Submicrometer elemental carbon as a selective measure of diesel particulate matter in coal mines

A monitoring method for diesel particulate matter was published as Method 5040 by the National Institute for Occupational Safety and Health (NIOSH). Organic and elemental carbon are determined by the method, but elemental carbon (EC) is a better exposure measure. The US Mine Safety and Health Administration (MSHA) proposed use of NIOSH 5040 for compliance determinations in metal and nonmetal mines. MSHA also published a rulemaking for coal mines, but no exposure standard was provided. A standard based on particulate carbon is not considered practical because of coal dust interference. Interference may not be a problem if an appropriate size-selective sampler and EC exposure standard are employed. Submicrometer dust concentrations found in previous surveys of nondieselized, underground coal mines were relatively low. If a large fraction of the submicrometer dust is organic and mineral matter, submicrometer EC concentrations would be much lower than submicrometer mass concentrations. Laboratory and field results reported herein indicate the amount of EC contributed by submicrometer coal dust is minor. In a laboratory test, a submicrometer EC concentration of 31 microg m(-3) was found when sampling a respirable coal dust concentration over three times the US compliance limit (2 mg m(-3)). Laboratory results are consistent with surveys of nondieselized coal mines, where EC results ranged from below the method limit of detection to 18 microg m(-3) when size-selective samplers were used to collect dust fractions having particle diameters below 1.5 microm-submicrometer EC concentrations were approximate 7 microg m(-3). In dieselized mines, submicrometer EC concentrations are much higher.     

因子分析法解析北京市大气颗粒物PM10的来源

2004年10月份在北京市6个采样点采集了大气PM10样品,分析了大气颗粒物的质量浓度、元素组成、离子、有机碳(OC)和元素碳(EC)的浓度,并用因子分析模型对颗粒物的来源进行了研究。结果显示,北京市大气颗粒物的来源主要有6类:建筑水泥尘/机动车尾气尘/燃煤尘、土壤风沙尘、二次粒子尘、工业粉尘、生物质燃烧尘和燃油尘。用模型计算得到的各源对PM10的贡献率分别为建筑水泥尘/机动车尾气尘/燃煤尘占36.57%、土壤风沙尘占16.07%、二次粒子尘占12.33%、工业粉尘占10.29%、生物质燃烧尘占6.07%、燃油尘占3.84%、其它占14.84%。其中建筑水泥/机动车尾气尘/燃煤尘、土壤风沙尘、二次粒子尘、工业粉尘是大气颗粒物PM10的主要来源。实验表明,在缺少源成分谱时可以用因子分析模型来分析大气颗粒物的来源及其相对贡献。     

Comparison of two carbon analysis methods for monitoring diesel particulate levels in mines

Two carbon analysis methods are currently being applied to the occupational monitoring of diesel particulate matter. Both methods are based on thermal techniques for the determination of organic and elemental carbon. In Germany, method ZH 1/120.44 has been published. This method, or a variation of it, is being used for compliance measurements in several European countries, and a Comité Européen de Normalization Working Group was formed recently to address the establishment of a European measurement standard. In the USA, a 'thermal-optical' method has been published as Method 5040 by the National Institute for Occupational Safety and Health. As with ZH 1/120.44, organic and elemental carbon are determined through temperature and atmosphere control, but different instrumentation and analysis conditions are used. Although the two methods are similar in principle, they gave statistically different results in a previous interlaboratory comparison. Because different instruments and operating conditions are used, between-method differences can be expected in some cases. Reasonable agreement is expected when the sample contains no other (i.e., non-diesel) sources of carbonaceous particulate and the organic fraction is essentially removed below about 500 degrees C. Airborne particulate samples from some mines may meet these criteria. Comparison data on samples from mines are important because the methods are being applied in this workplace for occupational monitoring and epidemiological studies. In this paper, results of a recent comparison on samples collected in a Canadian mine are reported. As seen in a previous comparison, there was good agreement between the total carbon results found by the two methods, with ZH 1/120.44 giving about 6% less carbon than Method 5040. Differences in the organic and elemental carbon results were again seen, but they were much smaller than those obtained in the previous comparison. The relatively small differences in the split between organic and elemental carbon are attributed to the different thermal programs used.     

