济南市PM2.5化学组分及污染特征分析

为探讨济南市大气PM_(2.5)主要化学组分和污染特征,2017年在济南市开展了PM_(2.5)样品采集工作,分析了PM_(2.5)中有机碳(OC)、元素碳(EC)和水溶性离子浓度水平。结果表明:采样期间济南市PM_(2.5)中OC、EC年均质量浓度分别为9.10、2.68μg/m~3,全年OC与EC质量浓度的比值为3.4,二次有机碳污染严重;OC、EC季节分布特征明显,均为冬季浓度最高,且秋、冬季两者相关系数较高,表明秋季和冬季OC、EC来源较为一致。NO_3~-、SO_4~(2-)、NH_4~+年均质量浓度之和为34.29μg/m~3,占水溶性离子总量的88.9%,是济南市PM_(2.5)中最重要的组分;各水溶性离子浓度具有明显的季节变化特征,NO_3~-、SO_4~(2-)、NH_4~+、Cl~-和K~+均冬季浓度最高,而Ca~(2+)春季浓度最高;PM_(2.5)中NO_3~-与SO_4~(2-)质量浓度的比值为1.10,说明相比于固定污染源,移动污染源对济南市PM_(2.5)影响更大。     

天津市PM 2.5水溶性无机离子污染特征与来源分析

比较了天津市雾霾天和非雾霾天PM_(2.5)中水溶性无机离子(SO_4~(2-)、NO_3~-、Cl~-、NH_4~+、Ca~(2+)、Na~+、Mg~(2+)、K~+)的污染特征,并对其来源进行分析。结果表明:(1)非雾霾天PM_(2.5)日均质量浓度为35～60μg/m~3,均值为43μg/m~3,雾霾天PM_(2.5)日均质量浓度为120～332μg/m~3,均值为242μg/m~3;雾霾天水溶性无机离子浓度均高于非雾霾天。(2)非雾霾天SO_4~(2-)主要来自大气中燃煤源的SO_2二次转化,NO_3~-主要来自一次污染源,雾霾天SO_4~(2-)、NO_3~-主要来自大气中燃煤源的SO_2、NO_2二次转化;非雾霾天NH_4~+主要以(NH_4)_2SO_4和NH_4NO_3的形式存在,雾霾天NH_4~+主要以NH_4NO_3和NH_4HSO_4的形式存在;Na~+、K~+、Cl~-除了海盐来源外,煤和生物质的燃烧及其二次转化是主要贡献源;Ca~(2+)和Mg~(2+)主要来自建筑扬尘源和土壤扬尘源。(3)风速和相对湿度是雾霾天SO_4~(2-)、NO_3~-、NH_4~+浓度变化的重要原因。     

西宁取暖季PM2.5水溶性离子的污染特征研究

于2017年1—5月(取暖季)在西宁市区、郊区、农村设置采样点采集PM_(2.5)样品,利用离子色谱法测定PM_(2.5)中水溶性无机离子浓度。结果表明:取暖季西宁大气PM_(2.5)日均质量浓度为(55.98±52.66)μg/m~3,呈现明显的市区郊区农村的浓度变化特征。PM_(2.5)中水溶性离子质量浓度之和占PM_(2.5)质量浓度的36.3%,水溶性离子平均浓度大小为SO_4~(2-)NO_3~-NH_4~+Na~+Cl~-C_2O_4~(2-)Ca~(2+)F~-K~+Mg~(2+);取暖季西宁大气硫氧化率(SOR)和氮氧化率(NOR)平均值分别为0.21、0.13,表明SO_4~(2-)、NO_3~-主要由二次转化形成,PM_(2.5)中NO_3~-/SO_4~(2-)(质量浓度比)为0.75,阳离子与阴离子电荷摩尔数比值为0.89,表明燃煤是PM_(2.5)主要贡献源,颗粒物总体呈酸性。后向轨迹分析表明,重污染期间西宁PM_(2.5)及其中水溶性离子的浓度变化不仅受本地污染源的影响,也受外来气团输送的影响。     

