Collaborative validation of the QuEChERS procedure for the determination of pesticides in food by LC-MS/MS

Seven FDA pesticide laboratories collaborated to develop and validate an LC-MS/MS method to determine 173 pesticides in <20 min. The average determination coefficient (r2) was >0.99 for all but two compounds tested. The limits of detection were <20 ng/mL for all compounds and <10 ng/mL for 363 of the 368 transitions reported. The method was used to determine pesticides in two AOAC sponsored proficiency samples. The LC-MS/MS determination was used for the analysis of oranges, carrots and spinach using the QuEChERS (Quick, Easy, Cheap, Effective, Rugged, Safe) method. Each matrix was fortified at 20, 100, 400, and 1000 ng/g. No false positive responses were detected in controls of the three matrices. 165 pesticides had recoveries between 70 and 130%, and 161 had minimum detection levels less than 10 ng/g. Recoveries of 169 compounds for the 1000 ng/g spikes were within 50-150%. A matrix effect study indicated all three matrices caused a small net suppressing effect, the most pronounced attributable to the citrus matrix. The procedure proved to be accurate, precise, linear, sensitive and rugged, and adds 100 pesticides to the scope of the FDA pesticide program.     

Evaluation of soil quality parameters in a tropical paddy soil amended with rice residues and tree litters

Laboratory and greenhouse experiments were conducted to study the effects of applications of rice residue and Pongamia pinnata and Azadirachta indica leaf litters on biochemical properties (extraction yield of humus, composition of humus, microbial biomass carbon, activities of urease and acid phosphatase) of a lowland rice soil under flooded conditions. Bulk soil sample collected from the Mandya paddy fields was used for the green house trials and the laboratory incubation studies. The organic materials were added at three rates – zero, 25.0 g carbon kg⁻¹ (2.5% C) and 50.0 g carbon kg⁻¹ dry soil (5.0% C). Results showed that tree leaf litter and rice residue at 5.0% C rate decreased instantaneous decay constant (k), there by retarded the rate of C mineralization. Carbon contents of HA increased with the rate of C added. Study of delta–log K values and C contents of humic acids revealed that greatest molecular weight of HA was in the pongamia litter treatment, followed by neem litter and rice residue. Grain and straw yields of rice crop in the pot culture study were statistically correlated to the soil quality parameters. Neem and pongamia tree litter incorporation at 2.5% C could be considered for improving soil health and crop yields of rice under flooded conditions; however, application at higher rates significantly (P ≤ 0.05) lowered total dry matter production in rice, despite favorable soil health parameters such as humic yields, microbial biomass – C content and acid phosphatase and urease activity. Among different soil health parameters, microbial quotient was found to be more sensitive indicator of decline in soil quality.     

Dissolution of slag fertilizers in a paddy soil and Si uptake by rice plant

Abstract

Maize (Zea mays L.) cv. Ganga 2 was grown in refined sand at three levels of copper: deficient (0.00065 mg L^-1), adequate (0.065 mg L^-1), and excess (6.5 mg L^-1), each at three levels, deficient (0.00065 mg L^-1), adequate (0.065 mg L^-1), and excess (6.5 mg L^-1) of zinc. Excess Cu magnified the zinc deficiency effects in maize by lowering further the biomass, the concentration of leaf Zn, activities of carbonic anhydrase, aldolase, and ribonuclease and intensified the visible foliar symptoms of Zn deficiency. The effects of Cu deficiency, low dry weight, the concentration of leaf Cu and activities of cytochrome oxidase and polyphenol oxidase were enhanced by excess Zn. Synergism was observed between combined deficiency of Cu and Zn and Cu or Zn deficiency, because the depression in the parameters characteristic of Cu or Zn deficiency was more pronounced when both Cu and Zn were deficient than when Cu or Zn was deficient. Antagonism was observed in some parameters between combined excess of Cu and Zn and Cu or Zn excess. Dry weight was decreased further when both Cu and Zn were in excess than when either Cu or Zn was in excess. After the infiltration of Cu and Zn together to the leaf discs from deficient Cu-deficient Zn treatment, the increase in the concentration of leaf Zn and the activities of aldolase, carbonic anhydrase, polyphenol oxidase, and cytochrome oxidase was more pronounced than after the infiltration of Cu or Zn singly. Discontinuance of excess Zn supply from the excess Zn-deficient Cu treatment increased the concentration of leaf Cu and activities of polyphenol oxidase and cytochrome oxidase and lowered the concentration of Zn. Similarly the discontinuance of excess Cu supply from the leaf discs in the “excess Cu-deficient Zn” treatment increased the leaf Zn concentration and the activities of carbonic anhydrase and aldolase.     

