活性炭负载催化剂去除燃煤烟气中单质汞的研究

以贵州凯里褐煤进行燃烧实验,研究采用CoCl2(负载量20%)改性的活性炭去除烟气中的单质汞。颗粒态汞占烟气总汞的87%,而单质汞占气态汞的80.4%。改性活性炭吸附了气态汞中97%的单质汞,而吸收液只吸收了3%的单质汞。可见改性活性炭也能有效地吸附煤燃烧实验中的烟气汞。实验结果表明,煤中汞的释放率为59.5%,1kg的改性活性炭可以吸附208t煤所产生的烟气中的气态单质汞。     

Analysis of Pesticides Using a Polyppyrole Modified Electrode

Electrochemical methods can provide fast, sensitive and sometimes real time detection of pesticides. In the course of this work, a dispersed mercury electrode has been used to detect pesticides electrochemically. The electrode was prepared by depositing a thin mercury film on a glassy carbon disc and then coating a layer of polypyrrole on the disc. The effect of coating thickness on detection sensitivity was studied. A thin mercury film of 0.34 µm dispersed by one cycle polymerization of pyrrole was preferred. The influence of electrolyte, pH and organic solvent content on pesticide response was also investigated. The polypyrrole dispersed mercury electrode (Hg-PPy/GC) was not suitable for a pH above 6 but it can tolerate acetonitrile up to 10% at which concentration the mercury film coated glassy carbon electrode (Hg/GC) failed to response. Methyl parathion, methyl azinphos, parathion and fenitrothion were detected. The sensitivity of the dispersed mercury electrode was similar to a normal thin mercury film electrode in this case. A good response can be obtained for 1 ppm pesticides using fast linear sweeping voltammetry.     

Maize tassel-modified carbon paste electrode for voltammetric determination of Cu(II)

The preparation and application of a practical electrochemical sensor for environmental monitoring and assessment of heavy metal ions in samples is a subject of considerable interest. In this paper, a carbon paste electrode modified with maize tassel for the determination of Cu(II) has been proposed. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) were used to study morphology and identify the functional groups on the modified electrode, respectively. First, Cu(II) was adsorbed on the carbon paste electrode surface at open circuit and voltammetric techniques were used to investigate the electrochemical performances of the sensor. The electrochemical sensor showed an excellent electrocatalytic activity towards Cu(II) at pH 5.0 and by increasing the amount of maize tassel biomass, a maximum response at 1:2.5 (maize tassel:carbon paste; w/w) was obtained. The electrocatalytic redox current of Cu(II) showed a linear response in the range (1.23 μM to 0.4 mM) with the correlation coefficient of 0.9980. The limit of detection and current–concentration sensitivity were calculated to be 0.13 (±0.01) μM and 0.012 (±0.001) μA/μM, respectively. The sensor gave good recovery of Cu(II) in the range from 96.0 to 98.0 % when applied to water samples.     

过氧化聚吡咯/聚乙烯吡咯烷酮修饰碳糊电极测定废水中苯酚

建立了过氧化聚吡咯(OPPy)和聚乙烯吡咯烷酮(PVP)修饰碳糊电极测定废水中苯酚的方法.优化了试验条件,苯酚的氧化峰电流在1.0×10-5 mol/L～1.0×10-3 mol/L之间线性关系良好,检出限为1.0×10-6 mol/L.该电极制作简单,选择性好,测定灵敏度高,精密度与准确度均符合要求.     

Simultaneous determination of hydroxylamine and phenol using a nanostructure-based electrochemical sensor

The electrochemical oxidation of hydroxylamine on the surface of a carbon paste electrode modified with carbon nanotubes and 2,7-bis(ferrocenyl ethyl)fluoren-9-one is studied. The electrochemical response characteristics of the modified electrode toward hydroxylamine and phenol were investigated. The results showed an efficient catalytic activity of the electrode for the electro-oxidation of hydroxylamine, which leads to lowering its overpotential. The modified electrode exhibits an efficient electron-mediating behavior together with well-separated oxidation peaks for hydroxylamine and phenol. Also, the modified electrode was used for determination of hydroxylamine and phenol in some real samples.     