西安市全年中PM_(2.5)水溶性无机离子变化特征

采用ICS-1100型离子色谱仪在2014年6月到2015年6月期间对西安市大气中PM_(2.5)水溶性离子(NO_3~-、NH_4~+、SO_4~(2-)、NO_2~-、Cl~-、Na~+、Ca~(2+)、Mg~(2+)、K+)进行的实时监测,分析了全年PM_(2.5)中水溶性无机离子变化特征。结果显示:采样期间,西安市PM_(2.5)中NO_3~-、NH_4~+、SO_4~(2-)和Cl~-年均值占总离子的89.49%,且有明显月变化趋势,峰值出现在11和12月份,月浓度均值较往年同期降低,最高达到30.26、15.19、11.43和16.60μg·m~(-3)。Na~+、Ca~(2+)、Mg~(2+)和K~+浓度变化趋势与主离子不完全一致。NO_3~-均值大于SO_4~(2-)均值,表明PM_(2.5)中水溶性离子的主要贡献者为移动源。NO_3~-小时均值高于SO_4~(2-)小时均值,且在10:00和20:00处形成2个峰值。PM_(2.5)中NO_3~-与NO_2~-在0.05水平上显著相关,SO_4~(2-)与Cl~-的在0.01水平上极显著相关。     

天津冬季PM_(2.5)中水溶性无机离子污染特征研究

2015年12月3—21日对天津冬季 PM2.5进行了采样分析,重点分析了 Na~+、Mg~(2+)、NH_4~+ 、Ca~(2+)、K~+、Cl~-、SO_4~(2-) 、NO_3~-8种水溶性无机离子,结合风速、相对湿度、温度等气象资料,并利用主成分分析对水溶性无机离子来源进行了解析。结果表明,风速小、气温高和相对湿度大的天气条件以及冬季燃煤的人为原因是引起霾天的重要原因。采样期间PM_(2.5)平均质量浓度为104.22μg/m~3。霾天中,轻微霾天、轻度霾天、中度霾天、重度霾天的PM_(2.5)中总离子平均质量浓度分别为27.63、26.89、105.03、143.92μg/m~3,远高于非霾天的15.43μg/m~3。SO_4~(2-)是水溶性无机离子中含量最高的离子,约占总离子的1/3,SO_4~(2-)、NO_3~-、Cl~-和NH_4~+浓度之和占总离子的90%以上。随着霾程度加重,NH_4NO_3占比增加,(NH_4)_2SO_4占比减少。水溶性无机离子主要来源于海盐粒子、生物质燃烧、机动车尾气排放和燃煤等。     

北京西山典型游憩林内PM_(2.5)质量浓度及水溶性离子特征分析

以北京西山森林公园为观测点,运用双通道颗粒物在线监测设备监测PM_(2.5)质量浓度,使用离子色谱仪测定样品中水溶性离子浓度,对北京西山油松林PM_(2.5)质量浓度及水溶性离子特征进行分析。结果表明:PM_(2.5)质量浓度为冬季(121.29±16.78)μg·m~(-3)春季(106.06±12.68)μg·m~(-3)秋季(88.01±17.44)μg·m~(-3)夏季(72.67±12.18)pg·m~(-3);SO-4~(2-)、Na~+、N0_3~-、HC0O~-是PM_(2.5)中最主要的水溶性离子成分,占所测水溶性离子浓度在四季分别为94.99%、72.66%,72.66%、89.52%,PM_(2.5)受SO_4~(2-)、Na~+、N0_3~_、NH_4~+影响较大基本呈正相关关系,SO_4~(2-)、Na~+、N0_3~-、NH_4~+、PM_(2.5)浓度季节变化一致,即在冬季最高,夏季最低春秋次之,且水溶性离子季节差异显著。SO_4~(2-)和N0_3~-、Na~+、NH_4~+的相关性极显著(r=0.85、0.80、0.92),NO_3~-和Na~+、NH_4~+之间关系也较大(r=0.87,0.66),Ca~(2+)和Mg~(2+)相关性极明显(r=0.98),其他水溶性离子间无明显的相关性,固定源和海洋源对水溶性离子贡献程度呈现出季节差异,秋季机动车尾气排放对空气硫和氮污染贡献达最高,春季最低,夏秋季海洋源对Cl~-影响明显。通过对森林植被区PM_(2.5)、水溶性离子特征及关系进行分析,更好地发挥植被的生态效益,提高空气质量。     

重庆城区PM_(2.5)化学组分特征及季节变化

2014年7月—2015年5月典型季节期间在重庆城区选择典型站点开展PM_(2.5)样品采集,并测量质量浓度,分析样品中水溶性离子、无机元素、OC和EC等组分,在此基础上对组分化学组成进行了质量重构。结果表明:观测期间PM_(2.5)年均值为76.4μg·m~(-3),浓度季节变化为冬季秋季春季夏季;组分方面,以二次转化为主的SO_4~(2-)、NH_4~+、NO_3~-和OC是PM_(2.5)组分中最主要成分,OC/EC比值4个季度均大于2,表明城区二次有机碳生成显著;硫氧化率(SOR)分析,气态污染物SO_2的二次转化效率较高,大气存在明显的二次转化过程。PM_(2.5)质量重构后主要组成为有机气溶胶(OM)、二次无机离子(SNA)和矿物尘,重庆城区应协同控制一次排放的颗粒物和气态污染物SO_2和NO_x,从而控制二次组分浓度。     

