燃煤烟气中汞形态分析的实验研究

在一维煤粉燃烧炉台架上采用EPA推荐的Ontario Hydro方法 ,测量了燃烧不同煤种排放的烟气中汞的形态分布情况 .结果表明 ,烟气中汞以颗粒态和气态汞的形式存在 .气态汞总量在 9— 2 3 μg·Nm- 3范围内 ,主要以单质汞的形式存在 ,占气态汞总量的 5 2 %—83 % ,而二价汞占 1 7%— 48% .飞灰中汞的浓度大大超过了底灰中汞的浓度 ,表明汞在飞灰中富集 ,在底灰中分散的行为     

零价铁对土壤中2-氯硝基苯的还原作用

在常温常压下利用零价铁(Fe0)还原土壤中的2-氯硝基苯(o-CNB),研究反应条件对还原率的影响以及反应产物在不同反应阶段的变化.GC-MS检测结果显示,o-CNB在还原过程中先生成2-氯亚硝基苯,最终生成2-氯苯胺.反应时间、Fe0用量、温度和土壤初始pH值等均会对o-CNB的还原率产生影响,其中土壤初始pH值控制在偏酸性、土壤温度较高时能显著提高其还原率.当o-CNB的初始浓度约为2.5×10-6 mol/g,Fe0加入量是25 mg/g时,经过4 h反应,o-CNB的还原率可达99%以上.此外,还初步探讨了Fe0还原o-CNB的反应机理.     

大气环境中汞的形态及其分析方法

本文引用了近二十年来与大气环境中汞的形态和分析方法有关的２０多篇文章,对各种方法的优缺点进行了比较。     

Heavy metals in surface water and stream sediments in Jamaica

The levels of heavy metals in water and stream sediments in Jamaica are presented and compared to levels in soils and environmental standards. Heavy metals (cadmium, chromium, copper, mercury, nickel, lead and zinc) appear to be less of a problem to Jamaica's freshwater environment than might be expected given the concentrations in soils. This can be explained by taking into account the dynamics of the Jamaican water environment and the relative absence of anthropogenic sources. The dynamics of the freshwater system on the other hand, could pass any environmental threat to the coastal environment. Because the stream sediments are relatively coarse and contain little organic material the bio-availability of micropollutants such as heavy metals from the sediments can be expected to be relatively high.     

零价铁对土壤中4-氯苯酚还原脱氯研究

氯苯酚是常见的环境污染物，它们在土壤中的加速分解可以减少对人类健康的危害。以恒温培养为方法，GC-MS为检测手段，研究了在常温常压下土壤中4-氯苯酚(4-CP)在零价铁作用下的还原脱氯反应。结果表明：4-CP可以被来自零价铁的电子还原，零价铁能够有效促进土壤中的4-CP脱除苯环上的氯原子，从而达到降低毒性、增加可生化性目的。反应条件如初始pH、时间、零价铁用量等均对4-CP还原脱氯效率有重要影响，特别是当初始pH值控制在偏酸时更有利于反应的进行。在零价铁加入量500mg、初始pH=4、反应时间7d的条件下，零价铁对土壤中4-CP还原脱氯效率最高可以达到65％。利用实验数据，对零价铁作用下4-CP还原脱氯的反应机理也进行了初步探讨。     

土壤中取代硝基苯化合物被零价铁还原的机理

以气相色谱-质谱联用仪(GC-MS)分析和密度泛函理论(DFT)计算,探讨了土壤中甲基、氯代硝基苯混合物在常温常压下被零价铁还原的机理.GC-MS数据证明,取代硝基苯在土壤中被零价铁还原的主要产物是苯胺,同时还检测到微量的亚硝基苯、甲基苯二氮烯(对二甲基偶氮苯)、氯苯二氮烯(对二氯偶氮苯)等分解和缩合中间产物.理论计算表明:随还原程度的加深,对硝基甲苯和对氯硝基苯反应体系的能量从高到低,还原反应通过逐步添加质子和电子到硝基而进行,质子亲和力、电子亲和力起主导作用.逐步还原的机理合理地解释了实验中还原反应对土壤pH值的敏感以及微量中间产物的生成过程.苯环上的氯或甲基对还原反应的影响没有明显的差异.     

Factors affecting food chain transfer of mercury in the vicinity of the Nyanza Site,Sudbury River,Massachusetts

