Development and validation of the volatile correction model for PM10 – An empirical method for adjusting TEOM measurements for their loss of volatile particulate matter

EU Directives stipulate that PM₁₀ should be measured using the gravimetric reference method as laid out in EN12341 [CEN, 1998. Air Quality – Determination of the PM₁₀ Fraction of Suspended Particulate Matter – Reference Method and Field Test Procedure to Demonstrate Reference Equivalence of Measurement Methods. European Committee for Standardisation], or an equivalent method as demonstrated using EC guidance [EC, 2005. Demonstration of Equivalence of Ambient Air Monitoring Methods. European Commission Working Group on Guidance for the Demonstration of Equivalence]. There is however a conflict between the requirement to measure PM₁₀ using the gravimetric reference method and the need for rapid public reporting, and many member states, including the UK, rely on non-gravimetric techniques to measure PM₁₀. In the UK the majority of PM₁₀ measurements are made using the Tapered Element Oscillating Microbalance (TEOM), which does not meet the equivalence criteria [Harrison, D., 2006. UK Equivalence Programme for Monitoring of Particulate Matter. Defra, London]. The implied need to upgrade or replace TEOMs with an equivalent automated measurement technique has significant cost implications. The model described in this paper was based on analysis of daily mean measurements of PM₁₀ by the Filter Dynamics Measurement System (FDMS) and the TEOM at UK sites. It uses the FDMS measurement of the volatile component of PM₁₀ (referred to here as FDMS purge) to correct for differences in the sensitivity to volatile PM₁₀ between the TEOM and the EU gravimetric reference method. The model equation for the correction of TEOM PM₁₀ measurements is: TEOM_VCM = TEOM ? 1.87 FDMS purge due to the regional homogeneity of volatile PM, the FDMS purge concentration may be measured at a site distant to the TEOM, allowing the possibility of using a single FDMS instrument to correct PM₁₀ measurements made by several TEOMs in a defined geographical area. The model was assessed against the criteria for the EC Working Group's Guidance for the Demonstration of Equivalence of Ambient Air Monitoring Methods [EC, 2005. Demonstration of Equivalence of Ambient Air Monitoring Methods. European Commission Working Group on Guidance for the Demonstration of Equivalence]. The model satisfies the equivalence criteria using remote FDMS purge measurements for distances up to 200 km (in 22 out of 23 data sets). These data provide strong evidence that the model is a viable tool for correcting measurements from TEOM instruments on the national and local government networks.     

Particulate Matter in California: Part 2—Spatial,Temporal, and Compositional Patterns of PM2.5, PM10–2.5, and PM10

Abstract

Geographic and temporal variations in the concentration and composition of particulate matter (PM) provide important insights into particle sources, atmospheric processes that influence particle formation, and PM management strategies. In the nonurban areas of California, annual-average PM_2.5 and PM₁₀ concentrations range from 3 to 10 [H9262]g/m³ and from 5 to 18 µg/m³, respectively. In the urban areas of California, annual-averages for PM_2.5 range from 7 to 30 [H9262]g/m³, with observed 24-hr peaks reaching levels as high as 160 [H9262]g/m³. Within each air basin, exceedances are a mixture of isolated events as well as periods of elevated PM_2.5 concentrations that are more prolonged and regional in nature. PM_2.5 concentrations are generally highest during the winter months. The exception is the South Coast Air Basin, where fairly high values occur throughout the year. Annual-average PM_2.5 mass, as well as the concentrations of major components, declined from 1988 to 2000. The declines are especially pronounced for the sulfate (SO₄ ^2?) and nitrate (NO₃ ^?) components of PM_2.5 and PM₁₀ and correlate with reductions in ambient levels of oxides of sulfur (SO_x) and oxides of nitrogen (NO_x). Annual averages for PM_10–2.5 and PM₁₀ exhibited similar downwind trends from 1994 to 1999, with a slightly less pronounced decrease in the coarse fraction.     