复合污染土壤中水稻根际元素特性及效应研究

【目的】以广东大宝山重金属复合污染农田为生长介质,通过研究水稻不同部位生长量、 金属含量、 对金属的富集系数,及其与根际、 非根际土金属含量、 形态变化的相关关系,探讨根际效应可能对水稻体内金属积累转运以及生物量的影响。【方法】选取了广东大宝山稻田重金属复合污染(As、 Pb、 Fe、 Cu、 Zn)土壤及当地常见的20个水稻品种进行根际袋试验,即将根际袋内的土视为根际土,根际袋外的土视为非根际土,将供试水稻品种种植于根际袋土壤中60天后收获,测定水稻各部位的生长量、 不同金属的含量,根际土和非根际土中各金属有效态的含量。【结果】Fe、 Cu、 Pb、 Zn、 As在根部的富集系数均大于其在茎叶的富集系数,各金属在茎叶和根部的富集能力排序分别为Zn Cu As ≈ Pb ≈ Fe和Fe Zn As Cu Pb。根际土和非根际土中各种金属有效态含量均为Fe Cu Pb Zn As。研究还发现,有效态Fe、 Cu和Zn浓度对整株干重的影响显著,作用强弱顺序为Cu Zn Fe,对水稻生长影响作用显著的三种有效态金属Fe、 Cu和Zn均为植物生长所必需的元素。供试土壤中有效态Cu浓度对水稻的生长所起的作用最强。根际土有效态Fe浓度对根系Fe的积累作用效果显著,有效态As浓度显著抑制了根系Fe的积累,且有效态As浓度的作用强于有效态Fe。【结论】根际土中有效态Fe对株高、 根干重、 茎叶干重和整株干重均起着抑制作用,有效态Cu对水稻生长起到了促进作用。根际土有效态As和非根际土有效态Zn对根部Fe的积累起到了抑制作用,根际土有效态Fe和非根际土有效态Cu则起到了促进作用。非根际土有效态Fe和有效态Zn对水稻根长的增加均起到了促进作用。     

QuEChERS结合高效液相色谱-串联质谱法测定土壤中11类47种药物残留

本文建立了一种QuEChERS结合高效液相色谱–串联质谱(UPLC-MS/MS)同时测定土壤中11类47种药物残留的分析方法。试验考察不同色谱柱和流动相对47种药物的分离效果,探究不同pH的EDTA-Mcllvaine缓冲液和净化填料对目标化合物的提取和净化效果,实现了对土壤中多类药物的定量分析。47种药物在对应线性范围内均呈现较好的线性关系(r≥0.995);方法的检出限为0.1 ~ 2.5 μg/kg,定量限为0.5 ~ 8 μg/kg;3水平加标试验的回收率为61.1% ~ 117.0%,相对标准偏差为1.9% ~ 11.4%。该方法适用于土壤多组分准确高通量定量分析,检出限、回收率、准确度均符合分析要求,为土壤中多种药物的赋存底数和潜在风险研究提供技术支撑。     