Pattern of Hexa-Valent Chromium in Air Borne Respirable Dust Generated at Various Workplaces in Opencast Chromite Mines

The paper presents a study into air borne respirable dust (ARD) concentration at various workplaces in two open cast chromite mines of Sukinda chromite belt, India. One of these mines is mechanised and the other one is semi-mechanised. The study has been conducted in three phases and ARD concentration has been measured at various workplaces in both the mines. Apart from the determination of ARD concentration, the dust samples collected on filter papers were analysed for hexa-valent chromium by colorimetric method and Cr(VI) direct absorption measurement. In addition, the particle size ranges in ARD have been determined by using cascade impactor fitted onto high volume samplers and laser guided particle size analyser. The paper finally presents a comparison between ARD concentration vis-à-vis the presence of hexa-valent chromium concentration in collected samples of both mechanised and semi-mechanised mines.     

桂林市细颗粒物部分典型排放源的粒径谱及成分分析

采用在线单颗粒气溶胶质谱技术源解析方法,对桂林市PM2.5典型排放源的粒径和化学成分进行质谱分析,采集燃煤/燃气源、工业工艺源、扬尘源、油烟源4类共计7个典型排放源。结果表明,桂林市4类排放源细颗粒物的粒径分布为0.25~1.25μm,80%以上的细颗粒分布在0.2~1.0μm的小粒径范围,峰值约0.68μm。细颗粒物离子成分含有Na~+、Mg~+、K~+、NH~+4、Fe~+、Pb~+、Cd~+、V~+、Mn~+、Li~+、Al~+、Ca~+、Cu~+、Zn~+、Cr~+、CN~-、PO_3~-、NO_2~-、NO_3~-、Cl~-、SO_4~(2-)、SiO_3~-等成分,桂林市细颗粒物为元素碳、有机碳元素碳、有机碳、富锰颗粒、富铁颗粒、富钾颗粒、矿物质、左旋葡聚糖以及其他金属等9类。     

Chemical compositions and sources of atmospheric PM10 in heating, non-heating and sand periods at a coal-based city in northeastern China

Mass concentrations and chemical components (18 elements, 9 ions, organic carbon [OC] and elemental carbon [EC]) in atmospheric PM(10) were measured at five sites in Fushun during heating, non-heating and sand periods in 2006-2007. PM(10) mass concentrations varied from 62.0 to 226.3 μg m(-3), with 21% of the total samples' mass concentrations exceeding the Chinese national secondary standard value of 150 μg m(-3), mainly concentrated in heating and sand periods. Crustal elements, trace elements, water-soluble ions, OC and EC represented 20-47%, 2-9%, 13-34%, 15-34% and 13-25% of the particulate matter mass concentrations, respectively. OC and crustal elements exhibited the highest mass percentages, at 27-34% and 30-47% during heating and sand period. Local agricultural residuals burning may contribute to EC and ion concentrations, as shown by ion temporal variation and OC and EC correlation analysis. Heavy metals (Cr, Ni, Zn, Cu and Mn) from coal combustion and industrial processes should be paid attention to in heating and sand periods. The anion/cation ratios exhibited their highest values for the background site with the influence of stationary sources on its upper wind direction during the sand period. Secondary organic carbon were 1.6-21.7, 1.5-23.0, 0.4-17.0, 0.2-33.0 and 0.2-21.1 μg m(-3), accounting for 20-77%, 44-88%, 4-77%, 8-69% and 4-73% of OC for the five sampling sites ZQ, DZ, XH, WH and SK, respectively. From the temporal and spatial variation analysis of major species, coal combustion, agricultural residual burning and industrial emission including dust re-suspended from raw material storage piles were important sources for atmospheric PM(10) in Fushun at heating, non-heating and sand periods, respectively. It was confirmed by principal component analysis that coal combustion, vehicle emission, industrial activities, soil dust, cement and construction dust and biomass burning were the main sources for PM(10) in this coal-based city.     

