焦作市冬季PM2.5中水溶性离子组成特征及来源解析

为探讨焦作市冬季PM_(2.5)中水溶性离子特征及其来源,于2017年12月至2018年2月在焦作市区连续采集大气颗粒物PM_(2.5)样品,测定其中9种水溶性离子浓度。结果表明,焦作市冬季PM_(2.5)质量浓度为(99.11±73.26)μg/m~3,总水溶性离子质量浓度为(66.88±48.68)μg/m~3,其中NO_3~-、SO_4~(2-)、NH4_+是水溶性离子的主要成分,3者合计占总水溶性离子的81.5%(质量分数)。与清洁天相比,污染天NO_3~-、SO_4~(2-)、NH_4~+在PM_(2.5)中的占比显著增加,表明人为活动排放的二次污染物是焦作市冬季污染天PM_(2.5)的主要贡献成分;随着相对湿度的增加,大气中存在明显的气溶胶二次转化过程;焦作市大气PM_(2.5)移动源贡献大于固定源。焦作市PM_(2.5)中水溶性离子在清洁天主要受工业和生物质燃烧影响,而在污染天主要受气态污染物二次转化影响;后向轨迹聚类显示,采样期间焦作市主要受京津冀地区、西北地区气团影响。     

冬季关中城市及农村颗粒物的污染特征

为比较冬季城市和农村大气颗粒物浓度及化学组分等特征,本文分别采集分析了西安市区、安康农村冬季大气PM2.5颗粒物与PM0.1颗粒物。分析结果表明:两地大气中PM2.5日均浓度均超过国家二级标准(75μg·m~(-3)),空气质量不容乐观;其中农村样品中PM0.1颗粒物约占PM2.5颗粒物浓度的36.8%左右;所有颗粒物中有机碳远高于无机碳组分,而市区大气颗粒物中多环芳烃浓度显著高于农村浓度,说明城市空气中来源于机动车尾气的污染较为严重;从颗粒物粒径分布特征来看,粒径为0.300~0.374μm颗粒物具有最高数浓度和比表面积浓度,粒径为0.374~0.465μm的颗粒物具有最高质量浓度;由于农村污染源较为单一,安康样品颗粒物浓度受燃煤和油烟的影响较大。此外,由于受燃煤机动车排放影响,西安大气中PM0.1颗粒物中水溶性离子主要为NO_3~-与SO24,而安康大气PM0.1颗粒物中水溶性离子主要以SO_4~(2-)与Ca2+为主,PM2.5颗粒物中水溶性离子以NO_3~-、SO_4~(2-)和NH_4~+为主,这与农村环境中使用燃煤、农田灌溉、家畜喂养以及有机质降解等有关。     

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。     

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。     

珠三角地区大气PM_(2.5)理化特性季节规律与成因

基于珠三角大气超级站2013年8月至2014年3月PM2.5、PM2.5中主要水溶性无机离子组分及其重要气态前体物等参数的逐时在线监测结果,揭示当地大气PM2.5中二次无机组分与其气态前体物的相互作用,以及PM2.5理化特性与成因的季节差异。结果表明,观测期间,PM2.5、PM10的年平均质量浓度分别为64.2、105.1μg/m3,PM2.5在PM10中所占比例(PM2.5/PM10)平均为61.1%。SO2-4、NO-3、NH+4的年平均质量浓度分别为16.6、9.0、10.2μg/m3,3者之和(SNA)占PM2.5的比例(SNA/PM2.5)平均为55.8%,体现了二次转化对珠三角地区PM2.5污染的重要影响;不同季节,SNA/PM2.5为46.0%~64.3%,夏季最低,冬季最高,其中SO2-4、NH+4对PM2.5的贡献相对稳定,NO-3贡献的季节差异较大;秋、冬季各项观测参数浓度的日变化规律相对明显,夏季除HNO3和NH3外,多项观测参数在低浓度水平波动,日变化规律不明显;珠三角大气中具有足量气态NH3以中和硫酸盐和硝酸盐,PM2.5中NH+4、SO2-4、NO-3主要以(NH4)2SO4和NH4NO3形式存在;本研究站点夏季的硫氧化率和氮氧化率均高于广州市,这充分体现了该站点的区域性特征。     

