Persistence of fipronil and its metabolites in soil under field conditions

Fipronil belongs to phenylpyrazole class of chemical compounds. Degradation of fipronil in sandy loam soil was investigated under field conditions by applying fipronil (Regent 5 % SC) at 50 (T ₁) and 100 g a.i. ha^?1 (T ₂) in field. Samples were drawn periodically in triplicate on 0 (1 h after treatment), 1, 3, 7, 10, 15, 30, 60, and 90 days after treatment and analyzed on GC-ECD system equipped with capillary column. The residues of fipronil in both the doses dissipated in the range of 93.33–100 % in 90 days. Limit of detection (LOD) and limit of determination (LODe/LOQ) were 0.0003 and 0.001 mg kg^?1, respectively. Dissipation followed a biphasic first-order kinetics with half-life values of 10.81 and 9.97 days for fipronil alone and 8.14 and 13.05 days for fipronil along with metabolites in soil at (T ₁) and (T ₂) treatments, respectively.     

Pyrimethanil residue and dissipation in tomatoes and soil under field conditions

A residue analytical method to detect pyrimethanil in tomatoes and soil was developed by using high-performance liquid chromatography with a diode array detector. The dissipation and residue level of pyrimethanil in tomatoes and soil were also investigated. Results showed that the average recoveries are in the range of 87.2 to 90.0 % with a relative standard difference of 2.22 to 7.61 % in tomatoes and soil. In Guangdong, Shandong, and Yunnan, the half-lives of pyrimethanil in tomatoes were 1.8, 3.6, and 4.2 days and those in soil were 4.0, 3.3, and 3.9 days, respectively. The dissipation rate of pyrimethanil in tomatoes and soil was affected by temperature, precipitation, and soil type. The terminal residue results showed that when pesticide pyrimethanil was used under the experiment design, all the results were far below the available maximum residue limits. Low residues in tomatoes and soil suggest that this pesticide is safe to use under the recommended dosage.     

Dissipation behavior and risk assessment of butralin in soybean and soil under field conditions

Dissipation behavior, final residue, and risk assessment of butralin in soybean, green soybean, plant, and soil were investigated. Butralin residues were extracted with acetonitrile and then soybean samples were detected with gas chromatography-mass spectrometer (GC-MS) and soil samples were determined with GC with nitrogen phosphorous detector (GC-NPD). The limit of quantification (LOQ) of the method was 0.01 mg/kg for soybean, green soybean, plant, and soil. Average recoveries ranged from 90.4 ~ 98.2% for green soybean, 86.2 ~ 86.6% for soybean, 86.0 ~ 98.8% for plant, and 85.0 ~ 106.8% for soil. The relative standard deviations (RSDs) were 2.0 ~ 7.2% for green soybean, 2.0 ~ 3.0% for soybean, 3.1 ~ 8.1% for plant, and 1.8 ~ 6.6% for soil. Half-lives of butralin in soil samples varied in the range of 11–22 days. At harvest time, final residues of butralin in soybean and green soybean were lower than LOQ. Risk assessment demonstrated that, at recommended dosage and frequency, butralin would not induce significant harm on humans. The study could be used as a quantitative basis for application of butralin on soybean.     

Effects of transgenic Bt cotton on soil fertility and biology under field conditions in subtropical inceptisol

Although there is large-scale adoption of Bt cotton by the farmers because of immediate financial gain, there is concern that Bt crops release Bt toxins into the soil environment which reduces soil chemical and biological activities. However, the majorities of such studies were mainly performed under pot experiments, relatively little research has examined the direct and indirect effects of associated cover crop of peanut with fertilization by combined application of organic and inorganic sources of nitrogen under field conditions. We compared soil chemical and biological parameters of Bt cotton with pure crop of peanut to arrive on a valid conclusion. Significantly higher dehydrogenase enzyme activity and KMnO₄-N content of soil were observed in Bt cotton with cover crop of peanut over pure Bt cotton followed by pure peanut at all the crop growth stages. However, higher microbial population was maintained by pure peanut over intercropped Bt cotton, but these differences were related to the presence of high amount of KMnO₄-N content of soil. By growing cover crop of peanut between Bt cotton rows, bacteria, fungi, and actinomycetes population increased by 60%, 14%, and 10%, respectively, over Bt cotton alone. Bt cotton fertilized by combined application of urea and farm yard manure (FYM) maintained higher dehydrogenase enzyme activity, KMnO₄-N content of soil and microbial population over urea alone. Significant positive correlations were observed for dry matter accumulation, dehydrogenase enzyme activity, KMnO₄-N content, and microbial population of soil of Bt cotton, which indicates no harmful effects of Bt cotton on soil biological parameters and associated cover crop. Our results suggest that inclusion of cover crop of peanut and FYM in Bt cotton enhanced soil chemical and biological parameters which can mask any negative effect of the Bt toxin on microbial activity and thus on enzymatic activities.     

