Field tests of a passive sampler for atmospheric ozone at California mountain forest locations

Field tests of a colorant-based ozone passive sampler have been carried out during the 1990 smog season at five mountain forest locations in California. Co-located measurements of ambient ozone were made at all field sites using the passive sampler and a reference method, ultraviolet (u.v.) photometry. The sampling duration ranged from 3 to 30 days. Nitrogen dioxide, aldehydes and the phytotoxic oxidants peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) were measured at one location to assess possible interferences. The average precision of the measurements, calculated from data for 42 sets of colocated passive samplers, was 12%. Data for all field locations could be reduced to a single equation relating color change (ΔE units) to ozone dose (units: ppb-days). This polynomial equation could be reduced to a linear equation for color changes not exceeding 8 ΔE units (equivalent to sampling durations of up to 15 days), with good agreement between field data and earlier calibration results obtained in the laboratory. Both polynomial and linear equations can be used to obtain quantitative, time-integrated measurements of ambient ozone. The performance of the passive sampler showed no dependence on changes in ambient temperature and humidity. Interferences from air pollutants other than ozone contributed a total positive bias of less than 5% to the measured ozone concentrations: 3% for NO₂, 1.3% for PAN, 0.2% for PPN, and 0.% or less for formaldehyde and acetaldehyde.     

宁南山区人工林草对土壤真菌群落的影响

以宁南山区天然草地（长芒草（Stipa bungeana Trin））为参照,选取2种典型人工恢复植被：人工草地（苜蓿（Medicago sativa））和人工林地（柠条（Caragana korshinskii Kom））的表层土壤（0-20cm）为研究对象,利用Miseq高通量测序技术分析土壤真菌的多样性、物种组成及其相对丰度变化特征,并采用冗余分析（RDA）的方法研究环境因子对不同植被土壤真菌群落的影响.结果表明：3种植被样地土壤样品共测得真菌27个门,44个纲,70个目,91个科.其中,优势菌门有子囊菌门（Ascomycota）和担子菌门（Basidiomycota）,丰度分别为71.8%和15.2%;优势菌纲主要有：粪壳菌纲（Sordariomycetes）、座囊菌纲（Dothideomycetes）、伞菌纲（Agaricomycetes）和盘菌纲（Pezizomycetes）;优势菌属有：赤霉菌属（Gibberella）、肾形虫属（Colpoda）、水球壳属（Hydropisphaera）、叶生壳属（Floricola）、管柄囊霉属（Funneliformis）和Marcelleina.土壤真菌丰富度和多样性在苜蓿地最大,柠条地最小.球囊菌门（Glomeromycota）在天然草地的丰度最高,为4.8%;子囊菌门丰度在苜蓿地里最大,达82.6%,在柠条地最低,为56.8%;担子菌门和分类不明确门（Unclassified）在柠条土壤中丰度最大,分别为：25.3%和7.9%,在苜蓿地中最低,分别为：7.1%和0.8%.盘菌纲在天然草地中的丰度最高,为17.8%,且显著高于柠条地.伞菌纲在（Agaricomycetes）柠条地中的丰度明显高于苜蓿地.Heatmap热图分析表明,尽管苜蓿地中土壤真菌群落与天然草地的相似度更高,但是天然草地中AM真菌（Arbuscular mycorrhizal Fungi）的相对丰度最大,种植苜蓿使土壤致病菌属的相对丰度增加,柠条地的肾形虫属相对丰度最高.人工林草对土壤真菌的群落组成和多样性有较明显的影响.土壤水分（SW）、有机碳（TOC）和全氮（TN）是影响宁南山区林草地土壤真菌群落的主要理化因子.     

Fine particle trace elements at a mountain site in southern China:Source identification,transport,and health risks

Trace elements in atmospheric particulate matter play a significant role in air quality, human health, and biogeochemical cycles. In this study, the trace elements(Ca, Al, K, Fe, Na,Mg, Zn, Pb, Mn, Ti, Cu, Cr, Sr, Ni) in PM2.5samples collected at the summit of Mt. Lushan were analyzed to quantify their abundance, source, transport, and health risks. During the whole sampling period, the major trace elements was Ca, Al, and K. While the trace metals with the lowest concentrations were Sr, Ni, Rb,...     