Concentration gradient patterns of aerosol particles near interstate highways in the Greater Cincinnati airshed

The objective of this study was to determine if there is an exposure gradient in particulate matter concentrations for people living near interstate highways, and to determine how far from the highway the gradient extends. Air samples were collected in a residential area of Greater Cincinnati in the vicinity of two major highways. The measurements were conducted at different distances from the highways by using ultrafine particle counters (measurement range: 0.02-1 microm), optical particle counters (0.3-20 microm), and PM2.5 Harvard Impactors (0.02-2.5 microm). The collected PM2.5 samples were analyzed for mass concentration, for elemental and organic carbon, and for elemental concentrations. The results show that the aerosol concentration gradient was most clearly seen in the particle number concentration measured by the ultrafine particle counters. The concentration of ultrafine particles decreased to half between the sampling points located at 50 m and 150 m downwind from the highway. Additionally, elemental analysis revealed a gradient in sulfur concentrations up to 400 m from the highway in a residential area that does not have major nearby industrial sources. This gradient was qualitatively attributed to the sulfate particle emissions from diesel engine exhausts, and was supported by the concentration data on several key elements indicative of traffic sources (road dust and diesel exhaust). As different particulate components gave different profiles of the diesel exposure gradient, these results indicate that no single element or component of diesel exhaust can be used as a surrogate for diesel exposure, but more comprehensive signature analysis is needed. This characterization is crucial especially when the exposure data are to be used in epidemiological studies.     

中国北方干旱地区沙尘矿物特征研究

为了开展对我国沙暴传输规律的研究,了解我国北方干旱地区沙尘矿物特征有重要意义。本文对我国新疆塔克拉玛干沙漠区,内蒙腾格里沙漠区,贺兰山及银川等处的沙尘样品用X射线粉末衍射法进行矿物分析鉴定,并用原子吸收法作了特征元素的分析对比,根据矿物的X射线粉末衍射结果,结合元素分析,对沙漠源区及其以东地区沙尘矿物特征作了比较,判析了两个源区的矿物组成,讨论了它们的传输过程。     

活性炭负载催化剂去除燃煤烟气中单质汞的研究

以贵州凯里褐煤进行燃烧实验,研究采用CoCl2(负载量20%)改性的活性炭去除烟气中的单质汞。颗粒态汞占烟气总汞的87%,而单质汞占气态汞的80.4%。改性活性炭吸附了气态汞中97%的单质汞,而吸收液只吸收了3%的单质汞。可见改性活性炭也能有效地吸附煤燃烧实验中的烟气汞。实验结果表明,煤中汞的释放率为59.5%,1kg的改性活性炭可以吸附208t煤所产生的烟气中的气态单质汞。     

Equivalency of a personal dust monitor to the current United States coal mine respirable dust sampler

The United States National Institute for Occupational Safety and Health, through an informal partnership with industry, labor, and the United States Mine Safety and Health Administration, has developed and tested a new instrument known as the Personal Dust Monitor (PDM). The new dust monitor is an integral part of the cap lamp that coal miners normally carry to work and provides continuous information about the concentration of respirable coal mine dust within the breathing zone of that individual. Previous laboratory testing demonstrated that there is a 95% confidence that greater than 95% of individual PDM measurements fall within +/-25% of reference measurements. The work presented in this paper focuses on the relationship between the PDM and respirable dust concentrations currently measured by a coal mine dust personal sampler unit utilizing a 10 mm Dorr-Oliver nylon cyclone. The United Kingdom Mining Research Establishment instrument, used as the basis for coal mine respirable dust standards, had been designed specifically to match the United Kingdom British Medical Research Council (BMRC) criterion. The personal sampler is used with a 1.38 multiplier to convert readings to the BMRC criterion. A stratified random sampling design incorporating a proportionate allocation strategy was used to select a sample of mechanized mining units representative of all US underground coal mines. A sample of 180 mechanized mining units was chosen, representing approximately 20% of the mechanized mining units in production at the time the sample was selected. A total of 129 valid PDM/personal sampler dust sample sets were obtained. A weighted linear regression analysis of this data base shows that, in comparison with the personal sampler, the PDM requires a mass equivalency conversion multiplier of 1.05 [95% C.I.=(1.03, 1.08)] when the small intercept term is removed from the analysis. Removal of the intercept term results in a personal sampler-equivalent concentration increase of 2.9% at a PDM measurement of 2.0 mg m(-3).     

