Karina S. B. Miglioranza

Fate of organochlorine pesticides in soils and terrestrial biota of “Los Padres” pond watershed, Argentina

Abstract Concentrations of organochlorine pesticides (OCPs) in soils and associated biota around “Los Padres” pond watershed were determined by gas chromatography with electron capture detector (GC–ECD). Pesticides were analyzed in different horizons (upper 0–15, middle 15–30, lower 45–55 cm) of natural and horticultural soils, developed in highlands and lowlands. Physical and chemical characteristics (organic matter content, pH, moisture, texture, etc.) were determined. Higher concentrations of total OCPs were found in highlands, because of the high content of clay material and organic matter. Lindane, heptachlor, aldrin, DDT and metabolites were found in soils. Depending on physical and chemical characteristics of pesticides and soils, different behaviours were found. Lindane could leach down to lower horizons, rich in clays, while hydrophobic pesticides remain in the upper horizons, retained by organic matter. Vegetables (carrots and potatoes) accumulated lindane with important contributions of DDTs and heptachlor. OCPs were taken up, accumulated and metabolized efficiently by terrestrial invertebrates (earthworms and beetles). The results obtained testify the pollution by OCPs in “Los Padres” pond watershed.

Occurrence of glyphosate and AMPA in an agricultural watershed from the southeastern region of Argentina.

Glyphosate (GLY) and AMPA concentrations were determined in sandy soil profiles, during pre- and post-application events in two agricultural soybean fields (S1 and S2). Streamwater and sediment samples were also analyzed. Post-application sampling was carried out one month later from the event. Concentrations of GLY+AMPA in surface soils (0-5 cm depth) during pre-application period showed values 20-fold higher (0.093-0.163 μg/g d.w.) than control area (0.005 μg/g d.w.). After application event soils showed markedly higher pesticide concentrations. A predominance of AMPA (80%) was observed in S1 (early application), while 34% in S2 for surface soils. GLY+AMPA concentrations decreased with depth and correlated strongly with organic carbon (r between 0.74 and 0.88, p<0.05) and pH (r between -0.81 and -0.76, p<0.001). The slight enrichment of pesticides observed from 25 cm depth to deeper layer, in addition to the alkaline pH along the profile, is of high concern about groundwater contamination. Sediments from pre-application period showed relatively lower pesticide levels (0.0053-0.0263 μg/g d.w.) than surface soil with a predominance of glyphosate, indicating a limited degradation. Levels of contaminants (mainly AMPA) in streamwater (ND-0.5 ng/mL) denote the low persistence of these compounds. However, a direct relationship in AMPA concentration was observed between sediment and streamwater. Despite the known relatively short half-life of glyphosate in soils, GLY+AMPA occurrence is registered in almost all matrices at different sampling times (pre- and post-application events). The physicochemical characteristics (organic carbon, texture, pH) and structure of soils and sediment in addition to the time elapsed from application determined the behavior of these contaminants in the environment. As a whole, the results warn us about vertical transport trough soil profile with the possibility of reaching groundwater.

Agricultural soil as a potential source of input of organochlorine pesticides into a nearby pond

A study was conducted in the southeastern region of Buenos Aires province, Argentina, to assess an agricultural soil as a potential source of organochlorine (OC) pesticides for the aquatic biota of a nearby pond. We analyzed γ-HCH (lindane), still in use, and the following banned compounds: DDT, DDE, DDD heptachlor, heptachlor epoxide, aldrin, dieldrin and endrin in soil, bulrush, grass shrimp and fish using gas chromatography with electron capture detection (GC-ECD). Among the OC pesticides, lindane was most dominant in the soil (32.6 ng/g dry wt in the upper and 173.9 ng/g dry wt in the lower horizon) and bulrush (1.9 μg/g lipid). Macrophyte also accumulated high levels of heptachlor epoxide (1.5 μg/g lipid). Heptachlor, although present in the soil, was below the detection limit in all aquatic biota studied. Its primary degradation product, heptachlor epoxide, was found in both soil and biota samples. DDT was found at low levels in the surface soil (6.8 ng/g dry wt), but at higher concentrations in fish (3.6 μg/g lipid), although levels were still below permissible levels for human consumption. Since most of the compounds were found in both soil and aquatic biota, our study suggests that agricultural soil could be an important source for OC pesticides in the nearby pond.

Land-based Sources of Marine Pollution: Organochlorine Pesticides in Stream Systems

BackgroundOrganochlorine pesticides (OCPs) have been dispersed ubiquitously in the environment. Bottom sediments act as sinks for these compounds and their concentrations often reflect the degree of anthropogenic pollution. This study was designed to evaluate the occurrence and distribution of OCPs in superficial streambed sediments and their relation to land use in two creeks that contribute to the coastal pollution of the southeastern region of Argentina.MethodsSampling sites were selected by a combination of land use and stream type. Las Brusquitas creek, which passes through vast agricultural areas, and La Tapera creek which originates in a natural wetland and passes through horticultural farming and urban areas. OCPs quantification was carried out by GC-ECD.Results and DiscussionResults showed similar total OCP concentrations in sediments from both creeks in the range of 6–25 ng/g dry wt. However, when OCPs were expressed in ng/g total organic carbon (TOC), La Tapera creek presented 4-fold higher total levels as a consequence of a higher OCP input during the recent past in that watershed. La Tapera outfall showed 4-fold higher levels than that seen in Las Brusquitas, although both values were below the sediment quality criteria demanded to protect wildlife. ΣZEndosulfans, ΣDDTs and Σchlordanes were the main OCP group in all samples, with Endosulfan sulfate being the most frequent and abundant compound. The predominance of metabolites with respect to parent compounds suggests a contamination mainly by runoff from aged and weathered agricultural soils.ConclusionsDespite OCPs being banned, they still exist in creek sediments from the studied region, representing continuous contributions of land-based source contaminants to the marine environment.OutlookFuture research on OCP levels in suspended sediments is recommended in order to determine the total OCP concentrations in the selected stream systems.

