Spatial analysis of volatile organic compounds in South Philadelphia using passive samplers

Select volatile organic compounds (VOCs) were measured in the vicinity of a petroleum refinery and related operations in South Philadelphia, Pennsylvania, USA, using passive air sampling and laboratory analysis methods. Two-week, time-integrated samplers were deployed at 17 sites, which were aggregated into five site groups of varying distances from the refinery. Benzene, toluene, ethylbenzene, and xylene isomers (BTEX) and styrene concentrations were higher near the refinery’s fenceline than for groups at the refinery’s south edge, mid-distance, and farther removed locations. The near fenceline group was significantly higher than the refinery’s north edge group for benzene and toluene but not for ethylbenzene or xylene isomers; styrene was lower at the near fenceline group versus the north edge group. For BTEX and styrene, the magnitude of estimated differences generally increased when proceeding through groups ever farther away from the petroleum refining. Perchloroethylene results were not suggestive of an influence from refining. These results suggest that emissions from the refinery complex contribute to higher concentrations of BTEX species and styrene in the vicinity of the plant, with this influence declining as distance from the petroleum refining increases.

Implications: Passive sampling methodology for VOCs as discussed here is employed in recently enacted U.S. Environmental Protection Agency Methods 325A/B for determination of benzene concentrations at refinery fenceline locations. Spatial gradients of VOC concentration near the refinery fenceline were discerned in an area containing traffic and other VOC-related sources. Though limited, these findings can be useful in application of the method at such facilities to ascertain source influence.     

Multiple-year black carbon measurements and source apportionment using delta-C in Rochester, New York

Black carbon (BC), an important component ofthe atmospheric aerosol, has climatic, environmental, and human health significance. In this study, BC was continuously measured using a two-wavelength aethalometer (370 nm and 880 nm) in Rochester; New York, from January 2007 to December 2010. The monitoring site is adjacent to two major urban highways (I-490 and I-590), where 14% to 21% of the total traffic was heavy-duty diesel vehicles. The annual average BC concentrations were 0.76 microg/m3, 0.67 microg/m3, 0.60 microg/m3, and 0.52 microg/m3 in 2007, 2008, 2009, and 2010, respectively. Positive matrix factorization (PMF) modeling was performed using PM2.5 elements, sulfate, nitrate, ammonia, elemental carbon (EC), and organic carbon (OC) data from the US. Environmental Protection Agency (EPA) speciation network and Delta-C (UVBC370nm-BC880nm) data. Delta-C has been previously shown to be a tracer of wood combustion factor It was used as an input variable in source apportionment models for the first time in this study and was found to play an important role in separating traffic (especially diesel) emissions from wood combustion emissions. The result showed the annual average PM2.5 concentrations apportioned to diesel emissions in 2007, 2008, 2009, and 2010 were 1.34 microg/m3, 1.25 microg/m3, 1.13 microg/m3, and 0.97 microg/m3, respectively. The BC conditional probability function (CPF) plots show a large contribution from the highway diesel traffic to elevated BC concentrations. The measurements and modeling results suggest an impact of the US Environmental Protection Agency (EPA) 2007 Heavy-Duty Highway Rule on the decrease ofBC and PM2.5 concentrations during the study period.     

A model for interprovincial air pollution control based on futures prices

Based on the current status of research on tradable emission rights futures, this paper introduces basic market-related assumptions for China’s interprovincial air pollution control problem. The authors construct an interprovincial air pollution control model based on futures prices: the model calculated the spot price of emission rights using a classic futures pricing formula, and determined the identities of buyers and sellers for various provinces according to a partitioning criterion, thereby revealing five trading markets. To ensure interprovincial cooperation, a rational allocation result for the benefits from this model was achieved using the Shapley value method to construct an optimal reduction program and to determine the optimal annual decisions for each province. Finally, the Beijing–Tianjin–Hebei region was used as a case study, as this region has recently experienced serious pollution. It was found that the model reduced the overall cost of reducing SO₂ pollution. Moreover, each province can lower its cost for air pollution reduction, resulting in a win–win solution. Adopting the model would therefore enhance regional cooperation and promote the control of China’s air pollution.

Implications: The authors construct an interprovincial air pollution control model based on futures prices. The Shapley value method is used to rationally allocate the cooperation benefit. Interprovincial pollution control reduces the overall reduction cost of SO₂. Each province can lower its cost for air pollution reduction by cooperation.     