Five years of formaldehyde and acetaldehyde monitoring in the Rio de Janeiro downtown area – Brazil

The fuel matrix used in Brazil is unique around the world. The intensive use of hydrated ethanol, gasohol (gasoline with 25% v/v of ethanol), compressed natural gas (CNG), and biodiesel leads to a peculiar composition of the urban atmosphere. From 1998 to 2002 an increase in formaldehyde levels was observed and since then, a reduction. This work presents a monitoring campaign that was executed from March 2004 to February 2009 by sampling at early morning on every sunny Wednesday for a total of 183 samples. The results indicate a strong reduction in formaldehyde levels from 2004 (average of 135.8 μg m^?3 with SD 28.4 μg m^?3) to 2009 (average of 49.3 μg m^?3 with SD 27.4 μg m^?3). The levels of acetaldehyde showed a slight reduction from 2004 (average of 34.9 μg m^?3 with SD 8.0 μg m^?3) to 2009 (average of 26.8 μg m^?3 with SD 11.5 μg m^?3). Comparing the results with the concurrent evolution of the fleet and of fuel composition indicates that the observed formaldehyde levels could be associated with the increase in ethanol use and in CNG use by engines with improved technology over the first converted CNG engines. Modelling studies using the OZIPR trajectory model and the SAPRC chemical mechanism indicate that formaldehyde is the main ozone precursor in Rio de Janeiro and acetaldehyde is the forth one.     

Do metal concentrations in moss from the Zackenberg area,Northeast Greenland,provide a baseline for monitoring?

Purpose  

This study aims at evaluating (a) whether concentrations of a suite of elements in mosses sampled in the arctic region around Zackenberg reflect background concentrations useful for estimating pollution levels in industrialized parts of the northern hemisphere as is attempted, e.g. in the framework of the UNECE ICP Vegetation monitoring programme, and (b) whether there are any influences from Zackenberg research station detectable in these concentrations.     

Particulate Matter in California: Part 1—Intercomparison of Several PM2.5, PM10–2.5, and PM10 Monitoring Networks

Abstract

It will be many years before the recently deployed network of fine particulate matter with an aerodynamic diameter less than 2.5 [H9262]m (PM_2.5) Federal Reference Method (FRM) samplers produces information on nonattainment areas, trends, and source impacts. However, data on PM_2.5 and its major constituents have been routinely collected in California for the past 20 years. The California Air Resources Board operated as many as 20 dichotomous (dichot) samplers for PM_2.5 and coarse PM (PM_10–2.5). The California Acid Deposition Monitoring Program (CADMP) collected 12-h-average PM_2.5 and PM₁₀ from 1988 to 1995 at ten urban and rural sites and 24-h-average PM_2.5 at five urban sites since 1995. Beginning in 1994, the Children’s Health Study collected 2-week averages of PM_2.5 in 12 communities in southern California using the Two-Week Sampler (TWS). Comparisons of collocated samples establish relationships between the dichot, CADMP, and TWS samplers and the 82-site network of PM_2.5 FRM samplers deployed since 1999 in California. PM mass data from the different monitoring programs have modest to high correlation to FRM mass data, fairly small systematic biases and negative proportional biases ranging from 7 to 22%. If the biases are taken into account, all of the programs should be considered comparable with the FRM program. Thus, historical data can be used to develop long-term PM trends in California.     

Characteristics of water-soluble inorganic ions in PM2.5 and PM2.5–10 in the coastal urban agglomeration along the Western Taiwan Strait Region,China

PM_2.5 and PM_2.5–10 aerosol samples were collected in four seasons during November 2010, January, April, and August 2011 at 13 urban/suburban sites and one background site in Western Taiwan Straits Region (WTSR), which is the coastal area with rapid urbanization, high population density, and deteriorating air quality. The 10 days average PM_2.5 concentrations were 92.92, 51.96, 74.48, and 89.69 μg/m³ in spring, summer, autumn, and winter, respectively, exceeding the Chinese ambient air quality standard for annual average value of PM_2.5 (grade II, 35 μg/m³). Temporal distribution of water-soluble inorganic ions (WSIIs) in PM_2.5 was coincident with PM_2.5 mass concentrations, showing highest in spring, lowest in summer, and middle in autumn and winter. WSIIs took considerable proportion (42.2～50.1 %) in PM_2.5 and PM_2.5–10. Generally, urban/suburban sites had obviously suffered severer pollution of fine particles compared with the background site. The WSIIs concentrations and characteristics were closely related to the local anthropogenic activities and natural environment, urban sites in cities with higher urbanization level, or sites with weaker diffuse condition suffered severer WSIIs pollution. Fossil fuel combustion, traffic emissions, crustal/soil dust, municipal constructions, and sea salt and biomass burnings were the major potential sources of WSIIs in PM_2.5 in WTSR according to the result of principal component analysis.     

