黑龙江黑土区农田土壤/大气界面汞交换通量特征研究

运用动力学通量箱与Tekran 2537B气态汞分析仪技术,对黑龙江省黑土区农田土壤/大气界面汞交换通量进行了实地监测,结果显示不同地区黑土的汞交换通量存在显著差异,7个监测点土壤/大气界面汞交换通量均值为(69.46±37.08)ng·m-2·h-1,接近我国典型城市城区土壤/大气界面汞交换通量平均水平。影响因素分析显示,土壤汞含量影响土壤释汞能力,汞交换通量与总辐射强度、土壤温度、土壤湿度和风速呈显著正相关,与相对湿度呈显著负相关,与大气压不相关。     

夏季红枫湖地区农田土壤-大气界面汞交换通量的初步研究

采用动力学通量箱法(Dynamic Flux Chamber)与高时间分辨率大气测汞仪联用技术对贵州红枫湖地区土壤-大气界面间汞交换通量进行了初步研究.结果显示,红枫湖地区土壤-大气界面间汞交换通量变化范围为-8.6 ng～215.3 ng@m-2@h-1,平均27.4士40.1 ng/m2@h(n=255);且土壤与大气界面间的汞交换是双向的既有土壤汞的释放,又有大气汞的沉降,主要以土壤汞的释放为主(n释放=253,n沉降=2n).土壤汞的释放通量与土壤温度、气温、光照强度有强相关关系,相关系数分别为0.80、0.83、0.74.     

贵州滥木厂汞矿区土壤与大气间气态汞交换通量及影响因素研究

利用动力学通量箱-大气自动测汞仪联用技术,分别于2002年12月和2003年5月对贵州省西南部滥木厂汞矿区5个采样点的土壤汞释放通量进行了系统的测定.结果表明该区土壤是大气的重要汞释放源.5个采样点土壤释汞通量最高值达10 543.7 ng/(m2·h),平均值最高达(2 283.3±2 434.2)ng/(m2·h)(n=152).结果显示土壤总汞含量与土壤释汞通量关系密切,是决定土壤汞释放的内在因素,光照、温度、湿度和大气汞含量等环境因素与土壤释汞通量有较好的相关性,对土壤汞的释放有显著的影响.     

植被生态系统汞的生物地球化学循环研究进展与挑战

汞是联合国环境规划署重点管控的全球性污染物.植被是联结大气圈与土壤圈的关键纽带,在全球汞生物地球化学循环中扮演着举足轻重的角色.植被生态系统是全球大气重要的汞汇,但由于大气-植被-土壤的汞界面交换过程及植物组织中汞的分布、来源与迁移转化规律及驱动机制认识不清,致使当前的全球汞生物地球化学循环模型缺失植被过程模块,无法厘定全球植被的大气汞汇通量.近年来迅速发展的汞同位素地球化学、同步辐射和微气象汞通量观测等新方法,为多层次解析不同类型植被与土壤及大气界面汞交换过程,阐明植物组织中汞的分布、来源与迁移规律提升了可能,能为进一步解决当前森林生态系统汞的生物地球化学循环的研究难点提供独辟蹊径的视角.     

福建省德化县金矿区民间冶炼活动相关的土壤与大气汞污染特征

民间小规模金矿混汞冶炼活动因缺乏环保措施常常造成周围环境严重的汞污染,目前已被认定为全球最大的人为汞污染排放源。福建省德化县山区土壤汞含量异常升高和该地区民间小规模金矿冶炼活动密切相关,对当地土壤总汞、大气总汞污染分布及土壤表面汞释放的调查研究表明:金矿区周边村子稻田土壤汞平均质量分数达(5.180±7.191)mg/kg,距金矿最近民间冶炼活动最集中的邱村稻田总汞质量分数平均值达到(15.658±12.726)mg/kg,随着距离金矿点越远民间冶炼活动减少,土壤总汞含量呈下降趋势。区域大气总汞平均质量浓度为(36.4±24.3)ng/m~3,邱村大气总汞质量浓度平均值(77.2±42.4)ng/m~3;工作区4个土-气界面汞通量均值分别为:华口(109.6±55.9)ng/(m~2h),邱村(97.1±36.1)ng/(m~2h),大安(63.5±12.6)ng/(m~2h),中仙(25.9±23.5ng/(m~2h)。因地形复杂,微气象条件差异及土地利用差异等综合因素制约,土壤汞含量与大气总汞含量、释放通量间没有显著相关关系,华口测点土壤释汞通量最大。工作区民间金矿冶炼活动历史造成当地环境的汞污染及其环境影响将长期存在。     

