LC-MS/MS determination of pesticide residues in fruits and vegetables

The aim of the research is to evaluate pesticide residue contamination of fresh and frozen fruits and vegetables, agricultural raw material, purchased from Polish farmers for production of frozen fruits and vegetables, and the estimation of the multiresidue method effectiveness expressed as the proportion of pesticides detected in food samples to the total number of pesticides analyzed by multiresidue methods. A total of 144 samples (of black currants, red currants, raspberries, cherries, strawberries, blackberries, cauliflowers and broccoli) were analyzed using LC-MS/MS method for the determination of 60 pesticides. QuEChERS extraction, matrix-matched calibration and dynamic multiple reaction monitoring method were used. Residues of 15 compounds, mainly fungicides and insecticides, were detected in 46 samples. The percentage of samples with residues above the maximum residue levels (MRL) was 15%, whereas samples with residues below MRL were 17%. A total of 13 samples contained more than one pesticide residue. Pesticide residues were detected most often in samples of black currants (50%), broccoli (36.4%), raspberries (29%) and red currants (21.8%). The most frequently detected pesticides were carbendazim and acetamiprid. The proportion of pesticides detected during our study to the total number of analyzed pesticides amounted to 25%. It was compared to literature findings. For three fourth of multiresidue methods, the proportion was below 50% for methods developed for the analysis of less than 100 pesticides, and below 30% for methods developed for the analysis of more than 100 pesticides. It appears that a lot of efforts and means is lost on pesticides never or rarely detected in examined samples. The workload and cost effectiveness of the development and application of multiresidue methods along with the range of pesticides covered by the method should be carefully and thoroughly considered anytime when a new method or workflow is developed. Including non-targeted screenings in pesticide residue control seems to be an alternative worth considering.     

Occurrence and distribution of trifluralin,ethalfluralin, and pendimethalin in soils used for long-term intensive cotton cultivation in central Greece

In the present study, a soil monitoring program was undertaken in Greek cotton cultivated areas in 2012. Twenty-seven soil samples were collected from the entire Thessaly plain in early summer of 2012, corresponding to approximately three months (current use of pendimethalin), up to one year (for the banned ethalfluralin), and three years (for the also banned trifluralin), after the last dinitroaniline application. Low but not negligible levels of dinitroanilines were detected, ranging from 0.01 to 0.21 μg g^?1 d.w. for trifluralin and 0.01–0.048 μg g^?1 d.w. for pendimethalin, respectively. Trifluralin was the herbicide most frequently detected (44.4%). The high historic application of trifluralin and its high persistence and accumulation potential is in line with the abundance of the detected residues. The present data indicate that soil samples contain extractable residues of banned trifluralin, but based on the comparison of the theoretical PECplateau for trifluralin (0.277 µg g^?1) and the maximum Measured Environmental Concentration, it was concluded that the detected residues should be attributed to previous years’ application. The latter suggested the need for continual monitoring of the dinitroaniline family of pesticides, including the banned substances, aiming thus to an improved environmental profile for agricultural areas.     

Dissipation,residues, and risk assessment of imidacloprid in Zizania latifolia and purple sweet potato under field conditions using LC-MS/MS

A shortened version of Quick, Easy, Cheap, Effective, Rugged, and Safe method (QuEChERS) for determining the dissipation and residue of imidacloprid present in Zizania latifolia and purple sweet potato was established by using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The average recoveries of imidacloprid in the two crops ranged from 82.12 to 113.79%, with relative standard deviation (RSD) of <7.32%. The dissipation dynamics of imidacloprid in Z. latifolia plants and purple sweet potato plants followed first-order kinetics, with half-lives of 3.2–5.5?days in each of sampling locations. The terminal imidacloprid residues in Z. latifolia and purple sweet potato at each of location were <0.005–0.120?mg kg^?1. According to the risk assessment results, both the acute dietary risk quotient and chronic dietary risk quotient values were <1, indicating that imidacloprid is unlikely to pose health risks to humans with normal recommended use. The present study may serve as a valuable reference for the safe and reasonable use of imidacloprid in Z. latifolia and purple sweet potato fields.     

Producing biogas from agricultural residues generated during phytoremediation process: Possibility,threshold, and challenges

In the past decades, a novel strategy has arisen, as required by time, to get a rational production of biogas from contaminated biomass, which may be, on purpose, harvested from contaminated soil phytoremediation process. The present review focuses on the possibility and potential of utilizing the agricultural residues generated during phytoremediation for production of biogas. As a general result of the studies compiled in this review, the harvested biomass can subsequently be utilized for the winning of biogas, and it provides a solution of waste disposal for phytoremediation technology. According to the analysis of previous results, not more than 1 mg/L of cadmium in fermenters shows promoting or at least no inhibitory effect on cumulative biogas yields. This strategy is promising for dealing with both environmental and energy problems in spite of many challenges in the coming future.     

Tolerance of Chrysantemum maximum to heavy metals: The potential for its use in the revegetation of tailings heaps

To find if ornamental plants are applicable to the remediation of metal-polluted areas, the tolerance of chrysanthemum plants (Chysanthemum maximum) var. Shasta to different metals under hydroponic conditions was studied. Their responses as influenced by the mycorrhizal fungus Glomus mosseae (Nicol. & Gerd.) Gerdemann & Trappe BEG25 on substrates containing mine residues were also investigated. Our results showed that chrysanthemum is a metal-tolerant plant under hydroponic conditions, plants behaving as Pb-excluders, whereas Cd, Cu and Ni were accumulated in roots. Low accumulation in flowers was observed for Cd and Cu but it was concentration-dependent. Ni and Pb were not translocated to flowers. Shoot biomass was not significantly affected by the different rates of mine residue addition for both mycorrhizal and non-mycorrhizal plants. Mycorrhizal plants accumulated less Pb and Cu in both shoots and roots than non-mycorrhizal plants. Chysanthemum could be a prospective plant for revegetation of tailings and the use of inoculation may decrease plant metal accumulation in polluted soils.     

