A comparison of the environmental impact of pesticide multiresidues and their occurrence in river waters surveyed by liquid chromatography coupled in tandem with UV diode array detection and mass spectrometry

Twenty-two pesticides and metabolites selected on the basis of a regional priority list, were surveyed in surface river waters by high performance liquid chromatography coupled in tandem with UV diode array detection and mass spectrometry, after an off-line pre-concentration step. Pesticide concentrations ranged between 0.07 and 4.8 microg/l according to the compound and sampling period. Analytical results were linked to the environmental risk of pesticides, evaluated by their system investigation of risk by integration of score (SIRIS) rank.     

Accelerated remediation of pesticide-contaminated soil with zerovalent iron

High pesticide concentrations in soil from spills or discharges can result in point-source contamination of ground and surface waters. Cost-effective technologies are needed for on-site treatment that meet clean-up goals and restore soil function. Remediation is particularly challenging when a mixture of pesticides is present. Zerovalent iron (Fe0) has been shown to promote reductive dechlorination and nitro group reduction of a wide range of contaminants in soil and water. We employed Fe0 for on-site treatment of soil containing > 1000 mg metolachlor, > 55 mg alachlor, > 64 mg atrazine, > 35 mg pendimethalin, and > 10 mg chlorpyrifos kg(-1). While concentrations were highly variable within the windrowed soil, treatment with 5% (w/w) Fe0 resulted in > 60% destruction of the five pesticides within 90 d and increased to > 90% when 2% (w/w) Al2(SO4)3 was added to the Fe0. GC/MS analysis confirmed dechlorination of metolachlor and alachlor during treatment. Our observations support the use of Fe0 for ex situ treatment of pesticide-contaminated soil.     

Trace Organic Matter in the Ria Formosa,Portugal

The Ria Formosa lagoon, Portugal, receives organic matter from many natural and anthropogenic sources. This paper presents an overview of the contribution these sources made through the use of lipid biomarkers. Sixty-one surface sediment samples were collected and analysed for a range of lipids. Sewage materials were confined to regions within 2 km of discharge points; phytoplankton biomarkers (sterols and fatty acids) suggest production was greatest in the inner parts of the lagoon that also have greatest inorganic nutrient enrichment; terrestrial organic matter was present in relatively low concentrations as shown by both sterol and fatty alcohols; bacteria were widespread although the Sulphate Reducing Bacteria (SRBs, shown by the presence of 3-OH fatty acids) were located near but not adjacent to sewage discharge points.     

Toxic elements leaching in different soils affected by the spill from the aznalcollar pyrite mine (Sevilla,Spain)

A study has been made of the leaching of Cd, Zn, Pb, Cu, Tl and As in three representative soils of the zone affected by the spill from a pyrite mine in Aznalcollar (Sevilla, Spain) employing packed soil columns. According to the breakthrough and cumulative leaching curves, the relative mobilities of the different toxic elements in the columns are as follows: Tl > Cd > Zn > As > Cu > Pb. The results also show that the soils themselves have a good capacity for immobilizing the soluble fraction of the elements from the spilled mud, this capacity varying as follows: clayey soil with a high carbonate content > clayey soil with a moderate carbonate content > sandy‐clay loam soil with a low carbonate content. The results obtained in the work are a valuable contribution to the necessary assessment of the impact of the toxic spill on underground waters.     

Vertical infiltration of fuel oil hydrocarbons in an agricultural soil

The influence of rainfall, air temperature and soil moisture on the vertical mobility in the soil of fuel oil hydrocarbons (HC) was investigated in a field experiment. A controlled spreading of fuel oil (nC10‐nC25) was performed at a rate of 5 L HCm^‐2 on an agricultural soil in summer and in winter. Concentration, chemical composition of HC and soil moisture were regularly determined at different soil depths between 0 and 140 cm, 1 h, 3, 8and 15 days (d) after the spreading of oil. Sorption of hydrocarbons onto the organo‐mineral matrix of the soil was studied in laboratory experiments. The results showed that in summer, with an air temperature of 24°C and without water leaching in the soil profile, 65% of the initial HC remained trapped in the 0–140 cm soil layer, about 20% of the HC volatilized and around 15% migrated deeper. A vertical selective migration of the lightest (nC10‐nC15) HC (naphthas) was shown lSd after the spreading of fuel oil. Naphthas progressively reached the 120–140 cm soil layers whereas the heavy fractions of oil (nC17‐nC25) migrated and concentrated in the 0–60 cm soil layers. In winter, when soil was regularly watered by rainfalls and at low air temperatures, only 47% of the initial HC remained in the 0–140 cm profile after 15 d. A fast vertical infiltration of naphthas occurred within the first 3 d. After 15 d, all HC were detected in the same relative amounts as in the initial oil in the whole profile. Volatilization was negligible in winter and an increase in the migration of total oil at depth in the soil profile was shown. As inferred from the laboratory experiments, the high soil moisture led to the decrease in HC sorption on the organo‐mineral matter of the soil.     

