主动采样技术在中国大气POPs监测中的应用

为了履行斯德哥尔摩公约,查明持久性有机污染物(POPs)在中国大气环境介质的存在水平,该研究首次采用主动采样技术,在中国境内大尺度范围内进行了环境大气中POPs的监测工作.利用主动采样技术,可以在短时间内采集数百立方米的大气样品.分别利用玻璃纤维滤膜采集大气颗粒物(固相)中的POPs,同时使用聚氨酯泡沫(PUF)吸附气态的POPs.该采样技术还便于样品的运输和保存.研究表明,大气主动采样技术可以很好地运用于区域大气POPs的监测工作并填补了我国在POPs履约监测中专用仪器设备的空白.     

多泥沙水体中六六六(HCH)残留SPE提取方法的优化

多泥沙河流中六六六(HCH)的提取一直是分析化学领域的难点之一。选定固相萃取法(SPE)作为样品的提取方法,并以α-HCH、β-HCH、γ-HCH、δ-HCH为标准溶液,对提取方法进行了优化,确定了适应于多泥沙水体中六六六农药残留的SPE提取流程。该流程适用于地表水和地下水、工业废水等含泥沙或不含泥沙的水体中六六六农药残留的提取,且有很强的适应性和可重复性。     

燃煤电厂煤中汞含量对烟气中汞排放水平的影响

对江苏省9家燃煤电厂入炉煤中ω（汞）及烟气中ρ（汞）进行了测试，结果表明，9家燃煤电厂入炉煤中ω（汞）为54．5～297 ng／g，平均值为139 ng／g，低于我国煤中ω（汞）的平均值（220 ng／g）。燃煤电厂排放烟气中ρ（汞）为0．08～16．97μg／m^3，远低于《火电厂大气污染物排放标准》（GB 13223－2011）汞及其化合物标准限值（30μg／m^3）。通过对燃煤电厂入炉煤中ω（汞）与最终排放的烟气中ρ（汞）进行分析，两者之间有一定的相关性。     

2 ,4-二硝基苯肼固相吸附/高效液相色谱法测定车内空气中醛酮类物质

建立了2，4-二硝基苯肼固相吸附／高效液相色谱同时测定车内空气中4种醛酮类物质的方法，研究了固相吸附采样和前处理方法，优化了试验条件。4种醛酮类物质在一定质量范围内工作曲线线性良好，甲醛、乙醛、丙烯醛、丙酮的检出限分别为0．075μg／m^3、0．207μg／m^3、0．715μg／m^3、0．159μg／m^3（按采样体积12L计），实际样品测定的RSD为7.5％-9．7％。     

气相色谱法测定赤水河中段水体中14种有机氯农药的残留

建立了用正己烷萃取,气相色谱—电子捕获（GC—ECD）测定水体中有机氯农药痕量残留的方法。结果表明：六氯苯、α-HCH、β-HCH、γ-HCH、δ-HCH、p,p′-DDD、p,p′-DDE、p,p′-DDT、艾氏剂、狄氏剂、异狄氏剂、七氯、环氧七氯、o,p′-DDT 14种农药在14 min内有较好的分离;2个不同浓...     

焦炉工人PAHs空气日均暴露浓度分析

用个体采样器对100名受试者进行了可吸入颗粒物和气态样品的24h跟踪采集，并通过梯度洗脱一反相HPLC／可编程序荧光检测法定量分析了样品中14种多环芳烃。结果表明，不同受试人员多环芳烃空气日均暴露浓度存在很大差异，其中焦炉工人受多环芳烃中BaP空气日均暴露浓度为0．5μg／m^3～1．7μg／m^3，炼纲厂工作人员和清洁区办公人员的BaP空气日均暴露浓度分别为0．02μg／m^3和0．01μg／m^3。不同受试人员多环芳烃空气日均暴露在PM10及气相中的分配比例也略有不同，焦炉工人的BaP空气日均暴露浓度有近99％来自PM10，一般人群为93％左右。指出2环、3环多环芳烃主要以气态形式存在，4环至6环多环芳烃主要分布在PM10中。     

