生物体内汞与硒的相互作用

对硒与汞在生物体内相互作用的一般规律进行了综合评述，概括介绍了生物体内汞与硒相互拮抗关系的实验研究基础，汞与硒拮抗作用的影响因素以及汞与硒拮抗机制的研究进展。     

Predicted no-effect concentrations for mercury species and ecological risk assessment for mercury pollution in aquatic environment

Mercury(Hg) exists in different chemical forms presenting varied toxic potentials. It is necessary to explore an ecological risk assessment method for different mercury species in aquatic environment. The predicted no-effect concentrations(PNECs) for Hg(Ⅱ) and methyl mercury(Me Hg) in the aqueous phase, calculated using the species sensitivity distribution method and the assessment factor method, were 0.39 and 6.5 × 10-3μg/L, respectively. The partition theory of Hg between sediment and aqueous phases was considered, along with PNECs for the aqueous phase to conduct an ecological risk assessment for Hg in the sediment phase. Two case studies, one in China and one in the Western Black Sea, were conducted using these PNECs. The toxicity of mercury is heavily dependent on their forms,and their potential ecological risk should be respectively evaluated on the basis of mercury species.     

Predicted no-effect concentrations for mercury species and ecological risk assessment for mercury pollution in aquatic environment

Mercury (Hg) exists in different chemical forms presenting varied toxic potentials. It is necessary to explore an ecological risk assessment method for different mercury species in aquatic environment. The predicted no-effect concentrations (PNECs) for Hg(II) and methyl mercury (MeHg) in the aqueous phase, calculated using the species sensitivity distribution method and the assessment factor method, were 0.39 and 6.5 × 10^-3 μg/L, respectively. The partition theory of Hg between sediment and aqueous phases was considered, along with PNECs for the aqueous phase to conduct an ecological risk assessment for Hg in the sediment phase. Two case studies, one in China and one in the Western Black Sea, were conducted using these PNECs. The toxicity of mercury is heavily dependent on their forms, and their potential ecological risk should be respectively evaluated on the basis of mercury species.     

Predicted no-effect concentrations for mercury species and ecological risk assessment for mercury pollution in aquatic environment

Mercury (Hg) exists in different chemical forms presenting varied toxic potentials. It is necessary to explore an ecological risk assessment method for different mercury species in aquatic environment. The predicted no-effect concentrations (PNECs) for Hg(II) and methyl mercury (MeHg) in the aqueous phase, calculated using the species sensitivity distribution method and the assessment factor method, were 0.39 and 6.5 × 10^− 3 μg/L, respectively. The partition theory of Hg between sediment and aqueous phases was considered, along with PNECs for the aqueous phase to conduct an ecological risk assessment for Hg in the sediment phase. Two case studies, one in China and one in the Western Black Sea, were conducted using these PNECs. The toxicity of mercury is heavily dependent on their forms, and their potential ecological risk should be respectively evaluated on the basis of mercury species.     

我国煤中汞含量水平及洗选过程汞流向分析

介绍了我国煤中汞含量与分布特征、煤中汞的赋存形态,分析了汞释放对环境的影响以及汞的脱除与控制技术。结果表明:我国(华南)晚三叠世(T3)煤中汞含量最高,平均含量为0.26μg/g;贫煤和无烟煤中汞含量最高,平均含量都超过0.20μg/g。含汞较高的晚三叠世、晚二叠世煤田主要分布于华南各地;多数煤中汞含量在0.300μg/g以下,但华南的江西、广西、贵州等地煤中汞含量总体水平较高;汞的赋存形态可分为有机结合态和无机结合态,煤中汞的控制方法可分为利用前脱汞、利用(燃烧)后脱汞和过程中汞形态转化。提出了煤炭洗选过程汞分布、脱除率和汞平衡等计算公式,指出了煤炭洗选过程中汞迁移行为的主要影响因素。     

淀山湖沉积物中硒的存在形态及分布特征

对淀山湖沉积物中硒的存在形态，水平分布及垂直分布进行了探讨，研究了在自然条件下沉积物中硒的分布特征。结果表明淀山湖沉积物中硒的有机物－硫化物结合态及元素态是订的存在形态，占３３％￣５７％，且各形态硒的分布与环境因素密切相关。     

