Determination of volatile organic compound emissions and ozone formation from spraying solvent-based pesticides

Large-scale agricultural activities have come under scrutiny for possible contributions to the emission of ozone precursors. The San Joaquin Valley (SJV) of California is an area with intense agricultural activity that exceeds the federal ozone standards for more than 30 to 40 d yr(-1) and the more stringent state standards for more than 100 d yr(-1). Pesticides are used widely in both agricultural and residential subregions of the SJV, but the largest use, by weight of "active ingredient," is in agriculture. The objective of the study was to determine the role of pesticide application on airborne volatile organic compounds (VOC) concentrations and ozone formation in the SJV. The ozone formation from the pesticide formulation sprayed on commercial orchards was studied using two transportable smog chambers at four application sites during the summers of 2007 and 2008. In addition to the direct measurements of ozone formation, airborne VOC concentrations were measured before and after pesticide spraying using canister and sorbent tube sampling techniques. Soil VOC concentrations were also measured to understand the distribution of VOCs between different environmental compartments. Numerous VOCs were detected in the air and soil samples throughout the experiment but higher molecular weight aromatic hydrocarbons were the primary compounds observed in elevated concentrations immediately after pesticide spraying. Measurements indicate that the ozone concentration formed by VOC downwind of the orchard may increase up to 15 ppb after pesticide application, with a return back to prespray levels after 1 to 2 d.     

Ground-level ozone in the Pearl River Delta and the roles of VOC and NO(x) in its production

In many regions of China, very rapid economic growth has been accompanied by air pollution caused by vehicle emissions. In one of these regions, the Pearl River Delta, the variations of ground-level ozone and its precursors were investigated. Overall, the ambient concentrations of NO(2) increased quickly between 1995 and 1996, but then slightly decreased due to stringent nitrogen oxide (NO(x)) emission controls. Nonetheless, ambient NO(2) levels in the Pearl River Delta remained high. The regional average concentrations of volatile organic compounds (VOCs) were 290 ppbC in summer and 190 ppbC in autumn. Local emissions and long-distance transportation of pollutants play important roles in the regional distribution of VOCs. Ambient O(3) production is significant in urban areas and also downwind of cities. The relative incremental reactivities (RIRs), determined by an observation-based model, showed that ground-level ozone formation in the Guangzhou urban area is generally limited by the concentrations of VOCs, but there are also measurable impacts of NO(x).     

Simultaneous chemical and sensory characterization of volatile organic compounds and semi-volatile organic compounds emitted from swine manure using solid phase microextraction and multidimensional gas chromatography-mass spectrometry-olfactometry

Swine manure is associated with emissions of odor, volatile organic compounds (VOCs) and other gases that can affect air quality on local and regional scales. In this research, a solid phase microextraction (SPME) and novel multidimensional gas chromatography-mass spectrometry-olfactometry (MDGC-MS-O) system were used to simultaneously identify VOCs and related odors emitted from swine manure. Gas samples were extracted from manure headspace using Carboxen/polydimethylsiloxane (PDMS) 85-microm SPME fibers. The MDGC-MS-O system was equipped with two columns in series with a system of valves allowing transfer of samples between columns (heartcutting). The heartcuts were used to maximize the isolation, separation, and identification of compounds. The odor impact of separated compounds was evaluated by a trained panelist for character and intensity. A total of 295 compounds with molecular weights ranging from 34 to 260 were identified. Seventy one compounds had a distinct odor. Nearly 68% of the compounds for which reaction rates with OH* radicals are known had an estimated atmospheric lifetime <24 h.     

