The formation of bound residues of diazinon in four UK soils: implications for risk assessment

The behaviour of diazinon in the soil determines the likelihood of further pollution incidents, particularly leaching to water. The most significant processes in the control of the fate of diazinon in the soil are microbial degradation and the formation of bound residues. Soils from four sites in the UK were amended with diazinon and its ¹⁴C labelled analogue and incubated for 100 days. After 0, 10, 21, 50 and 100 days, the formation of bound residues was assessed by solvent extraction, and the microbial degradation of diazinon by mineralisation assay. In microbially active soils, diazinon is degraded rapidly, reducing the risk of future pollution incidents. However, where there was limited mineralisation there was also significantly lower formation of bound residues, which may lead to water pollution via leaching. The formation of bound residues was dependent on extraction type. Acetonitrile extraction identified bound residues in all soils, with the bound residue fraction increasing with increasing incubation time.     

Influence of Suspended Clay Minerals and Humic Matter on the Solid Phase Extraction Efficiency of Selected Pesticides from Water

The purpose of this investigation was to determine the influence of humic acids (HA) and Ca-montmorillonite (CaM) on the solid-phase extraction (SPE) efficiency of atrazine, alachlor and α-cypermethrin from water samples at various pH-values. The nature and intensity of binding of the studied pesticides to CaM were determined by X-ray diffraction analysis and termogravimetric analysis (TGA) test. The studied pesticides eluted from discs were analysed by thin-layer chromatography (TLC). The effects of CaM and humic acid were generally pH-dependent and acted independently in extraction efficiency influence. Lower recovery of pesticides was observed at higher pH values when CaM was ≥0.1 g and was attributed to greater dispersion of clay, increased surface area and subsequent adsorption. Concentrations of dissolved organic carbon (DOC) in humic acid had less effect on the extraction efficiency when water was at pH 8 compared to water at pH 2, which was probably due to greater nonpolar interactions of the pesticides to the charge-neutralized humic acid molecule.     

The effect of soil:water ratios on the induction of isoproturon, cypermethrin and diazinon mineralisation

The rate of pesticide biodegradation does not remain constant with time, and is dependent on the physico-chemical properties of the soil and of the pesticide as well as on the biology of the soil. Prolonged or repeated contact between soil microbes and pesticides has been shown to result in an increase in the rate and extent of biodegradation. This work assessed the impact of the soil:water ratio on measurement of catabolic induction for ¹⁴C-isoproturon, ¹⁴C-diazinon and ¹⁴C-cypermethrin. Slurrying (1:1 and 1:3 soil:water) with agitation resulted in significantly higher rates and extents of mineralisation than the non-slurried system (P ? 0.05; 1:0 soil:water), except for the mineralisation of ¹⁴C-diazinon where the greatest extent of mineralisation occurred in non-slurried soil. Slurrying without agitation resulted in the significant lower mineralisation in all cases (P ? 0.05). There was a significant interaction between the soil:water ratio and length of contact (P ? 0.05). Whilst the use of slurried systems can enhance the extent and rate of mineralisation, there is no improvement in reproducibility, and so for the measurement of catabolic induction, the use of field conditions will lead to a more environmentally relevant measurement.     

The extractability and mineralisation of cypermethrin aged in four UK soils

Cypermethrin is a widely used insecticide that has caused concern due to its toxicity in the aquatic environment. As with all land applied pesticides, the most significant source of water pollution is from the soil, either due to leaching or washoff. The behaviour of cypermethrin in the soil controls the likelihood of future pollution incidents, with two of the most significant processes being the formation of bound residues and microbial degradation. The formation of bound residues and mineralisation was measured in four organically managed soils from the UK. The formation of bound residues was measured using three different extraction solutions, 0.01 M CaCl₂, 0.05 M HPCD and acetonitrile. Biodegradation was assessed by measurement of mineralisation of cypermethrin to CO₂. The formation of bound residues varied according to extraction method, soil type and length of ageing. In two of the four soils studied, acetonitrile extractability decreased from 100% initially to 12-14% following 100 d ageing. The extent of mineralisation increased after 10-21 d ageing, reaching 33% of remaining activity in one soil, however following 100 d ageing the extent of mineralisation was significantly reduced in three out of the four soils. As with the formation of bound residues, mineralisation was impacted by soil type and length of ageing.     

Effects of estrogen exposure in mussels, Mytilus edulis, at different stages of gametogenesis

Mytilus edulis were exposed to 17β-estradiol (E2) and the synthetic estrogens ethinyl estradiol (EE2) and estradiol benzoate (EB) for 10 days. Two exposures were performed to determine their effect on vitellogenin (VTG) and estrogen receptor 2 (ER2) mRNA expression at different stages of the reproductive cycle. Significant natural variation was not observed in VTG mRNA expression, though ER2 mRNA expression displayed significantly lower values during January, February and July compared with other times of the year. A significant increase in VTG and ER2 mRNA expression was observed in mussels exposed to estrogens at the early stage of gametogenesis. In contrast, mature mussels displayed no statistically significant change in the VTG or ER2 mRNA expression. The data presented suggests that the reproductive physiology of molluscs, in terms of VTG and ER2 mRNA expression, may be susceptible to damage by environmental estrogens at certain points in their gametogenesis process.     

Development of microbial degradation of cypermethrin and diazinon in organically and conventionally managed soils

The behaviour of pesticides in the soil is a complex issue and is controlled by the physical, chemical and biological properties of the soil. The ability of microorganisms to degrade pesticides is not only controlled by the bioavailability of a chemical but also by their capacity to develop the ability to utilise available chemicals. The development of catabolism in the indigenous soil microflora of four organically and one conventionally managed soils was investigated for two pesticides: cypermethrin and diazinon. Soils were amended with cypermethrin and diazinon and aged for 0, 2, 4, 6, 8, and 14 weeks and, at each time point, mineralisation of freshly added 14C-cypermethrin or 14C-diazinon was measured by trapping 14CO2. In general, contact times between the soil and the pesticide resulted in a reduction in the lag phase (the period of time before mineralisation exceeded 5% of the added activity), followed by increases in the extent of mineralisation. Cypermethrin was mineralised significantly in all soils; whereas, diazinon was only appreciably mineralised in two of the soils, most notably in the organic soil from Redesdale. Statistical analysis showed pH and organic matter content of the soil had a significant effect on the extent of mineralisation (P< or = 0.05) of the cypermethrin in the soils.