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.     

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。     

广州市土壤—大气界面Hg交换通量研究

运用Tekran 2537 A与动力学通量箱联测技术,对广州市5个绿化带和草地土壤—大气界面汞交换通量进行了实地监测,结果表明,广州市5个监测点土壤—大气界面汞交换通量密度均值为7.341±9.714 ng·m-2·h-1,不同地点土壤—大气汞交换通量密度有显著差异。汞交换通量密度随土壤汞含量的增加而增大,气象条件显著影响汞交换通量,汞交换通量密度与光照和土壤温度呈显著正相关关系,与土壤pH呈负相关关系,降雨和植被显著影响汞交换通量。     

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。     

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。     

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.      

雅克拉凝析油气田油水界面甲烷天然释放及其源示踪

为评价油气田天然释放CH₄对大气CH₄源与汇的贡献, 采用静态箱法实地监测了新疆塔里木盆地雅克拉凝析油气田油水界面处甲烷的释放通量, 并采用在线大气甲烷碳同位素制样系统与稳定同位素质谱仪联机测试了通量箱甲烷碳同位素组成.结果表明, 由于油水界面边水活跃程度不同, 甲烷通量在空间变化很大, 最高的日释放通量达2.28 mg/m2·d, 最低-1.32 mg/m2·d, 日平均释放通量0.51 mg/m2·d, 标准偏差达1.23 mg/m2·d.油水界面处甲烷通量日变化规律基本相同, 凌晨至清晨时达到相对高点, 随后逐渐降低, 下午至傍晚时段为释放低值甚至负值, 夜晚时分又逐渐增加.通量箱中甲烷δ13C组成白天随甲烷浓度的线性降低而逐渐偏重, 夜晚δ13C随着甲烷浓度的线性增加而逐渐偏重.可见, 油水界面边水活跃, 其上方的土壤形成相对氧化的环境, 油气藏甲烷及烃类在向地表运移的过程中不断被土壤吸收氧化, 仅有少量运移至地表并逸散到大气中, 局部甚至均被吸收氧化, 而成为大气甲烷的汇.      

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。     

北京市有机氯农药填图与风险评价

采用1个样/km2的密度、1个分析组合样/16km2的方法,对北京市784km2范围内的土壤、大气干湿沉降物、大气颗粒物中HCH、DDT的含量和空间分布特征进行有机氯农药填图.查明2000年北京市地表土壤HCH和DDT的平均含量分别为8.80±11.83ng/g、108.99±301.90ng/g.2006年大气干湿沉降物中HCH和DDT平均含量分别为10.09±9.60ng/g、12.99±13.51ng/g,HCH和DDT的年沉降通量分别为996.57±939.96g/a·km2、1291.53±1342.28g/a·km2.2006年大气颗粒物PM10和PM2.5中的HCH含量分别为0.294±0.205ng/m3和0.217±0.137ng/m3,DDT的平均含量分别为1.037±1.301ng/m3和0.522±0.773ng/m3,显著高于2002-2003年度大气颗粒物中HCH(PM100.01786ng/m3,PM250.01731ng/m3)和DDT(PM100.01672ng/m3,PM2.50.02353ng/m3)的含量,表明北京市或周边地区仍在使用含HCH和DDT化学成分的农药.以2000年北京地表土壤和2006年大气干湿沉降物中HCH和DDT的含量为基础,对2020年土壤中HCH和DDT的时空演变的预测显示,即使干湿沉降物中HCH和DDT的沉降通量每年以5%的速率递减,到2020年土壤中HCH和DDT的环境质量仍不能显著改善,而控制和削减北京及周边地区含HCH和DDT成分农药的使用将是改善北京地表土壤环境质量的关键措施.     