Determination of dissolved selenium species in environmental samples

This article reports on the technique for the determination of selenium at ppt level and the procedure for the speciation of dissolved selenium in the environmental samples. By combining the high-performance liquid chromatography (HPLC) and a fluorescent detector (FLD), this technique permits the determination of selenium at 0.001 μg/L for Se(IV) and 0.005 μg/L for Se(VI) and the total concentration of selenium for a sample volume of 20 ml. In the speciation procedure, Se(IV) is firstly determined based on the selectivity of 2, 4 - diaminonaphthalene (DAN), the Se (VI) and the total element concentration are determined after reduced to Se(IV) by boiling in 4 mol/L HCl and by digesting in HNO3-HClO4 mixture, respectively. Discussions are given on the relationship between selenium speciation in waters and soil water extract and solution pH, EH and total organic carbon concentration (TOC).     

Absorption characteristics of elemental mercury in mercury chloride solutions

Elemental mercury （Hg^0） in flue gases can be efficiently captured by mercury chloride （HgCl2） solution. However, the absorption behaviors and the influencing effects are still poorly understood. The mechanism of Hg^0 absorption by HgCl2 and the factors that control the removal were studied in this paper. It was found that when the mole ratio of Cl^- to HgCl2 is 10：1, the Hg^0 removal efficiency is the highest. Among the main mercury chloride species, HgCl3^- is the most efficient ion for Hg^0 removal in the HgCl2 absorption system when moderate concentrations of chloride ions exist. The Hg^0 absorption reactions in the aqueous phase were investigated computationaIIy using Moller-Plesset perturbation theory. The calculated Gibbs free energies and energy barriers are in excellent agreement with the results obtained from experiments. In the presence of SO3^2- and SO2, Hg^2＋ reduction occurred and Hg^0 removal efficiency decreased. The reduced Hg^0 removal can be controlled through increased chloride concentration to some degree. Low pH value in HgCla solution enhanced the Hg^0 removal efficiency, and the effect was more significant in dilute HgCl2 solutions. The presence of SO4^2- and NO3^- did not affect Hg^0 removal by HgCl2.     

苏州河底泥中重金属的烧结无害化研究

采用有氧烧结法和还原烧结法处理苏州河底泥,研究了底泥中重金属的无害化效果.结果表明,有氧烧结温度900℃以上时,对Cu、Pb、Zn、Cd去除率达40%～65%;烧结温度为500～900℃时,尽管对Cu、Pb、Zn、Cd去除效果不明显,但能有效抑制其溶出.有氧烧结法不仅不能实现Cr的去除,而且会增加Cr的溶出,这是由于有氧烧结过程中Cr(III)被转化为Cr(VI),而底泥对Cr(VI)的吸附能力很有限.还原烧结法则能有效防止底泥中Cr(III)向Cr(VI)的转化,从而抑制包括Cr在内的重金属的溶出.     

海洋真核微藻Ostreococcus tauri对砷的解毒机制研究

实验选取模式藻种——海洋真核微藻Ostreococcus tauri为材料,以毒性较强的三价砷(As(Ⅲ))为代表,采用液态纯培养法研究海洋微藻对As(Ⅲ)的解毒机制.结果表明,As(Ⅲ)的氧化是O.tauri体内主要的砷解毒机制.暴露于含30 μmol·L^-1和1.67 μmol·L^-1 As(Ⅲ)的培养基时,该微藻分别在培养的60 h和72 h内将培养基中90%以上的As(Ⅲ)氧化为毒性较低的五价砷(As(V)).随着培养时间的增加,培养6 d后在添加30 μmol·L^-1 As(Ⅲ)的培养基和藻体内均检测到二甲基砷(DMAs(V)),表明该海洋微藻同时具有砷甲基化功能.在O.tauri体内砷甲基化可作为另一种解毒机制,满足其对较高浓度砷的解毒需要.对O. tauri的气态砷挥发能力研究表明,该海洋微藻具有砷挥发功能,可通过将砷挥发出体外进行解毒.20、40、80 μmol·L^-1 As(Ⅲ)培养4周后,O.tauri可分别产生气态砷16.7、4.0和1.3 ng.O. tauri通过对砷的氧化来降低细胞周围环境的砷毒性,通过砷甲基化及挥发降低细胞体内的砷毒性.     