Spatial heterogeneity of PM10 and O3 in São Paulo, Brazil, and implications for human health studies

Developing exposure estimates is a challenging aspect of investigating the health effects of air pollution. Pollutant levels recorded at centrally located ambient air quality monitors in a community are commonly used as proxies for population exposures. However, if ample intraurban spatial variation in pollutants exists, city-wide averages of concentrations may introduce exposure misclassification. We assessed spatial heterogeneity of particulate matter with an aerodynamic diameter < or = 10 microm (PM10) and ozone (O3) and evaluated implications for epidemiological studies in S?o Paulo, Brazil, using daily (24-hr) and daytime (12-hr) averages and 1-hr daily maximums of pollutant levels recorded at the regulatory monitoring network. Monitor locations were also analyzed with respect to a socioeconomic status index developed by the municipal government. Hourly PM10 and O3 data for the Sāo Paulo Municipality and Metropolitan Region (1999-2006) were used to evaluate heterogeneity by comparing distance between monitors with pollutants' correlations and coefficients of divergence (CODs). Both pollutants showed high correlations across monitoring sites (median = 0.8 for daily averages). CODs across sites averaged 0.20. Distance was a good predictor of CODs for PM10 (p < 0.01) but not O3, whereas distance was a good predictor of correlations for O3 (p < 0.01) but not PM10. High COD values and low temporal correlation indicate a spatially heterogeneous distribution of PM10. Ozone levels were highly correlated (r > or = 0.75), but high CODs suggest that averaging over O3 levels may obscure important spatial variations. Of municipal districts in the highest of five socioeconomic groups, 40% have > or = 1 monitor, whereas districts in the lowest two groups, representing half the population, have no monitors. Results suggest that there is a potential for exposure misclassification based on the available monitoring network and that spatial heterogeneity depends on pollutant metric (e.g., daily average vs. daily 1-hr maximum). A denser monitoring network or alternative exposure methods may be needed for epidemiological research. Findings demonstrate the importance of considering spatial heterogeneity and differential exposure misclassification by subpopulation.     

A study of the particulate matter PM10 composition in the atmosphere of Chillán, Chile

Inhalable particulate matter (PM10) concentrations were measured over 24-h intervals at six different urban sites in the city of Chillán from September 2001 to April 2003. Sampling locations were selected to represent central city, commercial, residential, and industrial portions of the city. Chemical composition of PM10 was performed to samples of 47 mm diameter Teflon membranes within the city of Chillán. The spatial and temporal variability of the chemical composition of PM10 was evaluated taking into account additional data from meteorology and further air pollutants. The majority of PM mass was comprised of carbon, nitrate, sulfate, ammonium, and crustal components but in different proportion on different days and at different sites. The chemical analyses showed that carbonaceous substances and crustal material were the most abundant component of PM10 during the winter and summer, respectively. The concentrations of PM10 were higher during the cold season than during the warm season. The PM10 concentrations were higher in the downtown area of the city of Chillán, where also the chemical composition was more variable due to urban traffic and other anthropogenic sources.     

