水浴浸提-氢化物发生-原子荧光光谱法同时测定地质样品中痕量砷和汞

采用盐酸-硝酸混合酸(盐酸-硝酸-水体积比3∶1∶4)水浴浸取地质样品,在样品消解后的母液中直接加入硫脲-抗坏血酸混合溶液,以氢化物发生-原子荧光光谱法同时测定地质样品中的痕量砷和汞。方法检出限为砷0.033 6 ng/mL,汞0.003 7 ng/mL;相对标准偏差(RSD,n=1)为砷1.1%,汞3.0%。对国家一级标准物质GBW 07109~GBW 07114、GBW 07301~GBW 07312、GBW 07401~GBW 07408中的砷和汞进行测定,测定值与标准值相吻合。     

漓江水系汞的分布和污染研究

对漓江水系干流、支流、连体湖泊、较大的孤立湖塘和近岸水井设置40个采样点。水样采样周期为2个水文年,分枯水季和丰水季两次采样,现场测定水温、电导率、pH值等理化参数。系统采集水样112件、底泥样40件、水草样40件、近岸土壤样40件。底泥样用逐步浸提法进行不同形态汞分析。研究结果显示,干流河水、底泥和水草中汞的平均含量分别为0．12μg／L、0．20μg／g和0．032μg／g;主要支流河水、底泥和水草中汞的平均含量高于干流,分别为0．15—0．23μg／L、0．38～1．7μg／g和0．028—0．044μg／g。底泥中汞含量均高于近岸土壤汞含量。无论是干流还是支流,河水汞含量与底泥、水草汞含量有明显的相关关系。由上游至下游,漓江水系干流、主要支流河水样汞含量均不断增高,可高出源头河水汞含量的1．5—5倍。相应地指示重金属离子污染的参考指标——电导率值不断增高,河水的pH值亦逐渐增高。丰水期（5月至6月）河水中的汞含量（0．12—0．28μg／L）明显高于枯水期（9月至11月）河水中的汞含量（0．091—0．28μg／L）。不同断面河水汞含量均高于相应近岸井水汞含量。不同水体底泥中汞的形态分布一般顺序为：残渣态〉难氧化降解有机质结合态〉腐殖酸结合态〉碳酸盐和铁锰氧化物吸附态〉交换态〉易氧化降解有机质结合态〉水溶态。综合各项资料分析,认为漓江干流是桂林城市汞污染最大的汇。根据地表水环境质量标准（GB3838--2002）,仅汞而言,漓江水系均达到Ⅳ类水质标准（河水中汞含量≤1μg／L）。漓江支流汞污染高于干流,对干流存在较大的污染风险。     

西藏鄂雅错盐湖砷和汞的分布特征研究

本研究对西藏鄂雅错盐湖和主要支流中不同形态的砷(亚砷酸盐As(Ⅲ)、砷酸盐As(Ⅴ)、一甲基砷酸MMA、二甲基砷酸DMA)和总汞(THg)含量进行了测定,并与主要水质参数进行相关性分析研究,结果表明鄂雅错盐湖As主要以As(Ⅴ)形态存在,其次分别为As(Ⅲ)、DMA和MMA,其中无机砷的含量明显大于有机砷。相比较其他砷的形态,盐湖中As(Ⅲ)与主要水质参数的相关性显著,与总溶解性固体(TDS)、总溶解态氮(DTN)呈显著的强正相关性,与水温、溶解氧 (DO)、氧化还原电位(Eh)、pH呈显著负相关性。总汞浓度较低,且与主要水质参数相关性不显著。通过风险评价发现鄂雅错湖水中砷存在一定的致癌健康风险,汞不存在风险。本研究丰富了西藏盐湖和支流水体中砷、汞分布特征及其环境影响因素的认识,对于环境保护具有一定的意义。     

无色散原子荧光光谱法测定痕量汞

氯化亚锡还原冷蒸汽无色散原子荧光光谱法测定痕量汞,采用硫酸、双氧水、王水逐次加入低温分析样品,可以保证样品分解完全又可避免汞的损失。汞的检出限为6.0×10~(-10)g,精密度RSD％=4.1。该方法操作简便,快速、准确、费用低,可应用于大批量地球化学样品的分析。     