邯郸市PM_(2.5)及其化学组分的季节性变化

利用2013年邯郸市4个大气环境监测站连续1年的在线监测数据,并结合离线采样成分数据,对比分析了不同季节大气中PM_(2.5)及其主要成分的浓度水平和污染特征。结果表明,PM_(2.5)和PM10四季均存在不同程度的超标现象;污染物在4个站点之间的空间差异不太显著,邯郸市的污染为区域性污染。PM_(2.5)中水溶性无机离子和碳组分的季节变化均较为明显。SO_4~(2-)、NO_3~-和NH_4~+三者浓度之和占PM_(2.5)浓度的39.8%,占PM_(2.5)中总水溶性无机离子浓度的86.2%;四季均存在较强的光化学反应,但硫氧化率(SOR)和氮氧化率(NOR)呈现出不同的季节变化规律,与SO2-4和NO_3~-的来源和去除机制明显不同有关。秋、冬季有机碳(OC)和元素碳(EC)污染较为严重,总碳气溶胶(TCA)浓度分别占PM_(2.5)质量浓度的24.0%和32.9%;研究显示高浓度的OC较多来源于二次有机碳(SOC),高浓度碳易发生二次污染。进一步对PM_(2.5)中各组分进行来源分析得出燃煤、汽油车尾气、生物质燃烧、二次气溶胶和扬尘源对邯郸市PM_(2.5)贡献显著。     

长春春季PM_(2.5)及其水溶性离子特征分析

于2014年春季在长春采集大气PM_(2.5)样品,对PM_(2.5)及其水溶性离子特征进行了分析。结果表明,2014年长春春季PM_(2.5)质量浓度为34.9~237.5μg/m3,平均质量浓度为125.6μg/m3。9种水溶性离子的总质量浓度为24.3~71.2μg/m~3,平均质量浓度为39.8μg/m~3,平均浓度大小表现为SO_4~(2-)Ca~(2+)Cl~-NH_4~+NO_3~-Na~+K~+Mg~(2+)F~-。后向轨迹表明,长春春季PM_(2.5)污染主要来源于内蒙古西北方向和长春东南部渤海、黄海地区。     

一次强沙尘过程影响下的银川市大气污染物浓度及PM_(2.5)化学组成变化特征

2014年4月22—29日在中国西北地区发生强沙尘天气期间,对银川市大气污染物(PM_(10)、PM_(2.5)、SO_2、NO_2、O_3)进行了监测,并重点分析了PM_(2.5)的化学组成变化特征。结果表明,沙尘天气发生前,PM_(10)、PM_(2.5)、SO_2和NO_2平均小时质量浓度分别为99.33、36.89、25.84、47.21μg/m~3;沙尘天气发生时,PM_(10)、PM_(2.5)、SO_2和NO_2平均小时质量浓度分别为1 121.43、209.19、6.13、18.42μg/m~3:说明此次沙尘传输经过地区大气较为清洁,随沙尘气溶胶传输的NO_2和SO_2较少。沙尘气溶胶由于带有大量的Ca~(2+)、Mg~(2+),使得PM_(2.5)碱性增强,PM_(2.5)中的硫酸盐和硝酸盐存在形式主要为NH_4HSO_4和NH_4NO_3。沙尘气溶胶除了对PM_(2.5)中来源于自然源的无机元素浓度有显著提升外,对于水溶性离子、碳成分等直接或间接来源于人为源的组分浓度也有较大的提升。Ti、Fe、Al、Ca、Si、Sr、Mg、Na、K、Ba、P可以认为基本来源于沙尘矿物粒子。此外,沙尘气溶胶还能促进大气SO_2、NO_2向二次硫酸盐、硝酸盐转化,尤其是硫酸盐。     

Pesticides in rainfall in Europe

Papers and published reports investigating the presence of pesticides in rainfall in Europe were reviewed. Approximately half of the compounds that were analysed for were detected. For those detected, most concentrations were below about 100 ng/l, but larger concentrations, up to a few thousand nanograms per litre, were detected occasionally at most monitoring sites. The most frequently detected compounds were lindane (gamma-HCH) and its isomer (alpha-HCH), which were detected on 90-100% of sampling occasions at most of the sites where they were monitored. For compounds developed more recently, detection was usually limited to the spraying season. A classification of pesticides according to their deposition pattern is proposed.     