The influence of the Nyanza Chemical Waste Dump Superfund Site on the Sudbury River, Massachusetts, was assessed by analysis of sediment, fish prey organisms, and predator fish from four locations in the river system. Whitehall Reservoir is an impoundment upstream of the site, and Reservoir #2 is an impoundment downstream of the site. Cedar Street is a flowing reach upstream of the site, and Sherman Bridge is a flowing reach downstream of the site. Collections of material for analysis were made three times, in May, July, and October. Sediment was analyzed for acid-volatile sulfide (AVS), simultaneously-extracted (SEM) metals (As, Cd, Cr, Hg, Pb, Sb, Zn), and total recoverable Hg. The dominant predatory fish species collected at all sites, largemouth bass (Micropterussalmoides), was analyzed for the same suite of metals as sediment. Analysis of stomach contents of bass identified smallfish (yellow perch Perca flavescens, bluegill Lepomismacrochirus, and pumpkinseed Lepomis gibbosus), crayfish,and dragonfly larvae as the dominant prey organisms. Samples of the prey were collected from the same locations and at the sametimes as predator fish, and were analyzed for total and methyl mercury. Results of AVS and SEM analyses indicated that sediments were not toxic to aquatic invertebrates at any site. The SEM concentrations of As, Cd, and Cr were significantly higher at Reservoir #2 than at the reference sites, and SEM As and Cdwere significantly higher at Sherman Bridge than at Cedar St. Sediment total Hg was elevated only at Reservoir #2. Hg washigher at site-influenced locations in all fish speciesexcept brown bullhead (Ameiurus nebulosus). Cd washigher in bluegill, black crappie (Pomoxis nigromaculatus),and brown bullhead, and Cr was higher in largemouth bass filletsamples but not in whole-body samples. There were no seasonal differences in sediment or prey organism metals, but some metalsin some fish species did vary over time in an inconsistent manner. Predator fish Hg concentration was significantly linearlyrelated to weighted prey organism methyl Hg concentration. Largemouth bass Hg was significantly lower at Reservoir #2 in our study than in previous investigations in 1989 and 1990. High concentrations of inorganic Hg remain in river sediment asa result of operation of the Nyanza site, and fish Hg concentrations in river reaches downstream of the site areelevated compared to upstream reference sites. However, thedifferences are relatively small and Hg concentrations inlargemouth bass from the site-influenced locations are nohigher than those from some other, nearby uncontaminatedsites. We hypothesize that this results from burial ofcontaminated sediment with cleaner material, which reducesbioavailability of contaminants and possibly reducesmethylation of mercury.     

无汞开管法快速测定工业废水中的COD

采用无汞开管法测定 COD。方法使用硫酸 -磷酸介质、重铬酸钾氧化体系 ,以硫酸银作催化剂 ,其他试剂包括硝酸银和硫酸铬钾以排除氯离子的干扰。样品在玻璃试管中进行消化 ,用一台恒温器加热样品 ,反应温度 1 65℃ ,加热时间只需 1 0 min,消解后剩余的重铬酸盐用分光光度法或滴定法测定。试验结果表明 ,本法的检出限为 1 0 .9mg/ L,测定范围为 3 0～ 1 5 0 0 mg/ L。由于方法不使用剧毒的汞盐 ,也就避免了汞对环境的污染。应用本法测定了大批量工业废水样品 ,结果令人满意     

典型燃煤电厂汞的分布、迁移及释放特征研究

采集安徽不同地区两典型燃煤电厂火力发电中使用的原煤及其产生的3类固体副产物(飞灰,炉渣及脱硫石膏样品),对4类样品中汞含量分别进行测定,以此揭示电厂燃煤过程中汞的分布、迁移及转化规律。此外,采用质量平衡及二次排放模型分别初步估算了电厂燃煤及燃煤固体副产物再利用过程中汞的两次释放特征。结果显示,汞在原煤、飞灰、炉渣及脱硫石膏样品中的含量分别为174~321μg/kg、421~316μg/kg、6~3 143μg/kg和2 988~4 694μg/kg;燃煤过程中有20.9%~23.6%的汞转移到飞灰中,32.6%~59.9%的汞赋存于脱硫石膏中,16.5%~37.4%的汞通过烟囱首次排入大气,仅有0.02%~9.2%的汞残留在炉渣中。二次排放模拟结果显示,燃煤电厂1#和2#中飞灰和脱硫石膏的高温再利用过程将向大气二次释放汞量96.0 kg/a和165.8 kg/a,两次年排放总量分别为189.5 kg和640.8 kg。本研究可为燃煤电厂汞的污染过程控制提供参考依据。     

100 years of high GEM concentration in the Central Italian Herbarium and Tropical Herbarium Studies Centre (Florence, Italy)

Up to 1980s, the most used preservative for herbaria specimens was HgCl₂, sublimating at ambient air conditions; ionic Hg then reduces to Hg⁰ (gaseous elemental mercury, GEM) and diffuses throughout poor ventilated environments. High GEM levels may indeed persist for decades, representing a health hazard. In this study, we present new GEM data from the Central Italian Herbarium and Tropical Herbarium Studies Centre of the University of Florence (Italy). These herbaria host one of the largest collection of plants in the world. Here, HgCl₂ was documented as plant preservative up to the 1920s. GEM surveys were conducted in July 2013 and July and December 2017, to account for temporal and seasonal variations.Herbaria show GEM concentrations well above those of external locations, with peak levels within specimen storage cabinets, exceeding 50,000?ng/m³. GEM concentrations up to ~ 7800?ng/m³ were observed where the most ancient collections are stored and no ventilation systems were active. On the contrary, lower GEM concentrations were observed at the first floor. Here, lower and more homogeneously distributed GEM concentrations were measured in 2017 than in 2013 since the air-conditioning system was updated in early 2017.GEM concentrations were similar to other herbaria worldwide and lower than Italian permissible exposure limit of 20,000?ng/m³ (8-hr working day). Our results indicate that after a century from the latest HgCl₂ treatment GEM concentrations are still high, i.e., the treatment itself is almost irreversible. Air conditioning and renewing is probably the less expensive and more effective method for GEM lowering.