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.     

壤中气氡汞联测在监测汶川余震中的作用

四川省汶川县发生8级大地震以后,在陕西省宁强县设立余震监测点,实地定时观测了余震发生与壤中气中Rn、Hg含量变化的关系,观测时间17 a。结果发现:在发震断裂上盘的壤中气中,Hg含量一般大于200 ng/m3,是下盘的1倍以上(在有地裂缝的地段,Hg异常高达560 ng/m3),而Rn含量没有明显差异。沿发震主断裂走向,距震中越近,Rn、Hg的背景含量越高。在背景地段,壤中气Hg含量高于20 ng/m3,同时伴有Rn异常,预示300 km范围、4~48 h之内、高频率、4级以上余震发生的几率高;反之则预示无余震发生。     

兰州市表层土壤中汞的生态地球化学评价

对兰州市1663km2范围内的表层土壤和大气干湿沉降空间分布模式进行了分析,认为表层土壤中Hg的含量差异较大,其中Hg的平均含量为0．14×10^-6,最高值为6．38×10^-6。对土壤中Hg的存在形式进行了研究,认为燃煤是其主要来源。大气总汞浓度年平均值为28．62×10^-9,其中采暖期为48．48×10^-9,非采暖期为9．42×10^-9。根据国家土壤环境质量标准,兰州市№环境质量达到Ⅰ级标准的土壤面积为1376．1km2,占研究区总面积的82．75％;Ⅱ级土壤面积246．8km2,占14．84％;Ⅲ级土壤面积31．7km2,占1．91％;Ⅳ级土壤面积8．4km2,占0．51％。Ⅲ、Ⅳ级区域主要分布在兰州市西固区石化厂及其附近、七里河区西关十子一城关区二热电厂。     

南京沿江地区大气干湿沉降对农用地土壤重金属含量的影响

为查明大气干湿沉降对农用地土壤环境的影响大小,通过估算干湿沉降通量、计算并分析重金属元素含量及其变化率,探讨了南京沿江地区干湿沉降中8种重金属元素输入对农田土壤重金属累积的影响。结果表明：干湿沉降物中重金属元素含量明显高于周边土壤的重金属元素为Cd,干沉降中的Cd平均含量达0.84 mg/kg,是农用地土壤污染筛选值的2.8倍;As、Cd、Cr、Cu、Hg、Ni、Pb、Zn的年沉降通量平均值分别为12.1、1.60、89.1、47.9、0.092、46.6、36.6、116 g/(hm²·a);大气干湿沉降物对土壤影响最显著的重金属元素为Cd,大气干湿沉降1年后的增量为5.33 ng/g,年变化率达1.38%,表明大气沉降物为研究区农田土壤中重金属Cd的重要来源之一。     

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。     

江西省鄱阳湖流域农田生态系统土壤Se元素含量变化研究

以江西省鄱阳湖流域农田生态系统中Se元素为研究对象,以大气干湿沉降、灌溉、施肥、喷施农药为输入途径,以农作物收割、地表径流以及Se升华为输出途径对Se的生物地球化学循环规律进行研究。结果表明,鄱阳湖流域Se元素的大气干湿沉降通量密度平均值为6.90g/(hm2.a),灌溉、施肥、喷施农药通量密度明显较低,它们对土壤Se元素的富集贡献率分别为77%、20%、1%和2%。Se通过升华输出通量密度相对较小,土壤Se年净增量主要受大气干湿沉降的制约。以20cm厚的耕作土体为研究介质,经估算,当前的Se年平均通量密度可引起土壤Se质量分数升高0.007mg/kg。20a后研究区富硒土壤将由目前5 960km2增加至6 672km2。研究中未考虑天降水下渗问题,这对中国南方土壤中元素的地球化学行为有非常重要的影响。     