利用原子荧光光谱-电感耦合等离子体质谱法研究济南市大气干湿沉降重金属含量及年沉降通量特征

大气降尘是地表土壤重金属元素的重要来源,研究大气降尘中重金属元素的地球化学特征并进行源解析对制定污染防控政策具有重要的指导作用。本文采用原子荧光光谱法、电感耦合等离子体质谱法、X射线荧光光谱法分析济南市大气干湿沉降中8种重金属(砷镉铬铜汞镍铅锌)含量特征;采用相关分析及主成分分析方法对大气干湿沉降重金属进行源解析。结果表明,大气干湿沉降物中镉铬铜汞镍铅锌平均含量分别为2.07 mg/kg、135.9 mg/kg、65.7 mg/kg、218.6μg/kg、110.7 mg/kg、380 mg/kg,显著高于土壤背景值,且富集程度高,明显受人为活动污染。镉铜汞铅主要来源于燃煤,砷铬来源于道路尘,镍来源于土壤,锌来源于交通尘;燃煤和道路尘对大气降尘的贡献率为50.13%,两者是济南市大气降尘污染的主要来源。大气干湿沉降对城区表层土壤中镉汞铬铅锌及砷的含量水平影响显著,其中锌年沉降通量最高(均值148 mg·m-2·a-1),汞年沉降通量最低(均值0.085 mg·m-2·a-1),且镉汞含量增长速率较高;大气干湿沉降对砷铬在土壤中的累积影响显著。     

广州市黄埔港区土壤中汞的形态分析及分布特征

采用化学浸提技术对广州市黄埔港区土壤中的汞进行形态分析,通过实验确定了可交换态汞(包括水溶性汞)、盐酸溶汞、元素汞、腐殖酸结合态汞、有机质结合态汞、硫化汞、残渣态汞的浸提条件,探讨了各种形态汞在表层及总量在垂直方向上的分布特征。分析结果表明,广州市黄埔港区土壤中汞以比较稳定的形态存在,活动态约占6%。总汞含量随深度增加而降低,总汞在垂直方向中的含量差异在一定程度上反映出汞受人为污染的影响情况。     

广西中东部9县区农田土壤As输入通量研究

对广西中东部9县区农田土壤中的As输入通量进行了初步研究。综合各方面因素,计算获取了大气干湿沉降、施肥和灌溉水输入通量。结果表明,研究区大气干湿沉降和施肥As输入通量基本相当,平均值分别为9.92 g/(hm^2·a)和7.83 g/(hm^2·a),灌溉水通量最高,平均值为14.98 g/(hm^2·a),三者对土壤As污染的贡献率分别为30.31%、23.92%和45.77%。9个不同县区大气干湿沉降、施肥和灌溉水As输入通量占比略有不同,其中6个县区灌溉水和施肥输入通量占主导地位,另外3个县区大气干湿沉降输入通量比例较高。因此,灌溉水是研究区农田土壤As的主要输入途径,应重视灌溉水水质控制。在未考虑农田土壤As输出通量的情况下,以当前的As年平均输入通量估算得到耕层土壤As的质量分数每年升高0.01 mg/kg。与土壤As含量现状相比,As年增量比例很小,因此判断在短期内,外源输入对土壤As分布现状影响不大。该区土壤p H值较低,铁氧化物含量较高,因此外源输入农田土壤的As生物有效性较低。     