乌鲁木齐市大气PM2.5中重金属元素含量和富集特征

利用PM2.5／PM10便携式采样器采集了乌鲁木齐市5个功能区PM2.5，样品，用TAS-990石墨炉原子吸收光谱仪检测了PM2.5样品中Cd、Cu、Ni、Pb、Mn的含量。结果表明，乌鲁木齐大气PM2.5质量浓度变化趋势是冬季采暖盛期〉秋季采暖初期〉春季停暖初期〉夏季停暖期。参照《环境空气质量标准》（GB3095—2012）中的二级标准，采样期间卡子湾水泥厂区样品全部超标，其余4个采样点样品在冬季采暖盛期也全部超标，部分样品在非采暖期超标。富集因子法分析表明，乌鲁木齐市5个采样区PM2.5样品中Ni、Cu、Cd、Pb污染主要来自于人类活动，Mn则来源于地壳物质。     

南京市冬季大气颗粒态汞的分布特征

采集了南京市2012年冬季4个功能区的PM2．5、PM10、TSP样品，对不同粒径大气颗粒物中的颗粒态汞测试。结果表明，南京冬季大气颗粒物TSP中汞的质量浓度为49．26 pg/m3～257．14 pg/m3，平均质量浓度为161．27 pg/m3；PM10中汞的质量浓度为44．82 pg/m3～228．29 pg/m3，平均质量浓度为147．38 pg/m3；PM2．5中汞的质量浓度为35．98 pg/m3～178．58 pg/m3，平均质量浓度为104．10 pg/m3。不同功能区大气颗粒态汞质量浓度的分布趋势为：交通综合区＞旅游区＞住宿综合区＞商业区。大气颗粒态汞60％以上存在于可吸入肺的PM2．5中，细颗粒物富集汞的能力比粗颗粒物强。     

汞沉积物样品的采集方法与结果

1　汞沉积物样品的采集方法与结果1 1　采样方法使用ＭＩＣ(Ｔｈｏｒｎｈｉｌｌ,加拿大安大略 ,聚四氟乙烯涂覆的漏斗 ,面积 =0 2 1ｍ2 )和ＡｅｒｏｃｈｅｍＭｅｔｒｉｃｓ(迈阿密 ,ＦＬ ,面积 =0 0 70ｍ2 )湿沉淀采样器采集汞沉积物 ,采样器中的样品每周同时采集 ,利用Ｂｅｌｆｏｒｔ记录表对沉淀物厚度读数依次列表。按监测地点 ,由明尼苏达污染控制机构 (ＭＰＣＡ)或国家大气沉淀计划 (ＮＡＤＰ ,2 3 )组织负责实施主要离子与沉淀物厚度的测量。1 990年 1月 3日～ 1 992年 9月 1 5日采集的汞样盛装于 2Ｌ聚四氟乙烯瓶中 ,1 992年 9月 …     

广州市空气可吸入性颗粒物的污染水平

报告了中美合作“广州市大气污染对儿童肺功能影响研究”课题可吸入性颗粒物的两年监测结果。用安德森双道采样器、Ｔｅｆｌｏｎ膜采集细颗粒物（＜２５μｍ,ＰＭ２５）和粗颗粒物（２５≤＜１０μｍ,ＰＭ２５１０）,两者之和为ＰＭ１０,每季度采１５天,每天采一个２４小时样品。结果表明,广州市城区大气可吸入性颗粒物的污染相当严重,尤其是细颗粒物（ＰＭ２５）的污染,应引起公众和政府有关部门的重视。     

Occupational and indoor air exposure to persistent organic pollutants: a review of passive sampling techniques and needs

