QuEChERS-气相色谱法快速测定土壤中8种有机氯农药

建立QuEChERS-气相色谱法同时检测土壤中8种有机氯农药的方法,优化分散固相萃取剂用量。土壤样品通过分散固相萃取净化技术,氮吹浓缩后用正己烷定容,最后通过气相色谱测定。结果表明,在2.0~100μg/L质量浓度范围内呈线性,相关系数r为0.9895~0.9991。空白样品在0.5,5和20μg/kg加标浓度下的回收率为75.3%~92.3%,相对标准偏差为3.2%~5.6%(n=5),方法检出限为0.053~0.064μg/kg,测定下限为0.21~0.26μg/kg。该方法操作简单、结果准确、有机试剂用量少、分析成本低,适用于土壤中有机氯农药的残留检测与分析。     

电除尘器斜气流状态下粉尘沉降试验研究

针对电除尘器在实际运行过程中出现的除尘效率下降问题,提出斜气流这一新型技术,对均匀气流与斜气流分布状态进行可视化研究;在两种气流状态下进行粉尘沉降试验,对试验结果进行对比分析、总结相应规律;对我国电除尘器气流技术的发展提出了建议。     

Retention time profiling of all 136 tetra- through octa- chlorinated dibenzo-p-dioxins and dibenzofurans on a variety of Si-Arylene gas chromatographic stationary phases

The applicability of three different Silphenylene Silicone co-polymer (Si-Arylene) GC stationary phases (J&W Scientific DB-5ms, Varian VF-5ms, and VF-Xms) has been evaluated for the separation of all 136 tetra- through the octa- chlorinated dibenzo-p-dioxins (PCDD) and chlorinated dibenzofurans (PCDF) from closely eluting isomers using gas chromatography/high resolution mass spectrometry (GC/HRMS). Their relative performance data are compared to the “conventional” 5% diphenyl 95% dimethylpolysiloxane GC column (Supelco Equity-5) and to each other based on absolute retention times, visualized mass chromatograms, and the separation of 2,3,7,8-substituted isomers. VF-Xms GC column was able to demonstrate a better performance towards separation of 2,3,7,8-substituted PCDD/PCDF compared to other Si-Arylene GC columns tested, where only 2,3,4,7,8-PnCDF can not be resolved from 1,2,3,6,9-PnCDF and 2,3,4,6,7,8-/1,2,3,6,8,9-HxCDF and 1,2,3,7,8,9-/1,2,3,4,8,9-HxCDF can be at least partially resolved. These data suggest that the development of a single GC column for the separation of all 17 2,3,7,8-substituted dioxins and furans is feasible, which therefore could be used as a standard tool for the PCDD/PCDF methods globally including USEPA methods 1613b, 8290A, 8280B, European Standard Method EN 1948, Canadian methods DFPCB-E3418, EPS 1/RM/19, Japanese methods JIS K0311 and JIS K0312. Having one specific GC column to separate all 2,3,7,8-substituted PCDD/PCDF will significantly improve the data quality, comparability by the various methods and assessment techniques while simultaneously leading to a more cost and time efficient operation.     

泥石流V型排导槽防淤设计方法及其应用研究

排导槽是泥石流治理常用的工程措施,泥石流若在槽内淤积,将极大影响排导槽防治效果。目前国内现行规范中没有关于排导槽淤积情况计算的相关条款,导致排导槽被泥石流淤埋的工程事故时有发生。鉴于此,分析了排导槽淤堵的常见原因,对现有的一些排导槽淤积验算公式进行了分析和整理,提出了一套基于槽宽验算、槽内泥深及流速验算等公式的排导槽防淤设计验算方法。该方法在雅(安)泸(沽)高速公路沿线某泥石流沟V型排导槽淤埋事故的处理中进行了应用,重建的排导槽经受了2011年6月17日特大暴雨形成的泥石流的考验,说明该方法实施效果良好,可供相关研究与设计参考。     