武汉市典型地区PM_(2.5)化学组成及来源解析

采集了武汉市工业区和植物园2011年10月—2012年7月不同季节的PM_(2.5)样品,测定其化学组成并解析来源。结果表明,工业区和植物园PM_(2.5)年均质量浓度分别为179.7、92.8μg/m3,其中SO2-4、NO-3和NH+4是最主要的水溶性离子。通过气团的后向轨迹模型分析,本地源与远距离区域传输共同影响武汉市空气质量。采用正定矩阵因子分析(PMF)模型对PM_(2.5)来源进行了解析,工业区PM_(2.5)来源为二次气溶胶、生物质燃烧、扬尘、冶金、燃煤和残油燃烧,春、夏、秋、冬4季贡献率最高的因子分别为生物质燃烧(45.1%)、残油燃烧(23.1%)、扬尘(56.1%)和二次气溶胶(53.4%);植物园PM_(2.5)来源为二次气溶胶、机动车排放、扬尘、冶金、燃煤和残油燃烧,春、秋两季机动车排放贡献率最高,分别为42.7%、41.3%;夏季和冬季分别为扬尘和二次气溶胶贡献最高,贡献率分别为27.3%、57.4%。     

南昌市秋季大气PM_(2.5)浓度及化学组分特征分析

2013年秋季在南昌市6个空气自动站点连续采集了10d的大气PM2.5样品,对采集的样品进行无机元素、有机碳、元素碳和水溶性离子等组分的分析。结果表明,监测期间南昌市PM2.5均值都低于《环境空气质量标准》(GB 3095—2012)二级标准限值(75μg/m3)。南昌市大气PM2.5主要组成元素为S、Si、Ca、Al、Fe、Na和Mg,说明城市扬尘、建筑水泥尘和燃煤尘等源类贡献率高;SO2-4、NO-3和NH+4是最主要的水溶性离子,NO-3与SO2-4浓度比为0.63,说明相比于固定源,以机动车排放为代表的流动源对南昌市大气PM2.5浓度影响更大;有机碳/元素碳(质量比)为2.9,说明南昌市有显著的二次有机碳生成。     

百色市右江区大气PM10中水溶性无机离子的化学特征与来源

2010年10月至2011年9月采集百色市右江区大气PM10样品,分析PM10及其水溶性无机离子的化学特征与来源。结果表明:(1)百色市右江区大气PM10为13.89～319.44μg/m3,年均117.48μg/m3,年均值超过《环境空气质量标准》(GB 3095-2012)二级标准(100μg/m3)。百色市右江区大气可吸入颗粒物的污染主要出现在春冬季节。(2)水溶性无机离子浓度年均值依次为SO24->NO3->Cl->NH4+>K+>Na+>Mg2+>F-,SO24-、NO3-和Cl-浓度最高,分别占水溶性无机离子的57.7%、14.9%和14.5%。(3)百色市右江区大气PM10呈较强的酸性,高浓度的SO42-可能是导致百色市右江区大气PM10呈较强酸性的主要原因。(4)PM10的季节变化受气温和风速的影响极显著;气象因素对SO42-、NO3-、F-的影响不显著。(5)主因子分析表明,PM10中水溶性无机离子可能来自3个方面,Cl-和NO3-主要来自于当地低烟卤煤燃烧排放的烟气;Mg2+、K+和Na+主要来自于自然源;F-、SO24-和NH4+主要来自于混合源。     

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。     

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。     

Occurrence and treatment of arsenic in groundwater and soil in northern Mexico and southwestern USA

