Influence of land use on chlorpyrifos and persistent organic pollutant levels in honey bees, bee bread and honey: Beehive exposure assessment.

This work reports the spatial and temporal variations on the dynamics of OCPs, PCBs, PBDEs and chlorpyrifos in honey bee, bee bread and honey samples, as well as soil and flowers from the surrounding areas, considering, different land uses. Honey bee samples showed the highest pollutant levels, with a predominance of the industrial contaminants over pesticides. Chlorpyrifos showed the highest concentration during the application period in almost all samples from the soybean field (S2), in concordance with its current use. By other hand, the recalcitrant compounds such as, DDTs, BDE #47 and also light PCBs exhibited the highest levels in beehive samples from the field adjacent to urban disposal waste (S3). In both soils and flower samples a prevalence of obsolete compounds over chlorpyrifos was observed, and the 6-CB predominated among the homologous groups of PCBs These results highlights the importance of soils as sink of these persistent contaminants, which became available depending on environmental conditions. Results revealed that the land uses and seasonal variations have directly impacted on the levels of agrochemicals, PCBs and PBDEs found in the beehive matrixes. This survey provides novel evidence about the current situation of pollution on honey bee colonies under temperate climates and contributes to the knowledge of this poor studied topic in Argentina.

A multilevel response approach reveals the Asian clam Corbicula largillierti as a mirror of aquatic pollution.

The endobenthic bivalves are widely used as a bioindicators since they inhabit the sediment-water interface and are able to accumulate a different kind of contaminants. In the present work, we evaluated wild Corbicula largillierti (Phillippi, 1844) as a bioindicator of water quality in the central region of Argentina. The responses at different levels of the biological organization were used. We measured organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) levels in water and clams tissues. The biomarkers selected were enzymatic activities (Glutathione S-Transferase, Catalase, Acetyl-, Butyryl-cholinesterase, and Carboxylesterase) morphometry of the digestive gland, condition index and morphology of valves. In order to integrate all the responses a multivariate analysis and integrated stress index were applied. Our results showed the presence of contaminants along the studied river and the ability of C. largillierti to bioaccumulate them. All the biomarkers selected varied according to the water quality gradient, although there was no specific correlation with OCPs and PCBs levels. At the most polluted sites, the detoxification and oxidative stress enzymes, the morphometric analysis of the digestive gland and the variation in the morphology of the valves indicated the water quality degradation. The multivariate analyses allowed to discriminate the sites according to the different biomarker responses. The IBR index also showed a variation pattern according to the environmental quality gradient along the basin. According to the responses shown by C. largillierti we suggest this species as an useful bioindicator of aquatic pollution.

Spatio-temporal trends and body size differences of OCPs and PCBs in Laeonereis culveri (Polychaeta: Nereididae) from Southwest Atlantic estuaries.

Southwest Atlantic (SWA) estuaries have been historically impacted by industrial and agricultural activities that represent an important source of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). Intraspecific differences in OCPs and PCBs levels were evaluated in the benthic polychaete Laeonereis culveri from SWA estuaries (Samborombón; Mar Chiquita; Quequén Grande and Bahía Blanca) at different spatio-temporal scales. Regarding inter- and intra-estuarine spatial comparisons polychaetes showed significant differences in OCPs/PCBs levels (p < 0.05) being DDTs, endosulfan, penta- and hexa-CBs homologues the most representative compounds. Intra-estuarine comparisons also showed significant differences in terms of seasonality and body size (p < 0.05). OCPs/PCBs concentrations were negatively correlated with animal weight, but this covariable was not relevant on differences observed. OCPs/PCBs levels in polychaetes showed strong relationships with those of sediments, being suitable for estuarine biomonitoring studies. Seasonal and body-size differences found in OCPs and PCBs levels in tissues reveal the importance of these factors for intra-estuarine monitoring.

Sublethal effects in Perinereis gualpensis (Polychaeta: Nereididae) exposed to mercury-pyrene sediment mixture observed in a multipolluted estuary.