成都经济区农业生态系统土壤镉通量研究

以四川成都经济区农业生态系统中的重金属Cd为对象,对其在土壤中的输入输出通量进行初步探索。综合各方面的因素,确定以大气干湿沉降、灌溉水、化肥为输入途径和农作物为输出途径进行研究。经过计算,经济区大气干湿沉降通量平均值为17.76g/hm2·a,灌溉水和化肥通量明显较低,三者对土壤Cd污染的贡献率分别为86%、10%和4%。对于6个不同的地区,三者比例略有差别,大气干湿沉降所占比例最高达94%,最低也达到了77%。Cd通过农作物收割输出的量相对较小。土壤Cd年净增量主要受大气干湿沉降的制约,因此大气环境质量应是重点监控的对象。以耕作土体为研究介质,经估算,当前的Cd年平均通量可引起土壤Cd的质量分数升高0.006mg/kg。     

鲁西南平原区大气干湿沉降元素输入通量及来源浅析:以巨野县为例

大气干湿沉降是农耕区表层土壤中某些元素的主要输入途径,其沉降物质中的重金属等元素对土壤环境质量有着很大的影响。对山东省巨野县大气干湿沉降的调查研究发现,随着近年来区内煤炭开采和化工工业的快速发展,区内大气干湿沉降物质总量有明显升高,显著高于我国其他一些地区。同时,区内重金属元素沉降通量也较高,其中Pb、Cr、Cu、Ni可达我国其他地区的2～3倍。大气沉降物质中Cd、Pb、Hg等的富集程度较高,其富集因子(EF)的高值区与煤炭开采和煤炭化工排放源分布吻合,说明工业区大气干湿沉降是Cd、Pb、Hg等重金属污染元素进入土壤环境的重要途径,工矿业活动对区内大气干湿沉降的增加有重要影响。此外,富集因子显示燃煤尘是大气沉降物及当地土壤S、Se的主要来源,而大气沉降物中Ni、Cr、As主要源自土壤扬尘,Ca和Mg与区内石材开采或水泥制造密切相关。     

安徽旌德-宁国地区大气干湿沉降地球化学特征及评价研究

以安徽旌德-宁国地区大气干湿沉降物为研究对象,共采集6处干湿沉降物样品24件,对大气干湿沉降元素含量特征、通量特征进行对比分析,对干湿沉降元素含量及分布特征加以统计研究,并开展大气干湿沉降环境地球化学评价.结果显示：1）大气干湿沉降元素主要以矿物相形式存在或吸附在固体颗粒上,且受周边环境影响;2）干沉降中Cd、Se的高含量会对研究区土壤污染造成较大影响,湿沉降中部分样点pH超灌溉水水质标准,所有点均达到地表水Ⅱ类环境质量标准;3）区内重金属元素年沉降通量密度为,As年沉降通量低,Hg、Ni、Pb、Cr、Cu、Cd偏低,Zn偏高;4）大气干湿沉降重金属元素通量一般表现为丘陵山区小于城镇及工矿区,主要受燃煤燃烧、尾气排放及人为活动等影响;5）大气干湿沉降物环境地球化学单指标和综合指标评价结果均为一等.     

成都经济区As等元素大气干湿沉降通量及来源研究

2004年8月—2005年8月在四川省成都、德阳等6万km2的农田区进行了为期一年的大气样品采集,共采集干、湿沉降样品28件,分别测试干、湿沉降中B、Mo、Mn、Zn、As、Cd、Hg、Pb、K、Ca、Na和Mg元素含量,计算获得各元素的年沉降通量;其中4种有害元素年沉降通量平均值分别为As2.77mg.m-2.a-1、Cd1.77mg.m-2.a-1、Hg0.10mg.m-2.a-1、Pb45.95mg.m-2.a-1。应用主成分分析对大气干湿沉降中各元素进行区分,取得了相当好的结果。其中第一主成分为Hg、Pb、Zn、Cd、Mo和As;第二主成分为K、Mg、Na、Mn和B;第三主成分为Ca。主成分对原始变量解释度达到94.88%,第一主成分说明Hg、Pb、Zn、Cd、Mo和As是影响大气质量的主要因素。将各干湿沉降接收点元素沉降通量与相应点位土壤元素含量进行相关分析表明,Pb、Hg在两种介质中相关性显著,说明土壤中Pb、Hg积累与大气干湿沉降具有密切关系,其他元素来源则更为复杂。通过不同地区重金属元素沉降通量的比较发现,各地区元素沉降通量差异明显,其中成都和德阳两地As、Cd、Hg、Pb沉降量显著较高,说明沉降中污染元素来源与不同地区工矿企业类型和数量有关。     