This review focuses on the occurrence and treatment of arsenic (As) in the arid region of northern Mexico (states of Chihuahua and Coahuila) and bordering states of the southwestern US (New Mexico, Arizona, and Texas), an area known for having high As concentrations. Information assembled and assessed includes the content and probable source of As in water, soil, and sediments and treatment methods that have been applied in the area. High As concentrations were found mainly in groundwater, their source being mostly from natural origin related to volcanic processes with significant anthropogenic contributions near mining and smelting of ores containing arsenic. The affinity of As for solid phases in alkaline conditions common to arid areas precludes it from being present in surface waters, accumulating instead in sediments and shifting its threat to its potential remobilization in reservoir sediments and irrigation waterways. Factors such as oxidation and pH that affect the mobility of As in the subsurface environment are mentioned. Independent of socio-demographic variables, nutritional status, and levels of blood lead, cognitive development in children is being affected when exposed to As. Treatments known to effectively reduce As content to safe drinking water levels as well as those that are capable of reducing As content in soils are discussed. Besides conventional methods, emergent technologies, such as phytoremediation, offer a viable solution to As contamination in drinking water.     

Accumulation in and effects of lead and cadmium on waterfowl and passerines in northern Idaho

Waterfowl and passerines in northern Idaho in 1987 had high levels of lead in their blood and tissues that originated primarily from mining and smelting activities. Four Canada geese (Branta canadensis) and one common goldeneye (Bucephala clangula) found dead contained 8 to 38 microg/g (wet mass) of lead in their livers. These levels exceed the lower lethal limit of 5 microg/g in experimental birds. Two of the Canada geese (one each from the contaminated and reference areas) died with ingested lead shotgun pellets (shot) in their gizzards, whereas the other three birds from the contaminated area contained no ingested shot and evidently died from ingesting environmental lead in sediment or biota. Lead burdens in most American robins (Turdus migratorius) and mallards (Anas platyrhynchos) were high, whereas those in tree swallows (Tachycineta bicolor) were slightly elevated. Lead accumulated to potentially hazardous levels in blood and tissues of some nestling robins (maxima of 0.87 microg/g in blood and 5.6 microg/g in liver) and mallards (maxima of 10.2 microg/g in blood and 2.8 microg/g in liver). In mallards, lead levels and associated physiological characteristics of blood were significantly different in juveniles (HY) versus adults (AHY). Activity of delta-aminolevulinic acid dehydratase (ALAD) was about 87 to 95% lower than values for control birds in experimental studies. Activity of ALAD was significantly inversely correlated with blood lead levels. Cadmium was detected in kidneys of most birds, but even the maximum concentration of 7.5 microg/g in an AHY mallard was below known harmful levels.     

Kinetics of aerobic and anaerobic biomineralization of atrazine in surface and subsurface agricultural soils in Ohio

The purpose of this study was to assess atrazine mineralization in surface and subsurface samples retrieved from vertical cores of agricultural soils from two farm sites in Ohio. The Defiance site (NW-Ohio) was on soybean-corn rotation and Piketon (S-Ohio) was on continuous corn cultivation. Both sites had a history of atrazine application for at least a couple of decades. The clay fraction increased at the Defiance site and the organic matter and total N content decreased with depth at both sites. Mineralization of atrazine was assessed by measurement of ¹⁴CO₂ during incubation of soil samples with [U-ring-¹⁴C]-atrazine. Abiotic mineralization was negligible in all soil samples. Aerobic mineralization rate constants declined and the corresponding half-lives increased with depth at the Defiance site. Anaerobic mineralization (supplemented with nitrate) was mostly below the detection at the Defiance site. In Piketon samples, the kinetic parameters of aerobic and anaerobic biomineralization of atrazine displayed considerable scatter among replicate cores and duplicate biometers. In general, this study concludes that data especially for anaerobic biomineralization of atrazine can be more variable as compared to aerobic conditions and cannot be extrapolated from one agricultural site to another.     

