Exploring data quality for some inorganic and organic constituents of inhalable particulate matter (PM10)

Quality assurance (QA) assessments of air pollution data sets provide a basis for evaluating the significance of various substances in the atmosphere. For non-criteria pollutants, QA results are seldom reported in the technical literature and are often difficult to estimate. The present report provides a summary of QA results such as recovery, precision and accuracy data. Of the six trace elements and nine organic constituents compared in detail, recoveries, laboratory precision and laboratory accuracy values were 100%, ±3% to ±19% and-2 to-13% for the former group and 69% to 98%, ±7% to 23% and-15 to-34% for the later group. System precision varied from ±22% to ±47% for the trace elements and ±42% to ±83% for the organic constituents. Limitations in the interpretation of non-criteria particulate-phase pollutant data bases are discussed with some emphasis placed on receptor-modelling and risk assessment applications. Finally, the relevance of NBS certified materials for QA estimates in non-criteria air pollutant studies is also reviewed.     

大气总悬浮颗粒中有机碳的测定

本文提出一种新的高灵敏度测定总悬浮颗粒中有机碳的方法一元素分析法。该方法是在氧化炉最佳温度为６００℃时,一步测定出样品中有机碳的含量,并成功地对齐齐哈尔市大气总悬浮颗粒中的有机碳进行了连续的监测。结果表明,总悬浮颗粒中有机碳的含量有较明显的变化规律。     

TEOM(R)RP1400a(PM10)测尘仪日常维护和常见故障处理

介绍TEOM(R)RP1400a(PM10)测尘仪原理、工作过程以及日常维护、质量控制和常见故障的排除方法.     

大气可吸入颗粒物(PM10)中矿物组分的X射线衍射研究

利用X射线衍射技术对北京2002春季和夏季的可吸入颗粒物进行了研究.结果表明,北京春季和夏季可吸入颗粒物的矿物组成明显不同,春季可吸入颗粒物中的矿物以硅铝酸盐为主,同时存在碳酸盐、硫酸盐、硫化物、铁的氧化物、粘土矿物以及难以鉴定的矿物;在夏季的样品中,矿物的种类有所减少,却有新的物种出现,如氯化氨、硫酸氨等.XRD定量分析显示,在沙尘天气时,可吸入颗粒物中石英和粘土矿物以及非晶质分别占到24.1%、28.5%和2 0%,斜长石和方解石分别占到10.4%和8.1%,其他矿物总共不到10%.矿物组分的确定对可吸入颗粒物来源的识别有一定的指导作用.     

Carbon speciation in airborne particulate matter with C (1s) NEXAFS spectroscopy

Recent and current research activities on the chemical characterization of carbon in airborne carbonaceous particulate matter with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy are reviewed. NEXAFS spectroscopy uses soft X-rays from synchrotron radiation facilities and allows for the bulk and surface speciation of particulates smaller than 2.5 micrometres (PM 2.5). This relatively novel technique is often superior to TEM-EELS and FTIR spectroscopy. In the extreme case, one single PM particle is sufficient for characterization. Liquids, extracts, solid core and surface functional groups can be quantified. Preliminary data on combustion derived PM such as diesel soot, wood smoke and tobacco smoke are compared with ambient samples.     

The distribution of organic matter in songkhla lake basin (SLB)

The concentrations and the distribution of organic matter in SLB (e.g. the outer part of Thale Sap Songkhla area) were examined during the period of September 1988 to September 1989. Organic matter in water samples were analyzed by gravimetry. Total organic matter and dissolved organic matter concentrations ranged from 74 to 7908 mg/L and from 23 to 7813 mg/L, respectively. Except for a set of observations which showed low concentrations during the flood season in November 1988, organic matter was regularly distributed throughout SLB. Domestic effluent and aquaculture are hypothesized as major sources of organic matter contamination. The levels of organic matter concentrations in SLB are significantly higher than would be expected for an area considered to be uncontaminated. The data also indicated a linear relationship between concentrations of suspended organic matter and suspended solids. This may be due to the organic matter associated with suspended solids.     

Analysis of crystalline phases in airborne particulate matter by two-dimensional X-ray diffraction (XRD2)

In this work, the potentiality of two-dimensional X-ray diffraction (XRD(2)) to characterise aerosol particles collected on commercial glass filters is presented. Indeed, even if routine analysis usually requires only mass determination, and rarely chemical composition, phase determination is fundamental to recognize the primary or secondary origin of the particulate matter and thus to determine the main sources of the pollution and to model contamination events. The experiments were performed at Daresbury Synchrotron (UK) Laboratory on 14.1 Beamline. The analysis of filters collected in Tuscany (Italy) is discussed with particular attention to the presence of arsenic sulfide. The first results of these experiments are very promising, showing the presence of unexpected compounds in the particulate matter of the investigated area.     