高效木薯渣分解复合菌群RXS的构建及其发酵特性研究

从富含腐烂纤维质的环境中取样,通过以木薯渣及滤纸为碳源的蛋白胨纤维素培养基不断地富集培养,构建了一组高效稳定的纤维质分解复合菌群.考察了该复合菌群对不同纤维质底物的分解性能及其在木薯渣水解过程中主要参数的变化.研究发现该复合菌群对滤纸、脱脂棉、微晶纤维素、麦秸秆和木薯渣等原料均能够进行有效的降解.在该复合菌群应用于木薯渣的水解过程中,监测发现纤维素酶、半纤维素酶、果胶酶等关键酶的酶活力分别在第2～3 d达到最大值34.4、90.5和15.8U;经过10 d的发酵后,木薯渣中的纤维素、半纤维素及木质素分别降解了79.8%、85.9%和19.4%,且木薯渣的失重高达61.5%;此外,代谢产物主要是乙酸、丁酸、己酸和甘油;而溶解性COD、总糖和总挥发酸的变化表明第2 d时木薯渣的水解率最高.上述结果表明,该复合菌群能够有效地水解木薯燃料酒精生产过程中的废弃物木薯渣,并有望用于木薯渣高效沼气发酵的前处理中.     

Residual dynamics of thiacloprid in medical herbs marjoram, thyme, and camomile and in soil

Thiacloprid is a new insecticide of the chloronicotinyl family. To assess its risk after application, residual characteristics of thiacloprid in marjoram, thyme, and camomile and in soil were studied under field conditions. The active ingredient was extracted from the plant material using a mixture of acetone-water. After filtration, the extract was concentrated to the aqueous phase, diluted with water, and portioned against ethyl acetate on a matrix solid phase dispersion column. Thiacloprid was extracted from soil using a mixture of methanol-water, filtered, and re.extracted （clean up） with dichloromethane. The residues were quantified using HPLC-MS-MS. The methods were validated by recovery experiments. Thiacloprid residues in marjoram, thyme, and camomile and in soil persisted beyond 10, 14, 14, and 21 d but no residues were detected after 14, 21, 21, and 28 d, respectively. The data obtained in this study indicated that the biexponential model is more suitable than the first-order function to describe the decline of thiacloprid in fresh marjoram, fresh thyme, and dried camomile flowers with half-life （t1/2） of 1.1, 0.7, and 1.2 d, respectively. However, both the first-order function and biexponential model were found to be applicable for dissipation of thiacloprid in soil with almost the same t1/2 values of 3.5 and 3.6 d. The results indicated that thiacloprid dissipates rapidly and does not accumulate in the tested herbs and in soil.     

荧光桃红-溴化十六烷基三甲基铵检测有机磷农药残留总量

在pH为6.40的B-R缓冲溶液中,荧光桃红与一定浓度的溴化十六烷基三甲基胺发生荧光增强反应,加入有机磷农药后,体系的荧光强度降低,且降低程度与有机磷农药的加入量呈良好的线性关系,建立了用此荧光法来测定有机磷农药残留总量的新方法.在优化试验条件下,线性范围为0.008-0.72 mg·L-1,检出限为0.05 mg·L...     

池塘残饵对底泥氮、磷释放影响的模拟研究

运用室内静态模拟的方法,设置静态释放组(A组)和饲料添加组(B组),研究了池塘残饵分解对底泥氮、磷释放的影响.结果表明,A组DO高于B组(P<0.05),A组pH值为中性,B组pH值呈弱酸性.添加饲料后,B组硝态氮低于A组(P<0.05),而B组活性磷高于A组(P<0.05).实验第2~14 d,A组氨氮高于B组(P<0.05),此后B组氨氮升高,实验结束时B组氨氮高于A组(P<0.05).研究表明,添加饲料的B组,初期氨氮和硝态氮的释放都受到抑制.静态释放的A组,氮的释放变化是先上升,后降低的趋势,而饲料添加的B组,氮的释放变化趋势则是先降低,后升高.B组饲料分解向上覆水释放大量的磷,活性磷的变化呈现先上升后下降的趋势.     

Water pressure head and temperature impact on isoxaflutole degradation in crop residues and loamy surface soil under conventional and conservation tillage management

Laboratory incubations were performed in order to evaluate the dissipation of the proherbicide isoxaflutole in seedbed layer soil samples from conventional and conservation tillage systems and in maize and oat residues left at the soil surface under conservation tillage. The effects of temperature and water pressure head on radiolabelled isoxaflutole degradation were studied for each sample for 21 d. Mineralisation of isoxaflutole was low for all samples and ranged from 0.0% to 0.9% of applied ¹⁴C in soil samples and from 0.0% to 2.4% of applied ¹⁴C in residue samples. In soil samples, degradation half-life of isoxaflutole ranged from 9 to 26 h, with significantly higher values under conservation tillage. In residue samples, degradation half-life ranged from 3 to 31 h, with significantly higher values in maize residues, despite a higher mineralisation and bound residue formation than in oat residues. Whatever the sample, most of the applied ¹⁴C remained extractable during the experiment and, after 21 d, less than 15% of applied ¹⁴C were unextractable. This extractable fraction was composed of diketonitrile, benzoic acid derivative and several unidentified metabolites, with one of them accounting for more than 17% of applied ¹⁴C. This study showed that tillage system design, including crop residues management, could help reducing the environmental impacts of isoxaflutole.