高效液相色谱-氢化物发生-原子荧光光谱联用技术测定水中烷基汞

建立了高效液相色谱(HPLC)-氢化物发生(HG)-原子荧光光谱(AFS)联用技术分析地表水及废水中甲基汞和乙基汞的方法。样品经二氯甲烷萃取,再以半胱氨酸+乙酸铵溶液反萃取富集,并进入高效液相色谱分离,经形态分析预处理装置后,借助原子荧光光谱法检测。在优化分离条件下,甲基汞和乙基汞在1～50μg/L范围内呈现良好的线性关系,对于标准水样、地表水和废水实际水样,加标平均回收率均为80%～110%。平行进样7次1μg/L的汞混合标准溶液,甲基汞和乙基汞的色谱峰面积的相对标准偏差分别为5.2%和3.9%,检出限则分别为0.4 ng/L和0.7 ng/L。该检测方法前处理简单、回收率稳定、灵敏度和准确度高、检出限低、杂质干扰少、监测费用低,便于在普通实验室推广和应用。     

测定水中铁、锰、汞时前处理问题探讨

基于大量实测数据统计,比较了测定水中铁、锰、汞3种重金属时,样品是否过滤、加酸保存等前处理方式对测定结果的影响,提出铁、锰水样需过滤检测,汞水样不能过滤检测,且3种金属的水样均需加酸保存,这样测定的结果才能根据现行水环境质量标准进行评价。     

煤质样品中汞的直接测定

采用DMA-80型直接测汞仪测定煤中汞含量,样品经过筛（100目）预处理,干燥温度和时间分别为200 ℃和30 s,分解温度和时间分别为650 ℃和90 s,基体元素对测定无明显干扰。方法在高质量浓度（0.200 mg/L～10.0 mg/L）和低质量浓度（0.400 μg/L～200 μg/L）范围内均线性良好,对0.100 g煤质样品的最低检出限为0.4 μg/kg,平行测定的RSD＜5%,加标回收率＞97%,与原子荧光法的测定结果相一致。     

乳状液膜提取废汞触媒浸出液中的汞及 乳状液破乳

采用乳状液膜法分离提取废汞触媒浸出液中的Hg~(2+)。考察了影响乳状液膜体系分离富集汞的主要因素,并对分离提取后的乳液相进行了破乳研究。分离提取实验结果表明:乳状液膜体系的最佳配方为流动载体磷酸三丁酯体积分数10%、表面活性剂失水山梨糖醇脂肪酸酯体积分数4%、膜溶剂磺化煤油体积分数86%、内水相HCl溶液浓度0.10mol/L、油相与内水相的体积比1∶1;在乳状液与外水相的体积比为1∶10的条件下Hg~(2+)提取率达78.50%。破乳实验结果表明:加热破乳、离心破乳、加热离心联合破乳3种方法的破乳率分别为29.0%,54.0%,85.7%;采用加热离心联合法破乳后,Hg~(2+)富集倍数达8.5。     

活性焦烟气脱汞的试验研究与数值模拟

采用固定床吸附系统,对自制褐煤活性焦的脱汞性能进行了试验研究,研究发现自制活性焦对烟气中Hg0有一定的吸附能力,随着Hg0的入口浓度的增加,活性焦质量的增加,活性焦的吸附量也在增加。40mg时3号活性焦由10ng/min汞入1：2浓度时26．68％的最大吸附效率提高到40ng／min汞入口浓度时的53．12％。10ng/min汞入口浓度时3号活性焦在40mg时的最大吸附效率为26．68％,而在80mg时吸附效率提高到43．2％。烟气中的SO2、NO气体对活性焦吸附汞有一定的促进作用。在试验的基础上建立了固定床吸附系统的数学模型,基于Lan—mguir吸附系数,考虑吸附过程中颗粒内、外的传质控制过程,建立质量平衡方程。通过Matlab模型计算,计算结果与试验结果基本吻合,计算的活性焦脱汞效率要优于试验数值,计算的是理想情况下活性焦对汞的吸附效率,实际情况会有所降低。     

现有设备协同脱汞技术概述

介绍了燃煤电站汞的排放状况,并指出了汞危害性以及我国面临的脱汞压力,论述了烟气中汞存在形式以及影响其存在形式的因素.探讨了当前燃煤电站利用现有污染控制设备进行协同脱汞的研究进展,包括：燃烧器/反应器、选择性催化还原脱硝（SCR）、电除尘器（布袋除尘）（ESP/FF）、湿法烟气脱硫系统（WFGD）等设备.提出了脱汞吸附剂处理问题,并对今后烟气脱汞技术的研究趋势进行了展望.     