海-气间化学物质交换通量的研究

从以下几个方面简要分析了海—气间化学物质交换通量的参数化研究情况：如果不考虑物质间的化学反应,经典的通量—梯度关系（Ｋ理论）可用于估计从大气进入海表面的物质通量。在有化学反应的情形下,应根据化学反应速度与湍流交换速度的相对大小对Ｋ理论做修正;已知海表面的物质浓度和物质的沉降速度,可由二者的乘积来估计通量的大小。降水对大气中物质的清除作用是很大的,如何对降水的物理过程进行参数化,直接影响到对湿沉降通量的估计;计算海—气间气体交换通量的一种方法是利用界面两侧的分压差和气体转移系数。这两个参数都可能造成通量估计的不确定性。     

Wavelength-dispersive X-ray fluorescence spectrometric determination of Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in komatiites

Komatiites are mantle-derived ultramafic volcanic rocks. Komatiites have been discovered in several States of India, notably in Karnataka. Studies on the distribution of trace-elements in the komatiites of India are very few. This paper proposes a simple, accurate, precise, rapid, and non-destructive wavelength-dispersive x-ray fluorescence (WDXRF) spectrometric technique for determining Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in komatiites, and discusses the accuracy, precision, limits of detection, x-ray spectral-line interferences, inter-element effects, speed, advantages, and limitations of the technique. The accuracy of the technique is excellent (within 3%) for Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Zr, Nb, Ba, Pb, and Th and very good (within 4%) for Y. The precision is also excellent (within 3%) for Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th. The limits of detection are: 1 ppm for Sc and V; 2 ppm for Cr, Co, and Ni; 3 ppm for Cu, Zn, Rb, and Sr; 4 ppm for Y and Zr; 6 ppm for Nb; 10 ppm for Ba; 13 ppm for Pb; and 14 ppm for Th. The time taken for determining Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in a batch of 24 samples of komatiites, for a replication of four analyses per sample, by one operator, using a manual WDXRF spectrometer, is only 60 hours.     

高压微波消解法测定醋酸纤维过滤器采集的微尘粒子中的砷镉钴铬铜铁锰镍铅钒锌

最新的流行病学研究表明,空气中较高浓度的悬浮细颗粒可能对人类的健康有不利的影响。根据该项研究显示,由于心脏病、慢性呼吸问题和肺功能指标恶化而导致死亡率的升高与细尘粒子有关。这些研究结果已经促使欧盟于1999年4月出台了限制空气中二氧化硫、二氧化氮、氧化氮、铅和颗粒物含量的法案(1999/30/EC),对各项指标包括对可吸入PM10颗粒的浓度提出了新的限制性指标。PM10颗粒是指可以通过预分级器分离采集的气体动力学直径小于10μm的细颗粒。目前研究的兴趣重点逐步偏向PM2.5这些更细微颗粒物,PM2.5这种颗粒物对健康有明显的不利影响。在欧盟指令2008/50/EC中,对PM10和PM2.5都提     

硅酸盐类样品中硅、铁、铝、钛、锰、钙、镁、钾、钠和磷的x射线荧光光谱测定

本文拟定了一种以熔融法制备样片,用X射线荧光光谱测定硅酸盐类样品中Si、Fe、Al、Tj、Mn、Ca、Mg、K、Na、P等元素的分析方法。在对不同靶材X光管和分光晶体实验对比的基础上,选择了最佳的测量条件。该法具有快速、准确,测量范围广,检测限低,价格便宜等优点。经过近百个各种类型标样或管理样品的分析对比表明,本法不仅适用于硅酸盐类岩石样品的分析,还适用于铁矿、铝土矿、碳酸盐类岩矿样品以及水泥、耐火材料等样品的分析。     

Isotopic systematics of He,Ar, S,Cu, Ni,Re, Os,Pb, U,Sm, Nd,Rb, Sr,Lu, and Hf in the rocks and ores of the Norilsk deposits