Characterization of different road dusts in opencast coal mining areas of India

Dust from haul and transport roads are the major source of air pollution in opencast coal mining areas. Dust generated during mining operations pollutes air which causes different health problems. Various available techniques are implemented in the field to minimize and control dust in mining areas. However, they are not very effective because dust deposited on road surfaces are not removed by these techniques. For effective control of dust in opencast mining areas, it has to be regularly collected from road surfaces and may be converted into solid form, and subsequently can be used as a domestic fuel considering its physicochemical properties. The present paper describes a comparative study of qualitative and quantitative aspects of road dust samples of four coalfields of India. The pH of the dust was found to be in the range of 5.1–7.7. Moisture, ash, volatile matter, fixed carbon, water-holding capacity, bulk density, and specific gravity of dust samples were found to be in the range of 0.5–3.0%, 45–76%, 12.6–20.0%, 10.2–45.3%, 21.17–31.71%, 1.15–1.70, and 1.73–2.30 g cm⁻³, respectively. Observing the overall generation and characteristics of coal dust, it is suggested that coal dust from haul and transport roads of mining areas can be effectively collected and used as domestic fuel.     

北京市大气PM10源解析研究

于2004年在北京市定陵、车公庄、古城、亦庄、房山和奥体中心6个采样点采集大气PM10环境样品,针对北京市颗粒物主要排放源采集土壤尘、建筑水泥尘、燃煤等污染源PM10样品,分别对其中的无机元素、离子、有机碳(OC)和元素碳(EC)进行测定。采用代表北京市颗粒物主要排放源PM10组分特征的成分谱,利用CMB受体模型对PM10来源进行解析。结果表明,PM10的最大来源为土壤尘,其它贡献源类依次为燃煤排放、机动车/燃油排放、二次粒子(SO42-、NO3-和NH4 )、建筑水泥尘。污染源贡献具有明显的季节变化,并存在一定的地域变化。     

应用化学质量平衡模型解析西宁大气PM2.5的来源

为研究影响西宁市大气环境PM_(2.5)污染水平的主要来源,于2014年采暖季、风沙季和非采暖季依托西宁市大气地面观测网络在11个监测点采集大气PM_(2.5)样品,对其化学组分(元素、离子和碳)进行分析。研究同步采集了4类固定源、14类移动源和4类开放源的PM_(2.5)样品,并构建源排放成分谱。应用化学质量平衡受体模型(CMB)开展源解析研究。源解析结果表明,观测期间西宁市PM_(2.5)主要来源包括城市扬尘(分担率为26.4%)、燃煤尘(14.5%)、机动车尾气(12.8%)、二次硫酸盐(9.0%)、生物质燃烧(6.6%)、二次硝酸盐(5.7%)、钢铁尘(4.7%)、锌冶炼尘(3.4%)、建筑尘(4.4%)、土壤尘(4.4%)、餐饮排放(2.9%)和其他未识别的来源(5.2%)。大力开展城市扬尘为主的开放源污染控制,严格控制本地燃煤、机动车等污染源的PM_(2.5)排放,是改善西宁市空气质量的重要途径。     

