Fate of the 14C-labeled herbicide prosulfocarb in a soil and in a sediment-water system

The fate of ¹⁴C-labeled herbicide prosulfocarb was studied in an agricultural soil and in a sediment-water system, the sediment part of which was derived from Yangtze Three Gorges Reservoir, China. Time-course studies were performed for 28 d and 49 d, respectively. Main transformation routes of ¹⁴C-prosulfocarb were mineralization to ¹⁴CO₂ and formation of nonextractable residues amounting to 12.13% and 10.43%, respectively, after 28 days (soil), and 9.40% and 11.98%, respectively, after 49 d (sediment-water system). Traces of prosulfocarbsulfoxide were detected by means of TLC, HPLC, and LC-MS; other transformation products were not found. Initial extraction of soil assays using 0.01 M CaCl₂ solution showed that the bioavailability of the herbicide was considerably low; immediately after application (0.1 d of incubation), only 4.78% of applied radioactivity were detected in this aqueous fraction. DT₅₀ values of ¹⁴C-prosulfocarb estimated from radio-TLC and -HPLC analyses were above 28 d in soil and ranged between 29 d and 49 d in the sediment-water system. Partitioning of ¹⁴C from water to sediment phase occurred with DT₅₀ slightly above 2 d. With regard to the sediment-water system, adsorption occurred with log K_oc = 1.38 (calculated from 2 day assays) and 2.35 (49 d assays). As similarly estimated from portions of ¹⁴C found in CaCl₂ extracts of the 0.1 d assays, ¹⁴C-prosulfocarb's log K_oc in soil was 2.96. With both experiments, similar portions of nonextractable radioactivity were associated with all soil organic matter fractions, i.e. nonhumics, fulvic acids, humic acids, and humin/minerals. Throughout all sample preparation, the experiments were severely impaired by losses of radioactivity especially with concentration of samples containing water in vacuo. All findings pointed to volatility of parent prosulfocarb in presence of water rather than volatility of transformation products. According to literature data, this behavior of prosulfocarb was not expected, though volatility was demonstrated under field conditions.     

Testing the efficiency of extraction of incurred residues from soil with optimized multi-residue method

The reproducibility of extraction of residues from spiked soil samples and from soils containing incurred residues was tested with ¹⁴C-labeled test compounds of different physical-chemical properties. Nearly 100% of the compounds added to the sample before extraction could be recovered with an average reproducibility relative standard deviation (CV) of 5.4%. The additional steps of the determination process (cleanup, evaporation, etc.) contributed to the major part of the variability of the results (CV = 10–20%). The incurred residues were most efficiently extracted with acetone for 30 min followed by the mixture of acetone/ethyl acetate 1:1 for additional 30 min. However, they could only be recovered at various extent (64–90% of total residues), underlying the importance of testing the efficiency of extraction. The residues were identified and quantified by gas chromatography applying thermionic detector. The performance parameters of the method complied with the international method validation guidelines, and they proved to be robust and suitable for determination of pesticide residues in soils of widely different physical–chemical properties.     

Seed pre-soaking with 24-epibrassinolide reduces the imidacloprid pesticide residues in green pods of Brassica juncea L.

The effect of 24-epibrassinolide seed soaking on imidacloprid residues in green pods and mature seeds of Brassica juncea L. plants was investigated. The activities of the antioxidative enzymes glutathione-S-transferase, glutathione peroxidase, glutathione reductase, ascorbate peroxidase and guaiacol peroxidase, and the content of glutathione were determined. Imidacloprid residues in green pods were analyzed and quantified by gas chromatography-mass spectrometry, revealing that 24-epibrassinolide treatment resulted in a decrease of residues by almost 30%. In mature seeds, no pesticide residues were detected. Activities of all the antioxidative enzymes and glutathione content were found to be high in plants grown in soil amended with 300 mg imidacloprid kg^?1 soil, but pre-soaking with 100 nmol L^?1 24-epibrassinolide further enhanced the activities of all these enzymes and the glutathione content.     