Mercury speciation in the Persian Gulf sediments

The concentrations of total mercury (Hg) and methyl mercury (MMHg) were determined in 78 marine sediments in the Iranian coastal waters of the Persian Gulf along nine transects perpendicular to the coastline. Total Hg ranged from 10 to 56 ng g( - 1)d.w. and MMHg from 0.1 to 0.4 ng g( - 1) d.w. The fraction of methyl mercury accounted from 0.3% to 1.1% of the total mercury amount. The organic carbon (OC) content ranged from 0.4% to 1.8%. The present study indicates that the levels of Hg in the sediments of the Iranian coast of the Persian Gulf were all in the concentration range of unpolluted areas regarding Hg (<100 ng g( - 1)). The concentrations of total Hg, methyl mercury and organic carbon were generally higher in the deeper stations. Total Hg and MMHg were significantly correlated, but no significant correlations could be found between the Hg and OC levels.     

Mercury fractionation in contaminated soils from the Idrija mercury mine region

Mercury (Hg) fractionation was investigated in contaminated soil in the Idrija Hg-mine region, Slovenia. The main aim of this study was to test and apply sequential extraction and quantification of different Hg phases in order to estimate the mobility and potential bioavailability of Hg in contaminated soils. Separation of Hg phases was performed by means of a selective sequential extraction procedure complemented by volatilization of elemental mercury (Hg0). The influence of temperature, moisture and storage on Hg0 volatilization was also investigated. The total Hg concentrations varied between 8.4 and 415 mg kg(-1) and were up to 40-fold higher than the maximum permissible set by Slovenian legislation. Fractionation measurements indicated cinnabar as the predominant Hg fraction, followed by Hg0. Accumulation of cinnabar predominantly occurred in coarse grained flood plain sediments, where on average it constituted more than 80% of total Hg. In contrast non-cinnabar fractions were found to be enriched in areas where fine grained material was deposited, reaching up to 60% of total Hg. The strong positive correlation (R2 = 0.71-0.99) among non-cinnabar fractions suggested that these fractions predominantly control the mobility and potential bioavailability of Hg. Sample pretreatment before fractionation influenced the partition of Hg between different fractions, and therefore fractionation in fresh, nontreated samples is suggested. In addition, the specificity of the extraction steps needs further attention, as it was shown that some extraction steps, such as the organo-chelating Hg fraction, do not provide meaningful results. This further suggests that protocols for mercury fractionation need further harmonization in order to improve the comparability of the results and their use in risk assessment. Volatile mercury fluxes averaged between 0.04 and 6.5 ng g(-1) h(-1). Good agreement (R2 = 0.81-0.95) was found between the non-cinnabar fractions and evaporation of Hg0. Both the temperature and sample moisture had significant effects on mercury volatilization. The results in this study were obtained at 70 degrees C, which may be somewhat high, in particular for bacterial activity which may also play an important role in Hg volatilization. Therefore it is strongly suggested that further optimisation of the protocol to assess Hg volatilization from soil is required.     

Mercury concentration in fish from Piracicaba River (Minas Gerais, Brazil)

Mercury emissions from some upstream gold mining areas and recent findings of high natural Hg levels in sediments motivated studies on the Hg cycle in the Minas Gerais state. The study presents the total mercury amount found in Geophagus brasiliensis' muscular tissue (wet weight) and sediments from Piracicaba River. Mercury was analyzed using acid digestion followed by determination of total mercury by cold vapour atomic absorption spectrophotometry. This study was also complemented with the analysis of the limnological parameters (water temperature, conductivity, total dissolved solids, suspended particles, pH, dissolved oxygen, maximum depth, photic index and total carbon). The mercury concentration in sediments samples was higher than the mercury concentration in muscular tissue of fish. The lowest Hg level measured in fish was 0.0147 microg g( - 1), while the highest was 0.101 microg g( - 1). In the sediment samples, the lowest and highest levels were 0.02 microg g( - 1) and 0.16 microg g( - 1), respectively. The Hg concentrations in fish and sediment were both under the maximum limit permitted by the World Health Organization.     