Structural characterisation of macromolecular organic material in air particulate matter using Py-GC-MS and solid state 13C-NMR

Organic air particulate matter was analysed by applying the techniques of Py-GC-MS (pyrolysis-gas chromatography-mass spectrometry) and solid state 13C-NMR (nuclear magnetic resonance). Particles dislodged from air particulate filters and humic acid extracted from these filters were studied for structural components. The structural components of the air particles and extracted humic acid consisted of compounds originating from biomacromolecules, namely, lignin, carbohydrates, protein and lipids. The main components identified for each class included: (1) methoxyphenols originating from lignin; (2) furans, aldehydes and ketones from carbohydrates; (3) pyrrole, indoles from protein; and (4) many hydrocarbons from lipid structures. Single ion monitoring (SIM) and tetramethyl ammonium hydroxide (TMAH) methylation were utilised for detection of aliphatic hydrocarbons and acidic components, respectively. Hydrocarbons ranging from C9 to C28 were detected by SIM analysis, while aliphatic acids ranged from C9 to C18. The majority of components analysed directly in the air particles were similar to those from the humic acid extracts. Many of the structural components of air particles were typical of humic substances of soil and aqueous systems and these were attributed to both biogenic and anthropogenic sources.     

The organic composition of diesel particulate matter, diesel fuel and engine oil of a non-road diesel generator

Diesel-powered equipment is known to emit significant quantities of fine particulate matter to the atmosphere. Numerous organic compounds can be adsorbed onto the surfaces of these inhalable particles, among which polycyclic aromatic hydrocarbons (PAHs) are considered potential occupational carcinogens. Guidelines have been established by various agencies regarding diesel emissions and various control technologies are under development. The purpose of this study is to identify, quantify and compare the organic compounds in diesel particulate matter (DPM) with the diesel fuel and engine oil used in a non-road diesel generator. Approximately 90 organic compounds were quantified (with molecular weight ranging from 120 to 350), which include alkanes, PAHs, alkylated PAHs, alkylbenzenes and alkanoic acids. The low sulfur diesel fuel contains 61% alkanes and 7.1% of PAHs. The identifiable portion of the engine oil contains mainly the alkanoic and benzoic acids. The composition of DPM suggests that they may be originated from unburned diesel fuel, engine oil evaporation and combustion generated products. Compared with diesel fuel, DPM contains fewer fractions of alkanes and more PAH compounds, with the shift toward higher molecular weight ones. The enrichment of compounds with higher molecular weight in DPM may be combustion related (pyrogenic).     

Distribution of heavy metals in water, particulate matter and sediments of Gediz River (Eastern Aegean)

The present paper is the first document of heavy metal levels in surficial sediment, water and particulate matter of the Gediz River collected from five different sites in August, October 1998, February, June 1999. The present work attempts to establish the status of distribution and environmental implications of metals in the sediment, water and particulate matter and their possible sources of derivation. The concentrations of mercury ranged 0.037–0.81, 120–430; lead 0.59–1.5, 190–8,100; copper 0.24–1.6, 30–180; zinc 0.19–2.9, 10–80; manganese 30–170, 20–490; nickel 0.39–9.0, 100–510; iron 1.3–687, 100–6,200 μg/l in water and particulate matter, respectively. The maximum values in water were generally obtained in summer periods due to industrial and agricultural activities at Muradiye. The particulate metal concentrations also generally showed increased levels from the upper Gediz to the mouth of the river. Calculation of metal partition coefficients shows that the relative importance of the particulate and the water phases varies in response to water hydrochemistry and suspended solid content, but that most elements achieve a conditional equilibrium in the Gediz River. The metals ranged between Hg: 0.25–0.49, Cr: 59–814, Pb: 38–198, Cu: 15–148, Zn: 34–196, Mn: 235–1,371, Ni: 35–175, and Fe: 10,629–72,387 mg/kg in sediment. The significant increase of metals found in Muradiye suggested a pollution effect, related to anthropogenic wastes. Also, relatively high concentrations of Ni and Mn occurred in sampling site upstream, due to geochemical composition of the sediments. Maximum values of contamination factor for metals were noticed for sediment of Muradiye. The sampling stations have very high degree of contamination indicating serious anthropogenic pollution.     