Exposure to persistent organic pollutants (POPs) and related compounds such as PCBs, brominated flame retardants, organochlorine pesticides and PAHs is regarded as an important environmental risk factor for humans. Recently concerns about POPs resulted in the international protocol called the Stockholm Convention on POPs. Air quality standards (indoor, outdoor and occupational) for PAHs and other POPs will also be applied in the EU in the future. This will bring requirements for monitoring, to check for compliance and to reduce human exposures to POPs. This can occur from point sources and in various microenvironments, indoors, outdoors and in workplaces. Monitoring can be undertaken either by an active (pumped) method or using a passive (diffusive) air sampling (PAS) device. To date, PAS for POPs have mainly been used as integrating (long-term) samplers for ambient (outdoor) air. However, there are several reasons to develop PAS for monitoring of POPs in occupational and indoor environments. We discuss the potential advantages, limitations and developments needed, so that PAS can be used reliably and routinely indoors and in occupational settings for POPs.     

Hydrology-linked spatial distribution of pesticides in a fjord system in Greenland

A pilot study is presented evaluating selected chlorinated pesticides as chemical tracers for water masses in a sub-Arctic fjord system (Godth?bsfjord, western Greenland). Polyoxymethylene (POM) based passive water samplers were deployed during summer-autumn 2010. The levels of the analysed chlorinated pesticides in the fjord surface waters were found to be low compared to earlier studies. α-Hexachlorocyclohexane (α-HCH) and hexachlorobenzene (HCB) were the predominant contaminants. However, these two compounds have higher levels in oceanic water compared to freshwater influenced fjord waters. These chemicals can thus be considered as indicators for direct atmospheric long-range transport, while the organochlorine pesticides like trans-, cis-chlordane, trans-nonachlor and oxychlordane that are detected in the inner parts of the fjord are indicators for potential freshwater sources such as rivers and glacial meltwater runoff (secondary sources). The average values were 50 pg L(-1) for HCB and 11 pg L(-1) for α-HCH. These concentrations are comparable to levels in fjords in Svalbard (Norwegian Arctic), but lower than in open and/or ice covered oceans in the Canadian Arctic. Two air samplers were deployed for the identification of direct atmospheric contributions. Local contamination sources do not contribute significantly. The study demonstrated the value of passive water sampling devices for comprehensive hydrological characterization of Arctic coastal waters.     

太湖湖泛现象的卫星遥感监测

2010年8月20日太湖地区Landsat ETM影像显示,太湖西部沿岸带存在湖泛黑水团现象,对该景遥感影像进行了大气校正,提取了湖泛样区、其他水体样区的ETM各波段光谱反射率数据统计特征。结果表明,湖泛样区在可见光波长的ETM波段1、2、3具有很低的反射率,水色暗黑,与人眼观察一致,而在反射红外波长的ETM波段4则有比波段3高的反射率,差异植被指数DVI>0,其原因为湖泛黑水团中,虽然大量蓝藻死亡分解,然而水中还残留有一定数量的活体蓝藻,残余叶绿素及细胞造成了虽然较弱、但仍较为稳定的反射红外波长处的光谱反射能力。提出了识别湖泛现象的遥感判据为ρ0.485<0.05 andρ0.56<0.08 andρ0.66<0.065 and(ρ0.83-ρ0.66)>0 andρ0.83<0.1。     

室内空气中的气态多环芳烃的被动采样监测

利用自制被动采样装置,在2011年秋冬季对南京市部分地区室内空气中5种气态多环芳烃(PAHs)(萘、苊烯、苊、芴、菲)进行了为期100d的连续采样检测,被动采样器的采样速率为0.012m3/d,5种PAHs的回收率在63%～105%之间,方法检出限在1.1～2.4ng范围内。结果表明,南京市5处不同室内环境空气中萘的浓度最高,占总量的90%以上。室内环境空气中5种PAHs的总浓度为230～1564ng/m3。住宅内人体对5种PAHs的暴露速率为479～560ng/h。     

Measurement of environmental pollutants using passive sampling devices--a commentary on the current state of the art