Ozone concentrations at a remote mountain site and at two regional locations in southwestern Alberta

Ozone concentrations at a remote site in the Rocky Mountains of southwestern Alberta averaged 43.4 ppb over a 2 year period and the Canadian air quality objective of an 80 ppb hourly average was exceeded 1.5% of the time. The diurnal variation in O₃ concentrations was small, 2.9 ppb, indicative of a remote location, above the nocturnal inversion and not greatly influenced by local emissions. During the period when O₃ concentrations were highest, winds were generally from the southwest, suggestive of the long range transport of anthropogenic pollutants from distant sources rather than the generation of O₃ from local emissions. In contrast, hourly O₃ concentrations at two regional air quality monitoring sites showed an average diurnal variation of 14 ppb. Only two hourly averages exceeded 80 ppb during the 2 years, and the mean O₃ concentration was 26 ppb. When these regional sites were within the urban plume from Calgary, the O₃ concentrations were depressed to a mean of 18 ppb. Ozone concentrations in downtown Calgary averaged 13 ppb. Under Alberta climatological and meteorological conditions, hourly O₃ objectives are most likely to be exceeded in remote areas, rather than in cities or in areas under the direct influence of urban emissions.     

有机污染场地修复工程中的大气环境二次污染防治及案例分析

近年来,我国污染场地修复工程项目数量快速增长,其中有机污染场地修复工程中的大气二次污染问题受到广泛关注。为了实现污染场地的有效、安全治理,首先对我国目前污染场地修复现状及二次污染风险特点进行了分析,以北京焦化厂原址污染场地修复工程为例,对该类典型有机污染场地在异位修复工程中的主要施工工程和大气环境二次污染风险来源进行了详细分析,并针对修复工程中的气态污染物、尾气和扬尘3项关键要素建立了全面的大气环境二次污染防治措施体系。     

Gas- and aqueous-phase formic and acetic acids at a tropical cloud forest site

Atmospheric gas-phase and aqueous-phase (dew and fog) formic and acetic acids were measured over a cloud forest in Venezuela. The gaseous acids showed diurnal cycles, with higher mixing ratios during daytime. Higher concentrations were observed during the dry season (HCOOH 1.7 +/−0.5 ppb; CH₃COOH 1.4+/−0.6 ppb) in comparison with the rainy season (HCOOH 0.79+/−0.24 ppb; CH₃COOH 0.54+/−0.20 ppb). Liquid-phase concentrations in dew and fog are of the same order and range from 8.1 to 69.5 μM for HCOOH and 4.3 to 15.3 μM for CH₃COOH. The field-observed Henry's Law coefficients, calculated from the simultaneous measurements of gas- and liquid-phase acids, do not show a significant trend with the pH of the solution, in contrast to theoretical considerations. Dry deposition velocities to the nighttime dew are 1.1+/−0.6 and 0.68+/−0.42 cm s⁻¹ for formic and acetic acids, respectively. A loss of 0.054 ppb HCOOH and 0.022 ppb CH₃COOH from the atmospheric boundary layer to the dew is produced nightly.     

华东高山背景点大气气态汞含量与传输特征

利用高时间分辨率自动测汞仪（Tekran 2537B）于2017年6月~2018年5月对武夷山气态元素汞（GEM）进行了连续1a的观测.结果表明，武夷山GEM年均浓度为（1.70±0.43）ng/m³，稍高于北半球背景值，表明武夷山受到一定程度的大气汞污染.GEM浓度表现为冬季>秋季>春季>夏季，季风和风速是影响武夷山GEM季节变化的主要因素.武夷山四季GEM表现为不同的日变化特征，早上8：00之后，春秋季GEM继续呈现下降趋势，其他季节则呈现先升后降再上升，并在晚上不同时刻出现峰值.GEM值白天低于晚上，这与风速和汞的长距离迁移有关.后向轨迹和浓度权重轨迹分析结果表明，偏西风背景下污染气团经江西向武夷山输送是大气汞迁移的主要路径，而江西和福建中北部为武夷山大气汞污染的潜在源区.△GEM/△CO值表明武夷山GEM汞污染主要来源于人为工业排放，生物质燃烧贡献较弱.     