合肥市冬季灰霾天气PM_(2.5)源解析

于2016年12月30日—2017年2月4日,利用单颗粒气溶胶飞行时间质谱仪(SPAMS),对合肥市PM_(2.5)开展来源解析连续监测,共捕捉到4次较为明显的灰霾过程,对颗粒物种类及质谱特征进行了分析。结果显示,监测期间合肥市主要颗粒物成分为元素碳(EC)(31. 9%)、富钾(K)(16. 6%)、有机碳(OC)(16. 0%)及混合碳颗粒(ECOC)(15. 0%)等。主要污染源为机动车尾气源(24. 5%)、工业工艺源(22. 7%)、燃煤源(14. 1%)、二次无机源(13. 5%)等。污染天气发生时,工业工艺源占比上升2. 2个百分点,生物质燃烧和燃煤源占比分别下降1. 7和2. 7个百分点,机动车尾气和扬尘源基本持平,表明此次污染过程主要受到工业工艺源的累积影响。     

Increased levels of bacterial markers and CO2 in occupied school rooms

Our group previously demonstrated that carbon dioxide (CO2) levels in heavily occupied schools correlate with the levels of airborne bacterial markers. Since CO2 is derived from the room occupants, it was hypothesized that in schools, bacterial markers may be primarily increased in indoor air because of the presence of children; directly from skin microflora or indirectly, by stirring up dust from carpets and other sources. The purpose of this project was to test the hypothesis. Muramic acid (Mur) is found in almost all bacteria whereas 3-hydroxy fatty acids (3-OH FAs) are found only in Gram-negative bacteria. Thus Mur and 3-OH FA serve as markers to assess bacterial levels in indoor air (pmol m(-3)). In our previous school studies, airborne dust was collected only from occupied rooms. However, in the present study, additional dust samples were collected from the same rooms each weekend when unoccupied. Samples were also collected from outside air. The levels of dust, Mur and C10:0, C12:0, C14:0, and C16:0 3-OH FAs were each much higher (range 5-50 fold) in occupied rooms than in unoccupied school rooms. Levels in outdoor air were much lower than that of indoor air from occupied classrooms and higher than the levels in the same rooms when unoccupied. The mean CO2 concentrations were around 420 parts per million (ppm) in unoccupied rooms and outside air; and they ranged from 1017 to 1736 ppm in occupied rooms, regularly exceeding 800-1000 ppm, which are the maximum levels indicative of adequate indoor ventilation. This indicates that the children were responsible for the increased levels of bacterial markers. However, the concentration of Mur in dust was also 6 fold higher in occupied rooms (115.5 versus 18.2 pmole mg(-1)). This further suggests that airborne dust present in occupied and unoccupied rooms is quite distinct. In conclusion in unoccupied rooms, the dust was of environmental origin but the children were the primary source in occupied rooms.     

抚顺市PM10中元素分布特征及来源分析

为了确定抚顺市PM10中元素的浓度特征及其来源,于2006—2007年的采暖季、风沙季和非采暖季在抚顺市的6个采样点采集PM10样品,并用等离子体原子发射光谱法(ICP-AES)测定样品中Ti、Al、Mn、Mg、Ca、Na、K、Cu、Zn、As、Pb、Cr、Ni、Co、Cd、Fe、V等17种元素的含量。结果表明,Al、Mg、Ca、Na、K、Mn、Fe等地壳元素在17种元素中占有较大比重,全年平均达到97.0%。富集因子分析结果表明,Cu、Zn、Pb、Cr、Co、Cd等元素在各季和各采样点明显受到人为活动影响,是典型的污染元素。主因子分析结果显示,土壤风沙尘、建筑尘、燃煤尘、道路扬尘、机动车尾气排放、金属冶炼、锰、铜、钛工业源是抚顺市PM10中元素的主要来源。     

Assessment of particulate matter in the urban atmosphere: size distribution, metal composition and source characterization using principal component analysis