Differences in Cu content in selected mushroom species growing in the same unpolluted areas in Poland

The aim of the study was to estimate copper (Cu) accumulation efficiency in whole-fruiting bodies of 18 edible and non-edible wild growing mushrooms collected from 27 places in the Wielkopolska Voivodeship. Mushrooms were collected each time from the same places to estimate the diversity in Cu accumulation between tested mushroom species within 3 consecutive years of study (2011–2013). The study results revealed various accumulation of Cu in the whole-tested mushroom fruiting bodies. The highest mean accumulation of Cu was observed in Macrolepiota procera (119.4 ± 20.0 mg kg^?1 dm), while the lowest was in Suillus luteus and Russula fellea fruiting bodies (16.1 ± 3.0 and 18.8 ± 4.6 mg kg^?1 dm, respectively). Significant differences in Cu accumulation between mushroom species collected in 2011 and in the two following years (2012 and 2013) were observed. The results indicated that sporadic consumption of these mushrooms was not related to excessive intake of Cu for the human body (no toxic influence on health).     

Lead poisoning in swans in Japan

We investigated the occurrence, source and exposure time of lead poisoning in whooper swans (Cygnus cygnus cygnus) and Bewick's swans (Cygnus columbianus bewickii) in Japan during the winters of 1984-1987. Concentrations of lead in various tissues and physiological evidence of lead shot in some birds indicated that lead shotgun pellets were the source of lead, and exposure occurred after the birds arrived in Japan. Mortality probably occurred within 30 days after exposure to, and retention of, lead shot in the gizzard.     

Large-scale spatial variation in mercury concentrations in cattle in NW Spain

Mercury (Hg) is a highly toxic environmental contaminant and man-made emissions account for between a quarter and a third of total atmospheric levels. Point discharges, particularly coal-burning power stations, are major sources of atmospheric Hg and can result in marked spatial variation in mercury deposition and subsequent uptake by biota. The aims of this study were to quantify the extent to which major point and diffuse sources of atmospheric Hg emissions affected accumulation of Hg by biota throughout Galicia and Asturias, two of the major regions in northwest Spain. We did this by relating renal Hg concentrations in locally reared cattle (n=284) to the proximity of animals to point and diffuse sources of Hg emissions. Mercury residues in calf kidneys ranged between non-detected and 89.4 g/kg wet weight. Point discharges from coal-fired power plants in Galicia had the most dominant impact on Hg accumulation by calves in Galicia, affecting animals throughout the region and explaining some two-thirds of the variation in renal residues between animals located directly downwind from the plants. The effects of more diffuse emission sources on Hg accumulation in calves were not distinguishable in Galicia but were detected in cattle from neighbouring Asturias. The impact of both point and diffuse sources in elevating environmental levels of bioavailable Hg and subsequent accumulation by cattle extended to approximately 140-200 km downwind from source.     

Mercury in fish in Swedish lakes

The aim of this work has been to try to obtain a picture of the past, present and future mercury situation in fish in Swedish lakes, to make an estimate of the number of lakes threatened by 'blacklisting', and to see if the data can be used to reveal anything about the impact of liming on the Hg content in pike. The register contains a broad set of data from 1456 lakes. The main results are as follows. Trend analyses indicate that the Hg content in 1-kg pike seems to increase with time. This is interesting since there has been a significant decrease in mercury emissions from Swedish industries during the last two decades. High Hg contents in 1-kg pike appear in a very characteristic pattern, linked to specific sources of Hg emission. The data indicate that old Swedish 'sins' are still causing a lot of problems. The factors governing the leakage of Hg from soils to water ought to be a very important topic for further studies. The Hg content in pike shows the highest correlation with the following parameters: Hg in surficial sediments, pH, distance from point source and water hardness, lake water alkalinity and conductivity, water retention time, size of drainage area and lake surface. A formula which provides the best possible degree of explanation (r2 = 0.78) has been derived. At present there are about 250 lakes 'blacklisted' in Sweden due to high Hg content in fish. Our data show that there are at least 9400 lakes that ought to be 'blacklisted' today. A successful liming operation will alter the chemical conditions in lakes and also decrease the Hg content in fish.     