桂林典型岩溶区土壤CO2通量及其δ13CCO2季节性特征

通过选用静态暗箱/气相色谱法,探讨桂林毛村典型岩溶区土壤CO2通量及其δ13C CO2的季节性演变规律,旨在揭示野外条件下土壤CO2及其δ13CCO2对环境因子变化的影响机制。同时野外原位监测大气温度、压强、土壤温度等环境参数来明确环境因子对土壤CO2的影响过程。结果表明:岩溶区土壤CO2通量及其δ13C CO2在季节时间尺度上呈现出相似的季节性变化规律,夏季土壤CO2通量较高,土壤δ13C CO2偏轻,且土壤CO2通量与土壤温度呈显著正相关关系。此外,夏季10 cm处土壤CO2通量明显高于0 cm,且该处δ13C CO2也偏轻于0 cm;冬季10 cm处土壤CO2通量与0 cm相差并不明显,而该处δ13C CO2却仍是偏轻于0 cm。在日时间尺度上10 cm土壤δ13C CO2明显偏轻于0 cm。      

典型岩溶区土壤呼吸作用的昼夜变化特征及其影响因素

为揭示桂林毛村岩溶地区夏季表层土壤呼吸作用昼夜演变规律。本次研究选用静态暗箱/气相色谱法,监测了无降水影响下毛村岩溶区域的表层土壤呼吸通量的昼夜变化规律。同时野外监测表层土壤的温度、大气温度、大气压强等环境参数,以综合分析影响土壤呼吸作用昼夜变化的关键环境因子。结果表明:受到大气温度变化的影响,研究区域土壤表层温度呈现单峰型的昼夜变化规律,表层土壤呼吸作用也存在明显的昼夜变化特征。土壤呼吸最大值出现在12:40至14:40,最小值出现在4:40-6:40。土壤呼吸作用强度和变幅均是白天大于夜间。大气温度与土壤呼吸作用呈显著正相关关系（P<0.01）,说明在土壤含水量未超过阀值时,大气温度是影响土壤呼吸作用昼夜变化的关键环境因子。本次研究明确了土壤呼吸作用在昼夜变化上的变异性,对精确估算整个生态系统的碳收支有重要意义。      

不同耕作方式下川芎对土壤中铅、镉含量的富集特征

以彭州川芎种植区的菜园土、稻田翻耕土、稻田免耕土和旱地(未种过川芎和蔬菜)四种土壤为研究对象,探讨了不同耕作方式下川芎对土壤中Cd、Pb的富集特征。结果表明:在四种耕作方式下,菜园土中Cd、Pb含量显著高于其他三种土壤,分别为1.10mg·kg-1和29.78mg·kg-1;土壤Cd综合污染指数和Hacanson系数分别为3.76和133.07,处于重污染和强生态危害状态。稻田翻耕土、稻田免耕土和旱地三种类型土壤在Cd含量上差异显著,依次为稻田免耕土(0.86mg·kg-1)稻田翻耕土(0.59mg·kg-1)旱地(0.37mg·kg--1),在Pb含量上三者差异不显著。川芎植株对Cd的富集在菜园土中显著高于其他土壤,表现为菜园土稻田免耕土旱地稻田翻耕土;川芎植株对Pb的富集以在稻田免耕土中最大,依次为稻田免耕土旱地稻田翻耕土菜园土。在四种土壤中,川芎叶片对Cd、Pb的富集能力均大于根茎,其中川芎叶片对Cd的富集能力是根茎的1.37倍,对Pb的富集能力是根茎的1.42倍,二者对Cd的富集能力在菜园土中差异最大(叶/根为1.56),对Pb的富集能力在稻田免耕土中差异最大(叶/根为1.98)。川芎对Cd、Pb的富集主要受轮作作物种类和耕作措施的影响。     