Passive sampling devices have been used since the 1970s to measure time-weighted average (TWA) or equilibrium concentrations of pollutants in various environmental matrices (e.g. air, soils and sediments and water). In recent years the popularity of using such samplers has increased and the technology in now well established for the measurement of atmospheric pollutants. This sector has a long experience of using passive samplers in the short- and long-term assessment of air quality in the local environment and on a global scale (e.g. within the United Nations Stockholm Convention on the trans-boundary movement of persistent organic pollutants (POPs) where large networks of samplers on a continental scale have been established). In comparison, the use of passive samplers for monitoring the aquatic environment has been slower to take off. There has, however, been a recent research drive to develop devices for measuring the wide range of pollutants that can be found in environmental waters (e.g. ground, surface, and marine). It is now being recognised that passive samplers can play a valuable role in monitoring water quality within a legislative framework such as the European Union's Water Framework Directive (WFD). The data from these devices can be used alongside the results obtained from conventional spot or bottle sampling to improve risk assessments and to inform decisions on undertaking potentially expensive remedial actions. Such monitoring techniques may have uses within the European Registration, Evaluation, Authorisation & restriction of CHemicals (REACH) Directive and the forthcoming European Marine Strategy Directive. It is expected that the aquatic monitoring sector will follow a transition similar to that which occurred in air monitoring where data obtained from passive samplers can use used within a legal framework. There has also been increased interest in extending the role of passive samplers to both the measurement of equilibrium concentrations and investigating the movement and release of the dissolved fraction of various pollutants in the pore water of sediments and soils.     

PUF大气被动采样技术对POPs的采样计算

随着《斯德哥尔摩公约》的实施,大气中持久性有机污染物(POPs)的大气被动采样(PAS)观测技术得到了快速发展,相比于传统大气主动采样技术,PAS技术具有明显的优势。以应用最为广泛的聚氨酯软性泡沫材料大气被动采样(PUF-PAS)为例,重点阐述和讨论了3种通过大气被动采样技术来计算污染物在空气中的浓度的方法,并对其采样原理和发展趋势进行了简要介绍。     

南京大气细颗粒中有机碳与元素碳污染特征

为了解南京城区大气细颗粒物中有机碳与元素碳的污染特征,在国控点草场门进行了连续一年的PM2.5采样,分析了有机碳(OC)、元素碳(EC)、ρ(OC)/ρ(EC)污染特征和变化规律。结果表明,采样期间有些PM2.5的日均值超过了《环境空气质量标准》(GB 3095-2012)二级标准,ρ(OC)/ρ(EC)为0.77～4.98,平均值为1.92。PM2.5样品中OC约占18%、EC约占9%。     

Spatial mapping of city-wide PBDE levels using an exponential decay model

Passive air samplers (PAS) consisting of polyurethane foam (PUF) disks were deployed at 6 outdoor air monitoring stations in different land use categories (commercial, industrial, residential and semi-rural) to assess the spatial distribution of polybrominated diphenyl ethers (PBDEs) in the Brisbane airshed. Air monitoring sites covered an area of ~1143 km(2) and PAS were allowed to accumulate PBDEs in the city's airshed over three consecutive seasons commencing in the winter of 2008. The average sum of five (∑(5)) PBDEs (BDEs 28, 47, 99, 100 and 209) levels were highest at the commercial and industrial sites (12.7 ± 5.2 ng PUF(-1)), which were relatively close to the city center and were a factor of 8 times higher than residential and semi-rural sites located in outer Brisbane. To estimate the magnitude of the urban 'plume' an empirical exponential decay model was used to fit PAS data vs. distance from the CBD, with the best correlation observed when the particulate bound BDE-209 was not included (∑(5)-209) (r(2) = 0.99), rather than ∑(5) (r(2) = 0.84). At 95% confidence intervals the model predicts that regardless of site characterization, ∑(5)-209 concentrations in a PAS sample taken between 4-10 km from the city centre would be half that from a sample taken from the city centre and reach a baseline or plateau (0.6 to 1.3 ng PUF(-1)), approximately 30 km from the CBD. The observed exponential decay in ∑(5)-209 levels over distance corresponded with Brisbane's decreasing population density (persons/km(2)) from the city center. The residual error associated with the model increased significantly when including BDE-209 levels, primarily due to the highest level (11.4 ± 1.8 ng PUF(-1)) being consistently detected at the industrial site, indicating a potential primary source at this site. Active air samples collected alongside the PAS at the industrial air monitoring site (B) indicated BDE-209 dominated congener composition and was entirely associated with the particulate phase. This study demonstrates that PAS are effective tools for monitoring citywide regional differences however, interpretation of spatial trends for POPs which are predominantly associated with the particulate phase such as BDE-209, may be restricted to identifying 'hotspots' rather than broad spatial trends.     