大气污染物多时间分辨率的小波分析

利用Modet小波函数进行小波变换,利用Daubechies小波函数进行分解及滤波,以乌鲁木齐市的大气污染物时间序列为例,分析了当地单个大气监测站点NO2的多分辨率的演变特性,并对NO2的时间序列进行了滤波消噪.研究结果显示,NO2年际变化和季节性变化的时间尺度在尺度空间中分布不均匀,具有较明显的局部化特征;除了季节性变化的时间尺度和变化趋势之外,还存在大气污染物中、长期变化趋势.基于滤波消噪后的时间序列建立的预测模型可用于有效地提高大气污染物的预测预报精度.     

稳健变异函数在土壤污染物来源识别中的应用：以某重金属污染场地为例

空间特异值可以提供污染源的位置信息.以Genton稳健估计量为基础的变异函数为研究工具,对某重金属冶炼场地土壤中Cu、Zn、Pb、Cd、As、Se和Hg含量进行了空间特异值分析,并根据空间特异值的地理位置及土地利用方式等信息指示污染源.结果表明,7种元素变异函数曲线的理论模型符合球状模型,7种元素都具有较小的块金方差,Cu、Zn和Pb只为0.000.与Matheron估计量相比,该研究得到的变异函数具有更小的块金效应,说明Genton估计量能够消除或减弱特异值对变异函数的影响.7种元素的空间特异值多集中在个别小范围内,以簇状形式存在,与该区域冶炼高炉及尾渣堆放处的位置具有很好的相关性,说明冶炼行为及其相关过程是该区重金属的重要来源.     

Monitoring of non-point source pollutants load from a mixed forest land use

The aim of this study was to determine the unit load of NPS (non-point source) pollutants including organic variables such as BOD (biochemical oxygen demand),COD (chemical oxygen demand) and DOC (dissolved organic carbon),nitrogen and phosphorus constituents,and suspended solids (SS) and their event mean concentration (EMC) of runoff flows from a water-shed of mixed forest land use by intensive field experiments.Field monitoring for continuous measurements of rainfall,flow,and water quality was conducted over 12 storm events during 2008–2009 using automated and manual sampling methods.The EMCs of individual runoff event were estimated for each water quality constituent based on the flow rate and concentration data of runoff discharge.The average EMCs of BOD,COD,DOC,SS,TN (total nitrogen),NH 4+ -N,NO 3- -N,TP (total phosphorus),PO 43- -P from the mixed forest land were 1.794,3.498,1.462,10.269,0.862,0.044,0.634,0.034,and 0.005 mg/L,respectively.The annual unit loads of BOD,COD,DOC,SS,TN,NH 4+ -N,NO 3- -N,TP and PO 43--P were estimated as 66.9,133.2,55.5,429.8,36.5,1.6,26.9,1.3 and 0.1 kg/(ha·yr),respectively.In addition,affecting parameters on the EMCs were investigated by statistic analysis of the field data.As a result,significant correlations with precipitation,rainfall intensity,and total runoff flows were found in most constituents.     

基于MODIS火点数据分析南北方省份生物质开放式燃烧与排放特征

利用2018年全国范围内的MODIS火点数据,结合土地利用数据信息,运用地理信息系统空间分析方法和统计分析方法,以火点数据、生物量及各污染物排放量为指标,分析了南北方省份生物质开放燃烧的时空特征.计算结果显示,北方省份森林火灾、草原火灾、秸秆露天焚烧生物量分别为107× 104、74× 104、498× 104t,南方...     

