银膜富集法测定大气中的气态汞

探讨了用银膜富集管测定大气中气态汞的方法、影响气态汞吸收率的因素和银膜富集管的再生方法。结果表明 :银膜富集管对大气中的气态汞能有效富集。当银膜长 /管径大于 2 0 0 mm/4.5mm,流速为 0 .4L/min时 ,银膜富集管对气态汞的吸收率达 98%以上。     

石油裂解气中总汞采样方法的改进

石油裂解气中汞的形态主要有气态汞和颗粒态汞。《空气和废气监测分析方法》（第四版）,废气中汞有高锰酸钾溶液吸收法和玻璃纤维滤膜（滤筒）两种采样方法。溶液吸收法适合气态汞采样,滤膜（滤筒）采样法适合颗粒态汞采样。本文将两种采样方法串联对某石化企业的石油裂解气总汞进行监测分析,结果表明：石油裂解气中颗粒态汞与气态汞比例约为1：9;气态汞样品平行性较好,两个点位6次RSD值分别为17.2%和17.0%;颗粒态汞两个点位6次RSD值分别为25.3%和23.1%。建议对石油裂解气总汞监测采用玻璃纤维滤膜和高锰酸钾溶液吸收法串联采样。     

厦门市秋冬季节大气汞污染调查

文章采用两次金汞齐一冷原子荧光光谱法对厦门地区秋冬季节大气汞的污染状况作了初步调查分析,结果表明厦门地区大气中汞的浓度平均为11．037ng／m^3,其含量高于北半球大气气态总汞含量的背景值（1．5-2．0ng／m^3）,表明该地区已受到一定程度的大气汞污染;在一定的采样区域,大气汞浓度与温度、太阳辐射量、大气压、空气湿度成正相关,与风速成负相关;气态汞的含量在80％左右,这与该地区的人为活动多有关,与其他地区报道的类似区域情况的汞污染状况相符;工业区,学校实验室周边区域,生产过程中以汞为原料的工厂等附近区域,大气中汞的含量较高,开阔区域的海边含量较低,交通繁忙区域最低（所选采样点与交通要道有一定的距离）,这种浓度分布说明了大气中汞的存在具有区域性特征。     

垃圾填埋场大气汞的浓度和形态

对贵阳市和武汉市的5座城市生活垃圾填埋场大气中的ρ(气态总汞)进行了测定,并分析了填埋场的大气活性气态汞、颗粒态汞、单甲基汞和二甲基汞的质量浓度分布. 结果表明:5座填埋场ρ(气态总汞)为1.6～473.7 ng/m3,不同采样点的平均值为8.5～155.7 ng/m3,最高值出现在填埋场的工作面及工作面下风向区域;而封闭填埋场或运行填埋场的覆土区的ρ(气态总汞)较低. 天气条件和垃圾处理活动均可影响ρ(气态总汞)水平. 贵阳高雁垃圾填埋场大气ρ(活性气态汞),ρ(颗粒态汞),ρ(单甲基汞)和ρ(二甲基汞)的平均值分别为37.4,255.3,12.4和12.7 pg/m3. 虽然不同形态汞的质量浓度明显高于全球背景值,但其产生的环境风险不大.      

煤中汞燃烧过程析出规律试验研究

在小型煤粉燃烧实验台架上进行煤燃烧后汞的燃烧形态转化试验研究。采样过程利用了美国EPA推荐使用的On-tario-Hydro方法进行煤样燃烧产物的取样。研究认为，煤样燃烧后烟气中的气态汞总量在10－15μg/m^3范围内，其中二价汞在40％左右，较低的烟气冷却速率可以促进单质汞向二价汞的转化、烟气中的气态汞占总汞的70％左右。     

香港近海沉积物中汞残留研究

研究是测定了从 2 0 0 0～ 2 0 0 1年 ,对香港近海 16个采样点所采集的沉积物中残留汞的含量。通过沉积物中汞含量对香港近海的汞污染分布状况进行研究。测量的结果中 ,沉积物中汞含量的范围是 (45 7～ 384 4ng g ,干重 )。     

两次金汞齐-冷原子荧光光谱法测定大气中的痕量气态总汞

建立了两次金汞齐-冷原子荧光光谱法(CVAFS)测定大气中痕量气态总汞(TGM)的方法。研究表明:本方法的绝对检出限为2 pg;当以0.2~0.4 L·min-1 采样速度,采集12~48 h时,采样效率> 99%,精密度为9.63%;样品经2次循环加热分析,热解吸效率> 99%。这种分析方法还可以运用到其他环境样品痕量汞的测定。     

两次金汞齐–冷原子荧光光谱法测定大气中的痕量气态总汞

建立了两次金汞齐–冷原子荧光光谱法(CVAFS)测定大气中痕量气态总汞(TGM)的方法.研究表明:本方法的绝对检出限为2 pg;当以0.2～0.4 L·min-1采样速度,采集12～48 h时,采样效率 > 99%,精密度为9.63%;样品经2次循环加热分析,热解吸效率 > 99%.这种分析方法还可以运用到其他环境样品痕量汞的测定.     