Source apportionment and distribution of atmospheric mercury in urban Beijing,China

The concentration of gaseous elemental mercury (GEM) in the atmosphere of urban Beijing was measured from October 2003 to September 2004 to investigate the origins and spatial-temporal variations of atmospheric Hg. The mean value of Hg concentration is 17.1 ng·m-3 (n=653). The atmospheric Hg data showed spatial-temporal variations throughout the duration of our observation. The maximum GEM concentration (53.7 ng·m-3) was observed at Gucheng in the western area of urban Beijing. The GEM concentrations increased from the north to the south of the studied area, and were higher in winter than in summer. The highest and lowest monthly averages of GEM concentrations were measured to be 23.3 and 4.1 ng·m-3 in January and July, respectively. In addition, GEM concentrations are higher in the daytime than at night in Autumn and from 14 March to 15 April, but daily GEM variation showed an inverse pattern from 22 April to 22 May. In winter, two peak values of GEM concentrations occurred at 13:30 and 21:30. Daily variation of GEM concentrations in summer was the lowest in the four seasons. Mercury from coal combustion was estimated to be the main source of anthropogenic emissions in Beijing from October 2003 to September 2004. Additionally, Hg emission from natural gas burning was estimated to be another dominant source of atmospheric Hg in Beijing.     

Mercury exchange between the atmosphere and low mercury containing substrates

Mercury is emitted to the air from Hg-enriched and low Hg-containing (natural background) substrates. Emitted Hg can be geogenic, or can be derived from the re-emission of Hg that was previously deposited to the soil from the atmosphere. Atmospheric Hg can be derived from natural and/or anthropogenic sources and can be deposited by wet or dry processes. It is important to understand the relative magnitude of emission, deposition, and re-emission of Hg associated with terrestrial ecosystems with natural background soil Hg concentrations because these landscapes cover large terrestrial surface areas. This information is also important for developing biogeochemical mass balances, assessing the impacts of atmospheric Hg sources, and predicting the effectiveness of regulatory controls at local, regional, and global scales.The major focus of this paper is to discuss air–substrate Hg exchange for low Hg-containing soils (<0.1 μg Hg g⁻¹) from two areas in Nevada and one in Oklahoma, USA. Data collected with field and laboratory gas exchange systems are presented. Results indicate that in order to adequately characterize substrate–air Hg exchange, diel and seasonal data must be collected under a variety of environmental conditions. Field and laboratory data showed that dry deposition of gaseous Hg to substrates with low Hg concentrations is an important process. Environmental parameters important in influencing emissions include soil water content, incident light, temperature, atmospheric oxidants, and air Hg concentrations. There are synergistic and antagonistic effects between these parameters complicating prediction of flux.     

Variation of Hg content in low sulfur coals in relation to the coal-forming environment: a case study from Zhuji Coal Mine,Huainan Coalfield,North China

Twenty-nine low sulfur coal samples were selected to determine the magnitude and variability of mercury (Hg) content in a well-documented stratigraphy system including ten continuous coal seams in Zhuji Coal Mine, Huainan Coalfield, Anhui Province, North China. Mercury content of samples was measured on a direct mercury analyzer and confident results were obtained as evaluated by standard references, sample replicates and procedural blanks. The calculated overall mine average Hg content is 71.19?±?9.28 ng/g based on seam averages and weighting by the estimated reserve of each coal seam. The estimated Hg emission potential for Huainan coalfield is obviously lower than that calculated from coal emission factor in industrial use. An increasing trend of Hg content with the evolution of depositional environment was observed from Nos. 3 to 11-2 coal seams. Combining the evidence of sedimentology and paleontology, a better understanding was gained of the mechanism of Hg sequestration in specific coal benches. A large portion of Hg residing in the low sulfur coals presumably integrated to the functional groups of organic constitution, whereas pyrite was generally abundant in the high sulfur coals.     