电感耦合等离子体质谱-原子荧光光谱法研究上海口岸进口印度尼西亚煤炭微量元素的赋存形态特征

印度尼西亚是我国最大的煤炭进口国,本文应用电感耦合等离子体质谱、原子荧光光谱、直接测汞仪等技术分析了上海口岸31批进口印度尼西亚煤炭中的12种微量元素,结合数理统计方法研究该类煤炭中微量元素的赋存形态。结果表明,进口印尼煤炭中含有高汞煤、三级含砷煤,As、Hg的平均富集系数大于1,其迁移风险值得关注;Be、Cu、Mo、Cd、Sn、Pb含量均低于中国煤和世界煤炭的平均水平,体现出印尼煤炭低灰分的品质特征。12种微量元素和相关项目(灰分和全硫)可划分为3类:第一类归纳为黏土矿物吸附类,包括As、Be、Cr、Co、Ni、Cu、Mo、Cd、Sn、Pb、灰分;第二类归纳为硫铁矿类,包括Hg、全硫;第三类归纳为碳酸盐矿物类,包括Ba。本文研究结果对于指导进口煤炭开发、利用过程中的环境评价和洁净化处理具有一定的参考价值。     

贵州施秉白云岩溶蚀特性及孔隙特征实验研究

以贵州施秉白云岩为研究对象,从宏观和微观角度分析白云岩的溶蚀特性及孔隙特征,结果显示:(1)在众多影响施秉喀斯特发育的因素中,矿物成分是最基本的内因,水是最关键的外因,孔隙结构起辅助作用。(2)极细晶白云岩的单位表面积溶蚀量一般大于细晶白云岩的,在晶粒相同的情况下,白云岩的溶蚀量与Ca O和Mg O的含量分别成正比,且Mg O的含量影响较Ca O大。(3)施秉白云岩溶蚀速率不仅受岩石矿物颗粒粒径大小的控制,还受岩石内部孔隙结构特征的影响,颗粒粒径越大,孔隙度越高,连通性越好,越有利于水溶液进入,溶蚀量也就越大。(4)施秉白云岩的溶蚀特性是多种因素综合作用的结果,必须把各个因素分离开来,从宏观和微观角度逐个作详细的分析研究,然后综合起来,才能对喀斯特发育规律有更深入的了解。     

卧龙湖煤矿岩浆蚀变煤层中汞的分布与赋存特征

系统采集淮北卧龙湖煤矿岩浆蚀变煤层中岩浆岩、煤及顶底板岩石样品,测试分析了样品中汞、灰分、挥发分、水 分以及各形态硫的含量,探讨了岩浆蚀变煤层中汞的分布与赋存特征。结果表明：（1） 岩浆侵入导致煤中灰分升高,挥发 分降低,煤中硫主要以黄铁矿硫和有机硫存在;（2） 岩浆侵入导致煤中汞的富集,卧龙湖煤矿岩浆蚀变煤层中汞的平均含 量高达0.23×10-6,是华北石炭-二叠纪煤、中国煤以及美国煤中汞的平均含量的1.4 倍,1.2 倍和1.3 倍;（3） 煤中汞的含量 随离岩浆侵入体距离增大有逐渐降低的趋势,但在煤岩接触带附近,汞在岩浆侵入体上方和下方的煤中呈现不同的分布特 征;（4） 煤中的汞主要以无机结合态的形式存在,且大部分赋存在煤中的黄铁矿中,同时亦存在与有机硫结合的汞。岩浆 热液对煤层的侵入,导致煤质以及煤中汞的含量和赋存方式发生了显著变化。     

Mired in the past — looking to the future: Geochemistry of peat and the analysis of past environmental changes