Occurrence and profiles of organic sun-blocking agents in surface waters and sediments in Japanese rivers and lakes

Sun-blocking agents including eight UV filters (UVF) and 10 UV light stabilizers (UVLS) were measured in water and sediment collected from 22 rivers, four sewage treatment plant effluents (STPE) and three lakes in Japan. Total sun blocking agents levels ranged from N.D. to 4928 ng/L and from 2.0 to 3422 μg/kg dry wt in surface water and in sediment, respectively. Benzyl salicylate, benzophenone-3, 2-ethyl hexyl-4-methoxycinnamte (EHMC) and octyl salicylate were dominant in surface water receiving wastewater effluents and STPE, although UV-328, benzophenone and EHMC were dominant in other surface water except background sites. Three UVF and nine UVLS were observed from all sediment and their compositions showed similar patterns with UV-328 and UV-234 as the most prevalent compounds. Homosalate, octocrylene, UV-326, UV-327, UV-328 and UV-234 were significantly correlated with Galaxolide^® in sediments. Concentrations of UV-327 and UV-328 also had strong correlation between those of UV-326 in sediment.     

The role of sorption and bacteria in mercury partitioning and bioavailability in artificial sediments

This study compared the relative importance of three types of sorption (organic matter-particle, mercury-organic matter and mercury-particle) in controlling the overall mercury partitioning and bioavailability in sediments. We found that all three types of sorption were important for both inorganic mercury (Hg) and methylated mercury (MeHg). Mercury-particle sorption was more important than mercury-fulvic acid (FA) sorption in increasing the mercury concentrations with increasing aging. Bioavailability (quantified by gut juice extraction from sipunculans) was mainly controlled by mercury-particle sorption, while FA-particle and mercury-FA sorption were not as important, especially for MeHg. Bacterial activity also increased the partitioning of Hg or MeHg in the sediments and was further facilitated by the presence of organic matter. The bioavailability of Hg or MeHg from sediments was only slightly influenced by bacterial activity. This study highlights the importance of sorption from various sources (especially mercury-particle sorption) as well as bacteria in controlling the partitioning and bioavailability of Hg or MeHg in sediments.     

Photodegradation of polychlorinated dibenzo-p-dioxins and dibenzofurans in aqueous solutions and in organic solvents

Aqueous solutions of selected polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were prepared using a generator column and exposed to UV (300 nm) light in the laboratory and to sunlight in an outdoor environment. In the laboratory, additional exposures were also carried out using 60% acetonitrile/water solutions. At 300 nm di- and tetra PCDDs had higher first-order photodegradation rate constants in 60% acetonitrile/water than in pure water. The solvent effect was reversed for PCDFs. These results may be a reflection of the higher polarity of PCDFs compared to PCDDs. In both the indoor and outdoor exposures photodegradation rates decreased with increasing concentrations of chlorination. However, OCDF exposed to 300 nm light in 60% acetonitrile/water and to sunlight in pure water photodegraded more rapidly than tetra CDF. Photolysis rates in sunlight were considerably slower (t(1/2) of 6.4-23 h) than photolysis rates at 300 nm in the laboratory (t(1/2) of 4.3-680 min), reflecting the lower intensity of sunlight in the 300 nm region of the UV/Vis spectrum. The extent of dechlorination of the PCDDs/PCDFs was less than 20% and reductive dechlorination does not appear to be a major process in the photodegradation of PCDDs/PCDFs in aqueous solutions.     