Heavy metals concentrations in zooplankton and suspended particulate matter in a southwestern Atlantic temperate estuary (Argentina)

The present work includes part of the first studies of metals concentrations in the zooplankton from a heavily industrialized estuary of Argentina, the Bahía Blanca estuary. Cd, Cu, and Pb concentrations in the zooplankton (macro- and mesozooplankton) and the suspended particulate matter were measured at stations with different degree of pollution. Physicochemical variables and zooplankton composition and abundance were also analyzed. Thus, the aim of the present work was to analyze the spatial and temporal distribution of heavy metals in these two different fractions, and the possible relation among them due to their importance in the biogeochemical cycles of marine environments. Samplings were carried out during a year, from March 2005 to April 2006, every 2 months, at stations located near chemical and petrochemical industries, stations far from these points and one station in an intermediate location. In the mesozooplankton, the mean concentrations of Cd, Cu, and Pb were 3.63?±?1.46, 34.46?±?5.40, and 11.54?±?3.04 μg?g^?1 dry weight (d.w.) respectively, while in the macrozooplankton, 3.20?±?2.28, 21.86?±?4.79, and 8.36?±?1.85 μg?g^?1 d.w. On the other hand, particulate Cd, Cu, and Pb presented a mean concentration of 3.33?±?1.22, 12.75?±?2.67, and 12.53?±?3.20 μg?g^?1 d.w., respectively. Metals’ levels in both the SPM and zooplankton fluctuated throughout the study time and were relatively high in the particulate phase especially for Cu and Pb. Moreover, zooplankton accumulated important concentrations of the three metals. The sources of them are probably the discharges of the industries and domestic sewages located near the estuary.     

Characterisation of particulate matter emissions from the Zimbabwe Mining and Smelting Company (ZIMASCO) Kwekwe Division (Zimbabwe): a ferrochrome smelter

Particulate matter emissions from stack number 2 of a majorferrochrome smelter, Zimbabwe Mining and Smelting Company(ZIMASCO) were characterized and the rates at which the elementsCr, Fe, Cu and Zn and total ferrochrome dust are emitted into theatmosphere were determined. The extent of soil contamination bythe dust deposited around the smelter in the generally prevailingsoutheasterly wind direction around the smelter was carried out.The highest concentrations of Cr and Fe occurred in the fineparticulates of sizes less than 59 m whilst that of Cu and Znoccurred in the coarse particulates of size range 70-100 m.The emission rates from stack 2 were; total ferrochromeparticulates 62.17 kg h^-1, Cr 6.217 kg h^-1, Fe 2.423 kg h^-1, Zn42 mg h^-1 and 6 mg h^-1 for Cu. Particulate matter was emitted at arate of 289 mg m^-3 from stack number 2. This value exceeds thelegal limit of 200 mg m^-3. Chromium and iron are the metalsin the largest amounts. The particles that constitute the largestproportion of the dust were in the range of 58-107.5 m. Thisis a characteristic feature of the particulate matter emissionsfrom ZIMASCO. Soils in the downwind direction from the smelterwere polluted with Cr up to a distance of about 700 m outward fromthe perimeter of the boundary of the smelter.     

Distribution of suspended particulate matter with trace element composition and apportionment of possible sources in the Raniganj coalfield,India

Ambient air monitoring for suspended particulate matter was carried over a period of one year in some coal mining areas of the Raniganj coalfield. Concentrations of seven elements in suspended particulate matter were determined. The set of data obtained was analysed to determine the sources of trace elements by factor analysis. The data could be interpreted on the basis of five factors. These factors are attributed to various sources of particulate matter by noting the dependence of factors on the elements.     

Evolving Pb isotope signatures of London airborne particulate matter (PM 10)-constraints from on-filter and solution-mode MC-ICP-MS

Pb isotope compositions of biologically significant PM(10) atmospheric particulates from a busy roadside location in London UK were measured using solution- and laser ablation-mode MC-ICP-MS. The solution-mode data for PM(10) sampled between 1998-2001 document a dramatic shift to increasingly radiogenic compositions as leaded petrol was phased out. LA-MC-ICP-MS isotope analysis, piloted on a subset of the available samples, is shown to be a potential reconnaissance analytical technique. PM(10) particles trapped on quartz filters were liberated from the filter surface, without ablating the filter substrate, using a 266 nm UV laser and a dynamic, large diameter, low-fluence ablation protocol. The Pb isotope evolution noted in the London data set obtained by both analytical protocols is similar to that observed elsewhere in Western Europe following leaded petrol elimination. The data therefore provide important baseline isotope composition information useful for continued UK atmospheric monitoring through the early 21(st) century.     