Alcohol, volatile fatty acid, phenol, and methane emissions from dairy cows and fresh manure

There are approximately 2.5 million dairy cows in California. Emission inventories list dairy cows and their manure as the major source of regional air pollutants, but data on their actual emissions remain sparse, particularly for smog-forming volatile organic compounds (VOCs) and greenhouse gases (GHGs). We report measurements of alcohols, volatile fatty acids, phenols, and methane (CH4) emitted from nonlactating (dry) and lactating dairy cows and their manure under controlled conditions. The experiment was conducted in an environmental chamber that simulates commercial concrete-floored freestall cow housing conditions. The fluxes of methanol, ethanol, and CH4 were measured from cows and/or their fresh manure. The average estimated methanol and ethanol emissions were 0.33 and 0.51 g cow(-1) h(-1) from dry cows and manure and 0.7 and 1.27 g cow(-1) h(-1) from lactating cows and manure, respectively. Both alcohols increased over time, coinciding with increasing accumulation of manure on the chamber floor. Volatile fatty acids and phenols were emitted at concentrations close to their detection limit. Average estimated CH4 emissions were predominantly associated with enteric fermentation from cows rather than manure and were 12.35 and 18.23 g cow(-1) h(-1) for dry and lactating cows, respectively. Lactating cows produced considerably more gaseous VOCs and GHGs emissions than dry cows (P < 0.001). Dairy cows and fresh manure have the potential to emit considerable amounts of alcohols and CH4 and research is needed to determine effective mitigation.     

Estimation of biogenic emissions with satellite-derived land use and land cover data for air quality modeling of Houston-Galveston ozone nonattainment area

The Houston-Galveston Area (HGA) is one of the most severe ozone non-attainment regions in the US. To study the effectiveness of controlling anthropogenic emissions to mitigate regional ozone nonattainment problems, it is necessary to utilize adequate datasets describing the environmental conditions that influence the photochemical reactivity of the ambient atmosphere. Compared to the anthropogenic emissions from point and mobile sources, there are large uncertainties in the locations and amounts of biogenic emissions. For regional air quality modeling applications, biogenic emissions are not directly measured but are usually estimated with meteorological data such as photo-synthetically active solar radiation, surface temperature, land type, and vegetation database. In this paper, we characterize these meteorological input parameters and two different land use land cover datasets available for HGA: the conventional biogenic vegetation/land use data and satellite-derived high-resolution land cover data. We describe the procedures used for the estimation of biogenic emissions with the satellite derived land cover data and leaf mass density information. Air quality model simulations were performed using both the original and the new biogenic emissions estimates. The results showed that there were considerable uncertainties in biogenic emissions inputs. Subsequently, ozone predictions were affected up to 10 ppb, but the magnitudes and locations of peak ozone varied each day depending on the upwind or downwind positions of the biogenic emission sources relative to the anthropogenic NOx and VOC sources. Although the assessment had limitations such as heterogeneity in the spatial resolutions, the study highlighted the significance of biogenic emissions uncertainty on air quality predictions. However, the study did not allow extrapolation of the directional changes in air quality corresponding to the changes in LULC because the two datasets were based on vastly different LULC category definitions and uncertainties in the vegetation distributions.     

Functional classification of swine manure management systems based on effluent and gas emission characteristics

Gaseous emissions from swine (Sus scrofa) manure storage systems represent a concern to air quality due to the potential effects of hydrogen sulfide, ammonia, methane, and volatile organic compounds on environmental quality and human health. The lack of knowledge concerning functional aspects of swine manure management systems has been a major obstacle in the development and optimization of emission abatement technologies for these point sources. In this study, a classification system based on gas emission characteristics and effluent concentrations of total phosphorus (P) and total sulfur (S) was devised and tested on 29 swine manure management systems in Iowa, Oklahoma, and North Carolina in an effort to elucidate functional characteristics of these systems. Four swine manure management system classes were identified that differed in effluent concentrations of P and S, methane (CH4) emission rate, odor intensity, and air concentration of volatile organic compounds (VOCs). Odor intensity and the concentration of VOCs in air emitted from swine manure management systems were strongly correlated (r2 = 0.88). The concentration of VOC in air samples was highest with outdoor swine manure management systems that received a high input of volatile solids (Type 2). These systems were also shown to have the highest odor intensity levels. The emission rate for VOCs and the odor intensity associated with swine manure management systems were inversely correlated with CH4 and ammonia (NH3) emission rates. The emission rates of CH4, NH3, and VOCs were found to be dependent upon manure loading rate and were indirectly influenced by animal numbers.     