民用蜂窝煤燃烧排放颗粒物的化学组成和稳定碳同位素特征

本文选用了镜质组反射率在0.77%-1.88%之间5 种不同成熟度的煤, 将其制成民用蜂窝煤球, 研究民用蜂窝煤燃烧排放颗粒物（PM）的化学组成, 包括元素（C、N、O、S）、有机碳（OC）、元素碳（EC）和水溶性无机离子（WSII）, 稳定碳同位素组成特征和质量吸收效率值（MAE）, 并讨论了它们与煤成熟度之间的关系.结果表明, 5 种原煤C、N、O、S 元素组成差别不大, 但是燃烧后排放的PM 化学组成差别比较大.无烟煤燃烧排放的PM 粒径分布呈双峰结构, 峰值分别在0.09 μm 和0.25 μm; 而烟煤PM 的峰值为0.58 μm.无烟煤排放PM 的颗粒数远小于烟煤.PM、OC 和EC 的排放受煤成熟度的影响非常大, 无烟煤排放的量最小, 分别为2.21 g/kg、0.22 g/kg 和0.004 g/kg; 成熟度最低的烟煤排放量最大, 分别为70.3 g/kg 、46.1 g/kg 和2.42 g/kg.PM、OC 和EC 的排放因子与煤的成熟度成幂指数关系.EC 的MAE 在0.17-21.9 m^2/g 之间, 与煤成熟度呈指数相关关系.燃煤WSII 的平均排放因子为801 mg/kg, WSII 当中含量最高的是NH4^＋ 和24SO4^2- , 平均分别占WSII总量的23.5%和44.4%.燃煤排放PM 的δ^13C 变化范围为–24.5‰-–22.8‰, 平均值为–23.6‰.以上研究有助于人们从原煤性质的角度去考察民用燃煤对人类健康和气候变化的影响, 并为大气污染源解析提供一些科学依据.     

淮南采煤沉陷区土壤中汞的时空分布特征

以淮南采煤沉陷区土壤为研究对象,测试分析了样品中汞的含量,结合土壤pH值、有机质含量特征,探讨了采煤沉陷区土壤中汞的时空分布特征。结果表明:与未沉陷区土壤相比,沉陷区土壤有机质破坏严重,最高下降了46%;采煤沉陷区土壤中汞的含量为0.013~0.050 mg/kg,平均值为0.027 mg/kg,69.7%的采样点超过了淮南市土壤背景值;沉陷8 a后土壤汞含量最高,为0.033 mg/kg,是未沉陷土壤汞含量的1.74倍,且随着沉陷时间的增加,土壤中汞存在富集趋势;水稻土壤汞富集能力最高,高于玉米和大豆土壤;在垂直剖面上,汞含量由表层向下依次降低;且汞与pH值表现出显著负相关,有机质与汞显著正相关。      

煤汞同位素地球化学研究进展

汞是煤中普遍存在的痕量元素,煤炭消耗总量之巨使燃煤成为全球汞污染主要来源之一。汞具有7种稳定同位素, 并且兼具质量分馏和非质量分馏效应,使通过汞同位素对涉煤汞污染源和汞迁移、转化示踪成为理想途径。煤中汞同位素 研究获得长足进展。第一,初步给出了世界11个产煤国煤中汞同位素δ202Hg的特征值及分布范围,为示踪环境介质汞的燃 煤源污染源创造了条件。第二,发现了原煤中汞存在奇数质量汞的非质量分馏效应（Δ199Hg≠0）,有助于配合δ202Hg开展示 踪研究。第三,中国不同产煤地及不同成煤期原煤中汞同位素δ202Hg与Δ199Hg值已被测试,为中国开展煤源汞污染示踪研究 打下一定基础。进一步工作可能有待加强的4个方面：（1） 全球不同地域和时代煤中汞同位素数据库的不断补充、修正和 完善;（2） 煤炭生产遗存物,如残留煤和煤矸石等与气-水环境相互作用中的汞同位素问题;（3） 燃煤派生的且影响人类 健康的环境介质如大气细颗粒物（PM2.5） 的汞同位素问题;（4） 涉及煤火汞的迁移转化是复杂的,部分汞具有二次释放特 性,其中汞同位素问题仍是未知的。总之煤中汞及其关联的汞同位素研究方兴未艾。     

Meteorological noise in crustal gas emission and relevance to geochemical exploration