Fate of carbosulfan and monocrotophos in sandy loam soils of Pakistan under field conditions at different watertable depths

Information regarding pesticide mobility is critical for the evaluation of pesticide management practices. For this purpose, lysimetric studies were conducted to develop assessment schemes to protect groundwater from unacceptable effects caused by pesticide use. By using these studies, specific monitoring actions and prevention measures for the protection of waters can be studied, and the results thus obtained can provide the local authorities and the decision makers with an identification tool for demarcating risk areas. Pesticide residues were found at the bottom of lysimeters in the following pattern i.e., 1.52 > 2.1 > 2.74 m which could represent an "index of risk" for groundwater pollution. Regressions built for carbofuran and monocrotophos against watertable depths showed a decreasing trend of pesticide in higher watertable treatments. These findings support the existence of a significant role for chromatographic flow in sandy texture soil. Moreover, the higher values of pesticide residue at the bottom of lysimeters reflect that chromatographic flow as well as preferential flow pattern prevails during higher precipitation events. The precipitation received during the study was higher than the 10 year average and can be considered relatively as a worst case scenario. Finally, the authors have recommended a standardized pesticide monitoring scheme for groundwater in accordance with the already validated generic schemes in developed countries.     

Atmospheric dispersion of radon gas and its decay products under stable conditions in arid regions of Australia

The radon and radon daughter concentration-in-air from natural background are assessed along with the micrometeorology and synoptic weather systems in an arid region of Australia. The radon daughter contribution to population dose is biased towards the frequency of nocturnal inversions. Classical atmospheric models are not applicable during stable atmospheric conditions in inland Australia. An atmospheric Box Model is used along with measured data from tethersonde profiles in predicting radon/radon daughter concentration-in-air. Predicted and measured concentrations are compared for spatial and temporal variations.     

Dissipation and residue of azoxystrobin in banana under field condition

A method was developed for determining azoxystrobin in banana and cultivation soil using gas chromatography. The dissipation and residue of azoxystrobin in banana fields at GAP conditions were investigated. The average recoveries ranged from 80.3 to 96.0 % with relative standard deviations of 2.9 to 7.2 % at three different spiking levels for each matrix. The results indicated that the half-life of azoxystrobin in bananas and soil ranged from 7.5 to 13.5 days in Guangdong and from 8.7 to 12.7 days in Fujian. The dissipation rates of azoxystrobin in banana and soil were almost the same. Terminal residues in banana and banana flesh (0.01 mg/kg) were all below the maximum residue limit (2 mg/kg by Codex Alimentarius Commission and China). The results demonstrated that the safety of using azoxystrobin at the recommended agriculture dosage to protect bananas from diseases.     

The dissipation of ethofenprox in cabbage and soil under open conditions

The dissipation of ethofenprox in cabbage and soil under open conditions was investigated at two primary cabbage-growing regions, Beijing and Kunming in China. Samples were extracted with acetonitrile and determined by ultra-performance liquid chromatography with a single quadrupole detector. Dissipation of ethofenprox from cabbage and soil can be best explained by a first-order decay process. The half-lives of ethofenprox were 1.9 and 2.3 days in cabbage and 20.0 and 13.0 days in soil at Beijing and Kunming, respectively. The concentration of ethofenprox residue was reduced by 90% taking 7 and 60 days in cabbage and soil. Dissipation rates in cabbage and soil at two geographically separated experimental fields differed, suggesting that this was affected by complicated factors, such as local climate and soil characteristics. These data could provide guidance for the proper and safe use of this pesticide on cabbage in China.     

Persistence and effect of processing on reduction of fipronil and its metabolites in chilli pepper (Capsicum annum L.) fruits

A single laboratory UPLC-MS/MS method was developed and validated for the estimation of fipronil and its metabolites in fresh and dry chilli pepper fruits. Dissipation of fipronil on chilli fruits was studied following the application of fipronil (Jump 80 WG) at 40 and 80 g active ingredient (a.i.) ha^?1 in the fruiting stage of the crop. The initial deposits of total fipronil on fresh chilli fruits at single and double dose application were 0.69 and 1.43 μg g^?1, respectively, and were dissipated to below quantitation level at 27 days after application. The half-life of fipronil at single and double dose in fresh chilli pepper was 4.22 and 4.32 days and the waiting period was 25.9 and 30.6 days, respectively. Processing factor due to sun drying was calculated by measuring fipronil residues in dry chilli fruits, and it ranged from 2.96 to 3.50 during 0 to 21st day after application. Among the metabolites of fipronil, fipronil desulfenyl and fipronil sulfone had maximum residues in fresh and dried chilli, respectively, followed by fipronil sulfide. Dipping in solutions of tamarind, turmeric, vinegar and slaked lime and wet scrubbing could remove more than 90 % of fipronil residues in fruits.     