Trends in summer sulphate in Europe

A trend analysis of the sulphate concentration in Europe in the summer half-year was performed. Data from various measuring networks were analysed, but only stations with quality assured sampling methods and a record of more than 10 years were included in the study. 1978 served as the reference year for the trend, because in that year most stations started operation. The relatively dense network in Belgium provided the most valuable data, as evidenced by the fact that two sites at a distance of only 10 km apart correlated better than 95% over a month. The two sites also show a correlation of better than 90% over a season with two other stations at distances of 45 and 95 km. The relative decrease in summer-sulphate at the four stations in Belgium, as analysed by linear regression, was 3.3% per year which corresponds to an absolute decrease of 0.42 μgm⁻³ per year. In the Netherlands the average yearly decrease in summer-sulphate at two stations was 3.5% (−0.34 μgm⁻³). In other countries stations were further apart or only a single site wits in use, which limits the representativeness of the data. In northwestern Germany, a region with several monitoring stations, a yearly averaged decrease of 3.0% occurred. The lower absolute decrease (0.25 μgm⁻³) per year compared to that in the two neighbouring countries reflects the lower summer-time sulphate concentrations. In the remainder of Germany the average decrease was 1.6%. In South-Scandinavia the yearly relative decrease at two sites was 2.6% (0.13 μgm⁻³ absolute). There was no significant trend in the U.K. Al the Polish station the levels increased, it decreased at the Hungarian and Austrian station and remained constant at the Czechoslovakian site. Reasons for omission of the data from France from the trend analysis are discussed.     

Pesticide levels in surface waters in an agricultural-forestry basin in Southern Chile

Residues of five pesticides in surface water were surveyed during 2001 and 2003 in the Traiguen river basin in Southern Chile. Simazine, hexazinone, 2,4-D, picloram herbicides and carbendazim fungicide were selected through a pesticide risk classification index. Six sampling stations along the river were set up based on agricultural and forestry land use. The water sampling was carried out before and after the pesticide application periods and in correspondence to some rain events. Pesticides were analyzed by HPLC with DAD detection in a multiresidue analysis. During 2001, in the first sampling campaign (March), the highest concentrations of pesticides were 3.0 microg l(-1) for simazine and hexazinone and 1.8 microg l(-1) for carbendazim. In the second sampling (September), the highest concentration were 9.7 microg l(-1) for 2,4-D, 0.3 microg l(-1) for picloram and 0.4 microg l(-1) for carbendazim. In the last sampling period (December), samples indicated contamination with carbendazim fungicide at levels of up to 1.2 microg l(-1). In sampling carried out on May 2003, no pesticides were detected. In October 2003, the highest concentrations of pesticides were 4.5 microg l(-1) for carbendazim and 2.9 microg l(-1) for 2,4-D. Data are discussed in function of land use and application periods of the products, showing a clear seasonal pattern pollution in the Traiguen river. Risk assessment for these pesticides was calculated by using a risk quotient (RQ = PNEC/PEC). For picloram the calculated RQ < was 0, which indicates that no adverse effects may occur due to the exposure to this herbicide in the Traiguen river basin. For 2,4-D, simazine, hexazinone, carbendazim RQ > 1, meaning that adverse effects could occur and it is necessary to reduce pesticide exposure in surface waters. It is recommended to continue with a pesticide monitoring program and the implementation of ecotoxicological testing with local and standardized species in order to consider the probability of effects occurrence, with less uncertainty. Thus, it will be more feasible to make some recommendations to regulatory agencies regarding the pesticide use.     

Heavy metal contamination in bats in Britain

Toxic metals are bioaccumulated by insectivorous mammals but few studies (none from Britain) have quantified residues in bats. We measured renal mercury (Hg), lead (Pb) and cadmium (Cd) concentrations in bats from south-west England to determine how they varied with species, sex, age, and over time, and if they were likely to cause adverse effects. Residues were generally highest in whiskered bats (Myotis mystacinus). Compared with other species, pipistrelle (Pipistrellus spp) and Natterer's bats (Myotis nattereri) had significantly lower kidney Hg and Pb concentrations, respectively. Renal Hg increased over time in pipistrelles but the contributory sources are unknown. Kidney Pb did not decrease over time despite concurrent declines in atmospheric Pb. Overall, median renal metal concentrations were similar to those in bats from mainland Europe and 6- to 10-fold below those associated with clinical effect, although 5% of pipistrelles had kidney Pb residues diagnostic of acute lead poisoning.     

大气中二（口/恶）（口/英）研究进展

二（口/恶）（口/英）是世界公认的强致癌物质,对人体健康危害极大.近年来,大气中二（口/恶）（口/英）的研究已成为各国环境化学家研究的热点.本文总结了近年来国际上有关大气中二（口/恶）（口/英）研究的进展情况,以及所取得的主要研究成果,并在此基础上指出了我国目前研究中存在的问题及以后所应开展的工作.