成都市城区环境大气中典型特征VOCs示踪物种分析

VOCs排放来源较多且成分复杂,通过某些特征物种的浓度比值可以获得相应的VOCs来源信息,2018年12月至2019年11月使用TH-300B大气挥发性有机物快速在线监测系统在成都市内进行监测,并用比值法对VOCs的示踪物种进行分析,研究表明,在监测时间范围内,乙烷、丙烷、正戊烷、异戊烷、异戊二烯、乙炔、苯、甲苯、乙苯、间(对)二甲苯的平均浓度分别为5.49ppb、3.60ppb、0.54ppb、1.14ppb、0.1ppb、3.87ppb、0.53ppb、0.87ppb、0.25ppb和0.87ppb;甲苯/苯和异戊烷/正戊烷的比值分别为1.17和1.67,表明市区VOCs的排放受机动车尾气影响较为显著,需继续加强机动车的管控;对二甲苯/乙苯和苯/甲苯的比值分别为3.7和0.85,市区气团有一定老化,春季和冬季气团老化程度较大,光化学年龄较长。     

我国大气环境管理历程与展望

随着大气环境问题从煤烟型向以PM_2.5和O₃为特征的区域复合型污染演变，我国大气污染控制模式从以污染物排放浓度控制为核心、以污染物排放总量控制为核心逐渐走向以大气环境质量改善为核心。特别是近几年，全国各地在空气质量管理、科学精准治污等领域开展一系列积极的探索与实践，取得了显著成效。本文系统回顾了近50年来我国不同阶段大气环境管理工作的特点，重点梳理了2013年《大气污染防治行动计划》实施以来，空气质量管理经验与成绩，结合减污降碳总体部署对我国2035年“美丽中国建设目标基本实现”时的空气质量进行了展望，从PM_2.5与O₃协同控制的角度出发，提出了“十四五”期间我国大气环境管理的总体思路。     

Characterization of total volatile organic compound emissions from paints

Recently, Homeswest in Western Australia and Murdoch University developed a project to construct low allergen houses (LAH) in a newly developed suburb. All potential volatile organic compound (VOC) emission materials used in LAH are required to be measured before the construction of LAH, to ensure they are low VOCs emission materials. To protect people sensitive to exposure to VOCs it is important to evaluate and select low VOCs emitting paints. In this paper, therefore, twelve different paints provided by local manufacturers were selected for analysis to characterize total volatile organic compounds (TVOC) emissions. Emissions of TVOCs from six organic solvent-soluble paints and six water-soluble paints were evaluated using a small test chamber under controlled temperature, relative humidity and air exchange rates. The major volatile organic compounds in these paints were also identified. The time dependence of TVOC emissions from paint products in the chamber was evaluated. TVOC emissions from organic solvent-soluble and water-soluble paints were compared. The influence of air exchange rate on the TVOC concentrations emitted from organic solvent-soluble and water-soluble paints was also investigated. A double-exponential equation was used to evaluate emission characteristics of TVOC from paint products. With this double-exponential model, the physical processes of TVOC emissions can be explained. A variety of emission parameters can be calculated and used to estimate real indoor TVOCs concentrations.     