Peat cores from ombrotrophic bogs have been used as a valuable archive to study environmental change for over a century. Much of this focus on the peat record has been on biological proxies of environmental change, such as pollen and peat-forming macrofossils, but there is growing interest in the geochemical record to study environmental changes. Several studies of long-term peat records in Europe have reconstructed past changes in atmospheric lead pollution, for example, and the general cohesiveness of the results and their agreement with known historical trends in metal production exemplify the best potential of peat geochemistry as an environmental archive. Based on the success with lead, a current emphasis in peat reconstructions is to assess the record of past mercury deposition and results thus far show generally consistent trends, e.g., a pre-anthropogenic mercury accumulation rate of about 0.5–1.5 μg Hg m^− 2 year^− 1. Despite this general consistency there is increasing concern that there may be diagenetic effects on the quantitative record of some metals, which can be inferred based on a strong relationship between mercury and other organically bound elements and proxies for peat decomposition (C/N ratio). However, it is possible that changes in decomposition and the alteration of some metal records could provide climatic information. A few recent studies show that closer examination of the geochemical matrix, in some cases along with biological proxies, can provide valuable information on landscape changes and climate; for example, partitioning metals into different weight fractions and source regions can be applied to climate studies. The best interpretations of the peat geochemical record in the context of environmental and climate change will likely come when geochemical and biological records are considered simultaneously.     

掺杂锡的纳米二氧化钛的合成、表征及光催化性能

以Ti(OC4H9)4和SnCl4.5H2O为原料,乙醇为溶剂,离子液体1-丁基-3-甲基四氟硼酸咪唑盐([Bmim][BF4])为表面活性剂,12%的氨水为沉淀剂,采用共沉淀法合成了不同形态的掺杂锡的二氧化钛。利用X-射线粉末衍射仪(XRD)、场发射扫描电镜(FESEM)、同步热分析仪(TG-DSC)、紫外—可见吸收光谱仪(UV-Vis)、比表面积孔隙度分析仪(BET)和能量色散X射线光谱仪(EDS)表征所合成材料的结构、形貌、热稳定性、光学性能、比表面积。Sn掺杂后各样品在紫外和可见光区的吸收能力均有不同程度地增强。与未掺杂TiO2的吸收带边相比,Sn掺杂TiO2的吸收带边分别红移了约35 nm,从而提高了光催化降解甲基橙的活性。为了评估产品的光催化性能,进行了掺杂锡的纳米二氧化钛对甲基橙的光催化降解实验,实验结果表明在2 mL离子液体中合成掺杂锡为7%的纳米二氧化钛对甲基橙的光降解具有最好的催化作用。光照90 min对甲基橙的降解率就达到了97%以上,大幅度提高了TiO2的可见光催化活性,这是因为有效抑制了光生电子和空穴的复合,也明显降低了TiO2的禁带宽度。     

Mercury cycling during acid rain recovery at the forested Lesní potok catchment,Czech Republic

From 2011 to 2019, mercury (Hg) stores and fluxes were studied in the small forested catchment Lesní potok (LES) in the central Czech Republic using the watershed mass balance approach together with internal measurements. Mean input fluxes of Hg via open bulk deposition, beech throughfall and spruce throughfall during the periodwere 2.9, 3.9 and 7.6 μg m⁻² year⁻¹, respectively. These values were considerably lower than corresponding deposition Hg fluxes reported in the early years of the 21st century from catchments in Germany. Current bulk precipitation inputs at unimpacted Czech mountainous sites were lower than those in Germany. The largest Hg inputs to the catchment were via litterfall, averaging 22.6 and 17.8 μg m⁻² year⁻¹ for beech and spruce stands. The average Hg input, based on the sum of mean litterfall and throughfall deposition, was 23.0 μg m⁻² year⁻¹, compared to the estimated Hg output in runoff of 0.5 μg m⁻² year⁻¹, which is low compared to other reported values. Thus, only ~2% of Hg input is exported in stream runoff. Stream water Hg was only weakly related to dissolved organic carbon (DOC) but both concentrations were positively correlated with water temperature. The estimated total soil Hg pool averaged 47.5 mg m⁻², only 4% of which was in the O-horizon. Thus Hg in the O-horizon pool represents 72 years of deposition at the current input flux and 3800 years of export at the current runoff flux. Age-dating by ¹⁴C suggested that organic soil contains Hg from recent deposition, while mineral soil at 40–80 cm depth contained 4400-year old carbon, suggesting the soil had accumulated atmospheric Hg inputs through millennia to reach the highest soil Hg pool of the soil profile. These findings suggest that industrial era intensification of the Hg cycle is superimposed on a slower-paced Hg cycle during most of the Holocene.