大兴安岭北段三道湾子碲金型矿床的原生晕分带及意义

三道湾子金矿位于大兴安岭燕山期成矿带东南部,属于典型的富碲贫硫石英脉型金矿。以此为例,研究了该类矿床矿床原生晕的分布特征,并采用格里戈良分带指数的改进方法计算了原生晕轴向分带序列和分带指数,目的是揭示该类矿床的勘查地球化学特征,并为该矿区进一步找矿指明方向。研究结果表明,原生晕轴向分带序列为:Mo-Sb-Pb-As-Bi-W-Zn-Ag-Cu-Hg-Te-Au。[w(As)·w(Sb)]/[w(Au)·w(Zn)]、[w(Sb)·w(Mo)]/[w(Au)·w(Zn)]、[w(As)·w(Sb)·w(Mo)]/[w(Au)·w(Cu)·w(Zn)]等分带性指数指示主成矿元素Au、Ag在130中段下方异常形态尚未封闭,Ⅰ号矿体深部仍有找矿的潜力,矿石品位会有所降低。     

Annual emissions of mercury to the atmosphere from natural sources in Nevada and California

The impact of natural source emissions on atmospheric mercury concentrations and the biogeochemical cycle of mercury is not known. To begin to assess this impact, mercury emissions to the atmosphere were scaled up for three areas naturally enriched in mercury: the Steamboat Springs geothermal area, Nevada, the New Idria mercury mining district, California, and the Medicine Lake volcano, California. Data used to scale up area emissions included mercury fluxes, measured in-situ using field flux chambers, from undisturbed and disturbed geologic substrates, and relationships between mercury emissions and geologic rock types, soil mercury concentrations, and surface heat flux. At select locations mercury fluxes were measured for 24 h and the data were used to adjust fluxes measured at different times of the day to give an average daily flux. This adjustment minimized daily temporal variability, which is observed for mercury flux because of light and temperature effects. Area emissions were scaled spatially and temporally with GIS software. Measured fluxes ranged from 0.3 to approximately 50 ng m^-2 h^-1 at undisturbed sites devoid of mercury mineralization, and to greater than 10,000 ng m^-2 h^-1 from substrates that were in areas of mercury mining. Area-averaged fluxes calculated for bare soil at Steamboat Springs, New Idria, and Medicine Lake of 181, 9.2, and 2 ng m^-2 h^-1, respectively, are greater than fluxes previously ascribed to natural non-point sources, indicating that these sources may be more significant contributors of mercury to the atmosphere than previously realized.     

Mercury speciation in soil in vicinity of coal beds using sequential extraction

The sequential extraction procedure was proposed and used to study of mercury speciation in real samples of soil. Samples of soil profiles together with bedrock and coal were taken from sampling spots in the vicinity of surficial coal beds in an area with natural coal outcrops. The proposed sequential extraction procedure involves the following fractionation: organic mercury compounds, extractable mercury in an acidic medium, mercury bound to humic substances, elemental Hg and mercury bound to complexes, HgS and residual mercury. The significant distribution of mercury between the two portions—mercury bound to humic substance and HgS was determined in the majority of samples. The mercury bound to humic substances created a significant contribution, especially to the top layer of soil. On the other hand, HgS was the dominant form in the samples from lower layers of the soil profile. The mercury content in the samples did not show a distinct mobility. The influence of soil parameters on the mercury distribution in the studied samples was investigated and discussed.     

Review: evaporation of mercury from soils. An integration and synthesis of current knowledge

 Understanding the mechanisms of mercury evaporation from soil to the atmosphere is necessary for tracing the fate of mercury in the biological environment and for assessing potential health effects and the impact of anthropogenic mercury emissions on the environment. In this article an integrating overview of the current knowledge of the mechanisms of mercury evaporation is presented. Abiological and biological formation of Hg(0) and/or (CH₃)₂Hg in the uppermost soil layers are the rate limiting processes of mercury evaporation from soils in background areas; the evaporation rate in background areas is probably strongly influenced by deposited airborne mercury. The evaporation rate limiting factors in mercury enriched mineralized areas with large fractions of total mercury being volatile mercury species (relative to background soil in the non-mineralized vicinity) meteorological variations and the transport characteristics of soils for volatile mercury species. Mercury evaporation rates from background soils are usually <0.2 μg·m^–2·h^–1 and significantly smaller than from mercury-enriched mineralized areas. Received: 20 November 1995 / Accepted: 24 July 1996     