cry1Ac/cpti转基因大米水稻土中微生物群落的多样性研究

Two types of cry1Ac/cpti transgenic rice(GM1 and GM2)and their parental non-cry1Ac/cpti rice(CK1 and CK2)were planted in the field at Wufeng,Fujian Province,China for four years to investigate the influence of genetically modified rice on diversity of bacterial and fungal community in the paddy soil.The community composition and abundance of bacteria or fungi in the paddy soil were assessed at different growth stages of rice by denaturing gradient gel electrophoresis and real-time polymerase chain reaction based on 16S rRNA gene or SSU rRNA gene in the 4th year after the experimental establishment.The composition of bacterial or fungal community changed during rice growth,while no significant differences were observed between the fields cultivated with GM1and CK1,or between the fields cultivated with GM2 and CK2 in either bacterial or fungal community composition.The copy numbers of bacterial 16S rRNA gene in the soils with CK1,CK2,GM1 and GM2 ranged from 5.64×1011to 6.89×1011copies g-1dry soil at rice growth stages,and those of fungal SSU rRNA gene from 5.24×108to 8.68×108copies g-1dry soil.There were no marked differences in the copies of bacterial 16S rRNA gene or fungal SSU rRNA gene between CK1 and GM1 or between CK2 and GM2at any growth stage of rice.Planting cry1Ac/cpti transgenic rice had no significant effect on composition and abundance of bacterial and fungal community in paddy soil during the rice growing season at least in the short term.     

GEE平台下利用物候特征进行面向对象的水稻种植分布提取

为高效提取高精度水稻种植分布及其面积,该研究基于谷歌地球引擎（Google Earth Engine,GEE）平台,以辽宁省盘锦市为研究区,利用2020年Sentinel-2影像提取水稻生命周期内4个水稻物候期相应的光谱指数,利用简单非迭代聚类（Simple Non-Iterative Clustering,SNIC）算法来分割影像,灰度共生矩阵（Gray Level Co-occurrence Matrix,GLCM）来计算纹理特征,结合支持向量机（Support Vector Machine,SVM）和随机森林（Random Forest,RF）算法构建6种不同的模型进行水稻种植分布提取,并基于目视解译及实地调查数据,对比6种模型提取水稻的验证精度和实测精度,确定最优模型。结果表明：在水稻种植分布提取中,面向对象方法有助于提高水稻种植分布提取精度,且RF算法优于SVM算法。其中SNIC图像分割结合RF模型具有最高提取精度,总体精度和Kappa系数分别为96.83%、0.934,经实测数据验证,水稻实测精度为95.43%,可满足区域水稻种植分布和面积监测需求。     

Effect of seedling transplanting date on methane emission from rice paddy soil during cultivation

In most temperate mono-rice cultivation systems like Korea, the local recommended transplanting date of rice (Oryza sativa L.) seedlings is proposed by the government agency considering climate, rice cultivar, rice productivity and quality, etc. Recently the transplanting of rice seedlings earlier than the recommended transplanting date (RTD) has been adopted by the local farmers to get high yield and to harvest earlier for higher market value. Earlier transplanting than RTD might influence methane (CH₄) emission due to the prolonged cultivation period, but its effect was not evaluated well so far. In this study, the effects of seedling transplanting date on CH₄ emission and rice productivity were investigated for two years in a general paddy soil. The 30-day old seedlings were transplanted on the local RTD (every June 15) as the control, and at 30 and 15 days before and 15 days after the RTD for comparison. There was no difference on CH₄ flux pattern among the treatments, but the earlier transplanting before the RTD significantly (P ?≤?0.05) increased total CH₄ emissions during rice cultivation due to the extended soil flooding period and improved plant growth. Rice grain yield was increased by earlier transplanting, but the values were not significantly different from those of transplanting practices on RTD and 15 days before RTD. Therefore, among all the treatments, the lowest total CH₄ emission per grain yield was observed in the RTD treatment. Conclusively, rice transplanting following the RTD, rather than early or late transplanting, could be more effective to minimize CH₄ emission without significantly decreasing the rice productivity.     