This paper reports the first results of a study of 11 isotope systems (³He/⁴He, ⁴⁰Ar/³⁶Ar, ³⁴S/³²S, ⁶⁵Cu/⁶³Cu, ⁶²Ni/⁶⁰Ni, ⁸⁷Sr/⁸⁶Sr, ¹⁴³Nd/¹⁴⁴Nd, ^206–208Pb/²⁰⁴Pb, Hf–Nd, U–Pb, and Re–Os) in the rocks and ores of the Cu–Ni–PGE deposits of the Norilsk ore district. Almost all the results were obtained at the Center of Isotopic Research of the Karpinskii All-Russia Research Institute of Geology. The use of a number of independent genetic isotopic signatures and comprehensive isotopic knowledge provided a methodic basis for the interpretation of approximately 5000 isotopic analyses of various elements. The presence of materials from two sources, crust and mantle, was detected in the composition of the rocks and ores. The contribution of the crustal source is especially significant in the paleofluids (gas–liquid microinclusions) of the ore-forming medium. Crustal solutions were probably a transport medium during ore formation. Air argon is dominant in the ores, which indicates a connection between the paleofluids and the atmosphere. This suggests intense groundwater circulation during the crystallization of ore minerals. The age of the rocks and ores of the Norilsk deposits was determined. The stage of orebody formation is restricted to a narrow age interval of 250 ± 10 Ma. An isotopic criterion was proposed for the ore-bearing potential of mafic intrusions in the Norilsk–Taimyr region. It includes several interrelated isotopic ratios of various elements: He, Ar, S, and others.     

Viscous, cohesive, non-Newtonian, depositing, radial slurry flow

Mining induced subsidence can significantly affect mining costs where major surface facilities and natural environment need to be protected. Overburden grout injection is a technology used to control coal mine subsidence by injecting the mine waste material extracted from the coal back into the inter-burden rock during longwall mining. The flowing slurry is here categorised as a nonlinear viscous cohesive (Bingham plastic) fluid. During longwall mining the grout slurry is pumped into the separated beds of the rock mass through a central vertical borehole, which is drilled deep into the inter-burden rock strata above the coal seam. However, a blockage can occur in the injection system when the slurry velocity falls below a certain critical threshold velocity, indicating a material phase change from cohesive-viscous to cohesive-frictional. In situ field injection tests through boreholes have been simulated at a smaller scale at the CSIRO laboratory in Brisbane by pumping the slurry through a radial disk (gap = 4 mm) from its centre. Laboratory experiments indicate a general, nonlinear, cohesive, viscous, frictional model for shear behaviour of the slurry, in which the material shear parameters are functions of the disk radial distance. Complete dimensional and dimensionless analytical solutions have been developed based on an approach related to Bingham–Herschel–Bulkley fluid mechanics. The derived formulae include relations for minimum pump pressure, local pressure and pressure gradient, wall shear stress, volume rate, velocity and velocity gradient. The theoretical results match the experimental measurements. The experiments covered slurries with maximum particle sizes of 0.5 to 2 mm with about 50% being larger than 100 µm. The viscosities at the various solids concentrations were measured with a standard torsion viscometer. This study differs from the previous research in several distinct aspects, namely, consideration of the variable shear parameters rather than fixed values, inclusion of total nonlinear behaviour, and implementation of a friction function to mimic behaviour of the deposited and consolidating stiff slurry, which can cause a significant pressure rise as a result of the increased shear resistance.     

硅酸盐中铁、锰、钛、钙、钾、磷、硅、铝、镁、钠、锶、铷、钡的X-射线荧光光谱定量测定

本文介绍样品经四硼酸锂熔融制成玻璃小饼。采用Lachance模式和理论a系数来校正元素间的效应,由3080E型X-射线荧光谱仪和DF-350B数据处理系统完成硅酸盐中十三个项目的测定。     

岩石密度和超高压岩石折返速率

在常温常压条件下对中国大陆科学钻CCSD主孔100-3000米岩心样品进行了密度测量,建立了密度连续剖面,并界定了不同超高压岩石的密度值。通过对比高温高压物性实验资料,岩石密度随着退变程度增强而降低,榴辉岩密度变化序列为3.52g/cm3→3.49g/cm3→3.07g/cm3→2.93g/cm3。超高压长英质岩石密度变化序列为3.00g/cm→2.80g/cm3→2.65g/cm3。上述实验资料是讨论不同折返阶段岩石所受浮力的基础,为研究折返速率大小提供了基本参数。本文通过折返板块运动平衡时,上浮力与粘滞力平衡这一关系式,定量研究了大陆俯冲板块的折返速率,认为密度差产生上浮力从而引起折返,温度对板块折返速率的影响最为显著;密度差大小、折返角度、折返板块大小对折返速率也有直接的影响。定量模拟分析表明,在温度高于850℃时,板块的折返速率可以超过100mm/a;当温度降至700℃时,折返速率则低于1.5mm/a。作者认为在折返早期,温度较高,板块快速折返至60-70km榴辉岩相深度;随着传导散热,温度降低,板块以较慢的速率折返至中下地壳。折返速率的估算表明,浮力是板块折返第一阶段(从>100km深部折返至<40km的中下地壳)的主要驱动力。     