基于周围环境目标值估算的企业边界大气污染物限值分析

从40余项国家大气固定污染源污染物排放标准以及地方恶臭污染物排放标准中筛选出已制定企业边界限值的36种大气污染物,提出适用于限值分析的方法,基于周围环境目标值（AMEG）设置了参考区间,对比分析了我国与美国化学有害因素职业接触限值时间加权平均容许浓度（TWA）的差异。结果表明,36种大气污染物可分为3类：1）出现在国家大气污染物综合排放标准等制定和发布年限较长标准中且限值较为宽松的8种污染物;2）限值未受嗅阈值影响的13种污染物,其中12种污染物的限值与AMEG估算结果的8.4倍较为接近;3）限值受嗅阈值影响的15种污染物,其中部分污染物的限值接近AMEG估算结果,部分限值接近嗅阈值。参与对比分析的255种化学有害因素中,我国和美国的TWA相等的有44种,占比不超过20%,差异在±1倍之内的约占85%,在±5倍以上的约占7%。研究显示,现行大气污染物排放标准中的企业边界限值有效保护了人体健康和生态环境,应对制定和发布年限较长且限值较为宽松的标准,以及限值高于嗅阈值的标准开展研究,分析限值的合理性。在制定企业边界大气污染物限值时,应广泛收集更多来源的职业接触限值数据并分析其适用性。

     

Formic acid and acetic acid: Emissions,atmospheric formation and dry deposition at two southern California locations

Emission rates, in situ formation rates and removal rates by dry deposition are estimated for formic acid (HCOOH, C1) and acetic acid (CH₃COOH, C2), which are the most abundant acids in southern California air and together account for much of the airborne acidity and are the leading contributors to acid dry deposition. Using data for eight unreactive tracers, direct emission rates during the fall 1987 are estimated to be 5.6 and 12.8 metric tons d⁻¹ for C1 and C2, respectively, at a coastal source-dominated site. These emissions rates increase to 9.6(C1) and 20.4(C2) metric tons d⁻¹ during the summer. In situ formation in the atmosphere via the ozone-olefin reaction is an important source for both acids. This reaction produces an estimated 25.0 and 10.1 metric tons d⁻¹ of C1 and C2, respectively, during the day and 34.5 (C1) and 4.3 (C2) metric tons d⁻¹ at night. More acetic acid than formic acid is emitted by direct sources, with C2/C1 emission rate ratios of 2.1–2.3. The reverse is true of in situ formation, with C1/C2 production rate ratios of 2.5 (day) and 8.0 (night). Dry deposition removal rates depend on season (fall > summer) and location (inland > coastal) and are 22–52 metric tons d⁻¹ for C1, and 32–83 metric tons d⁻¹ for C2. Source (emissions + in situ formation) and sink (dry deposition) terms are of the same magnitude in all six cases studied and balance each other well in three of these cases. Uncertainties in emission, in situ production and removal rates are discussed and reflect uncertaintes in olefin and unreactive tracer emission rates, yields of organic acids from the Criegee biradical (ozone-olefin reaction), and dry deposition velocity, respectively.     

Chemical formation and source apportionment of PM2.5 at an urban site at the southern foot of the Taihang mountains

The region along the Taihang Mountains in the North China Plain (NCP) is characterized by serious fine particle pollution. To clarify the formation mechanism and controlling factors, an observational study was conducted to investigate the physical and chemical properties of the fine particulate matter in Jiaozuo city, China. Mass concentrations of the water-soluble ions (WSIs) in PM_2.5 and gaseous pollutant precursors were measured on an hourly basis from December 1, 2017, to February 27, 2018. The positive matrix factorization (PMF) method and the FLEXible PARTicle (FLEXPART) model were employed to identify the sources of PM_2.5. The results showed that the average mass concentration of PM_2.5 was 111 μg/m³ during the observation period. Among the major WSIs, sulfate, nitrate, and ammonium (SNA) constituted 62% of the total PM_2.5 mass, and NO₃^? ranked the highest with an average contribution of 24.6%. NH₄⁺ was abundant in most cases in Jiaozuo. According to chemical balance analysis, SO₄^2?, NO₃^?, and Cl^? might be present in the form of (NH₄)₂SO₄, NH₄NO₃, NH₄Cl, and KCl. The liquid-phase oxidation of SO₂ and NO₂ was severe during the haze period. The relative humidity and pH were the key factors influencing SO₄^2- formation. We found that NO₃^? mainly stemmed from homogeneous gas-phase reactions in the daytime and originated from the hydrolysis of N₂O₅ in the nighttime, which was inconsistent with previous studies. The PMF model identified five sources of PM_2.5: secondary origin (37.8%), vehicular emissions (34.7%), biomass burning (11.5%), coal combustion (9.4%), and crustal dust (6.6%).     