洪泽湖水产品中渔药残留量调查

通过对洪泽湖水产品中部分渔药残留的检测和研究,对洪泽湖水产品的渔药残留量以及相关的水质情况有了初步掌握。结果表明,洪泽湖水产品中渔药残留量总体情况较好,但在网箱和围网养殖区域中,土霉素和磺胺类两种渔药在水体中存在量较大。     

MODIS derived fire characteristics and aerosol optical depth variations during the agricultural residue burning season, north India

Agricultural residue burning is one of the major causes of greenhouse gas emissions and aerosols in the Indo-Ganges region. In this study, we characterize the fire intensity, seasonality, variability, fire radiative energy (FRE) and aerosol optical depth (AOD) variations during the agricultural residue burning season using MODIS data. Fire counts exhibited significant bi-modal activity, with peak occurrences during April-May and October-November corresponding to wheat and rice residue burning episodes. The FRE variations coincided with the amount of residues burnt. The mean AOD (2003-2008) was 0.60 with 0.87 (+1σ) and 0.32 (−1σ). The increased AOD during the winter coincided well with the fire counts during rice residue burning season. In contrast, the AOD-fire signal was weak during the summer wheat residue burning and attributed to dust and fossil fuel combustion. Our results highlight the need for ‘full accounting of GHG’s and aerosols’, for addressing the air quality in the study area.     

优势菌种浸取电解锰渣中锰的影响因素研究

采用电解锰废渣中分离出的一种锰抗性强的微生物Fusarium sp.浸取电解锰渣中的锰。研究了不同矿浆浓度、微生物生长活动、锰渣和培养基等对锰浸取效率的影响。结果表明,接种体积比为2%（v/v）时,矿浆浓度（m/v）对锰浸取效率影响显著,矿浆浓度过低（〈2%）或者过高（〉10%）对锰浸取效率都有不利影响。矿浆浓度为10%时锰浸取效率最高,达80%以上;微生物的生长活动对浸取过程有显著的影响;而锰渣的存在则能在一定程度上影响溶液的pH,进而影响锰浸取效率;培养基对锰浸取效率的贡献达50%左右。     

Plant uptake of pesticides and human health: dynamic modeling of residues in wheat and ingestion intake

Human intake of pesticide residues from consumption of processed food plays an important role for evaluating current agricultural practice. We take advantage of latest developments in crop-specific plant uptake modeling and propose an innovative dynamic model to estimate pesticide residues in the wheat-environment system, dynamiCROP. We used this model to analyze uptake and translocation of pesticides in wheat after foliar spray application and subsequent intake fractions by humans. Based on the evolution of residues in edible parts of harvested wheat we predict that between 22 mg and 2.1 g per kg applied pesticide are taken in by humans via consumption of processed wheat products. Model results were compared with experimentally derived concentrations in wheat ears and with estimated intake via inhalation and ingestion caused by indirect emissions, i.e. the amount lost to the environment during pesticide application. Modeled and measured concentrations in wheat fitted very well and deviate from less than a factor 1.5 for chlorothalonil to a maximum factor 3 for tebuconazole. Main aspects influencing pesticide fate behavior are degradation half-life in plant and time between pesticide application and crop harvest, leading to variations in harvest fraction of at least three orders of magnitude. Food processing may further reduce residues by approximately 63%. Intake fractions from residues in sprayed wheat were up to four orders of magnitude higher than intake fractions estimated from indirect emissions, thereby demonstrating the importance of exposure from consumption of food crops after direct pesticide treatment.     