Bellechester,Minnesota, USA,lagoon collapses

Bellechester, Minnesota, is a small community of approximately 155 residents located on the county line between Goodhue and Wabasha counties in southeast Minnesota's karst region. Bellechester is served by a 21-year-old wastewater treatment facility (WWTF) consisting of three waste-stabilization ponds. On 28 April 1992 six sinkholes were discovered to have drained cell 2 of the WWTF resulting in the loss of approximately 8.7×10⁶ 1 of partially treated effluent and about 600 m³ of soil into previously undetected subsurface voids of unknown dimensions. In the week following the collapse, approximately 200 water wells located within a 5-km radius of the WWTF were sampled in an after-the-fact, emergency sampling program. Twelve samples with elevated fecal coliform levels, 18 samples with nitrate-nitrogen greater than the 10 mg/1 standard, and no samples with elevated chlorides were found. However, the elevated levels could not be unambiguously attributed to the WWTF collapse. This is the third WWTF to fail by sinkhole collapse in southeast Minnesota since 1974. All three collapsed lagoons have been located in similar geomorphic and stratigraphic settings. However, at least two lagoons have collapsed in the adjacent area in northeast Iowa, and these lagoons are located at different stratigraphic positions. Twenty-two WWTFs constructed in southeast Minnesota's karst region in the last 25 years have been identified as subject to potential sinkhole collapse. An unknown but significant number of manure storage lagoons, flood control structures, etc., have also been constructed in the karst region and are at risk. Public agencies are beginning to develop plans to deal with the risk associated with existing and future waste lagoons in this environment. The critical hydrogeologic parameters that can be used to prioritize the risk of collapse at existing facilities include: (1) the lithology of the first bedrock beneath each lagoon, (2) the thickness of surficial materials between the lagoon and the bedrock surface, (3) the presence and construction of liners (seepage rate), and (4) the proximity to existing sinkholes.     

Mercury,arsenic, antimony,and selenium contents of sediment from the Kuskokwim River,Bethel, Alaska,USA

The Kuskokwim River at Bethel, Alaska, drains a major mercury-antimony metallogenic province in its upper reaches and tributaries. Bethel (population 4000) is situated on the Kuskokwim floodplain and also draws its water supply from wells located in river-deposited sediment. A boring through overbank and floodplain sediment has provided material to establish a baseline datum for sediment-hosted heavy metals. Mercury (total), arsenic, antimony, and selenium contents were determined; aluminum was also determined and used as normalizing factor. The contents of the heavy metals were relatively constant with depth and do not reflect any potential enrichment from upstream contaminant sources.     

滇东南花岗岩与锡、银、铜、铅、锌多金属矿床的成因关系

滇东南锡、银、铅、锌多金属矿床主要分布在个旧、白牛厂、都龙3个矿区,而滇东南较大的3个花岗岩体又分别出露在3个矿区或附近.花岗岩体均形成于燕山晚期,岩石化学、矿物成分相似,富含锡、银、铅、锌、钨、铜等成矿元素.矿床主金属元素组合与岩体之间的距离由远而近出现由锡、钨、(铍、铌、钽)→锡、钨、(铁)、铜、铟→锡、铅、锌、银、铟、(锑)有规律的变化.花岗岩浆是成矿物质来源和成矿热源.岩浆侵入初期使上覆地层隆起产生背斜(凹陷部位成向斜);同时使地层产生一系列裂隙、压性断层或层间断裂;岩浆侵入晚期,这些断层再次活动,表现为张性,岩浆产生的含矿热液沿由其活动所造成的断裂迁移、充填、交代、沉淀而形成矿床.