长沙市空气自动站周边区域大气污染物排放源清单

以长沙市空气自动站周边3 km为研究对象,基于统计年鉴和实地调查,获得了该地区2015年储存运输源、废弃物处理源、工艺过程源、化石燃料固定燃烧源、农业源、生物质燃烧源、扬尘源、移动源8个源类的活动水平数据。以大气污染物排放源清单编制技术指南为依据,建立了2015年长沙市空气自动站周边3 km区域NH_3、NO_x、PM_(10)、PM_(2.5)、SO_2、VOCs等6项污染物的源排放清单。结果表明,2015年长沙空气自动站周边3 km内,8类大气污染源排放的NH_3、NO_x、PM_(2.5)、PM_(10)、SO_2、VOCs总量分别为53.65t、4 899.35t、1 846.09t、6 257.75t、989.49t、4 383.31t。NH_3、NO_x、PM_(2.5)、PM_(10)、SO_2、VOCs排放量最大的源分别是农业源、移动源、扬尘源、扬尘源、化石燃料固定燃烧源和移动源,贡献率分别为98.45%、84.24%、60.82%、85.90%、97.33%、49.88%。优化道路交通、减少燃煤、减少建筑工地扬尘排放可促进长沙市空气自动站周边空气质量改善。     

The cost of crop damage caused by ozone air pollution from motor vehicles

The effects of ozone air pollution on the agricultural sector are an important environmental challenge facing policy makers. Most studies of the economic impact of air pollution on agriculture have found that a 25% reduction in ambient ozone would provide benefits of at least $1–2 billion annually in the United States. This paper extends existing research by estimating the benefits of a reduction in emissions from a major source of ozone formation: motor-vehicle emissions. An agricultural production model is combined with an analysis of motor-vehicle emissions and air quality to estimate the impacts of emissions from six different motor-vehicle classes, at both the regional and national level. The benefits to the agricultural sector from completely eliminating ozone precursor emissions from motor vehicles ranges between $3·5 and $6·1 billion annually.     

南通市典型臭氧污染过程VOCs特征及来源分析

利用在线挥发性有机物自动监测仪TH300B对2020年8月12—17日南通市典型臭氧污染过程中VOCs排放进行监测。结果表明,南通市此次臭氧污染过程主要受VOCs排放影响,污染中VOCs体积浓度均值为23.44 ppb,较污染前下降了12.0%,其中芳香烃体积浓度占比下降幅度最大,较污染前下降23.4%,OVOCs体积浓度绝对值下降最大,较污染前下降1.42 ppb。污染中,VOCs总OFP贡献为162.0μg/m3,较污染前下降22.2%,OPF与臭氧的日变化呈明显的相反关系,关键活性物种为甲苯、乙烯和异戊烷等。PMF模型解析结果显示,机动车尾气、工业排放、油气挥发、涂料和溶剂使用、天然气源对VOCs的贡献占比分别为38.6%,35.4%,9.5%,8.8%和7.8%。     

运用机器学习方法预测空气中臭氧浓度

臭氧(O_3)浓度变化与天然源、移动源和点源的排放量存在某些隐含的关联。根据臭氧浓度变化的特性,基于污染源在线排放数据、气象监测数据以及空气质量监测数据构造特征,运用机器学习方法进行逐小时臭氧浓度预测。该方法不仅充分利用了臭氧浓度变化时序数据,而且考虑了气象条件变化对污染物浓度变化的影响,最重要的是将点源排放氮氧化物这一臭氧生成的重要前体物纳入模型考虑。在金砖国家领导人厦门会晤前后(2017年8月31日至9月9日),运用该方法对厦门市溪东、洪文、鼓浪屿和湖里中学四个大气自动监测站的臭氧小时浓度平均值进行滚动预报,比较准确地模拟出臭氧浓度的日周期性变化,同时对峰值和低谷能够进行较为有效的捕捉和刻画。按照《环境空气质量标准》(GB3095—2012)臭氧日最大八小时浓度平均值进行评价,四个站点均取得了90%的预报等级准确率。     

生活生产类产品VOCs含量限值法规与标准研究

本文对国内生活生产类产品VOCs含量限值的国家标准、地方标准、行业标准以及中国香港、欧美等发达地区精细化的生活生产类产品VOCs含量限值法规和标准做了比较全面的综述,并从产品限值种类以及限值要求两个方面进行了对比研究和分析,提出了我国生产生活类产品VOCs 含量限值法规标准制定建议。笔者认为,应借鉴发达国家成功的生活生产类产品VOCs含量限值法规及标准制定经验,从做好标准和产品技术要求衔接、建立区域协同制定标准模式、结合经济因素或环境空气质量,分步推进相关标准制定和发布等方面入手,建立符合实际国情的产品种类较为全面、标准要求较高的生产生活类产品VOCs含量限值法规与标准体系,尤其是生活消费品方面,减少直接与人体接触的生活消费品VOCs排放。     