Study on ambient concentrations of PM10, PM10–2.5, PM2.5 and gaseous pollutants. Trace elements and chemical speciation of atmospheric particulates

This study provides the first comprehensive report on mass concentrations of particulate matter of various sizes, inorganic and organic gas concentrations monitored at three sampling sites in the city of Palermo (Sicily, Italy). It also provides information on the water-soluble species and trace elements. A total of 2054 PM₁₀ (1333) and PM_2.5 (721) daily measurements were collected from November 2006 to February 2008. The highest mass concentrations were observed at the urban stations, average values being about two times higher than those at the suburban (control) site. Time variations in PM₁₀ and also PM_10–2.5 were observed at the urban stations, the highest concentrations being measured in autumn and winter. CO, NOx, NO₂, benzene, toluene and o-xylene concentrations peaked in autumn and winter, a pattern similar to those recorded for PM₁₀ and PM_10–2.5 mass levels, indicating the importance of traffic emissions in urban air pollution. 91% and 51% of the benzene measurements exceeded the limit of 5 μg m^?3 at the two urban monitoring sites. Trace elements (As, Ba, Cr, Cu, Mo, Pb, Sb) suspected of being introduced into the atmosphere mainly by anthropogenic activities, were highly enriched with respect to local soil. Results indicate that a large fraction of PM₁₀ (31–47% in weight) and PM_2.5 (29% in weight) is made up of water-soluble ions. Ammonium sulphate and nitrate particles accounted for 14–29 wt% of particulate matter mass concentrations. Crustal and marine components, combined, account for 41% and 49% in PM_2.5 and PM₁₀, respectively. The calculated deficits in Cl^- and NH₄⁺ ions suggest that a proportion of these ions are lost, via the formation of gaseous NH₄Cl or HCl and NH₃.     

Comparative receptor modelling study of TSP,PM2 and PM2−10 in Ho Chi Minh City

Elemental compositions were measured for TSP (total suspended particulate matter), PM₂₋₁₀ and PM₂ (particulate matter with aerodynamic diameters from 2 to 10 μm and less than 2 μm, respectively) in Ho Chi Minh City. Concentrations of 23 elements and particulate mass (PM) were used for receptor modelling to identify and quantify aerosol sources using principal component factor analysis (PCFA). A suite of factors containing similar elements with significant factor loadings were revealed among the factor matrices, thus facilitating the identification of common sources for different aerosol types. These sources include vehicular emissions (Br and Zn), coal burning (Se), industrial processes (Ce, Co, Cr, Pb and Sb), road dust (Al, Ti, V), soil dust (Fe and Th) and biomass burning (K). Marine aerosols (Na and Cl) and mineral fly ash (Sc and La) were revealed only in the PM₂₋₁₀ model. For TSP, the last four sources are combined in one factor. The last (9th) factor in the PM₂ model, characterised by a high loading from PM and insignificant loadings from elements, was attributed to secondary sulphates and organics, although these constituents were not measured in the experiments. Such a remarkable source identification capability of the modelling technique highlights the significance of achieving an optimal factor solution as a crucial step in PCFA, that was done by systematically varying the number of factors retained and carefully evaluating each factor matrix for both model fitting performance and physical reasonableness.     

Characterization of PM25 and PM10 in the South Coast Air Basin of Southern California: Part 2—Temporal Variations

ABSTRACT

The South Coast Air Quality Management District (SCAQMD) conducted a 1-year special particulate monitoring study from January 1995 to February 1996. This monitoring data indicates that high PM₁₀ and PM_{2 5} concentrations were observed in the fall (October, November, and December), with November concentrations being the highest. During the rest of the year, PM_2.5 and PM₁₀ masses gradually increased from January to September. Monthly PM₁₀ mass varied from 20 to 120 |ig/m³, and monthly PM₂₅ mass varied from 13 to 63 |j.g/m³. The PM_2.5-to-PM₁₀ ratio varied daily and ranged between 22 and 96%. Two types of high-PM days were observed. The first type was observed under fall stagnation conditions, which lead to high secondary species concentrations. The second type was observed under high wind conditions, which lead to high primary coarse particles of crustal components. The highest 24-hr average PM₁₀ concentration (226.3 |ig/m³) was observed at the Fontana station, while the highest PM₂₅ concentration (129.3 |ig/m³) was observed at the Diamond Bar station.     