川东观音峡背斜地区地下水水化学分类研究

地下水化学特征合理的分类有利于更好地认识区域水文地质条件。本文通过采用spss聚类分析软件对观音峡背斜区地下水水化学特征进行分类研究。当并类距离取2时,将研究区所取水样分为5类,研究区地下水化学特征主要表现：岩溶水化学类型主要为HCO3＆#183;SO4- Ca或SO4＆#183;HCO3-Ca型水,碎屑岩裂隙水化学类型则主要为HCO3＆#183;SO4-Ca＆#183;Mg型水。     

北京市土壤Hg污染的区域生态地球化学评价

城市土壤Hg异常/污染是中国普遍存在的重大生态环境问题。文章对北京市近1000km2范围内的地表土壤、壤中气、大气干湿沉降、大气颗粒物、大气中的Hg含量水平和空间分布模式进行了系统研究,查明北京地表土壤Hg平均含量为0.41mg/kg,大气干湿沉降物中的Hg平均含量为0.194mg/kg,壤中气Hg的平均含量为559.65ng/m3,大气颗粒物PM10和PM2.5中的Hg含量分别为0.59和0.67ng/m3,大气中的Hg平均含量为3.13ng/m3。北京市自2000年起实现了由燃煤转变为燃气的减排措施,导致干湿沉降物中的Hg沉降通量显著减少,2006年大气干湿沉降物中Hg的沉降通量1.837mg·m-2·a-1,北京市城区(近1000km2)Hg全年沉降为1837kg,空气中总Hg浓度由1998年的8.3~24.7ng/m3下降到2006年的3.13ng/m3,大气颗粒物中Hg含量由2003年的1.18ng/m3下降到2006年的0.59ng/m3(PM10)和0.67ng/m3(PM2.5),表明北京市煤改气减排措施的实施显著改善了大气环境质量。通过对土壤中Hg的存在形式研究,发现土壤中有硫化物(辰砂)及各种Hg盐(HgCl2)的含Hg矿物,Hg也可以各种吸附方式或壤中气方式存在。研究证实北京壤中气Hg与大气Hg存在显著的相关性(n=131,R=0.267,p<0.01),表明壤中气Hg是大气Hg的重要来源之一。利用2005年地表土壤总Hg与Hg释放速率的线性方程估算,土壤Hg平均释放速率为102.42ng·m-2·h-1,2005年土壤释放进大气的Hg通量为936.70kg。在查明土壤中存在大量辰砂矿物的同时,还分布有大量具有高温熔融特征的金属微球粒和玻璃质微球粒,证明燃煤和冶金烟尘是地表土壤Hg的主要来源。土壤中Hg、S、pH和辰砂颗粒浓度在空间上的高度耦合性表明,碱性条件下,土壤中高含量的S和Hg是辰砂形成的重要原因。按国家土壤环境质量标准,北京市I级土壤Hg环境质量的面积为176km2,Ⅱ级为808km2,Ⅲ级为24km2,超Ⅲ为36km2。Ⅲ级、超Ⅲ级主要分布在二环路以内的中心城区。城南(长安街为界)大气Hg环境质量明显优于城北,在北四、北五环之间的部分地区,大气颗粒Hg的环境质量为Ⅲ级或超Ⅲ级。在地表土壤Hg含量较高的中心城区,居民每天因呼吸摄入的Hg高达364ng,对人体健康构成潜在风险。根据我国"十一五"规划中每年实现10%节能减排的目标,对北京市未来50年土壤Hg含量的时空演变趋势预测,预测2050年北京因干湿沉降带来的Hg输入量为16.03kg,地表土壤释放Hg的输出量为37.36kg,明显大于Hg的输入通量,土壤Hg的环境质量将得到根本改善。预测到2040年Ⅲ级土壤Hg环境质量的区域将完全消失,到2060年以Ⅰ级土壤为主。     

