Chemical Mass Balance Model with Fractionation for Apportioning PM2.5: A Test Case for Los Angeles Traffic Sources

Abstract

Chemical mass balance receptor models (CMBs) use measured pollutant concentrations, along with source information, to apportion the contributions of primary sources to the measured concentrations. CMBs can be used to evaluate the accuracy of the emission inventories that underlie State Implementation Plan (SIP) modeling, by providing an allocation of emissions to individual source categories. CMBs, however, traditionally have not accounted for the chemical reaction and differential deposition or fractionation that occur between the source and receptor. This means that they have historically had severe limitations in apportioning secondary particulate matter (PM), which is an especially important component of fine PM (PM_2.5). Stafford and Liljestrand developed a method to account for fractionation in CMBs using depletion factors based on a solution of the steady-state advection-dispersion equation, including gravitational settling, dry deposition, and first-order chemical reaction. In the research presented here, the method of Stafford and Liljestrand was tested using gaseous and PM ambient concentration data from the Los Angeles, CA, air shed, along with traffic source profiles specific to Los Angeles and the CMB7 receptor model of the U.S. Environment Protection Agency. Including fractionation increased nitrate apportioned from 5% and 6% to 83% and 86% for Claremont, CA, and Long Beach, CA, respectively. This is significant, because CMBs have historically had difficulty apportioning nitrate. Including fractionation increased the ammonium apportioned by a factor of 7. The method could be used in future case studies to apportion secondary organic carbon as well.     

Effects of oil sands process-affected waters and naphthenic acids on yellow perch (Perca flavescens) and Japanese medaka (Orizias latipes) embryonic development

Syncrude Canada Ltd. is currently developing environmentally acceptable oil sands process-affected water management methods as part of their land reclamation strategy. Surface waters of the “wet landscape” reclamation option characteristically have elevated concentrations of sodium sulphate and naphthenic acids (NAs), with low levels of PAHs. The following experiment compared early-life stage responses of yellow perch (Perca flavescens) to those of Japanese medaka (Oryzias latipes) when exposed to Mildred Lake settling basin (MLSB) surface water and a commercial sodium naphthenate (Na-NA) standard. Perch eggs were fertilized and incubated in: 100%, 50%, 20%, 4%, 0.8%, and 0.16% dilutions of MLSB water, as well as 20, 10, 5, 2.5, and 1.25 mg/l solutions of the commercial standard. Medaka embryos were exposed to the same treatments, post-fertilization. Both species demonstrated an increase in the incidence of deformity, and a decrease in length at hatch as NA concentrations increased. MLSB surface water contained higher levels of NAs than the commercial standard, however, showed consistently higher NA threshold effect concentrations for both species. Significant differences between the MLSB water and the Na-NA standard suggest that they contain NA congeners with different toxicity, or other compounds such as PAHs. Species differences in thresholds could be explained by the difference in developmental stage in which the exposures were initiated.     

Which meteorological conditions produce worst-case odors from area sources?

Two competing meteorological factors influence atmospheric concentrations of pollutants from open liquid area sources such as wastewater treatment plant units: temperature and stability. High temperatures in summer produce greater emissions from liquid area sources because of increased compound volatility; however, these emissions tend to disperse more readily because of frequent occurrence of unstable conditions. An opposite scenario occurs in winter, with lesser emissions due to lower temperatures, but also frequently less dispersion, due to stable atmospheric conditions. The primary objective of this modeling study was thus to determine whether higher atmospheric concentrations from open liquid area sources occur more frequently in summer, when emissions are greater but so is dispersion, or in winter, when emissions are lesser but so is dispersion. The study utilized a rectangular clarifier emitting hydrogen sulfide as a sample open liquid area source. Dispersion modeling runs were conducted using ISCST3 and AERMOD, encompassing 5 yr of hourly meteorological data divided by season. Emission rates were varied hourly on the basis of a curve-fit developed from previously collected field data. Model output for each season was used to determine (1) maximum 2-min average concentrations, (2) the number of odor events (2-min average concentrations greater than odor detection thresholds), and (3) areas of impact. On the basis of these 3 types of output, it was found that the worst-case odors were associated with summer, considering impacts of meteorology upon both emissions and dispersion. Not accounting for the impact of meteorology on emissions (using a constant worst-case emission rate) caused concentrations to be overpredicted compared with a variable emission rate case. The highest concentrations occurred during stability classes D, E, and F, as anticipated. A comparison of ISCST3 and AERMOD found that for the area source modeled, ISCST3 predicted higher concentrations and more odor events for all seasons.     