Long-range atmospheric transport of persistent organochlorinated compounds from south and mainland south-eastern Asia to a remote mountain site in south-western China

A range of organochlorinated compounds have been consumed in China, India and the countries of mainland southeast Asia (MSA). Considering their persistence in the environment and ability in long-range atmospheric transport (LRAT), the potential outflow of these compounds from this region is therefore of great concern in the context of the global distribution of toxic chemicals. As part of a monitoring campaign aimed at investigating the LRAT of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) from southern China, MSA and northern India, atmospheric levels of OCPs and PCBs were measured once a week from October 2005 through December 2006 at Tengchong Mountain (TM), a remote site located in south-western China. The average concentrations of OCPs were found to be higher than those in other remote stations in the Arctic and the Tibetan plateau, except for α-hexachlorocyclohexane (α-HCH). A high level of β-HCH and low α-HCH/β-HCH ratio was attributed to an accidental release of β-HCH from unknown sources, besides obvious evidence of lindane (γ-HCH) and technical HCH usage. Temporal variations of chlordanes and endosulfan were related to the usage pattern of these compounds, as well as LRAT. In contrast, dichlorodiphenyltrichloroethane (DDT) exhibited a relatively minor seasonal variation. The OCP levels at the monitoring site were found to be related to the air parcel back trajectories on the basis of four distinct clusters. Elevated levels of HCHs and DDTs were observed when air parcels originated from northern India where considerable OCP usage was reported recently, while high levels of γ-HCH and TC (trans-chlordane) were mainly associated with air masses from southern China and northern MSA. The study highlighted the high background level of OCPs as well as their temporal patterns of trans-boundary LRAT in the MSA region.     

Residue levels of hexachlorocyclohexane and dichlorodiphenyltrichloroethane in human milk collected from Beijing

Forty-eight human breast milk samples were collected from mothers in Beijing. The hexachlorocyclohexane (HCH) and dichlorodiphenyltrichloroethane (DDT) (including α-HCH, β-HCH, γ-HCH, δ-HCH, p,p′-DDE, p,p′-DDD, o,p′-DDT, and p,p′-DDT) contents of the samples were determined by gas chromatography/electron capture detection and gas chromatography/mass spectrometry. α-HCH, β-HCH, γ-HCH, p,p′-DDE, p,p′-DDD, and p,p′-DDT were detected at rates of 20, 100, 10, 100, 10, and 22 %, respectively. The average residue levels in the samples were 174.6 ng/g fat for β-HCH, 333.8 ng/g fat for p,p′-DDE, 6.57 ng/g fat for α-HCH, 7.67 ng/g fat for γ-HCH, 4.18 ng/g fat for p,p′-DDD, and 11.4 ng/g fat for p,p′-DDT. The results showed that the infants’ daily intake levels of HCH and DDT were 0.95 and 1.76 μg/kg body weight/day, respectively. Our result suggested that the total residue level of these organochlorine pesticides in breast milk from Beijing decreased and was lower than that from other coastal and heavy industrial cities in China. On the other hand, the levels of HCH and DDT were higher than those from some developed countries, but lower than those from other developing countries such as India.