稻田土壤和稻米中重金属潜在污染风险评估与来源解析

该文选择贵州省典型城市(都匀市)周边水稻种植区为研究区,系统采集了稻田土壤和稻米样品各110个,测定土壤和稻米中Cd、Hg、As、Pb和Cr含量,基于多元统计分析和污染风险评价等分析方法,揭示了研究区稻田土壤重金属污染的主要来源及土壤和稻米中重金属存在的潜在风险。结果表明,与贵州土壤重金属背景值相比,稻田土壤中Cd、Hg、As、Pb和Cr超标率分别为14.55%、40.00%、16.36%、22.72%和13.64%,主要以Hg污染问题最为突出。稻米中只存在3.64%Cd超标,Hg、As、Pb和Cr平均含量均低于国家食品安全标准限定值(GB 2762-2017),说明当地居民食用稻米存在最大的潜在威胁为Cd污染稻米。稻田土壤重金属来源分析结果表明,稻田土壤中Cd、Hg、As和Pb之间呈显著正相关关系,说明土壤中Cd、Hg、As和Pb具有相同的来源,主要来源于当地铅锌矿冶炼、火电厂等污染点源排放的污染物;Cr与其他元素相关性不显著,主要来源于成土母质,为自然来源元素。     

水稻对水稻土中甲磺隆结合残留的响应

Metsulfuron-methyl is one of the widely used sulfonylurea herbicides. However, approximately half of the applied metsulfuron-methyl may remain as bound residues in soil. To characterize the response of rice plants to residual metsulfuron-methyl in soil, the activities of acetolactate synthase （ALS）, superoxide dismutase （SOD）, peroxidase （POD）, and catalase （CAT） were investigated in two rice varieties that differed in susceptibility to the herbicide. Changes in the activity of these enzymes in leaves and roots of Xiushui 63, a sensitive rice variety, were greater than those in a resistant variety Zhenong 952. Irrespective of variety, changes in the enzyme activity were greater in the roots than in the leaves. The activities of ALS and CAT decreased, while the SOD activity increased with the increase in the amounts of bound residues of metsulfuron-methyl （BRM） in soil. The POD activity increased at the BRM level of 0.025 mg kg^-1, but decreased at the BRM level of 0.05 mg kg^-1. The results showed that the bound residues of sulfonylurea herbicides may affect metabolism of rice plants.     

Ethanol outperforms multiple solvents in the extraction of chlorophyll-a from biological soil crusts

In order to estimate the biomass of photoautotrophic organisms in biological soil crusts (BSCs), based on the extraction and determination of phytoplanktonic chlorophyll-a (Chl-a) in aquatic ecosystems, this paper comparatively studied the Chl-a extraction efficiencies in ethanol, acetone, N, N -dimethyl -formamide (DMF) and dimethyl sulphoxide (DMSO) from algae, lichen, and moss crusts, analyzed the effects of dominant organisms or development degree of BSCs, mass of sample, and soil characteristics on the extraction efficiency. The results showed that the extraction efficiencies of different organic solvents were significantly different, and such efficiencies declined with the increase of mass of sample. DMSO resulted in the greatest extraction efficiency, but was not suitable for lichen crusts; DMF strongly underestimated the Chl-a content of man-made crusts relative to the other extractants, and was particularly affected by interfering pigments from the well-developed crusts. Generally, the extraction efficiency of ethanol was greater than that of acetone, and ethanol method showed the greatest stability compared with other 3 solvents. In addition, Chl-a content showed an increasing trend with the succession of BSCs when it was expressed on an areal basis. On the basis of this and related experiments we suggest Chl-a content of BSCs be extracted by ethanol and expressed on an areal basis.     