Source analysis of particulate matter associated polycyclic aromatic hydrocarbons (PAHs) in an industrial city in northeastern China

Particle-associated polycyclic aromatic hydrocarbon (PAH) concentrations were investigated at eight sampling sites during cold periods where heating is used (heating period) (February to March, 2005) and warm periods where heating is not required (non-heating periods) (August to September 2006) in the urban area of Anshan, an iron and steel city in northeastern China. Eleven PAH species were measured using GC-MS. The total average concentrations of PAHs ranged from 46.14 to 385.60 ng m(-3) in the heating period and from 5.28 to 146.40 ng m(-3) in the non-heating period. The lowest concentration of ∑PAHs was observed at Qianshan, a monitoring site far from the city and industrial area, and the highest concentration occurred in the site located at the factory area of Anshan Iron and Steel Incorporation. Moreover, ambient PAH profiles were studied and high molecular weight PAH (including 4-6 rings) species occurred in the high fractions. Toxic equivalent factors analysis gave the potential carcinogenic risks in Anshan. For the heating sampling period, BaP equivalent concentration is in the range of 41.98 to 220.83 ng m(-3), and 9.23 to 126.00 ng m(-3) for the non-heating sampling period. By diagnostic ratio analysis, traffic emission and combustion (coal or biomass) were potential sources for PAHs in Anshan. Finally, PCA results indicated the major sources were vehicle emission, steel industry emission, and coal combustion for both heating and non-heating seasons, which agreed with the results from the diagnostic ratio analysis.     

Reactivity, interactions and transport of trace elements, organic carbon and particulate material in a mountain range river system (Adour River, France)

The background levels, variability, partitioning and transport of eleven trace elements-Ag, Al, As, Cd, Co, Cr, Cu, Mn, Pb, Zn and U-were investigated in a mountain range river system (Adour River, France). This particular river system displayed a turbulent hydrodynamic regime, characterized by flash-transient discharge conditions leading to fast shifts in suspended particulate matter (SPM) concentrations as high as two orders of magnitude (12 to 600 mg l(-1)). The distribution of SPM was accurately predicted with a "hysteresis" transport model, indicating that about 75% of the annual solids load was exported within 20 to 40 days. Dissolved and particulate concentrations of most trace elements were low compared to their concentrations in other reference river systems expect for Pb and Cr, associated with historical anthropogenic activities. Although dissolved and particulate metal concentrations were steady for most elements during low and average discharge conditions, significant changes were observed with increasing river discharge. The changes in trace element concentrations in the two compartments was found to induce a partitioning anomaly referred to as the particulate concentration effect. This anomaly was significant for Cr, Mn, Pb, Zn, Cu and organic carbon (p < 0.03). The processes driving this anomaly were possibly linked to the modification and/or increase of colloidal organic and inorganic vectors, suggested by the significant increase of DOC (p < 0.001) and dissolved Al concentrations (p < 0.05) during flood conditions. A complementary process linked to the influence of coarse particles of low complexation capacity and transported mainly during high discharge may also effect trace element concentrations. Annual metal fluxes transported by this river system were estimated using the hysteresis SPM model with consideration of these fate processes. Metals in the Adour River system are primarily exported into the Bay of Biscay (Atlantic Ocean).     

Effects of salinity and organic matter on the partitioning of perfluoroalkyl acid (PFAs) to clay particles

The influence of salinity and organic matter on the distribution coefficient (K(d)) for perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) in a brackish water-clay system was studied. The distribution coefficients (K(d)) for PFAs onto inorganic clay surfaces increased with salinity, providing evidence for electrostatic interaction for the sorption of PFAs, whereas the relationship between K(d) and organic carbon content (f(oc)) suggested that hydrophobic interaction is the primary driving force for the sorption of PFAs onto organic matter. The organic carbon normalized adsorption coefficient (K(oc)) of PFAs can be slightly overestimated due to the electrostatic interaction within uncoated inorganic surfaces. In addition, the dissolved organic matter released from coated clay particles seemed to solvate PFA molecules in solution, which contributed to a decrease in K(d). A positive relationship between K(d) and salinity was apparent, but an empirical relationship for the 'salting-out' effect was not evident. The K(d) values of PFAs are relatively small compared with those reported for persistent organic pollutants. Thus, sorption may not be a significant route of mass transfer of PFAs from water columns in estuarine environments. However, enhancement of sorption of PFAs to particulate matter at high salinity values could evoke potential risks to benthic organisms in estuarine areas.     