Mercury mobility and bioavailability in soil from contaminated area

The mobility and bioavailability of mercury in the soil from the area near a plant using elemental mercury for manufacturing thermometers, areometers, glass energy switches and other articles made of technical glass has been evaluated. Mercury has been determined by sequential extraction method and with additional thermo desorption stage to determine elemental mercury. The procedure of sequential extraction involves five subsequent stages performed with the solutions of chloroform, deionized water, 0.5 M HCl, 0.2 M NaOH and aqua regia. The mean concentration of total mercury in soil was 147 ± 107 μg g⁻¹ dry mass (range 62–393), and the fractionation revealed that mercury was mainly bound to sulfides 56 ± 8% (range 45–66), one of the most biounavailable and immobile species of mercury in the environment. The fractions that brought lower contribution to the total mercury content were semi-mobile humic matter 22 ± 9% (range 11–34) and elemental mercury 17 ± 5% (range 8–23). The contributions brought by the highly mobile and toxic organomercury compounds were still lower 2.3 ± 2.7% (range 0.01–6.5). The lowest contributions brought the acid-soluble mercury 1.5 ± 1.3% (range 0.1–3.5) and water-soluble mercury 1.0 ± 0.3% (range 0.6–1.7). The surface layer of soil (0–20 cm) was characterized by higher mercury concentrations than that of the subsurface soil (60–80 cm), but the fractional contributions were comparable. The comparison of mercury fractionation results obtained in this study for highly polluted soils with results of fractionation of uncontaminated or moderately contaminated samples of soil and sediments had not shown significant statistical differences; however, in the last samples elemental mercury is usually present at very low concentrations. On the basis of obtained correlation coefficients it seems that elemental mercury soils from “Areometer” plant are contaminated; the main transformation is its vaporization to atmosphere and oxidation to divalent mercury, probably mainly mediated by organic matter, and next bound to humic matter and sulfides.     

Spatial variability of mercury emissions from soils in a southeastern US urban environment

We quantified gaseous mercury (Hg⁰) fluxes over soil surfaces in an urban setting during the winters of 2003 and 2004 across the metropolitan area of Tuscaloosa, AL. The objective was to provide a first inspection of the local spatial variability of mercury flux in an urban area. Flux sampling took place on bare, undisturbed, soil surfaces within four evenly spaced landuse areas of Tuscaloosa: industrial, commercial, residential, and mixed landuse. Median total gaseous mercury fluxes (ng/m² h) from each site were as follows: 4.45 (residential site), 1.40 (industrial site), 2.14 (commercial site), and 0.87 (mixed landuse site). Using non-parametric statistical analyses, the residential and mixed landuse sites were found to be statistically different from the overall median flux. Landuse and soil type are the suspected factors primarily controlling the observed spatially variable fluxes. The presence of statistically different fluxes over soil surfaces on a local scale in this preliminary study warrants additional investigation, particularly during the spring and summer seasons when terrestrial mercury emission is the highest. Providing such information will help develop better estimates of mercury emission from urban areas and, ultimately, lead to more accurate and useful spatially relevant inventories.     

Distribution of trace Hg and its mode of occurrence over Fankou Pb---Zn deposit, Guangdong, China

Blind ore bodies more than 200 m below the surface and ore-bearing faults are clearly indicated by soil-air Hg anomalies through an overburden 20–40 m thick over the Fankou Pb---Zn deposit. The background of soil-air mercury in this area is 50 ng m⁻³ and the highest value encountered is 2000 ng m⁻³. The maximum anomaly to background contrast is 40. The width of anomalies higher than 500 ng m⁻³ can be greater than 600 m. The background Hg in soils of the area is 0.06 ppm and increases to 0.15 ppm where there are soil-air anomalies. The contrast of Hg in soils is only 2.5. Mercury in the unconsolidated overburden is in the form of free gas and is absorbed onto soil colloids such as clay minerals and Fe-Mn oxides. The primary sulphides contain 14–320 ppm Hg where Hg is incorporated isomorphically in sulphide minerals, which is confirmed by microprobe analysis.Based on a systematic analysis of the materials from surface and underground workings for the mode of occurrence of Hg, the authors suggest that the Hg-vapour anomalies in soil-air are the oxidation products of the ore.