Photodegradation of organophosphorus insecticides - investigations of products and their toxicity using gas chromatography-mass spectrometry and AChE-thermal lens spectrometric bioassay

Four organophosphorus compounds: azinphos-methyl, chlorpyrifos, malathion and malaoxon in aqueous solution were degraded by using a 125 W xenon parabolic lamp. Gas chromatography-mass spectrometry (GC-MS) was used to monitor the disappearance of starting compounds and formation of degradation products as a function of time. AChE-thermal lens spectrometric bioassay was employed to assess the toxicity of photoproducts. The photodegradation kinetics can be described by a first-order degradation curve C=C0e(-kt), resulting in the following half lives: 2.5min for azinphos-methyl, 11.6 min for malathion, 13.3 min for chlorpyrifos and 45.5 min for malaoxon, under given experimental conditions. During the photoprocess several intermediates were identified by GC-MS suggesting the pathway of OP degradation. The oxidation of chlorpyrifos results in the formation of chlorpyrifos-oxon as the main identified photoproduct. In case of malathion and azinphos-methyl the corresponding oxon analogues were not detected. The formation of diethyl (dimethoxy-phosphoryl) succinate in traces was observed during photodegradation of malaoxon and malathion. Several other photoproducts including trimethyl phosphate esters, which are known to be AChE inhibitors and 1,2,3-benzotriazin-4(3H)-one as a member of triazine compounds were identified in photodegraded samples of malathion, malaoxon, and azinphos-methyl. Based on this, two main degradation pathways can be proposed, both result of the (P-S-C) bond cleavage taking place at the side of leaving group. The enhanced inhibition of AChE observed with the TLS bioassay during the initial 30 min of photodegradation in case of all four OPs, confirmed the formation of toxic intermediates. With the continuation of irradiation, the AChE inhibition decreased, indicating that the formed toxic compounds were further degraded to AChE non-inhibiting products. The presented results demonstrate the importance of toxicity monitoring during the degradation of OPs in processes of waste water remediation, before releasing it into the environment.     

Determination of selected neonicotinoid insecticides by liquid chromatography with thermal lens spectrometric detection

We studied the analysis of trace amounts of neonicotinoid insecticides by liquid chromatography coupled with a thermal lens spectrometric detector (TLS). This multi-residue analysis method is based on the reversed phase separation on C₁₈ column, isocratic elution and collinear dual beam TLS detection. The insecticides thiamethoxam, imidacloprid, acetamiprid and thiacloprid were detected with retention times of 4.4, 5.7, 6.5 and 8.5 min and limits of quantifications of 50, 89, 10, and 25 μg/L, respectively. The retention times agreed well with those obtained by the same chromatographic method but using a diode-array detector (DAD). The limits of quantifications for imidacloprid were identical in both techniques. However, the limits of quantifications for thiamethoxam, acetamiprid and thiacloprid were up to 8.5 times lower using the TLS detector compared to the diode-array detector. The applicability of the developed procedure was tested on spiked river water and potato samples.     

Oxidation of organophosphorus pesticides with chloroperoxidase enzyme in the presence of an ionic liquid as co-solvent

Effects of selected ionic liquids on the efficiency of CPO oxidation of methyl-parathion were studied. In general, the activity of CPO decreases with the increased concentration of ionic liquid. For ionic liquids with the same cation, those with PF₆ ^? exhibit strongest inhibition toward CPO, while those with either BF₄ ^? or metSO₄ ^? show relatively lesser inhibition. It was further demonstrated that even for buffer solutions containing up to 30% concentration of ionic liquids such as EAN, BMIMmetSO₄, and EtPyTFA, CPO still can retain high activity (70–100% compared to that in citrate buffer) for oxidation of methyl-parathion. Photothermal enhancement factors of 3.5 times and corresponding improvements of sensitivity in the determination of organophosphates by the FIA-TLS method are predicted in 30% ionic liquids.     