Validation of a QuEChERS-based gas chromatographic method for analysis of pesticide residues in Cassia angustifolia (senna)

A simple multi-residue method based on modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) approach was established for the determination of 17 organochlorine (OC), 15 organophosphorous (OP) and 7 synthetic pyrethroid (SP) pesticides in an economically important medicinal plant of India, Senna (Cassia angustifolia), by gas chromatography coupled to electron capture and flame thermionic detectors (GC/ECD/FTD) and confirmation of residues was done on gas chromatograph coupled with mass spectrometry (GC-MS). The developed method was validated by testing the following parameters: linearity, limit of detection (LOD), limit of quantification (LOQ), matrix effect, accuracy–precision and measurement uncertainty; the validation study clearly demonstrated the suitability of the method for its intended application. All pesticides showed good linearity in the range 0.01–1.0 μg mL^?1 for OCs and OPs and 0.05–2.5 μg mL^?1 for SPs with correlation coefficients higher than 0.98. The method gave good recoveries for most of the pesticides (70–120%) with intra-day and inter-day precision < 20% in most of the cases. The limits of detection varied from 0.003 to 0.03 mg kg^?1, and the LOQs were determined as 0.01-0.049 mg kg^?1. The expanded uncertainties were <30%, which was distinctively less than a maximum default value of ±50%. The proposed method was successfully applied to determine pesticide residues in 12 commercial market samples obtained from different locations in India.     

Rapid determination of residues of pesticides in honey by µGC-ECD and GC-MS/MS: Method validation and estimation of measurement uncertainty according to document No. SANCO/12571/2013

A simple and straightforward method for simultaneous determination of residues of 13 pesticides in honey samples (acrinathrin, bifenthrin, bromopropylate, cyhalothrin-lambda, cypermethrin, chlorfenvinphos, chlorpyrifos, coumaphos, deltamethrin, fluvalinate-tau, malathion, permethrin and tetradifon) from different pesticide classes has been developed and validated. The analytical method provides dissolution of honey in water and an extraction of pesticide residues by n-Hexane followed by clean-up on a Florisil SPE column. The extract was evaporated and taken up by a solution of an injection internal standard (I-IS), ethion, and finally analyzed by capillary gas chromatography with electron capture detection (GC-µECD). Identification for qualitative purpose was conducted by gas chromatography with triple quadrupole mass spectrometer (GC-MS/MS). A matrix-matched calibration curve was performed for quantitative purposes by plotting the area ratio (analyte/I-IS) against concentration using a GC-µECD instrument. According to document No. SANCO/12571/2013, the method was validated by testing the following parameters: linearity, matrix effect, specificity, precision, trueness (bias) and measurement uncertainty. The analytical process was validated analyzing blank honey samples spiked at levels equal to and greater than 0.010 mg/kg (limit of quantification). All parameters were satisfactorily compared with the values established by document No. SANCO/12571/2013. The analytical performance was verified by participating in eight multi-residue proficiency tests organized by BIPEA, obtaining satisfactory z-scores in all 70 determinations. Measurement uncertainty was estimated according to the top-down approaches described in Appendix C of the SANCO document using the within-laboratory reproducibility relative standard deviation combined with laboratory bias using the proficiency test data.     

Evaluation of microbially enhanced composting of sophora flavescens residues

The effects of inoculants on the composting of Sophora flavescens residues were evaluated based on several physical, chemical and biological parameters, as well as the infrared spectra. Compared to the control compost without inoculants, the treatment compost with inoculants (Bacillus subtilis strain G-13 and Chaetomium thermophilum strain GF-1) had a significantly longer thermophilic duration, higher cellulase activity and a higher degradation rate of cellulose, hemicellulose and lignin (P < 0.05). Thus, a higher maturity degree of compost with apparently lower C:N ratio (15.88 vs. 17.77) and NH₄-N:NO₃-N ratio (0.16 vs. 0.20) was obtained with the inoculation comparing with the control (P < 0.05). Besides, the inoculants could markedly accelerate the composting process and increase the maturity degree of compost as indicated by the germination index (GI) in which the treatment reached the highest GI of 133.2% at day 15 while the control achieved the highest GI of 125.7% at day 30 of the composting. Inoculation with B. subtilis and C. thermophilum is a useful method to enhance the S. flavescens residues composting according to this study.