不同土壤层中4种菊酯类农药残留量的测定

采集农田中表层、里层、深层土壤,采用正己烷 ∶ 丙酮＝1 ∶ 1(V/V)作为提取剂^[1,2],土壤样品于Florisil柱中净化,浓缩定容后,用电子捕获检测器检测,石英毛细管柱气相色谱法测定,用外标法定量。以农田表层土壤测定结果为例,甲氰菊酯的回收率为85.2%~102.7%,RSD为2.27%~5.41%;氯氰菊酯的回收率为80.5%~102.7%,RSD为2.84%~6.70%;氰戊菊酯的回收率为80.2%~103.0%,RSD为2.33%~5.95%;溴氰菊酯的回收率为80.8%~102.7%,RSD为2.45%~6.24%。方法简便、快速、成本低。     

快速溶剂萃取-分子筛脱水净化-气质联用法测土壤有机氯农药

用丙酮和正己烷(体积比为1∶1)作溶剂,在100℃和1 500 psi的压力下,用快速溶剂萃取仪从土壤中萃取出有机氯农药,用分子筛进行脱水和净化,GC-MS进行分析,对土壤中有机氯农药进行测定。方法的检出限为0.000 4~0.000 7 mg/kg,曲线的相关系数在0.998以上。对进口标准土进行测定,回收率为77.1%~105.2%,相对误差为-22.9%~5.2%,测定结果在证书允许误差范围内。用硅藻土制成高、中、低3个浓度级别的加标回收和精密度实验,加标回收率为84.3%~101.5%,相对标准偏差为0.6%~11.4%,表明方法准确可靠,方法用于实际土壤测定时发现土壤有不同程度的有机氯农药污染。     

全自动石墨消解-原子荧光法测定土壤中砷和汞

采用全自动石墨消解仪代替水浴锅加热王水消解法处理土壤样品,用原子荧光法测定消解液中的砷和汞。该方法在0μg/L~20.0μg/L范围内线性良好,测定有证标准土壤样品的结果均在标准值允许范围内,砷、汞测定结果的RSD分别为2.5%~4.8%、2.9%~5.4%,比王水消解法的测定结果更靠近标准值,实际土壤样品的加标回收率分别为94.6%~104%、92.6%~105%。     

弗罗里硅土净化和凝胶色谱净化在土壤苯并(a)芘测定中的应用

采用ASE萃取-弗罗里硅土净化-HPLC法和ASE萃取-GPC净化-HPLC法测定土壤中苯并(a)芘,并将2种方法的测定结果作比对。试验表明,方法在0.02 mg/L~0.500 mg/L之间线性良好,当取样量为10 g时,弗罗里硅土净化土壤样品方法检出限为8.93×10~(-5)mg/kg,平均加标回收率为72.7%~73.8%,3次测定结果的RSD为4.0%~4.5%;凝胶色谱净化土壤样品方法检出限为1.98×10~(-5)mg/kg,平均加标回收率为88.8%~90.2%,3次测定结果的RSD为2.1%~2.8%。     

碱提取-丙基化衍生法同时测定土壤中的甲基汞和乙基汞

建立了碱提取-丙基化衍生方式同时测定土壤中甲基汞和乙基汞的方法。优化了仪器分析条件，研究了碱提取温度、提取时间、缓冲溶液加入量和衍生化试剂加入量对测定结果的影响。应用本方法对5种实际土壤样品进行测定，甲基汞和乙基汞的方法检出限分别为0.5 μg/kg和0.3 μg/kg，相对标准偏差分别为1.3%~17%和0.94%~16%，平均回收率分别为88.2%~110%和66.1%~110%。该法适用于批量土壤样品中甲基汞和乙基汞的分析测定。     

超声浸取-离子选择电极法测定土壤中水溶性氟

采用水平震荡和超声浸取2种方法进行预处理,离子选择电极法测定土壤中水溶性氟化物。结果显示:土壤中水溶性氟化物的最佳预处理条件为纯水与土壤按10∶1混合,常温35 k Hz超声浸取30 min。超声浸取-离子选择电极法测定土壤中水溶性氟化物具有较好的精密度和准确性,此法在5.00~500μg范围内线性良好,检出限为0.5 mg/kg。对实际样品进行分析,氟的加标回收率为82.0%~110%,相对标准偏差为2.8%~6.4%(n=6)。对土壤有证标准物质进行分析,相对标准偏差为2.9%~4.6%(n=6),相对误差为-3.9%~2.7%。     

超高效液相色谱-串联质谱法测定土壤中多种全氟化合物

采用超声提取、固相萃取法处理土壤,用超高效液相色谱-电喷雾串联三重四极杆质谱测定样品中11种全氟化合物,通过优化测定条件,使方法在0.100μg/L~150μg/L范围内线性良好(r~20.995)。当取样量为2.0 g时,方法检出限为0.1 ng/g~0.4 ng/g。实际土壤样品的加标回收率为67.2%~106%,测定6次结果的RSD为6.6%~17.3%。     