The emission of gas from the earth's crust is a complex process influenced by meteorological and seasonal processes which must be understood for effective application of gas emission to geochemical exploration. Free mercury vapor emission and radon emanation are being measured in a shallow instrument vault at a single nonmineralized site in order to evaluate these influences on gas emission.Mercury concentrations in the instrument vault average 9.5 ng/m³ and range from < 1 ng/m³ to 53 ng/m³ with a strong seasonal effect. Mercury has a direct relationship to vault temperature, air temperature, soil temperature, barometric pressure, water table, and the frozen or thawed state of the soil. Air and soil temperature, barometric pressure, and relative humidity are most important in influencing mercury emission while soil moisture is also important in radon emanation. Diurnal cycles are common but do not occur on all days. A heavy precipitation event on a dry soil seals the soil resulting in a rise in mercury concentration. Precipitation on a soil that is already wet does not increase mercury emission because of the compensation caused by lowering of the soil temperature by the precipitation event. Freezing of the soil changes the physical state of the vault-soil-soil gas-atmosphere system and emits the lowest concentrations of mercury. Phase lag effects are likely important. Stepwise multiple regression of mercury as dependent variable with meteorological and seasonal parameters as independent variables gives a cumulative R value of 0.563 and R² of 0.317. The short-term noise coupled with phase lags are an important factor.The radon measurements integrated over weekly intervals smooth out much of the short-term noise. Stepwise multiple regression of radon as dependent variable with meteorological and seasonal parameters as independent variables gives a cumulative R value of 0.967 and R² of 0.934. In this portion of the study the variation in the radon emanation is adequately predicted by meteorological and seasonal parameters.     

Application of spatial analysis and multivariate analysis techniques in distribution and source study of polycyclic aromatic hydrocarbons in the topsoil of Beijing,China

Surface soil samples were collected from 161 sites throughout the downtown and suburban area of Beijing, China. The samples were analyzed for polycyclic aromatic hydrocarbons (PAHs) concentrations. Through Kriging analysis, five heavily contaminated zones were identified in the study area. Sources of PAHs in the soil were apportioned using principal factor analysis and multiple linear regression. Three factors were identified representing coal combustion/vehicle emission, coking emission, and petroleum sources, respectively. The relative contributions of the three sources were 48% for coal/vehicle emission, 28% for coking emission, and 24% for petroleum sources. The contributions of total PAHs from the three sources were 16.4, 4.63 and 3.70 ng g⁻¹, respectively. Spatial analysis indicated that the contribution of coal/vehicle sources was higher in the downtown area than in the suburban area, the petroleum sources had a high contribution in the urban area, and the contribution of coking sources was high in the suburban area. The results indicated that PAH contamination in the surface soil in Beijing was closely related to the spatial characteristics of energy consumption and functional zoning. Improvement of the energy consumption structure and relocation of industries with heavy pollution are effective ways to control PAH contamination in surface soil in the area.     

北京市大气可吸入颗粒物的化学成分和来源

2007年3月至2008年5月,在北京市成府路东口设立采样点,共采集监测周期为一周的PM2.5(直径小于2.5μm的大气可吸入颗粒物)样品56个,用HR-ICP-MS方法测量了15种元素的含量,并在此基础上应用主因子分析法对PM2.5中这些元素的来源进行探讨。同时,在2008年奥运会和残奥会期间开展了24h时间间隔的密集采样,特别分析了机动车限行期间细颗粒污染物的浓度特征。结果表明,2007年春季至2008年春季期间北京市大气PM2.5平均浓度为72.9μg/m3,超过美国环保局（USEPA）制定的PM2.5年平均浓度限值15μg/m3的近5倍。机动车限行期间北京成府路东口采样点大气PM2.5的平均浓度为40.7μg/m3。通过因子分析方法确定北京PM2.5的3种可能来源：①交通排放、工业排放和燃煤,特征元素为Cu、Zn、As、Sn、Sb、Cd、Pb;②本地扬尘和远源沙尘细颗粒;③可能与成土母岩风化有关的土壤颗粒的再悬浮和/或迁移,其方差贡献率分别为41.2%、31.4%和12.2%。