Voltammetric trace determination of mercury using plant refuse modified carbon paste electrodes

Citrus limon peel (kitchen waste) and Leucaena leucocephala seeds (agricultural waste) were used as a modifier for fabrication of modified carbon paste electrode for determination of mercury in aqueous sample using differential pulse anodic stripping voltammetry. Mercury was adsorbed on electrode surface at open circuit and anodic stripping voltammetric scan was run from ?0.5 to 0.5 V. Various electrochemical parameters including amount of modifier, supporting electrolyte, accumulating solvent, pH of the accumulating solvent, and accumulation time were investigated. The effect of presence of other metal ions and surfactants was also studied. In comparison C. limon peel proved to be a better modifier than L. leucocephala seed biomass. This was justified by electrode characterization using cyclic voltammetry that indicated decrease in resistance of electrode when C. limon peel was used as modifier and increase when modifier was L. leucocephala seeds. Maximum current response was obtained using 5 % C. limon peel biomass, hydrochloric acid as supporting electrolyte, acetate buffer of pH 6 as an accumulating solvent, 10-min accumulation time, and scan rate of 50 mV/s. Linear calibration curves were obtained in the concentration range 100 to 1,000 μg L^?1 of mercury for accumulation time of 10 min with limit of detection of 57.75 μg L^?1 and limit of quantification of 192.48 μg L^?1. This technique does not use mercury as electrode material and, therefore, has a positive environmental benefit.     

贵州东部某燃煤电厂汞排放对周边环境空气及土壤的影响

结合当地气象条件,测定贵州省东部某燃煤电厂下风向环境空气汞浓度分布情况,同时测定该燃煤电厂周边表层土壤中汞含量,并对其污染程度进行评价,探讨了土壤汞与理化性质间的相关性。结果表明,该燃煤电厂下风向环境空气汞浓度远高于北半球大气气态总汞背景值,空气汞浓度在2.7 km范围内随距离的增大而增大,在2.7~5.0 km范围内汞浓度随距离的增大而减小。电厂周边表层土壤汞含量是贵州省A层土壤Hg背景值的8.5倍,存在中度到重度程度的污染,土壤Hg与土壤pH呈正相关性,但与土壤有机质未表现出相关性。     

Landscape Controls on Mercury in Streamwater at Acadia National Park, USA

Fall and spring streamwater samples were analyzed for total mercury (Hg) and major ions from 47 locations on Mount Desert Island in Maine. Samples were collected in zones that were burned in a major wildfire in 1947 and in zones that were not burned. We hypothesized that Hg concentrations in streamwater would be higher from unburned sites than burned watersheds, because fire would volatilize stored Hg. The Hg concentrations, based on burn history, were not statistically distinct. However, significant statistical associations were noted between Hg and the amount of wetlands in the drainage systems and with streamwater dissolved organic carbon (DOC). An unexpected result was that wetlands mobilized more Hg by generating more DOC in total, but upland DOC was more efficient at transporting Hg because it transports more Hg per unit DOC. Mercury concentrations were higher in samples collected at lower elevations. Mercury was positively correlated with relative discharge, although this effect was not distinguished from the DOC association. In this research, sample site elevation and the presence of upstream wetlands and their associated DOC affected Hg concentrations more strongly than burn history.     

Mercury wet deposition in rural Korea: concentrations and fluxes

The characteristics of Hg wet deposition were investigated in a rural area of Korea from August 2006 to July 2008. The volume weighted mean (VWM) Hg(T) concentration and cumulative Hg(T) flux were 8.8 ng L(-1) and 9.4 μg m(-2) per year, respectively. The VWM Hg(T) concentration varied seasonally, similar to the seasonal pattern in atmospheric Hg(p) concentration. The enhancement of both VWM Hg(T) and atmospheric Hg(p) concentrations in spring and winter was likely caused by the long-range transport of Hg from China. Monthly VWM Hg(T) and atmospheric Hg(p) concentrations were well correlated (R(2) = 0.36); however, there was no correlation between VWM Hg(T) and RGM (reactive gaseous mercury) concentrations, suggesting that Hg(p) was responsible for the majority of the Hg in wet deposition at this site. The VWM Hg(T) concentration in snow was statistically higher than in rain. In addition, the atmospheric Hg(p) concentration appeared to be elevated for snow events as well. This suggests that both elevated Hg(p) concentrations and the enhanced scavenging efficiency of snow for Hg(p) were responsible for the elevated VWM Hg(T) concentrations measured during snow events.     