European starling nestling response to chlorpyrifos exposure in a corn agroecosystem

European starling (Sturnus vulgaris) nestlings were used as a surrogate to study the effect of chlorpyrifos application to a corn agroecosystem on songbird reproduction. Chlorpyrifos was applied in a T‐band at 1.3 kg AI/ha, and residues were measured in soil, earthworms, ground‐dwelling insects, and diet items collected from the crop of starling nestlings. Chlorpyrifos levels in soil peaked at 34.2 μg/g, 4 days post‐application, and dissipated to trace levels by 64 days post‐application. Concentrations of chlorpyrifos in earthworms and ground‐dwelling insects reached 0.9 and 0.7 ug/g, respectively. Starling nestling diet items included invertebrates from eight orders with chlorpyrifos concentrations ranging from trace levels to 10.6 μg/g in earthworms. Nestling brain and plasma cholinesterase (ChE) activity and body mass measurements were taken at 3, 8, and 13 days post‐hatch (DPH). Adult starling fecundity was also measured. Body mass differences between treatment and reference site nestlings at 3 and 13 DPH were not significant at α = 0.05. However, 8 DPH nestlings from the Treatment Site had a transient reduction in weight (p = 0.03) when compared with 8 DPH reference nestlings. There were no significant differences in brain or plasma ChE activities of 3, 8, or 13 DPH nestlings. Further, multiple measures of fecundity (i.e., clutch size, hatching percentage, and fledging percentage) indicated that chlorpyrifos application did not affect starling nestling survival to fledging, as the values from the Treatment and Reference Site were nearly identical. This screening‐level study suggests that although one age group of starling nestlings from the Treatment Site weighed less than their Reference Site counterparts, a single T‐band application of chlorpyrifos did not impair starling nesting success.     

Tessaria absinthioides: a possible bio‐monitor for Cd,Pb, and Cu,in the middle and lower basin of the loa river,North Chile

Some ecotoxic metals such as Cd, Pb, and Cu in Tessaria absinthioides were quantified to study its possible use as a bio‐indicator and/or bio‐monitor of these metals. This plant was chosen for its abundance in the area under study, along Chile and even in southern Latin America. For Cd, Pb, and Cu in all three parts of the plant (leaves, stems and roots) a different concentration pattern in each sampling areas was observed. In sampling areas Coya Sur and La Cascada copper and cadmium concentration decrease in order: leaves > roots > stems. In samples collected in Xalquincha the lowest concentrations of Cd and Pb were observed in stems. A maximum of cadmium concentration (9ug/gd.w. in leaves) was found in samples from La Cascada, a inflow to river Loa in Calama. High concentrations of lead were found in roots and leaves. Collected data demonstrate that the main pathway for cadmium is from ground water via roots into the plant. Some data obtained for lead and copper indicate that the influence of dust particles adsorbed on leaves and stems can be higher than uptake from ground water.     

Exposure of ground water to alachlor,atrazine and metolachlor in maize areas of ribatejo and oeste (Portugal)

In irrigated maize areas of an important Portuguese agricultural area, Ribatejo and Oeste Region, alachlor, atrazine and metolachlor were detected in ground water.

During the study performed from 1996 to 1998 atrazine was the herbicide that showed the highest frequency of detection. In the 177 ground water samples collected 62% were contaminated with atrazine, 30% with alachlor and 12% with metolachlor. All these herbicides were detected both in ground water for human consumption and for irrigation, in some cases above 0.1 ug/L. The maximum levels quantified were 13μg/L for alachlor, 30μg/L for atrazine and 56 μg/L for metolachlor.

Seasonal variation of residues in ground water it is also presented through several examples of studies performed during the period 1991–1999.     

An evidence of salinity impact on the bioaccumulation of heavy metals in fishes collected from the Messolonghi lagoon in Greece

The impact of salinity and water exchange rate on the accumulation of heavy metals in the benthic fish Zosterissesor ophiocephalus, collected from the shallow sublagoons Tholi and Paleopotamos, was studied. Both sublagoons are influenced by the intensive agricultural activity of the surrounding area in terms of the chemical substances’ drainage, and by the untreated sewage discharges of an urbanized area with Paleopotamos being affected in lesser extent. Paleopotamos is characterised by restricted water renovation, resulting to much higher salinity than Tholi. The bioaccumulation of the heavy metals studied (Manganese, Zinc and Copper), reveals differences among the metals with females showing higher values. Specimens from Paleopotamos showed statistically significant higher bioaccumulation of the heavy metals in both sexes, which is attributed to the extremely high salinity of this sublagoon.     

The distribution,metabolism and toxicity of 14c-DDT in model aquarium tanks with fish and sediment simulating a tropical marine environment

Studies conducted on the distribution, fate and metabolism of DDT in a model ecosystem simulating a tropical marine environment of fish, Gobious nudiceps, Lethrinus harak, Gobious keinesis, Gobious nebulosis and white shrimp (Panaeus setiferus), show that DDT concentration in the water decreases rapidly within the first 24?h. Rapid accumulation of the pesticide in the biota also reaches a maximum level in 24?h before gradually declining. The bioaccumulation factors calculated for the fish species (G. keinesis) and white shrimp (P. Setiferus) were 270 and 351, respectively, after 24?h. There was a steady build up of DDT residues in the sediment during the first 24?h which continued to a maximum concentration of 6.66?ng/g in the seawater/fish/sediment ecosystem after 3 weeks and 5.27?ng/g in the seawater/shrimps/sediment ecosystem after 2.7 days. The depuration of the accumulated pesticide was slow with only 54% lost in G. nudiceps within 3 days of exposure in fresh sea water. By contrast, depuration was fast in the white shrimp, which lost 97% of the accumulated pesticide under the same conditions. DDT was found to be toxic to two of the fish species (G. nebulosis and L. harak) and to white shrimp, and the degree of toxicity was dependent on the particular species. The 24?h LC₅₀ at room temperature for the fish species G. nebulosis and white shrimp was found to be 0.011 and 0.116?mg/kg, respectively. These levels are comparable to the ones recorded for the temperate organisms. Degradation of DDT to its primary metabolites, DDE and DDD, was found in all the compartments of the ecosystem with DDE being the major metabolite in the fish, shrimps and sediment, while in seawater, DDD dominated as the major metabolite.