基于现代化思想的工业化与城市化互动发展探讨 --以徐州都市(经济)圈为例

以徐州都市(经济)圈为例,就其现代化道路上的工业化和城市化互动发展机制与模式进行了探讨。     

原子荧光光谱法测定土壤中的汞

采用微波消解土壤并结合螯合树脂类SPE预处理柱去除消解液中重金属,原子荧光光谱法测定土壤中的汞。本方法前处理操作过程简单,用酸量少,避免了测定元素的挥发损失,汞加标回收率为92．8％-104．5％,方法准确度与精密度均令人满意。     

Mercury remediation potential of a mercury resistant strain Sphingopyxis sp. SE2 isolated from contaminated soil

A mercury resistant bacterial strain SE2 was isolated from contaminated soil.The 16 s rRNA gene sequencing confirms the strain as Sphingopyxis belongs to the Sphingomonadaceae family of the α-Proteobacteria group.The isolate showed high resistance to mercury with estimated concentrations of Hg that caused 50%reduction in growth(EC_(50)) of 5.97 and 6.22 mg/L and minimum inhibitory concentrations(MICs) of 32.19 and 34.95 mg/L in minimal and rich media,respectively.The qualitative detection of volatilized mercury and the presence of mercuric reductase enzyme proved that the strain SE2 can potentially remediate mercury.ICP-QQQ-MS analysis of the remaining mercury in experimental broths indicated that a maximum of 44%mercury was volatilized within 6 hr by live SE2 culture.Furthermore a small quantity(23%) of mercury was accumulated in live cell pellets.While no volatilization was caused by dead cells,sorption of mercury was confirmed.The mercuric reductase gene merA was amplified and sequenced.Homology was observed among the amino acid sequences of mercuric reductase enzyme of different organisms from a-Proteobacteria and ascomycota groups,     

长反应时间条件下乙醛废水碱解脱毒预处理效果

乙醛废水含有高浓度醛类及有机氯类有毒有机物,对废水生物处理系统中的微生物抑制性强,直接生物处理难度较大,需进行脱毒预处理。考察了延长反应时间和提高反应温度对乙醛废水碱解脱毒所需碱(NaOH)投加量的影响。结果表明:碱解预处理可有效去除废水中的醛类和有机氯类有毒有机物,显著降低废水厌氧生物毒性和好氧生物毒性;以厌氧生物毒性作为脱毒评价指标较有毒物质浓度更为合理;延长反应时间、提高反应温度有利于降低乙醛废水充分脱毒所需碱的投加量;将反应时间由3 h延长至10 h,反应温度由60 ℃升至70 ℃,乙醛废水充分脱毒所需碱的投加量降低了50%,节省药剂成本约3.7元∕t(以废水计)。     

总汞、甲基汞和硒在汞暴露大鼠脑、肝、肾中的分布

利用自动汞分析仪、GC-ECD和原子荧光分析了汞污染暴露1,3,7,20,30,90d后,大鼠脑、肝、肾中的总汞、甲基汞和硒的含量.结果表明,总汞、甲基汞含量随暴露时间的延长而显著增加;各组织对总汞和甲基汞蓄积量的顺序是肾>肝>脑;从甲基汞和总汞的比率分析发现,甲基汞很容易透过血脑屏障,并且在脑中有较高的蓄积;硒能够拮抗汞在脑、肝、肾中的蓄积水平.     

Effects of soil properties on production and bioaccumulation of methylmercury in rice paddies at a mercury mining area, China

Rice paddy soil is recognized as the hotspot of mercury(Hg) methylation, which is mainly a biotic process mediated by many abiotic factors. In this study, effects of key soil properties on the production and bioaccumulation of Hg and methylmercury(MeHg) in Hg-contaminated rice paddies were investigated. Rice and soil samples were collected from the active Hg smelting site and abandoned Hg mining sites(a total of 124 paddy fields) in the Wanshan Mercury Mine, China. Total Hg(THg) and MeHg in soils and rice grains, together with sulfur(S),selenium(Se), organic matter(OM), nitrogen(N), phosphorus(P), mineral compositions(e.g., SiO_2, Al_2O_3 and Fe_2O_3) and pH in soils were quantified. The results showed that long-term Hg mining activities had resulted in THg and MeHg contaminations in soil-rice system. The newly-deposited atmospheric Hg was more readily methylated relative to the native Hg already in soils, which could be responsible for the elevated MeHg levels in soils and rice grains around the active artificial Hg smelting site. The MeHg concentrations in soils and rice grains showed a significantly negative relationship with soil N/Hg, S/Hg and OM/Hg ratio possibly due to the formation of low-bioavailability Hg–S(N)–OM complexes in rhizosphere. The Hg–Se antagonism undoubtedly occurred in soil-rice system, while its role in bioaccumulation of MeHg in the MeHg-contaminated rice paddies was minor. However, other soil properties showed less influence on the production and bioaccumulation of MeHg in rice paddies located at the Wanshan Mercury Mine zone.     