Characterization of PM25 and PM10 in the South Coast Air Basin of Southern California: Part 1—Spatial Variations

ABSTRACT

In December 1994, the South Coast Air Quality Management District (SCAQMD) initiated a comprehensive program, the PM₁₀ Technical Enhancement Program (PTEP), to characterize fine PM in the South Coast Air Basin (SCAB). A 1-year special particulate monitoring project was conducted from January 1995 to February 1996 as part of the PTEP. Under this enhanced monitoring, HNO₃, NH₃, and speciated PM₁₀ and PM_2.5 concentrations were measured at five stations (Anaheim, downtown Los Angeles, Diamond Bar, Fontana, and Rubidoux) in the SCAB and at one background station at San Nicolas Island. PM_2.5 and PM₁₀ mass and 43 individual species were analyzed for a full chemical speciation of the particle data. The PTEP data indicate that the most abundant chemical components of PM₁₀ and PM₂₅ in the SCAB are NH₄+ (8-9% of PM₁₀ and 14-17% of PM₂₅), NO₃ ^- (23-26% of PM₁₀ and 28-41% of PM₂₅), SO₄= (6-11% of PM₁₀ and 9-18% of PM_{2 5}), organic carbon (OC) (15-19% of PM₁₀ and 18-26% of PM_2.5), and elemental carbon (EC) (5-8% of PM₁₀ and 8-13% of PM₂₅). On an annual average basis, PM₂₅ comprises 52-59% of the SCAB PM₁₀. Annual average PM₁₀ and PM_2.5 concentrations showed strong spatial variations, low at coastal sites and high at inland sites. Annual average PM₁₀ concentrations varied from 40.8 ug/m³ at Anaheim to 76.8 ug/m³ at Rubidoux, while annual average PM_2.5 concentrations varied from 21.7 ug/m³ at Anaheim to 39.8 ug/m³ at Rubidoux. The chemical characterizations of the PM_2.5 and PM₁₀ concentrations, as well as their spatial variations, were examined; the important findings are summarized in this paper, and the temporal variations are discussed in the companion paper.¹     

Temporal analysis of PM10 in Metropolitan Monterrey, México

The Monterrey Metropolitan Area (MMA) is the third largest city in Mexico. Few studies have been carried out regarding its air pollution. The aim of this study was to analyze the temporal behavior of PM10 (particulate matter < or =10 microm in aerodynamic diameter). Data reported by the "Sistema Integral de Monitoreo Ambiental" (Integrated Environmental Monitoring System) network from 2006 to 2008 were used. PM10 levels were compared among the stations by year, season, and day of week. A bootstrap technique was used to obtain subsamples to which Student's t test and ANOVA were applied. PM10 levels were high and exceeded the annual limit of 50 microg/m3 set up by the Mexican standard Norma Oficial Mexicana NOM-025-SSA1-1993. These levels could have serious health effects. The southwest zone of MMA had the highest levels of PM10 during the period studied. Winter was the most polluted season, and summer was the least polluted season. Thursday and Friday were the most polluted days, and Sunday was the least polluted day. The hours with the highest levels of PM10 were 8:00 to 10:00 a.m., whereas nighttime hours were the cleanest.     

Fifteen years of monitoring of POPs in the breast milk, Czech Republic, 1994–2009: trends and factors

Background, aim and scope

The breast milk has been recommended to carry out as a monitoring tool for effectiveness evaluation of the Stockholm Convention on Persistent Organic Pollutants (POPs). Polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloro-ethane (DDT) and its metabolites (DDX), hexachlorbenzene (HCB) and isomers of hexachlocyklohexane (HCHs) have been monitored in the breast milk of nursing mothers in the Czech Republic since 1994 as a part of The Environmental Health Monitoring System. Knowledge about long-term POPs distribution and accumulation in the human body is crucial to understanding uptake, degradation and subsequent effects as well as to conduct risk assessments. The main aim of this study is to evaluate 15-years long-term trends of selected POPs in human milk in the Czech Republic and to elucidate the questionnaire information about the age, parity and social habits, to the final concentrations. This effectiveness evaluation of POPs restriction is quite precisely after 15-years monitoring campaigns.