Mobility of spiromesifen in packed soil columns under laboratory conditions

On percolating water equivalent to 1,156 mm of rainfall, spiromesifen formulation did not leach out of 25-cm long columns, and 62.7 % of this was recovered in 5–10-cm soil depth. In columns treated with the analytical grade, 52.40 % of the recovered spiromesifen was confined to 0–5-cm soil depth, with 0.04 % in leachate fraction, suggesting high adsorption in soil. Results revealed that percolating 400 mL of water, residues of enol metabolite of spiromesifen was detected up to 20–25-cm soil layer, with 23.50 % residues of spiromesifen in this layer and 1.73 % in the leachate fraction indicating that metabolite is more mobile as compared to the parent compound. Results suggested a significant reduction in leaching losses of enol metabolite in amended soil columns with 5 % nano clay, farmyard manure (FYM), and vermicompost. No enol spiromesifen was recovered in the leachate in columns amended with nano clay, vermicompost, and FYM; however, 85.30, 70.5, and 65.40 %, respectively, was recovered from 0–5 cm-soil depth of column after percolating water equivalent to 1,156 mm of rainfall. Spiromesifen formulation is less mobile in sandy loam soil than analytical grade spiromesifen. The metabolite, enol spiromesifen, is relatively more mobile than the parent compound and may leach into groundwater. The study suggested that amendments were very effective in reducing the downward mobility of enol metabolite in soil column. Further, it resulted in greater retention of enol metabolite in the amendment application zone.     

Dissipation and residue of metalaxyl and cymoxanil in pepper and soil

A simple and accurate method of determining metalaxyl and cymoxanil in pepper and soil was developed by ultra-performance liquid chromatography–photodiode array detection. The limits of detection were 0.015 mg/kg for metalaxyl and 0.003 mg/kg for cymoxanil. The limits of quantification were 0.05 mg/kg for metalaxyl in pepper and soil as well as 0.01 mg/kg for cymoxanil in pepper and soil. Recoveries of pepper and soil were investigated at three spiking levels and ranged within 77.52 to 102.05 % for metalaxyl and 87.15 to 103.21 % for cymoxanil, with relative standard deviations below 9.30 %. For field experiments, the half-lives of metalaxyl were 3.2 to 3.9 days in pepper and 4.4 to 9.5 days in soil at the three experimental locations in China. At harvest, pepper samples were found to contain metalaxyl and cymoxanil well below the maximum residue limit MRLs of the European Union (EU) following the recommended dosage and the interval of 21 days after last application.     

Simulation of pyrite oxidation in fresh mine tailings under near-neutral conditions

Sulphidic residual products from ore processing may produce acid rock drainage, when exposed to oxygen and water. Predictions of the magnitude of ARD and sulphide oxidation rates are of great importance in mine planning because they can be used to minimize or eliminate ARD and the associated economic and environmental costs. To address the lack of field data of sulphide oxidation rate in fresh sulphide-rich tailings under near-neutral conditions, determination and simulation of the rate was performed in pilot-scale at Kristineberg, northern Sweden. The quality of the drainage water was monitored, along with oxygen and carbon dioxide concentrations. The chemical composition of the solid tailings was also determined. The field data were compared to predictions from simulations of pyrite oxidation using a 1-D numerical model. The simulations' estimates of the amount of Fe and S released over a seven year period (52 kg and 178 kg, respectively) were in reasonably good agreement with those obtained by analysing the tailings (34 kg and 155 kg, respectively). The discrepancy is probably due to the formation of secondary precipitates such as iron hydroxides and gypsum; which are not accounted for in the model. The observed mass transport of Fe and S (0.05 and 1.0 kg per year, respectively) was much lower than expected on the basis of the simulations and the core data. Neutralization reactions involving carbonates in the tailings result in a near-neutral pH at all depths except at the oxidation front (pH < 5), indicating that the dissolution of carbonates was too slow for the acid to be neutralized, which instead neutralized deeper down in the tailings. This was also indicated by the reduced abundance of solid Ca at greater depths and the high levels of carbon dioxide both of which are consistent with the dissolution of carbonates. It could be concluded that the near-neutral pH in the tailings has no decreasing effect on the rate of sulphide oxidation, but does reduce the concentrations of dissolved elements in the drainage water due to the formation of secondary minerals. This means that sulphide oxidation rates may be underestimated if determined from drainage alone.     