Determination of chlorinated paraffins in sediments from the Firth of Clyde by gas chromatography with electron capture negative ionisation mass spectrometry and carbon skeleton analysis by gas chromatography with flame ionisation detection

Short chain chlorinated paraffins (SCCPs) are a group of persistent organic pollutants (POPs) of increasing concern, but are to date not widely investigated in the environment, largely due to the challenges involved in their quantification. Here, SCCPs were quantified in marine sediments from the Firth of Clyde, Scotland, by gas chromatography with electron capture negative ionisation mass spectrometry (GC-ECNIMS) and through carbon skeleton analysis by gas chromatography with flame ionisation detection (GC-FID), and the analytical challenges encountered are discussed. Concentrations in the sediments ranged from 0.4 to 69 μg kg⁻¹ when determined by GC-ECNIMS, and from 5.6 to 379 μg kg⁻¹ when determined by GC-FID. For 8 out of 11 samples, analysis by GC-FID gave higher results than analysis by GC-ECNIMS. Unexpected aspects of the analysis, such as the presence of high concentrations of longer chain chlorinated paraffins in the samples, are also presented.     

Analysis of Organophosphorus Pesticides in Whole Milk by Solid Phase Microextraction Gas Chromatography Method

Solid phase microextraction (SPME) was used for the extraction of residual coumaphos and dichlorvos in whole milk. The residues were analyzed by capillary gas chromatography equipped with nitrogen phosphorus detector (GC-NPD). A manual SPME holder with a 100-μm polyacrylate fiber was used. The optimized conditions for extraction by SPME method were: sample agitation, absorption temperature of 30°C, absorption time of 40 min, desorption time of 10 min, and sample volume was 16.0 mL in the vial. Under these conditions, the calibration graphs were linear in the range of 0.17 μgL^?1 to 1.75 μgL^?1 for coumaphos and 0.69 μgL^?1 to 6.90 μgL^?1 for dichlorvos. Precision was good with RSD values of 13% for coumaphos and 14% for dichlorvos. The detection limits (LOD) were 0.060 μgL^?1 for dichlorvos and 0.052 for coumaphos. The quantification limits (LOQ) were 0.086 μgL^?1 for dichlorvos and 0.066 μgL^?1 for coumaphos. The results obtained in this study suggest that SPME is a suitable technique for residual pesticide analysis of milk. The data demonstrate that particular OP pesticides used in dairy farming in the region of Minas Gerais were found to contaminate cow whole milk, and the residues are not removed by treating the milk by boiling.     

Model Development for Nutrient Loading Estimates from Paddy Rice Fields in Korea

Abstract

A field experiment was performed to evaluate water and nutrient balances in paddy rice culture operations during 2001–2002. The water balance analysis indicated that about half (50–60%) of the total outflow was lost by surface drainage, with the remainder occurring by evapotranspiration (490–530 mm). The surface drainage from paddy fields was mainly caused by rainfall and forced-drainage, and in particular, the runoff during early rice culture periods depends more on the forced-drainage due to fertilization practices. Most of the total phosphorus (T-P) inflow was supplied by fertilization at transplanting, while the total nitrogen (T-N) inflow was supplied by the three fertilizations, precipitation, and from the upper paddy field, which comprised 13–33% of the total inflow. Although most of the nutrient outflow was attributed to plant uptake, nutrient loss by surface drainage was substantial, comprising 20% for T-N and 10% for T-P. Water and nutrient balances indicate that reduction of surface drainage from paddy rice fields is imperative for nonpoint source pollution control. The simplified computer model, PADDIMOD, was developed to simulate water and nutrient (T-N and T-P) behavior in the paddy rice field. The model predicts daily ponded water depth, surface drainage, and nutrient concentrations. It was formulated with a few equations and simplified assumptions, but its application and a model fitness test indicated that the simulation results reasonably matched the observed data. It is a simple and convenient planning model that could be used to evaluate BMPs of paddy rice fields alone or in combination with other complex watershed models. Application of the PADDIMOD to other paddy rice fields with different agricultural environments might require further calibration and validation.     