Blowing Smoke in Yellowstone: Air Quality Impacts of Oversnow Motorized Recreation in the Park

Snowmobile use in Yellowstone National Park has been shown to impact air quality, with implications for the safety and welfare of Park staff and other Park resource values. Localized impacts have been documented at several high-use sites in the Park, but the broader spatial variability of snowmobile emissions and air quality was not understood. Measurements of 87 volatile organic compounds (VOCs) were made for ambient air sampled across the Park and West Yellowstone, Montana, during 2 days of the 2002–2003 winter use season, 1 year before the implementation of a new snowmobile policy. The data were compared with similar data from pristine West Coast sites at similar latitudes. Backward trajectories of local air masses, alkyl nitrate-parent alkane ratios, and atmospheric soundings were used to identify the VOC sources and assess their impact. Different oversnow vehicle types used in the Park were sampled to determine their relative influence on air mass pollutant composition. VOCs were of local origin and demonstrated strong spatiotemporal variability that is primarily influenced by levels of snowmobile traffic on given road segments at different times of day. High levels of snowmobile traffic in and around West Yellowstone produced consistently high levels of benzene, toluene, and carbon monoxide.     

Abundances and flux estimates of volatile organic compounds from a dairy cowshed in Germany

Animal husbandry and manure treatment have been specifically documented as significant sources of methane, ammonia, nitrous oxide, and particulate matter. Although volatile organic compounds (VOCs) are also produced, much less information exists concerning their impact. We report on chemical ionization mass spectrometry and photo-acoustic spectroscopy measurements of mixing ratios of VOCs over a 2-wk measurement period in a large cowshed at the Federal Agricultural Research Centre (FAL) in Mariensee, Germany. The high time resolution of these measurements enables insight into the sources of the emissions in a typical livestock management setting. During feeding hours and solid manure removal, large mixing ratio spikes of several VOCs were observed and correlated with simultaneous methane, carbon dioxide, and ammonia level enhancements. The subsequent decay of cowshed concentration due to passive cowshed ventilation was used to model emission rates, which were dominated by ethanol and acetic acid, followed by methanol. Correlations of VOC mixing ratios with methane or ammonia were also used to calculate cowshed emission factors and to estimate potential nationwide VOC emissions from dairy cows. The results ranged from around 0.1 Gg carbon per year (1 Gg = 10(9) g) for nonanal and dimethylsulfide, several Gg carbon per year for volatile fatty acids and methanol, to over 10 Gg carbon per year of emitted ethanol. While some estimates were not consistent between the two extrapolation methods, the results indicate that animal husbandry VOC emissions are dominated by oxygenated compounds and may be a nationally but not globally significant emission to the atmosphere.     

Urban sprawl and air quality in large US cities

This study presents the results of a paper of urban spatial structure and exceedances of the 8-h national ambient air quality standard for ozone in 45 large US metropolitan regions. Through the integration of a published index of sprawl with metropolitan level data on annual ozone exceedances, precursor emissions, and regional climate over a 13-year period, the association between the extent of urban decentralization and the average number of ozone exceedances per year, while controlling for precursor emissions and temperature, is measured. The results of this analysis support the hypothesis that large metropolitan regions ranking highly on a quantitative index of sprawl experience a greater number of ozone exceedances than more spatially compact metropolitan regions. Importantly, this relationship was found to hold when controlling for population size, average ozone season temperatures, and regional emissions of nitrogen oxides and volatile organic compounds, suggesting that urban spatial structure may have effects on ozone formation that are independent of its effects on precursor emissions from transportation, industry, and power generation facilities.     