Mercury proxies and mercury dynamics in a forested watershed of the US Northeast

Although many studies focus on mercury (Hg) and methylmercury (MeHg) dynamics in streams, challenges remain in identifying the relative importance of land cover and seasonality at regulating Hg and MeHg dynamics at the watershed scale. Developing robust proxies for Hg and/or MeHg determination also remains a challenge. Our study used Hg, MeHg, and dissolved organic carbon (DOC) concentration measurements and various DOC fluorescence indices to characterize Hg and DOC dynamics in a forested watershed of the US Northeast. Principal component analysis indicated that land cover/landscape position (i.e., headwater vs. wetland-influenced area vs. lake-influenced area) explained 44 % of the variance in Hg, MeHg, DOC concentrations, and DOC quality during the snow-free season, while seasonality (i.e., air temperature and discharge) explained only 21 % of the variance in the results. Furthermore, finding a good proxy for Hg that is valid across a range of landscape positions remains a challenge; however, regression analysis indicated that the fluorescence peak Humic C (excitation?=?350 nm; emission?=?max (420–480)), which corresponds to the presence of melanoidins in water, explained 21 % of the variability in MeHg concentrations across both space and time (p?=?0.001), and thus appears to be a possible proxy for MeHg determination in our study watershed. From a management perspective, land cover modifications (lake, reservoir, and wetland) are likely to play more important roles at regulating Hg, MeHg, and DOC exports at the watershed scale than long-term changes in the climate of this region.     

Mercury speciation in plankton from the Cabo Frio Bay,SE - Brazil

Mercury (Hg) is considered a global pollutant, and the scientific community has shown great concern about its toxicity as it may affect the biota of entire systems, through bioaccumulation and bioamplification processes of its organic form, methylmercury (MeHg), along food web. However, few research studies deal with bioaccumulation of Hg from marine primary producers and the first-order consumers. So, this study aims to determine Hg distribution and concentration levels in phytoplankton and zooplankton in the Cabo Frio Bay, Brazil, a site influenced by coastal upwelling. The results from Hg speciation analyses show that inorganic mercury Hg(II) was the predominant specie in plankton from this bay. The annual Hg species distribution in plankton shown mean concentration of 2.00?±?1.28 ng Hg(II)?g^?1 and 0.15?±?0.08 ng MeHg g^?1 wet weight (phytoplankton) and 2.5?±?2.03 ng Hg(II)?g^?1 and 0.25?±?0.09 ng MeHg g^?1 wet weight (zooplankton). Therefore, upwelling zones should be considered in the Hg biogeochemical cycle models as a process that enhances Hg(II) bioaccumulation in plankton, raising its bioavailability and shelf deposition.     

大气中不同形态汞的采集和分析方法

作为一种环境优先污染物,汞对人体和其它生物毒性很大。大气是全球汞生物地球化学循环的重要场所。不同形态的汞由于理化性质不同,迁移转化过程及其对生态环境的影响也不同,准确测定大气环境中各种形态的汞对于了解其在大气中的行为具有重要意义。1990年以来,大气汞的采集和分析方法技术已经取得了长足进步,一些自动测汞仪、低汞空白和高时间分辨率的采样及分析技术相继出现,使得准确测定大气中不同形态的痕量汞成为可能。文章就国内外近10多年来在这些方面所取得的研究进展进行了回顾和总结,主要介绍了气态总汞、颗粒态汞、活性气态汞、甲基汞等的采集和分析方法。     

Mercury emission and dispersion models from soils contaminated by cinnabar mining and metallurgy