Sediment-living organisms can be subjected to a multi-pollution condition due to an increase in the diversity of contaminants. Sediment mixtures of Mercury (Hg) and some polycyclic aromatics hydrocarbons like Pyrene (Pyr) are common in heavily industrialized coastal zones. In the present study, greater than (>) and less than (<) probable effect concentration levels (PELs) of Hg and Pyr were assessed using spiked sediments in order to determine combined (Hg + Pyr) effects in uptake, metabolization and oxidative balance in the polychaete Perinereis gualpensis at short and medium-term exposure. Hg + Pyr significantly influenced the uptake/kinetics of Hg and Pyr metabolite 1-OH-pyrene in polychaete tissues during the exposure time compared with separate treatments of each analyte (p < 0.05). Both the Hg-only and Pyr-only exposures significantly influenced both enzymatic and non-enzymatic responses respect to control groups (p < 0.05). The Hg-only treatment showed the worst scenario related to the activation and subsequent inhibition of glutathione S- transferase (GST) and peroxidase (GPx) activities, high levels of Thiol-groups (SH-groups), low antioxidant capacity (ACAP) and enhanced lipid peroxidation (TBARS) in the last days of exposure (p < 0.05). In contrast, ragworms exposed to Hg + Pyr showed a significant increase in both enzymatic and non-enzymatic activity during the first days of exposure and the absence of lipid peroxidation during the whole experiment. Our results suggest different oxidative stress scenarios in P. gualpensis when exposed to >PEL Hg concentration with

Evaluation of the Health Status of the Silverside (Odontesthes bonariensis) at a RAMSAR Site in South America.

The objective of this work was to evaluate the health status of an economic and ecologically important fish species from Mar Chiquita Lake, a RAMSAR site located in Cordoba, Argentina, relative to the levels of selected persistent organic pollutants (POPs) in lake water and fish tissues. Odontesthes bonariensis was used as a model species, and its health was estimated by means of histological indices in gills and liver. Sampling was performed according to rainy and dry seasons (i.e. dry, rainy and post-rainy). Gill and liver histopathology were evaluated by semi-quantitative indices and morphometric analysis. Although epithelial lifting in gills and lipid degeneration in liver were frequently registered, they are considered as reversible if environmental conditions improve. During rainy and post-rainy seasons fish presented significantly higher scores of liver and total indices. These higher index scores were correlated with increased levels of POPs in gill and liver tissue. Therefore, preventive measures are needed to mitigate the entry of these compounds into the lake.

Uptake, metabolism and sub-lethal effects of BDE-47 in two estuarine invertebrates with different trophic positions.

Two microcosm types -sediment-biota and biota-biota- were constructed to simulate different pathways of BDE-47 uptake, metabolism and oxidative stress effects in two key estuarine invertebrates (polychaete Laeonereis acuta and crab Cyrtograpsus angulatus). In the sediment-biota experiment, both species were exposed to spiked sediments; an environmentally reported and a high concentration of BDE-47 for 2 weeks. In the biota-biota experiment, crabs were fed with polychaetes pre-exposed to BDE-47 in the sediment-biota experiment. The sediment-biota experiment first revealed that polychaetes significantly accumulated BDE-47 (biota-sediment accumulation factor >2; p < 0.05) to a much greater extent than the crab organs (muscle, hepatopancreas, gills) at both sediment concentrations. For oxidative stress responses, polychaete and crab tissues exposed to spiked sediment showed a significant increase (p < 0.05) of only glutathione S-transferase (GST) activity with respect to controls in both BDE-47 concentrations. No lipid peroxidation (TBARS) or total antioxidant capacity (ACAP) changes were evident in the species or organs exposed to either BDE-47 sediment concentration. The biota-biota experiment showed that feeding crabs with pre-exposed polychaetes caused BDE-47 accumulation in organs as well as significant amounts of BDE-47 eliminated through feces (p < 0.05). Unlike the sediment-biota exposure, crabs fed with pre-exposed BDE-47 polychaetes showed the most conspicuous oxidative stress responses. Significant changes in GST and ACAP in both hepatopancreas and gills, in addition to enhanced TBARS levels in the hepatopancreas with respect to controls (p < 0.05), revealed that BDE-47 assimilated by invertebrates represents a potential source of toxicity to their predators. No methoxylated metabolites (MeO-PBDEs) were detected during BDE-47 metabolism in the invertebrates in either of the two different exposure types. In contrast, hydroxylated metabolites (OH-PBDEs) were detected in polychaetes and crab organs/feces in both experiments. Our results demonstrate that PBDE hydroxylation is one of the main biotransformation routes of BDE-47 in estuarine animals, which could be associated with the oxidative stress responses found.

Different carbon sources affect PCB accumulation by marine bivalves.