Validation of the CANDY model with Russian long-term experiments

The CANDY model has been qualitatively assessed for simulating long-term dynamics of soil organic carbon and tested against different long-term experiments representing various land uses and geographical sites, but never before against conditions of the Former Soviet Union (FSU). Our goal was to simulate long-term trends in soil organic carbon for the long-term experiments of Barybino (Moscow region, Russia), Grakov (Kharkow region, Ukraine) and Yachenka (Minsk region, Belarus) representing the predominant arable soil types, climate conditions and typical management strategies for the investigated arable areas. The fit of modelled results to the observed data was evaluated to assess the suitability of the model for further applications in the FSU. The crop parameters of the CANDY model had to be adapted to the low yields observed under the Russian site conditions resulting in a higher sensitivity to crop-derived carbon input as a function of yield. The results show that the approach of treating the organic carbon situated in micro pores as inert, is an applicable solution for simulating soil carbon dynamics under Russian conditions. This evaluation of CANDY, against long-term experiments from Russia, gives confidence for its wider application in this region.     

Photolytic and photocatalytic degradation of 6-chloronicotinic acid

This work describes for the first time the photolytic and photocatalytic degradation of 6-chloronicotinic acid (6CNA) in double deionised water, which is a degradation product of neonicotinoid insecticides imidacloprid and acetamiprid, and it is known to appear in different environmental matrices. Photolytic experiments were performed with three UVA (ultraviolet A) polychromatic fluorescent lamps with broad maximum at 355 nm, while photocatalytic experiments were performed using immobilised titanium dioxide (TiO₂) on six glass slides in the spinning basket inside a photocatalytic quartz cell under similar irradiation conditions. Photolytic degradation revealed no change in concentration of 6CNA within 120 min of irradiation, while the photocatalytic degradation within 120 min, obeyed first-order kinetics. The observed disappearance rate constant was k = 0.011 ± 0.001 min⁻¹ and t_1/2 was 63.1 ± 5.5 min. Mineralisation rate was estimated through total organic carbon (TOC) and measurements revealed no carbon removal in case of photolysis after 120 min of exposure. However in photocatalytic experiments 46 ± 7% mineralisation was achieved within 120 min of irradiation. Nevertheless, the removal of total nitrogen (TN) was not observed across all experiments. Ion chromatographic analyses indicated transformation of chlorine atoms to chloride and increase of nitrate(V) ions only via photocatalytic experiments. Efficiency of selected advanced oxidation process (AOP) was investigated through toxicity assessment with Vibrio fischeri luminescent bacteria and revealed higher adverse effects of treated samples on bacteria following photocatalytic degradation in spite of the fact that higher mineralisation was achieved. New hydroxylated product generated in photocatalytic experiments with TiO₂, was confirmed with liquid chromatography-electro spray ionisation mass spectrometry (LC-ESI-MS/MS) analyses, gas chromatography-mass spectrometry (GC-MS) and nuclear magnetic resonance spectroscopy (¹H NMR).     

Future land use and land cover in Southern Amazonia and resulting greenhouse gas emissions from agricultural soils

Regional Environmental Change - The calculation of robust estimates of future greenhouse gas emissions due to agriculture is essential to support the framing of the Brazilian climate change...     

Changes in mineral soil organic carbon stocks in the croplands of European Russia and the Ukraine, 1990–2070; comparison of three models and implications for climate mitigation

Three soil carbon models (RothC, CANDY and the Model of Humus Balance) were used to estimate the impacts of climate change on agricultural mineral soil carbon stocks in European Russia and the Ukraine using detailed spatial data on land-use, future land-use, cropping patterns, agricultural management, climate and soil type. Scenarios of climate were derived from the Hadley Centre climate Version 3 (HadCM3) model; future yields were determined using the Soil–Climate–Yield model, and land use was determined from regional agricultural and economic data and a model of agricultural economics. The models suggest that optimal management, which entails the replacement of row crops with other crops, and the use of extra years of grass in the rotation could reduce Soil organic carbon (SOC) loss in the croplands of European Russia and the Ukraine by 30–44% compared to the business-as-usual management. The environmentally sustainable management scenario (SUS), though applied for a limited area within the total region, suggests that much of this optimisation could be realised without damaging profitability for farmers.