Persistence and dissipation kinetics of trifloxystrobin and tebuconazole in onion and soil

The persistence and dissipation kinetics of trifloxystrobin and tebuconazole on onion were studied after application of their combination formulation at a standard and double dose of 75 + 150 and 150 + 300 g a.i. ha^?1. The fungicides were extracted with acetone, cleaned-up using activated charcoal (trifloxystrobin) and neutral alumina (tebuconazole). Analysis was carried out by gas chromatograph (GC) and confirmed by gas chromatograph mass spectrometry (GC-MS). The recovery was above 80% and limit of quantification (LOQ) 0.05 mg kg^?1 for both fungicides. Initial residue deposits of trifloxystrobin were 0.68 and 1.01 mg kg^?1 and tebuconazole 0.673 and 1.95 mg kg^?1 from standard and double dose treatments, respectively. Dissipation of the fungicides followed first-order kinetics and the half life of degradation was 6–6.6 days. Matured onion bulb (and field soil) harvested after 30 days was free from fungicide residues. These findings suggest recommended safe pre-harvest interval (PHI) of 14 and 25 days for spring onion consumption after treatment of Nativo 75 WG at the standard and double doses, respectively. Matured onion bulbs at harvest were free from fungicide residues.     

Persistence of granular and EC formulations of chlorpyrifos in a mineral and an organic soil incubated in open and closed containers

Abstract

Samples of a mineral soil (Plainfield sand) and an organic soil (muck) were treated with granular and EC formulations of chlorpyrifos and incubated at 27±1°C and 65±5% RH in open and closed containers. Duplicate samples of each soil‐formulation‐container combination were analyzed for residual chlorpyrifos during a 23 wk period. The disappearance rates observed demonstrate that the relative importance of formulation and containment on overall persistence depends on soil type. For the mineral soil, disappearance was slower from closed containers and formulation had only a slight effect while, in the organic soil the granular formulation disappeared slower than the EC and there was little difference between open and closed containers. The relative importance of degradation and volatilization in the disappearance of chlorpyrifos from soil is discussed.     

Evaluation of photolysis and hydrolysis of pyraclostrobin in aqueous solutions and its degradation products in paddy water

This study evaluated the hydrolysis and photolysis kinetics of pyraclostrobin in an aqueous solution using ultra-high-performance liquid chromatography–photodiode array detection and identified the resulting metabolites of pyraclostrobin by hydrolysis and photolysis in paddy water using high-resolution mass spectrometry coupled with liquid chromatography. The effect of solution pH, metal ions and surfactants on the hydrolysis of pyraclostrobin was explored. The hydrolysis half-lives of pyraclostrobin were 23.1–115.5?days and were stable in buffer solution at pH 5.0. The degradation rate of pyraclostrobin in an aqueous solution under sunlight was slower than that under UV photolysis reaction. The half-lives of pyraclostrobin in a buffer solution at pH 5.0, 7.0, 9.0 and in paddy water were less than 12?h under the two light irradiation types. The metabolites of the two processes were identified and compared to further understand the mechanisms underlying hydrolysis and photolysis of pyraclostrobin in natural water. The extracted ions obtained from paddy water were automatically annotated by Compound Discoverer software with manual confirmation of their fragments. Two metabolites were detected and identified in the pyraclostrobin hydrolysis, whereas three metabolites were detected and identified in the photolysis in paddy water.     

Toxicity and metabolism of acephate in adult and larval insects

Abstract

Adult and larval insects from the terrestrial and aquatic environments were exposed to acephate. The chemical was more toxic to adult insects than to larvae, and was a poor insect cholinesterase inhibitor in vitro compared to methamidophos which was a much stronger inhibitor. Both acephate and methamidophos inhibited the adult cholinesterase in vitro much more strongly than they did the larval enzymes. Acephate was metabolized by the insects to methamidophos which did not appear to be the only metabolite, although no other metabolites were looked for. The cholinesterase of insects exposed to sublethal levels of acephate was inhibited, but this inhibition appeared to be due to the combined effect of acephate and methamidophos and not to any hypothetical substance with greater anticholinesterase activity. This was bourne out when acephate was incubated with mixed function oxidases (MFO). No activated product with potent anticholinesterase activity was identified. Methamidophos was not produced by the MFO system but by some other unidentified mechanism.