In this study, the size distribution of airborne particles and related heavy metals Co, Cd, Sn, Cu, Ni, Cr, Pb and V in two urban areas in Istanbul: Yenibosna and Goztepe, were examined. The different inhalable particles were collected by using a cascade impactor in eight size fractions (<0.4 μm, 0.4-0.7 μm, 1.1-2.1 μm, 2.1-3.3 μm, 3.3-4.7 μm, 4.7-5.8 μm, 5.8-9 μm and >9 μm) for six months at each station. Samples were collected on glass fiber filters and filters were extracted and analyzed using ICP-MS. Log-normal distributions showed that the particles collected at the Yenibosna site have a smaller size compared to the Goztepe samples and the size distribution of PM was represented the best by the tri-modal. The average total particle concentrations and standard deviations were obtained as 67.7 ± 17.0 μg m(-3) and 82.1 ± 21.2 μg m(-3), at the Yenibosna and G?ztepe sites, respectively. The higher metal rate in fine and medium coarse PM showed that the anthropogenic sources were the most significant pollutant source. Principal component analysis identified five components for PM namely traffic, road dust, coal and fuel oil combustion, and industrial.     

PM source apportionment and trace metallic aerosol affinities during atmospheric pollution episodes: a case study from Puertollano, Spain

Source apportionment study was performed, applying principal component analysis to the results of 221 chemical analyses of PM10 and PM2.5 samples collected daily from the industrial (but low traffic) Spanish town of Puertollano over a 14-month period during 2004-2005. Results reveal compositional variations attributable to different mixtures of natural and anthropogenic materials, mainly soil and rock dust (crustal), marine salt (only in PM10), petrochemical refinery emissions, and particles attributed to the combustion of local coal, which is unusually rich in Pb and Sb. During the study period there were 34 pollution episodes when PM10 exceeded 50 tg m(-3), mostly due to winter air temperature inversions, regional atmospheric stagnation, or African dust incursions (North African, NAF days: usually in summer). Whereas the crustal component during NAF episodes averaged 52% with a PM2.5/PM10 ratio of 0.54, this dropped to 29% and a PM2.5/PM10 of 0.67 during non-NAF days when anthropogenic materials predominated. Abnormally enhanced concentrations of pathfinder metallic trace elements provide additional evidence for source apportionment: thus aerosols with raised levels of Pb and Sb are associated with local coal combustion, Ni and V can be linked to petrochemical PM emissions, and Ti, Mn, Rb, and Ce are particularly characteristic of crustal dust incursions.     

西安城北地区秋季PM_(2.5)中的矿尘颗粒污染特征

采用单颗粒气溶胶飞行时间质谱仪(Single Particle Aerosol Mass Spectrometer,SPAMS)对西安市大气矿尘颗粒物进行连续12 d在线分析,共采集到107 425个同时含有正负质谱信息的矿尘颗粒,矿尘颗粒物占PM_(2.5)样本数的8.44%。结果表明,矿尘颗粒物的正离子碎片成分以Na~+、K~+、Al~+、Ca~+、CaO~+、Fe~+为主,同时还含有Pb~+等,负离子碎片成分以NO~-_2和NO~-_3为主,另外还含有HSO~-_4、SiO~-_3、HSiO~-_3、H(NO_3)~-_2等。在西安市大气细颗粒物中,矿尘颗粒物中贡献较大的几类(如含钙、含铁、铁氧颗粒物等)大多是老化的成分。将观测阶段采集到的矿尘颗粒纳入本地污染源谱进行来源分析,其主要来源为扬尘源、工业源、燃煤源和汽车尾气源等。     

Methods for determination of elemental carbon in ambient air

A few analytical methods of elemental carbon determination are described. The purpose of the work is to choose the best method for determination of its content in dust suspended in air in industrial regions. The reflectance and chromatographic methods were investigated. It was shown that the reflectance methods could be used only when the particle size and form of elemental carbons constant. The chromatographic method, which includes the step of combustion of the sample in oxygen and chromatographic determination of evolved CO₂ is recommended, since it is independent of the form of carbon. Organic carbon is removed from dust samples by extraction with benzene-methanol mixture.