气态汞污染源的扩散污染及其特点

对汞扩散污染源的现状和行为的规律性进行了分析和研究。结果表明,汞污染源对环境的污染较符合气体扩散规律;大部分气态汞污染源的污染方式为无组织排放,相对风速影响较小,不同距离间浓度梯度明显;受汞污染的室内空气的汞浓度分布,有一定规律,特别可见垂直分布的差异,这与汞性质和污染方式有关;气温对空气中汞浓度的影响是明显的,因此,降温可作为一个控制汞浓度的有效措施。     

被动采样器(MerPAS)在气态汞含量和同位素分馏研究中的应用

汞（Hg）是一种具有生物毒性、易挥发的有害金属元素。在大气中主要以气态单质汞Hg⁰的形态存在,具有较长的大气滞留时间,能随大气环流扩散到全球。多尺度监测大气Hg⁰的浓度对于评估《关于汞的水俣公约》履行效果极为关键。由于操作简易且不易受恶劣环境影响,被动采样器是现有大气Hg⁰主动监测技术的有效补充。近期研究表明被动采样器（MerPAS）采集到的大气Hg⁰可以同时应用于汞浓度与稳定汞同位素的分析。鉴于MerPAS在大气汞的研究中的广泛应用前景,本文对MerPAS的结构、原理以及其在大气Hg⁰浓度和同位素研究方面的进展进行综述,并通过实地采集天津市市区的大气汞来验证其汞浓度和同位素测试的可靠性。结果显示：MerPAS能够准确地监测大气汞的浓度,并很好地保存大气Hg⁰的同位素信号,特别是非质量分馏信号。     

天津市夏季蜂窝状溶蚀器涂层溶液浓度确定的实验研究

于2013年7月1日～8月31日,在天津市南开大学理化楼楼顶,采用蜂窝状溶蚀器进行了溶蚀器涂层溶液最适浓度的探究实验.结果表明,在天津夏季,蜂窝状溶蚀器的碳酸钠涂层溶液最适浓度为3%,柠檬酸涂层溶液最适浓度为6%.含有溶蚀器系统的颗粒物采样法与传统采样法对比发现,含蜂窝状溶蚀器的采样系统所得到的PM2.5样品浓度有86%低于传统方法所得到的PM2.5样品浓度,其原因主要为1酸/碱性气体被去除,使其无法与富集在采样膜上的颗粒物发生反应,也无法吸附到颗粒物上;2溶蚀器系统采样过程中,部分颗粒物被捕集到溶蚀器上;3酸/碱性气体被去除,导致气-粒平衡被打破,部分颗粒物组分向气态转化.     

天津市冬季蜂窝状溶蚀器涂层溶液最适浓度研究

在特定时间特定地点利用溶蚀器PM2.5采样系统进行PM2.5采样前,应首先确定溶蚀器涂层溶液最适浓度.为确定在天津市冬季利用蜂窝状溶蚀器PM2.5采样系统采样的最优化条件,于2014年1月1日~2月24日,在南开大学理化楼楼顶进行蜂窝状溶蚀器涂层溶液最适浓度的条件实验.结果表明:在天津地区冬季, 蜂窝状溶蚀器的碳酸钠涂层溶液最适浓度为4%,柠檬酸涂层溶液最适浓度为5%; 环境空气中HCl气体对PM2.5中Cl-的质量浓度测定影响不大,而HNO3、SO2、NH3等酸/碱性气体对PM2.5中相对应离子的质量浓度测定影响较大.     

A multiple-system,multi-channel diffusion denuder sampler for the determination of fine-particulate organic material in the atmosphere

Measurement of the loss of semi-volatile organic compounds from particles collected with a filter is carried out by comparing the amounts collected by comparable filter pack and diffusion denuder samplers. The sorbents used to collect organic compounds in the denuder and sorbent filters must have the same efficiency for collection of all gas-phase organic compounds present. Interpretation of the data requires that the efficiency of collection of gas-phase compounds by the denuder be known. In theory this can be accomplished by determination of the deposition pattern of all organic compounds collected in the denuder, but in practice this is very difficult if the organic material consists of a wide variety of compounds. An alternative approach is to determine the breakthrough of organic compounds in a sampler with a particle-collection filter preceding the denuder and sorbent filter. In such a sampler only gas-phase organic material enters the denuder. We have developed both a multi-channel parallel plate diffusion denuder sampler and a comparable sampler in which the denuder is preceded by a filter. Samples can be collected with the multisystem sampler at a flow rate of 35 sLpm. The denuder surfaces and the sorbent filters are made from sheets of an activated charcoal-impregnated filter paper. Collection of semi-volatile compounds by the samplers has been characterized and the systems have been field tested. The samplers are now being used for the routine collection and determination of semi-volatile organic compounds in particles at Canyonlands National Park in southeastern Utah. Available data from this field program show significant losses of particulate organic compounds on a quartz filter due to volatilization during sampling.     