Trends in Soil Science: Organochlorine Pesticides in Argentinean Soils

Argentina covers an area of 2,766,890 km 2 at the southern end of South America. The combination of temperate weather, soil richness (organic matter > 7%) and proper rainfall lead to the enormous tracts of land that are claimed for agricultural use. As a consequence, intensification of land use for agricultural purpose has had a wide range of environmental effects. The development of agriculture interferes with the natural processes of soil formation and exposes the land to both wind and water erosion, the immediate effect of which is a loss of the topsoil. The gradual change in Argentina towards modern and intensive agricultural activities has led to an increase in the

Organic pollutant levels in an agricultural watershed: the importance of analyzing multiple matrices for assessing streamwater pollution

This study is aimed at analyzing the occurrence and transport of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in the Quequén Grande river basin, as representative of a catchment under diffuse pollution sources. Pollutant levels in soils, river bottom sediments (RBS), streamwater (Sw), suspended particle materials (SPMs), macrophytes and muscle of silverside were determined by GC-ECD. Soil K(d) values for the current-used insecticides, endosulfans and cypermethrin, were established. Total levels (ng g(-1) dry weight) in soil ranged between 0.07–0.9 for OCPs, 0.03–0.37 for PCBs and 0.01–0.05 for PBDEs. Endosulfan insecticide (α- + b- + sulfate metabolite) represented up to 72.5% of OCPs. The low soil retention for α-endosulfan (K(d): 77) and endosulfan sulfate (K(d): 100) allows their transport to Sw, SPM and RBS. Levels of endosulfan in Sw in some cases exceeded the value postulated by international guidelines for aquatic biota protection (3 ng L(-1)). PCB and PBDE pollution was related to harbour, dumping sites and pile tire burning. Tri and hexa PCB congeners predominated in all matrices and exceeded the quality guideline value of 0.04 ng L(-1) in Sw. Considering levels in silverside muscle, none of the oral reference doses were exceeded, however, PCBs accounted for 18.6% of the total daily allowed ingest for a 70 kg individual. Although the levels of PCBs and OCPs in soil and RBS were low and did not go beyond quality guidelines, these compounds could still represent a risk to aquatic biota and humanbeings, and thus actions towards preventing this situation should be undertaken.

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.

Potential use of edible crops in the phytoremediation of endosulfan residues in soil

Endosulfan is a persistent and toxic organochlorine pesticide of banned or restricted use in several countries. It has been found in soil, water, and air and is bioaccumulated and magnified in ecosystems. Phytoremediation is a technology that promises effective and inexpensive cleanup of contaminated hazardous sites. The potential use of tomato, sunflower, soybean and alfalfa species to remove endosulfan from soil was investigated. All species were seeded and grown in endosulfan-spiked soils (8000 ng g(-1) dry weight) for 15 and 60 days. The phytoremediation potential was evaluated by studying the endosulfan levels and distribution in the soil-plant system, including the evaluation of soil dehydrogenase activity and toxic effects on plants. Plant endosulfan uptake leads to lower insecticide levels in the rhizosphere with regards to bulk soil or near root soil at 15 days of growth. Furthermore, plant growth-induced physical-chemical changes in soil were evidenced by differences in soil dehydrogenase activity and endosulfan metabolism. Sunflower showed differences in the uptake and distribution of endosulfan with regard to the other species, with a distribution pesticide pattern of aerial tissues > roots at 15 days of growth. Moreover, at 60 days, sunflower presented the highest pesticide levels in roots and leaves along with the highest phytoextraction capacity. Lipid peroxidation levels correlated positively with endosulfan accumulation, reflecting the negative effect of this insecticide on plant tissues. Considering biomass production and accumulation potential, in conjunction with the reduction of soil pesticide levels, sunflower plants seem to be the best phytoremediation candidate for endosulfan residues in soils.

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.

Endosulfan leaching from Typic Argiudolls in soybean tillage areas and groundwater pollution implications

Endosulfan has been recently added to Persistent Organic Pollutants (POPs) list and due to its extensive and massive use and environmental persistence constitutes a potential hazard to groundwater resources. Undisturbed soil columns were used to evaluate endosulfan leaching in two series of Typic Argiudolls considering natural and agricultural land use. Columns were spiked with 10μgL(-1) of technical endosulfan and eluted under saturated flow with five pore volumes of distilled water. Alfa and beta isomer residues were detected in the upper soil level, with decreasing values through the profile, being influenced by soil texture and land use. The endosulfan sulfate metabolite was mainly found in the upper level linked to high dehydrogenase activity. Results from leachates (total endosulfan 27-87ngL(-1)) showed higher α-isomer mobility, and suggest alkaline hydrolysis of both endosulfan isomers. The agricultural use modified the physico-chemical properties and structure of soils leading to vertical migration of endosulfan isomers under saturated conditions. Intact column test provided information close to field data showing its utility for the assessment of groundwater pollution by endosulfan.