The laboratory flux measurement system (LFMS) and dispersion models were used to investigate the kinetics of mercury emission flux (MEF) from contaminated soils. Representative soil samples with respect to total Hg concentration (26-9770 μg g(-1)) surrounding a decommissioned mercury-mining area (Las Cuevas Mine), and a former mercury smelter (Cerco Metalúrgico de Almadenejos), in the Almadén mercury mining district (South Central Spain), were collected. Altogether, 14 samples were analyzed to determine the variation in mercury emission flux (MEF) versus distance from the sources, regulating two major environmental parameters comprising soil temperature and solar radiation. In addition, the fraction of the water-soluble mercury in these samples was determined in order to assess how MEF from soil is related to the mercury in the aqueous soil phase. Measured MEFs ranged from less than 140 to over 10,000 ng m(-2) h(-1), with the highest emissions from contaminated soils adjacent to point sources. A significant decrease of MEF was then observed with increasing distance from these sites. Strong positive effects of both temperature and solar radiation on MEF was observed. Moreover, MEF was found to occur more easily in soils with higher proportions of soluble mercury compared to soils where cinnabar prevails. Based on the calculated Hg emission rates and with the support of geographical information system (GIS) tools and ISC AERMOD software, dispersion models for atmospheric mercury were implemented. In this way, the gaseous mercury plume generated by the soil-originated emissions at different seasons was modeled. Modeling efforts revealed that much higher emissions and larger mercury plumes are generated in dry and warm periods (summer), while the plume is smaller and associated with lower concentrations of atmospheric mercury during colder periods with higher wind activity (fall). Based on the calculated emissions and the model implementation, yearly emissions from the "Cerco Metalúrgico de Almadenejos" decommissioned metallurgical precinct were estimated at 16.4 kg Hg y(-1), with significant differences between seasons.     

Mercury Contamination of Biota from Acadia National Park, Maine: A Review

We reviewed literature reporting both total and methylmercury from biota from Acadia National Park, Maine, USA. Our review of existing data indicates that 1) mercury contamination is widespread throughout the Park’s various aquatic ecosystems; 2) mercury pollution likely represents a moderate to high risk to biota inhabiting the Park; and 3) biota at all trophic levels possess elevated concentrations of both total and methylmercury. Watershed fire history and the resulting post-fire forest succession patterns are an important landscape attribute governing mercury cycling at Acadia National Park. Therefore, park service personnel should consider these factors when planning and implementing Hg biomonitoring efforts. Additional baseline funding from the National Park Service for Hg research and biomonitoring will likely be required in order to further evaluate the spatial and temporal patterns of mercury contamination in the park’s biota. An erratum to this article can be found at     

流动注射——薄层安培检测法测定水中亚硝酸盐和硝酸盐

将流动注射分析与薄层安培检测法相结合，以碳糊为工作电极，测定了水中ＮＯ－２－Ｎ和ＮＯ－３－Ｎ。研究结果表明，该方法与标准方法相比，具有简单、快速、准确，不受水体颜色干扰的优点。     

Biogeochemistry of mercury and methylmercury in sediment cores from Sundarban mangrove wetland, India—a UNESCO World Heritage Site

This study was performed to elucidate the distribution, concentration trend and possible sources of total mercury (Hg(T)) and methylmercury (MeHg) in sediment cores (<63 μm particle size; n?=?75) of Sundarban mangrove wetland, northeastern part of the Bay of Bengal, India. Total mercury was determined by atomic absorption spectrometry (AAS) in a Leco AMA 254 instrument and MeHg by gas chromatography-atomic fluorescence spectrometry (GC-AFS). A wide range of variation in Hg(T) (0.032-0.196 μg g(-1) dry wt.) as well as MeHg (0.04-0.13 ng g(-1) dry wt.) concentrations revealed a slight local contamination. The prevalent low Hg(T) levels in sediments could be explained by sediment transport by the tidal Hugli (Ganges) River that would dilute the Hg(T) values via sediment mixing processes. A broader variation of MeHg proportions (%) were also observed in samples suggesting that other environmental variables such as organic carbon and microbial activity may play a major role in the methylation process. An overall elevated concentration of Hg(T) in surface layers (0-4 cm) of the core is due to remobilization of mercury from deeper sediments. Based on the index of geoaccumulation (I (geo)) and low effects-range (ER-L) values, it is considered that the sediment is less polluted by Hg(T) and there is less ecotoxicological risk. The paper provides the first information of MeHg in sediments from this wetland environment and the authors strongly recommend further examination of Hg(T) fluxes for the development of a detailed coastal MeHg model. This could provide more refine estimates of a total flux into the water column.     

基于吸附原理的双路独立汞采样方法

参照美国EPA 30B方法,基于吸附原理,研制了用于燃煤燃烧源排放烟气中总气态汞的双路独立采样系统,结合热解析分析技术,现场测试结果符合30B方法的质控指标要求。建议加大国产吸附管的研制力度,开发适用于中国工况的汞采样器。