Reduced nitrogen has a greater effect than oxidised nitrogen on dry heathland vegetation

We investigated the effects of different ratios of reduced (NH4+) versus oxidised (NO3(-)) nitrogen in deposition on heathland and species-rich grassland vegetation at high nitrogen deposition levels in large mesocosms filled with nutrient-poor soils to which different NH4+/NO3(-) ratios were applied. The response of the forbs, Antennaria dioica, Arnica montana, Gentiana pneumonanthe, Thymus serpyllum, the grasses Danthonia decumbens, Deschampsia flexuosa, Nardus stricta and the shrub Calluna vulgaris was recorded. The forb A. dioica and the grass D.decumbens preferred low NH4+/NO3(-) ratios and were characterised by a negative correlation between NH4+/NO3(-) ratios and biomass and survival, whereas the grasses N. stricta and D. flexuosa showed no correlation with NH4+/NO3(-) ratios. Lime addition eliminated the negative effects of high NH4+ concentrations in deposition for A. dioica and the grass D. decumbens. The implications of these findings for heathland vegetations are discussed.     

Characterization of spatially homogeneous regions based on temporal patterns of fine particulate matter in the continental United States

Statistical analyses of time-series or spatial data have been widely used to investigate the behavior of ambient air pollutants. Because air pollution data are generally collected in a wide area of interest over a relatively long period, such analyses should take into account both spatial and temporal characteristics. The objective of this study is 2-fold: (1) to identify an efficient way to characterize the spatial variations of fine particulate matter (PM2.5) concentrations based solely upon their temporal patterns, and (2) to analyze the temporal and seasonal patterns of PM2.5 concentrations in spatially homogenous regions. This study used 24-hr average PM2.5 concentrations measured every third day during a period between 2001 and 2005 at 522 monitoring sites in the continental United States. A k-means clustering algorithm using the correlation distance was used to investigate the similarity in patterns between temporal profiles observed at the monitoring sites. A k-means clustering analysis produced six clusters of sites with distinct temporal patterns that were able to identify and characterize spatially homogeneous regions of the United States. The study also presents a rotated principal component analysis (RPCA) that has been used for characterizing spatial patterns of air pollution and discusses the difference between the clustering algorithm and RPCA.     

Mercury speciation in Pacific coastal rainwater,Monterey Bay,California

We measured mercury speciation in coastal rainwater samples from Monterey Bay, California in 2007–2008 to investigate the source of monomethylmercury (MMHg) in rainwater and determine the relative importance of wet atmospheric deposition of MMHg to coastal waters compared to other sources on the central Pacific coast. Total mercury (HgT) ranged from 10 to 88 pM, with a sample mean ± standard deviation of 33 ± 22 pM (volume-weighted average 29 pM). MMHg concentrations ranged from 0.12 to 2.3 pM with a sample mean of 0.7 ± 0.5 pM (volume-weighted average 0.68 pM). Reactive mercury (HgR) concentrations ranged from 0.87 to 47 pM, sample mean 7.8 ± 8.3 pM (volume-weighted average 6.1 pM). Acetate concentration in rainwater, measured in a subset of samples, ranged from 0.34 to 3.1 μM, and averaged 1.6 ± 0.9 μM (volume-weighted average 1.3 μM). Dimethylmercury (DMHg) concentrations were below the limit of detection in air (<0.01 ng m^?3) and rainwater (<0.05 pM). Despite previous suggestions that DMHg in upwelled ocean waters is a potential source of MMHg in coastal rainwater, MMHg in rain was not related to coastal upwelling seasons or surface water DMHg concentrations. Instead, a multiple linear regression analysis demonstrated that MMHg concentrations were positively and significantly correlated (p = 0.002, adjusted R² = 0.88) with those of acetate and HgR. These data appear to support previous suggestions that the aqueous phase methylation of Hg(II) by acetate may be the source of MMHg in rainwater, but imply that acetate concentrations in rainwater play a more important role relative to HgR than previously hypothesized. However, the calculated chemical speciation of Hg(II) in rainwater and the minimal predicted complexation of Hg(II) by acetate suggest that the aqueous phase methylation of Hg(II) by acetate is unlikely to account for the MMHg found in precipitation, or that the mechanism of this reaction in the atmosphere differs from that previously reported (Gardfeldt et al., 2003).     

Low emission zones reduce PM10 mass concentrations and diesel soot in German cities

In many European cities mass concentrations of PM₁₀ (particles less than 10 μm in size) are still exceeding air quality standards as set by the European Commission in 1999. As a consequence, many cities introduced low emission zones (LEZs) to improve air quality and to meet the limit values. In Germany currently 48 LEZs are in operation. By means of dispersion modeling, PM₁₀ concentrations were estimated to decrease up to 10%. Analysis of PM₁₀ levels conducted for Cologne, Berlin, and Munich some time after the LEZs were introduced showed reduction of PM₁₀ mass concentration in the estimated range. The PM₁₀ particle fraction is, however, composed of particles with varying toxicity, of which diesel soot is highly health relevant. An evaluation of air quality data conducted in Berlin showed that in 2010 traffic-related soot concentrations measured along major roads decreased by 52% compared to 2007. Diesel particle emissions in Berlin were reduced in 2012 by 63% compared to a business-as-usual scenario (reference year 2007). A strong reduction of the traffic-related particle fraction of PM_2.5 was also reported for Munich. Therefore, it is likely that the effects of LEZs are considerably more significant to human health than was anticipated when only considering the reduction of PM₁₀ mass concentrations.