Concentrations, sources, and exposure profiles of polycyclic aromatic hydrocarbons (PAHs) in particulate matter (PM10) in the north central part of India

Airborne particulates (PM₁₀) from four different areas within Agra city (a semi-arid region) were collected using respirable dust samplers during the winter season (Nov. 2005–Feb 2006) and were then extracted with methylene chloride using an automated Soxhlet Extraction System (Soxtherm^®). The extracts were analyzed for 17 target polycyclic aromatic hydrocarbons (PAHs) and the heterocycle carbazole. The average concentration of total PAH (TPAH) ranged from 8.04 to 97.93 ng m^???3. The industrial site had the highest TPAH concentration followed by the residential, roadside, and agricultural sites. Indeno(1,2,3-cd)pyrene, benzo(g,h,i)perylene, and benzo(b)fluoranthene were the predominant compounds found in the samples collected from all of the sites. The average B(a)P-equivalent exposure, calculated by using toxic equivalent factors derived from literature and the USEPA, was approximately 7.6 ng m^???3. Source identification using factor analysis identified prominent three, four, four, and four probable factors at industrial, residential, roadside, and agricultural sites, respectively.     

Ascorbic acid reduction of active chlorine prior to determining Ames mutagenicity of chlorinated natural organic matter (NOM)

Many potable water disinfection byproducts (DBPs) that result from the reaction of natural organic matter (NOM) with oxidizing chlorine are known or suspected to be carcinogenic and mutagenic. The Ames assay is routinely used to assess an overall level of mutagenicity for all compounds in samples from potable water supplies or laboratory studies of DBP formation. Reduction of oxidizing disinfectants is required since these compounds can kill the bacteria or react with the agar, producing chlorinated byproducts. When mutagens are collected by passing potable water through adsorbing resins, active chlorine compounds react with the resin, producing undesirable mutagenic artifacts. The bioanalytical and chemoanalytical needs of drinking water DBP studies required a suitable reductant. Many of the candidate compounds failed to meet those needs, including 2,4-hexadienoic (sorbic) acid, 2,4-pentanedione (acetylacetone), 2-butenoic (crotonic) acid, 2-butenedioic (maleic and fumaric) acids and buten-2-ol (crotyl alcohol). Candidates were rejected if they (1) reacted too slowly with active chlorine, (2) formed mutagenic byproducts, or (3) interfered in the quantitation of known chlorination DBPs. L-Ascorbic acid reacts rapidly and stoichiometrically with active chlorine and has limited interactions with halogenated DBPs. In this work, we found no interference from L-ascorbic acid or its oxidation product (dehydroascorbic acid) in mutagenicity assays of chlorinated NOM using Salmonella typhimurium TA100, with or without metabolic activation (S9). This was demonstrated for both aqueous solutions of chlorinated NOM and concentrates derived from the involatile, ether-extractable chlorinated byproducts of those solutions.     

Suspended particulate matter estimates using optical and acoustic sensors: application in Nestos River plume (Thracian Sea,North Aegean Sea)

The present study investigates the use of combined methods of optical and acoustic sensors, in collaboration with direct in situ measurements, for the calibration and validation of a model transforming acoustic backscatter intensity series into suspended particulate matter (SPM) concentration datasets. The model follows previously elaborated techniques, placing particular attention to the parameterization of the acoustic absorption index as a function of water physical properties. Results were obtained from the annual deployment (during 2007–2008) of an upward-facing acoustic Doppler current profiler (ADCP) (307 kHz), equipped with a Wave Array, and an optical backscatter sensor (OBS), at the bottom of Thassos Passage near Nestos River plume (Thracian Sea, Northern Greece). The OBS was calibrated through linear regression, using 2007 and 2012 field sampling data, exhibiting an error of 13–14 % due to chlorophyll presence. The ADCP signal was calibrated through simultaneous measurements of backscatter intensity and turbidity profiles. Harmonic analysis on the model-produced SPM concentrations explained the tidal influence on their variability, especially during the summer. Empirical orthogonal functions analysis revealed the impact of waves and wave-induced currents on SPM variability. Finally, Nestos River sediment load was found uncorrelated to the SPM change in Thassos Passage, due to the dispersal and sediment deposition near the river mouth.