Estimation of bioaccessibility and potential human health risk of mercury in Chinese patent medicines

Mercury(Hg), mainly in cinnabar species, has been used in medicine for thousands of years in China, and worldwide concern has been raised on its toxicity. In this work, the amount of bioaccessible mercury in 16 Chinese patent medicines(CPMs) was measured by using an in vitro simulated digestion system, consisting of simulated gastric and intestinal fluid, to investigate the bioavailability of mercury in CPMs and evaluate its potential risk to human health. Total mercury and mercury in the gastrointestinal extracts were measured by inductively coupled plasma mass spectrometry(ICP-MS). The levels of total Hg in 16 CPMs ranged from not detected to 11.89 mg/g, with a mean value of 1.13 mg/g, while the extractable Hg ranged from not detected to 4.37 μg/g, with a mean value of 0.42 μg/g.Mercury bioaccessibility varied significantly in the investigated CPMs, depending on the ingredient. Compared to the CPMs without cinnabar(2.5%–30.9%), the percentage of mercury in the gastrointestinal supernatants for CPMs with cinnabar was quite a bit lower(0.037%). By comparing with the Food and Agricultural Organization/World Health Organization Joint Expert Committee on Food Additives(FAO/WHO) safety guideline, the average daily intake dose(ADD) of Hg in the medicines was then calculated to access the risk of mercury to human health from taking CPMs.     

从废旧锌锰电池中回收汞和铵的工艺研究

针对废旧锌锰电池中汞分散存在给回收处理废旧锌锰电池工作完全回收汞所带来的困难 ,利用汞和铵的性质特点 ,找到了从废旧锌锰电池中集中回收汞和铵的工艺条件 ,为废旧锌锰电池的资源化和防止二次污染创造了有利条件。     

Enhancement of elemental mercury adsorption by silver supported material

Mercury, generally found in natural gas, is extremely hazardous. Although average mercury levels are relatively low, they are further reduced to comply with future mercury regulations, which are stringent in order to avoid releasing to the environment. Herein, vapor mercury adsorption was therefore investigated using two kinds of supports, granular activated carbon (GAC) and titanium dioxide (TiO₂). Both supports were impregnated by silver (5 and 15 wt.%), before testing against a commercial adsorbent (sulfur-impregnated activated carbon, SAC). The adsorption isotherm, kinetics, and its thermodynamics of mercury adsorption were reported. The results revealed that Langmuir isotherm provided a better fit to the experimental data. Pseudo second-order was applicable to describe adsorption kinetics. The higher uniform Ag dispersion was a key factor for the higher mercury uptake. TiO₂ supported silver adsorbent showed higher mercury adsorption than the commercial one by approximately 2 times. Chemisorption of mercury onto silver active sites was confirmed by an amalgam formation found in the spent adsorbents.     

Rapid field testing of mercury pollution by designed fluorescent biosensor and its cells-alginate hydrogel-based paper assay

With increasing industrial activities, mercury has been largely discharged into environment and caused serious environmental problems. The growing level of mercury pollution has become a huge threat to human health due to its significant biotoxicity. Therefore, the simple and fast means for on-site monitoring discharged mercury pollution are highly necessary to protect human beings from its pernicious effects in time. Herein, a “turn off” fluorescent biosensor (mCherry L199C) for sensing Hg²⁺ was successfully designed based on direct modification of the chromophore environment of fluorescent protein mCherry. For rapid screening and characterization, the designed variant of mCherry (mCherry L199C) was directly expressed on outer-membrane of  Escherichia coli cells by cell surface display technique. The fluorescent biosensor was characterized to have favorable response to Hg²⁺ at micromole level among other metal ions and over a broad pH range. Further, the cells of the fluorescent biosensor were encapsulated in alginate hydrogel to develop the cells-alginate hydrogel-based paper. The cells-alginate hydrogel-based paper could detect mercury pollution in 5 min with simple operation process and inexpensive equipment, and it could keep fluorescence and activity stable at 4?°C for 24 hr, which would be a high-throughput screening tool in preliminarily reporting the presence of mercury pollution in natural setting.