土壤中挥发性有机物的快速测定方法

本文建立了用便携式气相色谱-质谱仪快速测定土壤中VOCs的方法。该方法能够快速对土壤样品中VOCs进行定性分析和定量测定。当采样量达到5 g时,方法检出限0.02~2.11μg/L,相对标准偏差2.0%~13.5%;加标20μg/L时,回收率63%~123%。采用该方法测定北京地区5个土壤样品,总体质量浓度为0~873μg/kg。     

气相色谱法测定黄瓜和土壤中代森锰锌的残留及其消解动态分析

采用GC-FPD(S)法测代森锰锌在黄瓜和土壤中的残留,通过优化前处理和检测条件,使方法在0.007 6 mg/L~3.80 mg/L范围内线性良好,在黄瓜和土壤中的方法检出限分别为5.12μg/kg和2.35μg/kg。黄瓜和土壤3个质量比水平的空白加标回收率分别为91.1%~96.5%和82.4%~90.5%,7次测定结果的RSD为5.0%~6.5%和2.4%~4.1%。将该方法用于研究代森锰锌在黄瓜和土壤中的消解动态,得知代森锰锌在黄瓜中的半衰期为3.63 d~4.77 d,在土壤中的半衰期为4.19 d~7.33 d。     

砷铈催化分光光度法测定土壤中的碘

用碱灰化处理试样,采用砷铈催化分光光度法测定土壤中的碘,讨论了温度与时间对测定的影响。方法在0 ng~250 ng范围内线性良好,检出限为2.58μg/kg,土壤样品测定的RSD≤2.9%,加标回收率为78.0%~116%。     

Exposure Assessment to Mercury Vapor in Chloralkali Industry

The aim of the study was to develop a sampling method aimed at individual sampling of mercury vapor and subsequent individualexposure assessment of the worker. Hopcalite available fromInowrocawskie Zakady Chemiczne (in Poland) was founduseful for mercury vapor sampling in active and passive individual samplers. However the sampling rate determined forpassive sampler in steady-state laboratory chamber cannot be usedunder fluctuating conditions of mercury vapor concentration andair movement typical for field measurement. In order to check comparativeness of passive and active sampling methods, sampleswere taken in the same time and individual samplers fixed toworker's clothes were used. Mercury vapor concentration wasmeasured at two chloralkali industries in Poland and the resultswere presented. Excessive exposure in both industries wasconfirmed by finding elevated mercury concentration in urinesamples from the workers.     

提高环境水中纳克级超痕量汞测定灵敏度的研究

对ｎｇ／Ｌ级超痕量汞测定中的消解、测定各步骤对灵敏度的影响进行了研究。得出结论：采用高纯氩气作载、屏气，选择高负压值和高扩展倍率能明显提高灵敏度；选择合适的消解时间和缩短测定时间能使灵敏度略有提高；试剂和玻璃器皿所带给空白的痕量汞对提高灵敏度不利，应作除汞处理。     

全自动甲基汞分析仪测定水和废水中甲基汞

建立了全自动甲基汞分析仪测定水和废水中甲基汞的方法,对较清洁的地表水和一般废水样品可直接衍生化测定,对基体复杂水样则需蒸馏后再衍生化测定。该法在水样中甲基汞含量为0~1 000 pg范围内线性良好,相关系数r为0.999 7,检出限为0.002 ng/L,标准参考物质测定结果均在参考值范围内,相对标准偏差为1.1%,加标回收率为83.2%~96.6%。该法适用于水及废水中甲基汞的检测。     

氯磺酚偶氮硫代若丹宁光度法测定环境水样中的汞

研究了氯磺酚偶氮硫代若丹宁(HSCT)与汞的显色反应。在pH3 8的HAc-NaAc缓冲介质中,TritonX-100存在下,HSCT与汞反应生成2∶1稳定络合物,λmax=550nm,体系ε=8 46×104L·mol-1·cm-1。汞含量在0—1 5mg/L内符合比耳定律。方法可用于水样中痕量汞含量的测定。     

冷原子吸收法对水中汞溶液浓度测量结果的不确定度评定

对冷原子吸收法测量水中汞溶液浓度的影响因素作了全面分析,对各因素的不确定度进行评估,评定了冷原子吸收法对水中汞溶液浓度测量结果的不确定度。     

总汞环境样品的前处理技术及分析方法研究进展

对2005—2012年间的环境样品中总汞检测的前处理技术及分析方法文献进行了综述。总结了水体、土壤及废气中总汞样品前处理采用的主要方法及存在的问题,并且对环境样品总汞的现行国标分析方法及新方法(光度法、冷原子吸收法、原子荧光法、电感耦合等离子体-质谱法及生化检测等)的原理和应用进行了归纳。展望了环境样品中总汞检测的发展趋势,为研究者进行总汞新分析方法的开发和标准化提供了借鉴。     

Atmospheric Monitoring at Abandoned Mercury Mine Sites in Asturias (NW Spain)

