. PBDEs levels in gonads, gills, liver and muscle exceeded 80 ng g(-1) (lipid weight) and were higher than other values reported in the Southern Hemisphere. BDE-47 was the predominant congener, suggesting higher bioaccumulation potential and possible brown trout metabolism of higher congeners. Since there is no point source of PBDEs in the region and residues were dominated by lower brominated congeners, atmospheric transport could be the main source of these compounds. This first report of PBDEs levels in fish from Argentina contributes to the knowledge about environmental trends of these persistent organic pollutants (POPs) in remote areas such as the Andean Patagonia.