Temporal shifts in diversity and quantity of nirS and nirK in a rice paddy field soil

Denitrification is an important part of the nitrogen cycle in the environment, and diverse bacteria, archaea, and fungi are known to have denitrifying ability. Rice paddy field soils have been known to have strong denitrifying activity, but the microbes responsible for denitrification in rice paddy field soils are not well known. Present study analyzed the diversity and quantity of the nitrite reductase genes (nirS and nirK) in a rice paddy field soil, sampled four times in one rice-growing season. Clone library analyses suggested that the denitrifier community composition varied over sampling time. Although many clones were distantly related to the known NirS or NirK, some clones were related to the NirS from Burkholderiales and Rhodocyclales bacteria, and some were related to the NirK from Rhizobiales bacteria. These denitrifiers may play an important role in denitrification in the rice paddy field soil. The quantitative PCR results showed that nirK was more abundant than nirS in all soil samples, but the nirK/nirS ratio decreased after water logging. These results suggest that both diversity and quantity changed over time in the rice paddy field soil, in response to the soil condition.     

水稻土基底呼吸与CO2排放强度的日动态及长期不同施肥下的变化

土壤呼吸排放是陆地生态系统土气交换快速而活跃的途径之一,对大气CO2浓度的变化有显著的影响。本文对太湖地区一个代表性水稻土水稻收割后土壤基底呼吸CO2排放进行了昼夜观测和采样分析。结果表明,不同小区平均土壤呼吸与CO2排放速率在CO2-C.12.2～25.2.mg/(m2h)之间,日排放量在CO2-C.327.2～604.1mg/(m2d)之间,低于文献报道的森林和草地及旱作农田的土壤呼吸;与长期有机-无机配施处理相比,长期单施化肥CO2日排放量提高了55%～85%,并且显著提高了土壤呼吸对土壤(5.cm)温度的响应敏感性。相关分析表明,土壤呼吸CO2排放强度与土壤微生物N(Nmic)、微生物C∶N(Cmic/Nmic)和P的有效性有密切的关系;生物有效N和P的有效性显著地影响着土壤呼吸与CO2的生成和排放。本试验结果进一步支持了水稻土的固碳效应。但是,供试不同小区土壤呼吸排放强度的变异隐含着长期不同施肥处理可能使与高呼吸活性有关的微生物群落发生改变,有待于进一步研究。     

Cyanobacterial communities of rice straw left on the soil surface of a paddy field

To estimate diversity, seasonal variation, and phylogeny of the cyanobacterial communities in rice straw placed in nylon mesh bags and left on the soil surface of a paddy field, total DNA was extracted from straw, amplified by polymerase chain reaction targeting 16S rRNA genes of cyanobacteria, and the amplicons were separated by denaturing gradient gel electrophoresis (DGGE). These DGGE bands were sequenced. The paddy field was under flooded condition after transplanting of rice (Experiment 1) and under drained conditions after harvest (Experiment 2). The residual samples on the soil surface under upland conditions were collected just before spring plowing and were placed again on the soil surface after transplanting under flooded conditions. DGGE band patterns of cyanobacterial communities of rice straw were different under drained conditions, under flooded conditions when fresh rice straw samples were placed (Experiment 1), and under flooded conditions when residual rice straw samples were replaced (Experiment 2), indicating that the communities were influenced by both water regime of the paddy field and the degree of the rice straw decomposition. Sequence analysis of DGGE bands indicated that most of the cyanobacteria in rice straw on the soil surface in the paddy field were filamentous members belonging to Subsections III and IV. Filamentous cyanobacterial cells were observed in rice straw under flooded conditions by epifluorescence microscopy.     

微波辅助萃取ICP—MS法测定土壤中有效硼

建立了一种应用微波辅助萃取ICP-MS法测定土壤中有效硼的方法,该方法与NY/T148-1990和NY/T1121.8-2006(姜黄素比色法和甲亚胺比色法)相比,不仅操作简便快速、无污染,而且具有很好的准确度和精密度,其相对标准偏差(RSD)为3.5%,回收率为94.0%～107.3%,方法的检出限为1.13 ng·g-1.     