Pampean creeks were evaluated in the present study as potential land-based sources of PCB marine contamination. Different carbon and nitrogen sources from such creeks were analysed as boosters of PCB bioaccumulation by the filter feeder bivalve Brachidontes rodriguezii and grazer limpet Siphonaria lessoni. Carbon of different source than marine and anthropogenic nitrogen assimilated by organisms were estimated through their C and N isotopic composition. PCB concentration in surface sediments and mollusc samples ranged from 2.68 to 6.46 ng g(-1) (wet weight) and from 1074 to 4583 ng g(-1) lipid, respectively, reflecting a punctual source of PCB contamination related to a landfill area. Thus, despite the low flow of creeks, they should not be underestimated as contamination vectors to the marine environment. On the other hand, mussels PCB bioaccumulation was related with the carbon source uptake which highlights the importance to consider this factor when studying PCB distribution in organisms of coastal systems.

Organochlorine pesticides and PCBs in Southern Right Whales (Eubalaena australis) breeding at Península Valdés, Argentina.

Organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) were assessed in blubber from 35 dead Southern Right Whales (SRW - Eubalaena australis) stranded at Península Valdés, Argentina. The life cycle includes a feeding period in high productivity areas of the South West Atlantic and a reproductive period in coastal template waters of Argentina. Organochlorine pesticides showed higher concentrations (22.6±13.8 ng·g(-1)ww) than PCBs (7.5±10 ng·g(-1)ww). Among pesticides, HCHs, DDTs, endosulfans, dieldrin, chlordans, heptachlor epoxide, and trans-nonachlor were detected. p,p'-DDE and p,p'-DDT were present in 69% and 26% of samples, respectively. p,p'-DDT/p,p'-DDE ratio showed low values (<0.33) as a result of aged DDT inputs. However, the occurrence of only p,p'-DDT in some samples suggests a recent pesticide input. α-HCH/γ-HCH ratio (

Multimatrix measurement of persistent organic pollutants in Mar Chiquita, a continental saline shallow lake.

RAMSAR sites are determined by specific characteristics of the environment in terms of ecological productivity as well services for human development, but they are also one of the most threatened ecosystems. Thus, the objective of this work was to evaluate the dynamic of Persistent Organic Pollutants (POPs) in different biotic and abiotic matrixes of the RAMSAR site (wetlands with international importance), Mar Chiquita Lake. Sampling was performed according to land use (agricultural, urban, and industrial) at two stations: Laguna del Plata and Campo Mare. POPs were analyzed in superficial water (Sw), suspended particulate material (SPM), bottom sediment (Bs) and fish tissues (Odontesthes bonariensis). Organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were analyzed by GC-ECD. HCHs, Endosulfans, DDTs, PCBs and PBDEs were found in all matrixes at both stations. The high persistence and transport processes are responsible for the occurrence of HCHs, DDTs and PCBs in Bs, SPM and fish tissues, even many years after their prohibition. PBDEs showed lower levels according to the scarcity of punctual sources in the area. Endosulfan showed variable amounts in agreement with application periods since this pesticide was used until a few years ago in this area. Finally, PCB levels overpassed the acceptable daily intake for human consumption being a risk for human health Thus, the present report confirms the occurrence of POPs in Mar Chiquita lake, alerting on the contribution of agricultural and urban pollutants in a RAMSAR site. Current results also raise concerns on biomagnification processes through the food web.

Antioxidant, phase II and III responses induced by lipoic acid in the fish Jenynsia multidentata (Anablapidae) and its influence on endolsulfan accumulation and toxicity.

Antioxidants like lipoic acid (LA) are known to trigger augmented antioxidant and phase II and III responses. This study aimed to evaluate the effect of LA in P-glycoprotein (Pgp) expression, glutathione-S-transferase (GST) activity, total antioxidant competence, levels of lipid peroxides (TBARS) and accumulation of the organochlorine insecticide endosulfan (Endo: α-, ß-isomers and sulfate metabolite) in different organs of the fish Jenynsia multidentata. One hundred and twenty females (1.55±0.07 g) were fed during 8 days with (n=60) or without (n=60) a LA enriched ration (6000 mg/kg). Four experimental groups were defined: -LA/-Endo; +LA/-Endo; -LA/+Endo; and +LA/+Endo. Endo groups were exposed during 24 h to 1.4 µg of insecticide/L. Results showed that only LA induced a significant increment in liver Pgp expression. GST activity was augmented in liver after exposure to LA or Endo. TBARS levels were lowered in liver and gills after LA pre-treatment. Total antioxidant capacity was lowered in liver of Endo exposed fish, a result that was reversed by LA pre-treatment. It is concluded that LA induced the expected effects in terms of Pgp expression, GST activity and reduced TBARS levels although favored α-Endo accumulation in brain. However, the Endo metabolism to the more persistent endosulfan sulfate was not facilitated by LA pre-treatment.