Materials, methods and results

The human milk samples (4,753 samples) were analysed for a number of chlorinated organic chemicals including PCBs and selected chlorinated pesticides (OCPs, HCB, HCHs, DDX). The relative change of concentration per year for all chemicals was analysed. The remaining percentages of POPs in breast milk in comparison to 1994 are also expressed. Czech population half-lives of POPs in breast milk, derived from either linear or exponential models were computed.

Conclusions and perspectives

The long-term data indicates a continuation of a decreasing trend of POPs concentrations on breast milk. Our study did not confirm lactation and parity as an important outflux resulting in the decrease in concentrations in mothers, which is in the antagonism with most of the studies. The higher BMI was associated with higher amounts of HCB and lower amounts of higher chlorinated PCBs. The results confirm the effectiveness of restrictions of POPs usage in the Czech Republic. This ongoing long-term study is very useful tool for parametric effectiveness evaluation of Stockholm Convention.     

Characterization of PM2.5-bound polycyclic aromatic hydrocarbons in Atlanta—Seasonal variations at urban,suburban, and rural ambient air monitoring sites

Twenty-eight polycyclic aromatic hydrocarbons (PAH) and methylated PAHs (Me-PAH) were measured in daily PM_2.5 samples collected at an urban site, a suburban site, and a rural site in and near Atlanta during 2004 (5 samples/month/site). The suburban site, located near a major highway, had higher PM_2.5-bound PAH concentrations than did the urban site, and the rural site had the lowest PAH levels. Monthly variations are described for concentrations of total PAHs (∑PAHs) and individual PAHs. PAH concentrations were much higher in cold months than in warm months, with average monthly ∑PAH concentrations at the urban and suburban-highway monitoring sites ranging from 2.12 to 6.85 ng m^?3 during January–February and November–December 2004, compared to 0.38–0.98 ng m^?3 during May–September 2004. ∑PAH concentrations were found to be well correlated with PM_2.5 and organic carbon (OC) within seasons, and the fractions of PAHs in PM_2.5 and OC were higher in winter than in summer. Methyl phenanthrenes were present at higher levels than their un-substituted homologue (phenanthrene), suggesting a petrogenic (unburned petroleum products) input. Retene, a proposed tracer for biomass burning, peaked in March, the month with the highest acreage and frequency of prescribed burning and unplanned fires, and in December, during the high residential wood-burning season, indicating that retene might be a good marker for burning of all biomass materials. In contrast, potassium peaked only in December, indicating that it might be a more specific tracer for wood-burning.     

Field application of evaluated methodology for determining 1,2‐dibromoethane,EDB, in ambient air

Abstract

EDB (ethylene dibromide) is of regulatory interest because it has cancer inducing properties and is a causative agent of aspermia. Previously evaluated methodology was used to determine the extent of exposure of workers to EDB in citrus fumigation stations and a warehouse used as a holding site before shipment. The purpose of this effort was to carry out environmental sampling, and to determine the exposure level of workers and related administrative personnel at two citrus fumigation centers and at a warehouse     

Evaluation of TEOMTM ‘correction factors’ for assessing the EU Stage 1 limit values for PM10

A study has been carried out to compare the results of PM10 determinations using TEOM^TM and gravimetric instruments. Whilst the TEOM instruments have been used by the UK Government for many years to develop a National Air Quality Objective, the European Directive (99/30/EC) Stage 1 limit values for PM10 require a gravimetric method (or an approved equivalent method) to be used. However, there are significant differences between the two techniques, which have been investigated by co-locating a TEOM PM10 monitor and a gravimetric (Partisol) PM10 sampler at Marylebone Road, London between June 1997 and January 2000. This paper investigates the current practice of using a single ‘correction factor’ on TEOM PM10 data when these data are being used to assess the EU Stage 1 limit values for PM10, which should be measured using a gravimetric technique. The ability of the ‘corrected’ TEOM PM10 values to accurately reflect the annual mean and the number of 24 h means above 50 μg m⁻³ produced by the co-located Partisol PM10 sampler is used as the test for the suitability of the single correction factor. This study demonstrates that a single ‘correction factor’ will not reflect the site and season specificity.     

NORMAN—network of reference laboratories,research centres and related organisations for monitoring of emerging substances

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