2011年6~8月平流输送对黄山顶污染物浓度的影响

基于单条后向轨迹的滞留时间场和污染物排放强度场,设计了一种可以评估该轨迹对污染物的平流输送强度参数.利用2011年6~8月光明顶CO和O3浓度资料对该参数进行了验证,进而分析了该观测时段平流输送对光明顶污染物的影响;此外将O3浓度分成3档,利用改进的PSCF(Potential source contribution function)方法分析了各档浓度对应的源区分布.结果表明:(1)平流输送评估参数与污染物浓度的变化具有很好的一致性,表明平流输送对光明顶污染物浓度的变化具有重要作用.其中,安徽、湖北和江西三省交界区域的城市群向光明顶输送的污染物占到输送总量的一半以上;(2)光明顶O3浓度 >55×10-9、(30~55)×10-9、<30×10-9时所对应的主要源区分别为华北及长三角发达工业区、黄山西南方向的工业区、较远的南部沿海地区;(3)影响光明顶污染物浓度变化的输送类型可以分为秸秆燃烧输送、发达工业区气团输送、西南方向气团输送和海洋性气团输送4种类型,对应的污染物浓度(CO/O3)(×10-9)依次为474.47/72.50、221.16/57.71、86.31/30.41、51.67/27.45.     

民用固体燃料燃烧大气污染物排放稀释采样器的研制与应用

为研究民用固体燃料燃烧大气污染物的排放特征,研制开发了一套紧凑型稀释采样器,主要由烟气进气部分、稀释空气部分、稀释混合部分及采样部分四部分组成.结果表明,该采样器可测量排放的一次PM_(2.5)、CO_2、CO、SO_2、NO_x等气态污染物排放浓度,并可根据碳平衡法获得各污染物的排放因子.稀释采样器的稀释比在20∶1～30∶1范围内,样气在稀释器内的停留时间为10 s.性能评价表明,稀释器气密性良好,稀释空气中颗粒物浓度低于3μg·m~(-3),气流混合均匀,理论稀释比与实际稀释比的偏差均小于2%,细颗粒在采样器内的损失小.利用稀释器测试了两种典型民用炉具和煤种组合的大气污染物的排放,发现高效反烧炉与无烟煤球组合的PM_(2.5)的排放因子要显著低于传统正烧炉与烟煤组合,且前者CO和NO_x的排放因子也要低于后者,两种CO_2排放因子相当.     

Thermal internal boundary layer and its effects on air pollutants during summer in a coastal city in North China

The thermal internal boundary layer(TIBL) is associated with coastal pollution dispersion,which can result in high concentrations of air pollutants near the surface of the Earth. In this study, boundary layer height data which were obtained using a ceilometer were used to assess the effect of the TIBL on atmospheric pollutants in Qinhuangdao, a coastal city in North China.A TIBL formed on 33% of summer days. When a TIBL formed, the sunshine duration was 2.4 hr longer, the wind speed was higher, the wind direction reflected a typical sea breeze, and the boundary layer height was lower from 9:00 LT to 20:00 LT compared to days without a TIBL. If no TIBL formed, the average concentrations of PM_(2.5) and PM_(10) decreased with increasing boundary layer height. However, when a TIBL was observed, the average concentrations of PM_(2.5) and PM_(10) increased with increasing boundary layer height. Because the air from the sea is clean, PM_(2.5) and PM_(10) concentrations reached minimums in the daytime at 16:00 LT. After16:00 LT, the PM_(2.5) and PM_(10) concentrations increased rapidly on days when a TIBL formed,which indicated that the TIBL leads to the rapid accumulation of atmospheric pollutants in the evening. Therefore, the maximum concentrations of particulate matters were larger when a TIBL formed compared to when no TIBL was present during the night. These results indicate that it is suitable for outdoor activities in the daytime on days with a TIBL in coastal cities.     