Implications: The implementation of low emission zones in German cities might result in a reduction of PM₁₀ levels concentrations by up to 10%. However, it is difficult to show a reduction of PM₁₀ annual averages in this order of magnitude as meteorology has a large impact on the year-to-year variation of PM mass concentrations. Monitoring of other PM metrics such as black smoke (BS) or elemental carbon (EC) might be a better strategy for evaluating LEZs effects. The benefit of low emission zones on human health is far greater than is presently visible from routine measurements of PM₁₀.     

淋洗剂对多金属污染尾矿土壤的修复效应及技术研究

以我国南方某多金属复合污染尾矿土壤为研究对象,对土壤中重金属全量和各形态含量进行分析.通过系列振荡淋洗试验研究了蒸馏水、草酸、柠檬酸、乙酸、硝酸和EDTA对污染土壤的淋洗效果,筛选合适的淋洗剂及其最佳的液土比、液洗时间、淋洗次数等技术参数,并提出利用综合毒性消减指数来综合评价淋洗剂对污染土壤的修复效果.结果表明,该土壤以Cd和Pb污染最为严重,含量分别达52.2 mg.kg-1和4 836.5 mg.kg-1;淋洗剂对土壤中不同重金属元素的淋洗效果差异明显,其中对Cr的去除率最高仅为2.7%,而最多能去除约60%的Cd和Pb;蒸馏水对重金属几乎没有脱除效果,去除率都在0.1%以下,草酸和乙酸对重金属的去除率也较低,0.1 mol.L-1的EDTA是适合的高效淋洗剂;基于综合毒性消减指数和经济成本,选择在1∶6土水比2次淋洗3 h的技术条件.     

Denitrification in alluvial wetlands in an urban landscape

Riparian wetlands have been shown to be effective "sinks" for nitrate N (NO3-), minimizing the downstream export of N to streams and coastal water bodies. However, the vast majority of riparian denitrification research has been in agricultural and forested watersheds, with relatively little work on riparian wetland function in urban watersheds. We investigated the variation and magnitude of denitrification in three constructed and two relict oxbow urban wetlands, and in two forested reference wetlands in the Baltimore metropolitan area. Denitrification rates in wetland sediments were measured with a 15N-enriched NO3- "push-pull" groundwater tracer method during the summer and winter of 2008. Mean denitrification rates did not differ among the wetland types and ranged from 147 +/- 29 microg N kg soil(-1) d(-1) in constructed stormwater wetlands to 100 +/- 11 microg N kg soil(-1) d(-1) in relict oxbows to 106 +/- 32 microg N kg soil(-1) d(-1) in forested reference wetlands. High denitrification rates were observed in both summer and winter, suggesting that these wetlands are sinks for NO3- year round. Comparison of denitrification rates with NO3- standing stocks in the wetland water column and stream NO3- loads indicated that mass removal of NO3- in urban wetland sediments by denitrification could be substantial. Our results suggest that urban wetlands have the potential to reduce NO3- in urban landscapes and should be considered as a means to manage N in urban watersheds.     

PCB and dioxin-like PCB in indoor air of public buildings contaminated with different PCB sources--deriving toxicity equivalent concentrations from standard PCB congeners

Data on dioxin-like PCB in indoor air of buildings with PCB-containing materials and on possible correlation between toxicity equivalent concentrations (TEQ) and levels of non-dioxin-like standard PCB is sparse. As part of a larger survey on indoor-air contamination with PCB, the connection between the concentration of standard PCB congeners and the dioxin-like toxicity expressed as TEQ was investigated. Indoor air samples (n=8) were collected in four public buildings with known PCB sources and total PCB levels in the range from 715 to 2250 ng/m3 and analyzed for the six non-dioxin-like standard PCB (congeners 28, 52, 101, 138, 153, 180), the twelve dioxin-like PCB congeners according to WHO and the 17 2,3,7,8-substituted PCDD/PCDF congeners. In three buildings where PCB were used as flame retardant coatings of acoustic ceiling tiles, PCB 101 had the maximum level among the six standard PCB, while in the building with permanent elastic sealants as PCB source, congeners 28 and 52 dominated the pattern by far. In the case of permanent elastic sealants as PCB source (n=3) a total PCB concentration of 1000 ng/m3 corresponded to a total TEQ level of 0.3-0.6 pg/m3. In contrast, in rooms with acoustic ceiling tiles as PCB source, 1.8-4.7 pg TEQ/m3 per 1000 ng total PCB/m3 were found. Linear regression analysis between PCB and TEQ indicated that PCB 118 might be used to calculate the total TEQ of dioxin-like PCB and PCDD/PCDF. By means of such a correlation it is possible to estimate TEQ by extrapolation from the results of less sophisticated analytical methods. It is tentatively recommended to use PCB 118 for screening purposes or re-evaluation of standard PCB indoor-air measurements. If only the six non-dioxin-like PCB standard congeners are available, a regression algorithm using the sum of PCB 101, 138, 153 and 180 might be used instead.