Use of soil nonexchangeable potassium by paddy rice with clay structural changes under long-term fertilizer management

To prove the hypothesis that paddy rice utilizes soil nonexchangeable potassium (neK) and causes associated structural changes in clay minerals, K status and clay mineralogy of 22 surface soils from three paddy fields under long-term fertilizer management for 51–93 years were investigated. Soil neK content was determined as the difference between 1 mol L⁻¹ hot HNO₃ extractable K and 1 mol L⁻¹ ammonium acetate exchangeable K. Clay mineralogy was identified by X-ray diffraction (XRD). The radiocesium interception potential (RIP), an index of frayed edge sites in the interlayer sites of 2:1 type clay minerals, was also determined. The neK contents under the -K and NPK treatments were considerably lower than those under the unfertilized treatment in all the fields, indicating the exploitation of soil neK by rice. XRD analysis of the clay samples revealed 7% shift from the 1.0 peak to 1.4 nm one under the -K treatment compared with the unfertilized one, and the amounts of neK were negatively correlated with those of RIP (p < .01), suggesting the expansion of interlayer spaces of the 2:1 type phyllosilicates such as mica due to the release of neK. In addition, the neK content positively correlated with K balance of the long-term experiments (p < .05). The differences of neK between unfertilized K and -K treatments corresponded to 22–157 kg K ha⁻¹, or 0.42–1.68 kg K ha⁻¹ year⁻¹. In conclusion, utilization of considerable amount of soil neK under K depleted conditions should be considered to establish sustainable K management for paddy rice.     

黑麦草鲜草翻压还田对双季稻CH4与N2O排放的影响

为了研究黑麦草鲜草翻压还田对稻田温室气体排放的影响,该文利用静态箱-盆栽装置观测了尿素、黑麦草鲜草翻压还田、半量尿素与半量黑麦草鲜草混施和对照4个处理稻田CH4和N2O排放.结果表明:黑麦草鲜草翻压还田、半量尿素与半量黑麦草鲜草混施的CH4排放通量分别比对照增加了371％和210％,比尿素增加了152％和66％:尿素的CH4排放比对照高87％,差异均达到显著水平(P＜0.05).黑麦草鲜草翻压还田的CH4排放在3个时期(早稻移栽前,早稻生长期和晚稻生长期)分布均匀,约60％的CH4排放于早稻移栽前和早稻生长期.尿素的N2O排放分别为黑麦草鲜草翻压还田、半量尿素与半量黑麦草鲜草混施和对照的18倍、6.6倍和25倍.CH4和N2O的全球增温潜势(GWP)依次为黑麦草鲜草翻压还田＞半量尿素与半量黑麦草鲜草混施＞尿素＞对照,差异均显著(P＜0.05).黑麦草鲜草翻压还田虽然增加了稻田CH4排放,但减少了N2O排放,抑制了 尿素对N2O的排放.     

Possibilities to reduce rice straw-induced global warming potential of a sandy paddy soil by combining hydrological manipulations and urea-N fertilizations

Global warming potential (GWP) of sandy paddy soils may be reduced by trade-offs between N₂O, CH₄ and CO₂ emissions. Laboratory experiments using either rice straw (1% or 0.5%) or together with urea-N (25 or 50 mg N kg⁻¹ soil) at various levels of soil water were carried out for 30 days each, to test this assumption. Waterlogging combined with urea-N increased total N₂O emissions, with greater release upon rewaterlogging (7.4 mg N kg⁻¹ soil) than experienced by removing waterlogging only. Rice straw±urea-N either emitted small amounts of N₂O or resulted in negative values at all water levels, including saturated and aerobic. Total CH₄ fluxes declined with the decreased water levels and amount of rice straw (<193 mg C kg⁻¹ soil), and also for CO₂ with the latter (<1340 mg C kg⁻¹ soil), and rewaterlogging had little influence on both. N₂O under rewaterlogged and waterlogged±urea-N, CH₄ under waterlogged with rice straw, and CO₂ for the remainder were the major contributors to GWP. Results show that waterlogging following aerobic decomposition of rice straw (1%) with urea-N, applied either at the beginning or at the end of the aerobic conditions, could decrease GWP by 56-64% and 32-42% over the sole addition of rice straw (1% and 0.5%) under waterlogged and saturated conditions, respectively.