Criteria for the choice of a denuder sampling technique devoted to the measurement of atmospheric nirous and nitric acids

The criteria for the choice of the most appropriate denuder coating and set-up devoted to the measurement of atmospheric gaseous species are discussed and applied ton the problem of nitrous and nitric acid determination in real conditions. The various phenomena which may bias these determinations (instability of nitrate ion, collection of interferent compounds, oxidation of nitrate ion etc.) are exmined. A denuder method for a reliable measurement of nitrous and nitric acids in all en vironmental conditions is described and validated in the field.     

A continuous-flow denuder for the measurement of ambient concentrations and surface-exchange fluxes of ammonia

A new diffusion denuder is described for the continuous measurement of atmospheric ammonia. Ammonia is collected in an absorption solution in a rotating denuder, separated from interfering compounds by diffusion through a semi-permeable membrane and detected by conductometry. The method is free from interferences by other atmospheric gases, with the exception of volatile amines. The detection limit is 6 ng m⁻³ for a 30-min integration time. This compact instrument is fully automated and suited for routine deployment in field studies. The precision is sufficiently high for micrometeorological studies of air-surface exchange of ammonia.     

A comparison of measurements of atmospheric ammonia by filter packs,transition-flow reactors,simple and annular denuders and fourier transform infrared spectroscopy

Using data obtained during the 1985 Nitrogen Species Methods Comparison Study (1988,Atmospheric Environment22, 1517), several measurement methods for sampling ambient NH₃ are compared. Eight days of continuous measurements at Pomona College, a smog receptor site in Los Angeles, provided an extensive data base for comparing the following methods: Fourier transform i.r. spectroscopy (FTIR), three filter pack configurations, a simple and an annular denuder, and the transition flow reactor. FTIR was defined as the reference method and it reported hourly NH₃ concentrations ranging from > 60 to 2280 nmol m⁻³ (1.5−57ppb) during the course of the study, the highest values coming from the influence of nearby livestock operations.Although only limited quality assurance procedures were carried out, the following conclusions can, nevertheless, be drawn: most of the methods correlated highly with the FTIR method (correlation coefficientr > 0.96); generally, the linear regression slopes were close to unity and the intercepts were insignificantly different from zero at the 95% confidence level); relative to the FTIR average values, (1) for 4–6 h sampling periods, the averages of the three filter packs from three research groups were 83–130% and the annular denuder average was 87%, and (2) for 10–12 h sampling periods, the simple denuder averaged 90% and the two transition flow reactors were 77–98%. Possible reasons for the reported systematic biases are presented, but these are not able to fully explain the large range of differences reported by the various methods.     

碱消解-P&T-GC-AFS法同时测定土壤中的甲基汞和乙基汞研究

建立了碱消解-吹扫捕集-气相色谱-原子荧光光谱法(P&T-GC-AFS)同时测定土壤中甲基汞和乙基汞的分析方法.样品在90℃条件下经氢氧化钾/甲醇消解2.5 h,调节pH为5.40,并丙基化衍生后,采用P&T-GC-AFS法测定.方法对甲基汞、乙基汞的线性相关系数分别为0.999 7、0.999 6,检出限分别为0.26、0.41 ng·g -1.在不同质量浓度水平上进行加标回收率实验,甲基汞、乙基汞的回收率分别为90.5%~93.3%、86.5%~89.6%.该方法样品前处理简单、检出限低,适合批量测定土壤中甲基汞和乙基汞.     

全自动烷基汞分析仪测定水中烷基汞的方法研究

建立了全自动烷基汞分析仪测定水中的烷基汞(甲基汞,乙基汞)的方法.实验中衍生化反应所用的试剂为含有2.0 mol/L醋酸缓冲液,1%(g/v)NaBEt4(四乙基硼化钠)和1%(g/v)NaBPr4(四丙基硼化钠)的2%(g/v)氢氧化钾-水溶液,经衍生化的水样直接吹扫捕集后,进入气相色谱柱中分离并高温裂解,最后进入冷原子荧光检测器(CVAFS)中检测甲基汞和乙基汞的含量.甲基汞和乙基汞的方法检出限分别为0.002 ng/L和0.005 ng/L.     

碱消解-HPLC同时测定土壤中的无机汞和甲基汞

建立了碱消解-高效液相色谱(HPLC)同时测定土壤中无机汞和甲基汞的分析方法。试验研究了KOH/甲醇提取液浓度、消解时间以及反萃取剂Na2S2O3浓度对碱消解过程中甲基汞提取率的影响,当KOH/甲醇提取液浓度为25%、消解时间为12 min、Na2S2O3浓度为0.01 mol/L时,KOH/甲醇溶液对土壤甲基汞的提取率最高。提取出的无机汞和甲基汞,经衍生后HPLC法测定,流动相最佳选择为0.01 mol/LTBABr和0.025 mol/L NaCl的水溶液:甲醇=45:55(v:v)。在优化检测条件下,土壤样品中无机汞和甲基汞的检出限分别为1 ng/g和10 ng/g。该方法样品前处理简单、线性范围宽、精密度高、准确性好,适用于土壤中汞化合物的形态分析。     

A numerical simulation of kinetic constraint on evaporation of ammonium nitrate in diffusion denuder

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