火电厂大气污染物排放标准对区域酸沉降影响的数值模拟

设计了火电厂实施2003版排放标准和2011版排放标准两种排放情景,运用Models-3/CMAQ模型系统分别模拟各情景到2015年的硫、氮沉降量,探讨2011版火电排放标准对我国大陆地区酸沉降的影响.研究表明,2011版火电标准能够有效改善我国的硫沉降状况,相比于实施2003版标准,2011版标准实施后至2015年我国大陆硫沉降总量降低了18.58%,年均硫沉降强度大于3.2t/km2的面积减少了86.40%;2011版火电标准对我国氮沉降状况也起到了一定的改善作用,标准实施后到2015年我国大陆氮沉降总量降低了9.28%,年均氮沉降强度大于4.0t/km2的面积减少了27.27%.     

Sources of methacrolein and methyl vinyl ketone and their contributions to methylglyoxal and formaldehyde at a receptor site in Pearl River Delta

Methacrolein(MACR) and methyl vinyl ketone(MVK) are two major intermediate products from the photochemical oxidation of isoprene, the most important biogenic volatile organic compound. In addition, MACR and MVK have primary emissions. Investigating the sources and evolution of MACR and MVK could provide helpful information for the oxidative capacity of the atmosphere. In this study, hourly measurements of isoprene, MACR, and MVK were conducted at a receptor site in the Pearl River Delta region(PRD), i.e., the Heshan site(HS), from 22 October to 20 November, 2014. The average mixing ratios of isoprene,MACR and MVK were 151 ± 17, 91 ± 6 and 79 ± 6 pptv, respectively. The daily variations and the ratios of MVK/MACR during daytime and nighttime suggested that other sources besides isoprene photooxidation influenced the MACR and MVK abundances at the HS.Positive matrix factorization was utilized to resolve the sources of MACR and MVK. Five sources were identified and quantified, including biogenic emissions, biomass burning,secondary formation, diesel, and gasoline vehicular emissions. Among them, secondary formation made the greatest contribution to observed MACR and MVK with average contributions of ～ 45% and ～ 70%, respectively. Through the yields of secondary products from the oxidation of MACR and MVK by the OH radical and the concentrations of MACR and MVK, it was found that methylglyoxal and formaldehyde were the main oxidation products of MACR and MVK at the HS site. Overall, this study evaluated the roles of primary emissions on ambient levels of MACR and MVK and advanced the understanding of photochemical oxidation of MACR and MVK in the PRD.     

Field measurements of dissociation of ammonium nitrate at a Beijing site

The atmospheric nitric acid, ammonia and ammonium nitrate aerosol was determined simultaneously in a Beijing site to teste quilibrium. Rather good agreement between measurements and theory was found at ambient temperature above 9oC at relative humidity below 70%. Below 9oC the kinetic constraints preventing rapid attainment equilibrium were observed. A procedure for calculation of dependence of NH4NO3 aerosol dissociation constants on temperature and relative humidity was given. The seasonal variation of concentration of NH3, total NH4+ and HNO3 was observed.The seasonal variation of concentration of HNO3 was caused by dissociation of aerosol of NH4NO3. The concentrations of NH3 were 1-2 order higher than those of HNO3. For formation of NH4NO3 aerosol the HNO3 was the control reagent. Any increase of HNO3 to formed from NOx would react with NH3 form NH4NO3 aerosol in Beijing area except for someday in summer time.