Mercury concentrations are usually significant in historic Hg mining districts all over the world, so the atmospheric environment is potentially affected. In Asturias, northern Spain, past mining operations have left a legacy of ruins and Hg-rich wastes, soils and sediments in abandoned sites. Total Hg concentrations in the ambient air of these abandoned mine sites have been investigated to evaluate the impact of the Hg emissions. This paper presents the synthesis of current knowledge about atmospheric Hg contents in the area of the abandoned Hg mining and smelting works at ‘La Peña–El Terronal’ and La Soterraña, located in Mieres and Pola de Lena districts, respectively, both within the Caudal River basin. It was found that average atmospheric Hg concentrations are higher than the background level in the area (0.1 μg Nm^?3), reaching up to 203.7 μg Nm^?3 at 0.2 m above the ground level, close to the old smelting chimney at El Terronal mine site. Data suggest that past Hg mining activities have big influences on the increased Hg concentrations around abandoned sites and that atmospheric transfer is a major pathway for Hg cycling in these environments.     

高效液相色谱-电感耦合等离子体质谱联用测水中有机汞

建立了高效液相色谱-电感耦合等离子体质谱联用技术(HPLC-ICP-MS)测定水样中甲基汞、乙基汞、苯基汞等3种有机汞的分析方法。采用醋酸铵-L-半胱氨酸缓冲盐及甲醇体系组成的流动相按一定比例进行梯度洗脱,Agilent Zorbax Plus C18柱分离,经前处理的水样在液相色谱中分离后,进入电感耦合等离子体质谱检测其甲基汞、乙基汞、苯基汞的浓度。3种有机汞化合物均在0.50~50.0μg/L范围内呈良好的线性关系,线性相关系数均大于0.999 5。仪器检出限为0.09~0.12μg/L,方法检出限为0.4×10-6~0.6×10-6mg/L,3种有机汞样品加标的RSD均小于11.3%,2个水平的加标回收率为74.4%~83.2%。     

Response of Mercury Contamination in Fish to Decreased Aqueous Concentrations and Loading of Inorganic Mercury in a Small Stream

Approximately 250 000 kg of mercury was lost towater and soils at the U.S. Dept. of Energy Y-12 Plantin Oak Ridge, Tennessee in the 1950s and early 1960s. A creek originating within the plant receivedcontinuous inputs of waterborne mercury, predominantlyas dissolved inorganic mercury, from groundwater,streambed contamination, and sump and process waterdischarges to the contaminated storm sewer network.These produce aqueous total mercury concentrations of1–2 g L^-1 in the upper reaches of the stream,decreasing to about 0.1–0.2 g L^-1 in its lowerreaches. A program to reduce mercury concentrationsin the creek identified specific sources (buildingsumps, contaminated springwater seeps, foundationdrains, and contaminated piping) and rerouted wateraround contaminated portions of the drain system orcollected and treated mercury-contaminated waterbefore discharging it. As a result, waterbornemercury concentrations in the creek and total mercuryloading were reduced from 1.8 g L^-1 to0.6 g L^-1 and 100 to 20 g d^-1, respectively, in the last 5 yr.Mean mercury concentrations in fish nearest sourceareas in the creek headwaters decreased at roughly thesame rate as waterborne total mercury concentrationsover the past five years, but at the facility boundarydownstream the decline in mercury bioaccumulation wasmuch less. At sites 5–15 km farther downstream, nodecrease was evident. Dissolved methylmercury tendedto increase with distance downstream in a patterninverse to that noted for its dissolved inorganicmercury precursor.Improvements in water quality and modification ofweirs to allow the passage of fish have resulted inthe establishment of large populations of fish inmercury-contaminated headwater areas previously devoidof fish. It may be that the accumulation, retention,and eventual downstream transport of this reservoir ofbiologically incorporated methylmercury has acted tobuffer against expected reductions in mercury in fishat downstream sites.     

A Method of Mercury Removal from Topsoil Using Low-Thermal Application

Mercury contamination in the environment is problematic due to the unusual physical properties and well-recognized toxicity of this common metal. The bioavailability of mercury depends strongly on its chemical speciation. Anthropogenic mercury and its compounds appear in soil as hot spots located close to industrial facilities that used or produced mercury. The nature of the chemical production process, transportation and disposal practices often determined the chemical composition and distribution of mercury in the surrounding soils. Current ex situ soil remediation methods are expensive, produce undesirable side effects to the environment and usually involve transportation of contaminated soil.In this project, sponsored by the U.S. Department of Energy, a low-cost, simple approach to removing mercury from soil was evaluated. The process uses low-temperature thermal desorption of volatile metallic mercury and its compounds, and subsequent vapor capture.The project consisted of laboratory and plot-scale experiments. The laboratory efforts evaluated theoretical calculations of mercury removal as a function of time and temperature. The plot-scale experiment was a practical application of the laboratory results. For both experiments, mercury-polluted soil was obtained from a chemical production facility located in southern Poland. In laboratory experiments, at temperature 373 K total mercury concentration decreased in soil by nearly 32%. In plot-scale experiments, at temperature 440 K, about 60–70% of total mercury was removed from the soil.At the end of the experiment, a test of soil biological activity was performed to check if the high temperature applied to the soil did not impair the soil growth properties. There was no negative effect of temperature found.