PBDEs, PCBs and organochlorine pesticides distribution in edible fish from Negro River basin, Argentinean Patagonia.

DDTs, endosulfans, HCHs, chlordanes, PCBs and PBDEs levels were determined in different tissues of patagonian silverside (Odontesthes hatcheri) from the Upper (UV), Middle (MV) and Lower (LV) valleys of the Negro River, Argentina. Results showed a direct relation between pollutant levels in fish and land uses along the basin. All tissues showed decreasing levels from headwaters (UV) to downstream (LV). A significant predominance of organochlorine pesticides (306-3,449 ng g(-1) lipid) followed by ΣPCBs (65-3,102 ng g(-1) lipid) and ΣPBDEs (22-870 ng g(-1) lipid) was observed in all tissues and valleys, suggesting agriculture as the main source of pollutants in this basin. Pesticides were dominated by DDTs (90% pp'-DDE) followed by endosulfan (α->ß->sulfate), γ-HCH and γ-chlordane showing the prevalence of legacy compounds. Endosulfan levels point out the current use of technical endosulfan in the surrounding areas. The highest PCBs and PBDEs concentrations observed in fish from UV were associated to hydroelectric power plants and industries established upstream. PCB fingerprint presented a prevailing contribution of hexa-CBs (66 ± 7%) and penta-CBs (27 ± 9%), with a similar composition to Aroclor 1254-1260. The predominance of BDE-47 (69 ± 17%) among PBDEs, followed by BDE-100 and BDE-99, suggests possible debromination processes. These results were similar to worldwide trends found in fishes and environmental compartments. PCBs levels in silverside muscles along the Negro River exceeded the maximum limits for safe consumption, suggesting a possible human health risk related to silverside ingest. Therefore, a continued long-term monitoring of organic contaminants in fishes is needed in order to assess the potential risk for human health.

Uptake, tissue distribution and metabolism of the insecticide endosulfan in Jenynsia multidentata (Anablepidae, Cyprinodontiformes).

The study reports the accumulation, distribution and metabolism of technical endosulfan in Jenynsia multidentata. Adult females were exposed to acute sublethal concentrations (0.072, 0.288 and 1.4 µg L⁻¹). After 24 h, fish were sacrificed and gills, liver, brain, intestine and muscle were removed. Results show that both isomers of technical-grade endosulfan (α- and ß-) are accumulated in fish tissues and biotransformation to endosulfan sulfate occurs at all concentrations tested. Significantly differences in endosulfan accumulation were only found at 1.4 µg L⁻¹ but not between the lowest concentrations. However a similar distribution pattern was observed at all exposure levels where liver, intestine and brain had the highest levels of α-, ß-endosulfan and endosulfan sulfate. Moreover, liver and brain showed the highest endosulfan sulfate:α-endosulfan ratios due to high biotransfomation capacity. J. multidentata demonstrated to be a sensitive species under exposure to technical endosulfan and, therefore, could be used to assess aquatic pollution.

Striped weakfish (Cynoscion guatucupa): a biomonitor of organochlorine pesticides in estuarine and near-coastal zones.

The general goal of this study was to investigate the role of Cynoscion guatucupa as a biomonitor of organochlorine pesticides (OCP) contamination in Bahía Blanca estuary. Thus, we evaluated whether or not OCP fish distribution pattern reflects the OCP land sources, and if size-related bioaccumulation and biomagnification of these contaminants does occur by comparing different tissues of juvenile and adults of C. guatucupa (Cuvier, 1830). Size-related bioaccumulation in C. guatucupa was observed and it was more important for the more lipophilic and biomagnifying OCP, being determined over time by diet influence. Endosulfan sulfate, chlordanes, HCH isomers and DDT compounds predominated in tissues and ingested food of C. guatucupa, being alpha-chlordane, heptachlor and p,p'-DDE highly bioaccumulated and biomagnificated. Our findings also showed that male adults of C. guatucupa are biomonitors of OCP pollution so we propose this species for further investigations in other coastal zones of South America.