Estimate of the uncertainty in measurement for the determination of mercury in seafood by TDA AAS

An approach for the estimate of the uncertainty in measurement considering the individual sources related to the different steps of the method under evaluation as well as the uncertainties estimated from the validation data for the determination of mercury in seafood by using thermal decomposition/amalgamation atomic absorption spectrometry (TDA AAS) is proposed. The considered method has been fully optimized and validated in an official laboratory of the Ministry of Agriculture, Livestock and Food Supply of Brazil, in order to comply with national and international food regulations and quality assurance. The referred method has been accredited under the ISO/IEC 17025 norm since 2010. The approach of the present work in order to reach the aim of estimating of the uncertainty in measurement was based on six sources of uncertainty for mercury determination in seafood by TDA AAS, following the validation process, which were: Linear least square regression, Repeatability, Intermediate precision, Correction factor of the analytical curve, Sample mass, and Standard reference solution. Those that most influenced the uncertainty in measurement were sample weight, repeatability, intermediate precision and calibration curve. The obtained result for the estimate of uncertainty in measurement in the present work reached a value of 13.39%, which complies with the European Regulation EC 836/2011. This figure represents a very realistic estimate of the routine conditions, since it fairly encompasses the dispersion obtained from the value attributed to the sample and the value measured by the laboratory analysts. From this outcome, it is possible to infer that the validation data (based on calibration curve, recovery and precision), together with the variation on sample mass, can offer a proper estimate of uncertainty in measurement.     

Long‐term mercury accumulation in the presence of cadmium and lead in oseochromis aureus (Steindachner)

Abstract

The effects of cadmium and lead on chronic mercury accumulation were investigated in O. aureus. After 140 days’ exposure the accumulation of mercury in the liver, brain, gill filaments, intestine, caudal muscle, spleen, trunk kidney and eye was analysed. The exposure concentrations were 0.05, 0.10 and 0.20 mg/L for mercury alone. O. aureus was also exposed to mixtures of 0.05 mg/L mercury with lead (0.05 mg/L and 0.50 mg/L or cadmium (0.05 mg/L) and 0.10 mg/L mercury with 0.10 mg/L cadmium. In food fish, a knowledge of toxic metal accumulation patterns is of great importance because of their contribution to the human diet and, as fishmeal, to the diet of agricultural animals. The trunk kidney consistently accumulated higher concentrations of mercury than any of the other tissues investigated.     

Rapid assays for environmental and biological monitoring

Abstract

Rapid, inexpensive, sensitive, and selective enzyme‐linked immunosorbent assays (ELISAs) now are utilized in environmental science. In this laboratory, many ELISAs have been developed for pesticides and other toxic substances and also for their metabolites. Compounds for which ELISAs have recently been devised include insecticides (organophosphates, carbaryl, pyrethroids, and fenoxycarb), herbicides (s‐triazines, arylureas, triclopyr, and bromacil), fungicides (myclobutanil), TCDD, and metabolites of naphthalene and toluene. New rapid assays have been developed for mercury.     

The sea–air exchange of mercury (Hg) in the marine boundary layer of the Augusta basin (southern Italy): Concentrations and evasion flux

The first attempt to systematically investigate the atmospheric mercury (Hg) in the MBL of the Augusta basin (SE Sicily, Italy) has been undertaken. In the past the basin was the receptor for Hg from an intense industrial activity which contaminated the bottom sediments of the Bay, making this area a potential source of pollution for the surrounding Mediterranean. Three oceanographic cruises have been thus performed in the basin during the winter and summer 2011/2012, where we estimated averaged Hg_atm concentrations of about 1.5 ± 0.4 (range 0.9–3.1) and 2.1 ± 0.98 (range 1.1–3.1) ng m⁻³ for the two seasons, respectively. These data are somewhat higher than the background Hg_atm value measured over the land (range 1.1 ± 0.3 ng m⁻³) at downtown Augusta, while are similar to those detected in other polluted regions elsewhere. Hg evasion fluxes estimated at the sea/air interface over the Bay range from 3.6 ± 0.3 (unpolluted site) to 72 ± 0.1 (polluted site of the basin) ng m⁻² h⁻¹. By extending these measurements to the entire area of the Augusta basin (∼23.5 km²), we calculated a total sea–air Hg evasion flux of about 9.7 ± 0.1 g d⁻¹ (∼0.004 t yr⁻¹), accounting for ∼0.0002% of the global Hg oceanic evasion (2000 t yr⁻¹). The new proposed data set offers a unique and original study on the potential outflow of Hg from the sea–air interface at the basin, and it represents an important step for a better comprehension of the processes occurring in the marine biogeochemical cycle of this element.