The evaluation of a low resolution fourier transform infrared (FTIR) gas analyser for monitoring of solvent emission rates under field conditions

The applicability of a low resolution (8 cm-1) Fourier transform infrared (FTIR) gas analyser with an absorption path length of 3 m was evaluated for the on-line monitoring of organic solvent mixture emissions in a flexographic ink manufacturing plant. The on-line monitoring revealed that the highest variations of solvent concentrations, up to three decades, occurred in the exhaust air. The FTIR analyser with a dynamic range of four decades covers well the concentration ranges typically found in the exhaust air and in the workroom air of ink manufacturing plants. The average emission rate of solvent mixture based on a sampling period of two days was 1.8 kg h-1 consisting of mainly ethanol (70%), ethyl acetate (15%) and propan-2-ol (11%). The detection limits of the analyser for the solvent compounds ranged from 0.3 to 4.3 mg m-3 and the measurement uncertainty was less than 10% in the concentration range of 8-15,000 mg m-3. These characteristics make the apparatus appropriate for most industrial hygiene applications. An FTIR spectrophotometer, equipped with an multipoint sampling unit, facilitates rapid identification of solvent components, real-time display of concentration data relevant to workroom air and environment monitoring as well as process control. Furthermore, the on-line concentration information enabled a rapid selection of representative sampling locations. The spectrophotometer is transportable, rugged and relatively simple to calibrate even in a hostile industrial environment.     

In utero and post-natal accumulation of organochlorine compounds in children under different environmental conditions

A study of intake of organochlorine compounds (OCs) in children both in utero and at the age of four years has been performed in two cohorts. One encompasses children born in Menorca Island between 1997 and 1998, and the other those born between 1997-1999 in Ribera d'Ebre, an in-land industrial-agricultural area of Catalonia. Comparison of the OC concentrations in serum samples from both populations, including those obtained from cord blood and blood collected at four years, provides information on the influence of local pollution sources in the accumulation of these compounds. Statistically significant differences (p < 0.01) have been found for hexachlorobenzene, indicating that chronic airborne contamination to this compound in Ribera d'Ebre involved higher in utero exposure, which increased in the first four years of growth. Similarly, in the cohort of Menorca, higher in utero exposure to PCBs was observed and this increased subsequently in the first four years of growth. Other compounds encompassing temporal contamination episodes such as gamma-HCH involved higher in utero exposure but strongly diminished in the first four years of growth. Overall, it can be concluded that local chronic pollution by OCs has a direct effect in children living in the surrounding areas. This influence is reflected in higher exposure, both in utero and in the first years of growth, that significantly stands out over the background contamination due to the ubiquity of these compounds.     

Residue and intake risk assessment of prothioconazole and its metabolite prothioconazole-desthio in wheat field

In the environment, plants and animals in vivo, pesticides can be degraded or metabolized to form transformation products (TPs) or metabolites, which are even more toxic than parent pesticides. Hence, it was necessary to evaluate residue and risk of pesticides and their TPs (or metabolites). Here, a rapid, simple, and reliable method using QuEChERS and LC-MS/MS had been developed for simultaneous analysis of prothioconazole and its toxic metabolite, prothioconazole-desthio, in soil, wheat plant, straw, and grain. The average recoveries of prothioconazole and prothioconazole-desthio in four matrices ranged from 86 to 108% with relative standard deviations (RSDs) of 0.53–11.87% at three spiking levels. The method was successfully applied to investigate the dissipation and terminal residues of the two compounds in wheat field. It was shown that prothioconazole was rapidly degraded to prothioconazole-desthio, with half-lives below 5.82 days. Prothioconazole-desthio was slowly dissipated in soil and plant. The terminal residues of prothioconazole in wheat grain with a pre-harvest interval (PHI) of 21 or 28 days were below the maximum residue limits (MRLs) (0.1 mg/kg, Codex Alimentarius Commission (CAC)). We also evaluated the intake risk of prothioconazole-desthio residues in wheat grain in China. For long-term intake assessment, the hazard quotients (HQ) ranged from 1.30 to 5.95%. For short-term intake assessment, the acute hazard indexes (aHI) ranged from 1.94 to 18.2%. It indicated that the intake risk of prothioconazole-desthio in wheat consumption was acceptable. Thus, the prothioconazole application on wheat with the scientific practices would not pose public health risk.     

The decline and residues of hexaconazole in tomato and soil

The decline and terminal residues of hexaconazole in tomato and soil in open field were studied. Hexaconazole residues were determined by gas chromatography coupled with an electron capture detector. Recoveries were between 89% and 110% with RSD of 2.99–5.88% in tomato and 90–119% with RSD of 1.15–5.76% in soil at spiked levels of 0.01, 0.1, and 1 mg/kg, respectively. The limit of detection of hexaconazole was 6.3 × 10⁻¹² g. The decline rates of hexaconazole were described using first-order kinetics and the mean half-lives of hexaconazole in tomato and soil were 4.3 and 18.1 days, respectively. The terminal residues in tomato at interval of 7 days at the dosage of 150 g.a.i./hm² for three or four times were all below 0.1 mg/kg. This work would be the guidance of establishing the maximum residue limit of hexaconazole in tomato in China.