Expansion of the MANAGE Database with Forest and Drainage Studies

The “Measured Annual Nutrient loads from AGricultural Environments” (MANAGE) database was published in 2006 to expand an early 1980s compilation of nutrient export (load) data from cultivated and pasture/range land at the field or farm scale. Then in 2008, MANAGE was updated with 15 additional studies, and nitrogen (N) and phosphorus (P) concentrations in runoff were added. Since then, MANAGE has undergone significant expansion adding N and P water quality along with relevant management and site characteristic data from: (1) 30 runoff studies from forested land uses, (2) 91 drainage water quality studies from drained land, and (3) 12 additional runoff studies from cultivated and pasture/range land uses. In this expansion, an application timing category was added to the existing fertilizer data categories (rate, placement, formulation) to facilitate analysis of 4R Nutrient Stewardship, which emphasizes right fertilizer source, rate, time, and place. In addition, crop yield and N and P uptake data were added, although this information was only available for 21 and 7% of studies, respectively. Inclusion of these additional data from cultivated, pasture/range, and forest land uses as well as artificially drained agricultural land should facilitate expanded spatial analyses and improved understanding of regional differences, management practice effectiveness, and impacts of land use conversions and management techniques. The current version is available at www.ars.usda.gov/spa/manage-nutrient .     

新型碳源驯化的SRB去除酸性矿山废水中SO_4~(2-)最佳反应条件

针对硫酸盐还原菌(SRB)处理酸性矿山废水缺乏有效有机碳源问题,运用生活污水、鸡粪和锯末质量比80∶7∶3混合物的发酵液作为新型有机碳源驯化硫酸盐还原菌SRB,并研究SRB以该新型有机碳源作为营养物质在不同COD/SO2-4(C/S)值、pH值、初始硫酸根(SO2-4)浓度、重金属离子(Fe2+、Mn2+、Cu2+和Zn2+)浓度条件下对SO2-4的去除效果,以确定SRB去除SO2-4的最佳反应条件。实验结果表明,在厌氧环境SRB接种量8%、生长温度35℃、转速50 r/min、C/S为1.5~2.0、pH值6~7、初始SO2-4浓度≤3 000 mg/L、Fe2+在100~300 mg/L、Mn2+为35 mg/L时反应条件最佳,SO2-4去除率均可达90%以上;其中Fe2+浓度≤500 mg/L、Mn2+浓度≤140 mg/L时均会促进SRB对SO2-4的还原,当Fe2+浓度≥600mg/L时会严重抑制SRB,Mn2+浓度140 mg/L时会抑制SRB;Cu2+、Zn2+的存在对SRB均有影响,当Cu2+浓度15 mg/L时、Zn2+浓度45 mg/L时对SRB均有抑制作用。新型有机碳源可作为SRB的优良有机碳源,同时可实现以废治废的目的。该成果为实际应用提供了参考。     

碳酸盐岩煅烧改性处理酸性矿山废水的研究

将碳酸盐岩在不同温度下进行煅烧改性,在保持颗粒机械强度的条件下将其应用于酸性矿山废水(AMD)的处理。结果表明,碳酸盐岩在600℃下煅烧基本不产生变化,当升至750℃时,碳酸盐岩开始分解,煅烧3.0h后,烧失量为1.86%,煅烧后产物仍保持较强颗粒强度。800℃以上煅烧的碳酸盐岩则出现颗粒断裂现象,放入AMD中会立即溶解产生白色沉淀。在750℃煅烧改性后的碳酸盐岩能有效提高AMD的pH,对各种金属离子都有非常好的去除效果,尤其克服了原岩对Mn2+去除效果不佳的缺点;将750℃煅烧改性后的碳酸盐岩应用到野外AMD处理工程中,能有效减少处理构筑物的体积和占地面积,从而降低建设成本。