A comparative study of US EPA 1996 and 1999 emission inventories in the west Gulf of Mexico coast region, USA

Emission inventory is one of the required inputs to air quality models. To assist in the urban and regional modeling efforts, United States Environmental Protection Agency (EPA) has compiled a National Emission Inventory (NEI) for criterion pollutants, and the precursors of ozone and particulate matter (PM). In December 2002, EPA released the 1999 NEI estimates (NEI99), which represent the most recent national emission data. However, the data sets are not in model-ready format for air quality simulations. This present work converts the NEI99 Final Version 2 data sets into Inventory Data Analyzer (IDA) format and processes the data using the Sparse Matrix Operator Kernel Emissions (SMOKE) modeling system to generate a gridded emission inventory in a domain covering the west Gulf Coast Region, USA. The spatial and diurnal emission characteristics of the gridded emission inventories are then assessed and compared with those of the National Emission Trend 1996 (NET96). The NEI99 database contains more complete emission records in both area and point sources. It is also found that NEI99 data exhibit greater emissions with respect to point and mobile sources but smaller emissions with respect to area sources when compared to the corresponding gridded NET96 data in the same study domain. The most distinct differences between the NEI99 and NET96 databases are CO emission of mobile sources, SO2 emissions of point sources, and VOC/PM/NH3/NOx emissions of area and non-road sources. The gridded NEI99 data show low VOC/NOx ratios (<2-5) in the urban areas of the study domain.     

A solid-phase microextraction chamber method for analysis of manure volatiles

Odors from livestock operations are a complex mixture of volatile carbon, sulfur, and nitrogen compounds. Currently, detailed volatiles analysis is both time consuming and requires specialized equipment and methods. This work describes a new method that utilizes a dynamic flux chamber, solid-phase microextraction (SPME), and gas chromatography-mass spectroscopy (GC-MS) to describe and compare the odorous compounds emitted from cattle and swine feces. Evaluation of method parameters produced a protocol for comparing relative emissions based on fixed sample temperature (20 degrees C) and exposed surface area (approximately 523 cm(2)), air flow rates (1 L min(-1) or 16 cm s(-1)), SPME exposure time (5 min), and chamber cleaning procedures (70% ethanol rinse and drying for 30 min at 105 degrees C) to minimize cross-contamination between samples. A variety of volatile organic compounds (VOCs) including alcohols, volatile fatty acids, aromatic ring compounds, ketones, esters, and sulfides were routinely detected and the relative emissions from fresh and incubated (37 degrees C overnight) swine and cattle feces were compared as a measure of potential to produce odorants during manure storage. Differences in the types and relative quantities of volatiles emitted were detected when animal species (cattle or swine), diet, fecal incubation, or sample storage conditions (20, 4, or -20 degrees C) were varied.     

青岛市挥发性有机物排放清单及重点行业排放特征研究

根据收集的青岛市九大类排放源的活动水平数据,本研究采用排放因子法结合调研实测等工作建立了青岛市VOCs源排放清单,结果表明,工业企业VOCs排放占总排放的比例达到43.17%。其中,工艺过程源类中排放占比较高的行业依次为橡胶和塑料制品业、非金属矿物制品业、原油加工及石油制品制造业、化学原料和化学制品制造业、黑色金属冶炼和压延加工业等;溶剂使用源类中排放占比较高的行业为金属制品业、皮革皮毛羽毛制品和制鞋业、印刷业、铁路船舶航空等设备制造业、汽车制造业等。通过对重点行业重点企业进行入场调研采样分析,本研究发现不同行业中VOCs组成特征有差异,多数行业VOCs物种排放以卤代烃、芳香烃、烷烃等为主,纺织印染业、制鞋业等部分行业以含氧有机物排放为主。通过调研和实测对部分行业的VOCs排放因子水平做了本地化深入研究,调研统计青岛市约49%的企业安装了VOCs治理设施;在企业所安装的VOCs治理设施中吸附法占比最大,占比为26%。