Abiotic degradation (photodegradation and hydrolysis) of imidazolinone herbicides

The abiotic degradation of the imidazolinone herbicides imazapyr, imazethapyr and imazaquin was investigated under controlled conditions. Hydrolysis, where it occurred, and photodegradation both followed first-order kinetics for all herbicides. There was no hydrolysis of any of the herbicides in buffer solutions at pH 3 or pH 7; however, slow hydrolysis occurred at pH 9. Estimated half-lives for the three herbicides in solution in the dark were 6.5, 9.2 and 9.6 months for imazaquin, imazethapyr and imazapyr, respectively. Degradation of the herbicides in the light was considerably more rapid than in the dark with half lives for the three herbicides of 1.8, 9.8 and 9.1 days for imazaquin, imazethapyr and imazapyr, respectively. The presence of humic acids in the solution reduced the rate of photodegradation for all three herbicides, with higher concentrations of humic acids generally having greater effect. Photodegradation of imazethapyr was the least sensitive to humic acids. The enantioselectivity of photodegradation was investigated using imazaquin, with photodegradation occurring at the same rate for both enantiomers. Abiotic degradation of imidazolinone herbicides on the soil surface only occurred in the presence of light. The rate of degradation for all herbicides was slower than in solution, with half-lives of 15.3, 24.6 and 30.9 days for imazaquin, imazethapyr and imazapyr, respectively. Abiotic degradation of these herbicides is likely to be slow in the environment and is only likely to occur in clear water or on the soil surface.     

Analysis of VOCs in Ambient Air Using Multisorbent Packings for VOC Accumulation and Sample Drying

Abstract

Solid multisorbent packings have been characterized for trapping and release efficiency of trace (10-20 ppbv in humidified zero air) volatile organic compounds (VOCs). The use of a two-stage trapping system reduces sample water content typically by more than 95.5% while maintaining a trapping and release efficiency of 100% for 49 VOCs, including eight water-soluble VOCs. Three combinations of primary tube and focusing tube are examined in detail by using an atomic emission detector to monitor hydrogen as an indication of residual water vapor, and to monitor either chlorine, bromine, or carbon for target VOCs. Linearity of response to individual VOCs, the presence of artifacts, and a laboratory monitoring application are also discussed.     

Distribution Equilibrium of Mercury (II) Chloride between Water and Air Applied to Flue Gas Scrubbing

ABSTRACT

In the literature, different values of the distribution coefficient K_H for HgCl₂ between water and air are present in a range that spans more than 3 orders of magnitude. In order to determine if a waste incineration scrubber solution could become saturated with regard to HgCl₂, an accurate experimental determination of the distribution constant of HgCl₂ at elevated temperatures is needed. In this work, the coefficient has been determined at four different temperatures between 10 and 50 °C. The Arrhenius expression obtained is 5.5 x 10⁵ x exp[-(8060 ± 2200)/7] with a corresponding enthalpy for the process HgCl₂(aq)<» HgCl₂(g) of 67 ± 20 kJ/mole. K_H at 293 K was found to be ~5 x 10^-7 atm M^-1, which is in almost perfect agreement with an earlier study. Applying the obtained K_H values to waste incineration scrubber conditions shows that no major saturation effect will occur.     

Evaluating pollution-related damage and restoration success in urban forests with participatory monitoring and digital tools

Peri-urban forest monitoring requires indicators of vegetation damage. An example is the sacred fir (Abies religiosa) forests surrounding Mexico City, which have been heavily exposed to tropospheric ozone, a harmful pollutant, for over 4 decades. We developed a participatory monitoring system with which local community members and scientists generated data on ozone tree damage. Santa Rosa Xochiac rangers (13) used the digital tool KoboToolBox to record ozone damage to trees, tree height, tree ages, tree condition, tree position, and whether the tree had been planted. Thirty-five percent of the trees (n = 1765) had ozone damage. Younger trees had a lower percentage of foliage damaged by ozone than older trees (p < 0.0001), and asymptomatic trees tended to be younger (p < 0.0001). Symptomatic trees were taller than asymptomatic trees of the same age (R²_c = 0.43, R²_m = 0.27). Involving local communities facilitated forest monitoring and using digital technology improved data quality. This participatory system can be used to monitor forest condition change over time and thus aids restoration efforts driven by government or local communities’ interests, facilitating local decision-making.     

Application of passive sorbent tube and canister samplers for volatile organic compounds at refinery fenceline locations in Whiting,Indiana

Select volatile organic compounds (VOCs) in ambient air were measured at four fenceline sites at a petroleum refinery in Whiting, IN, using modified EPA Method 325 A/B with passive tubes and EPA Compendium Method TO-15 with canister samplers. One-week, time-integrated samplers were deployed for 8 weeks with tubes and canister samplers deployed in duplicate. Good precision was obtained from the duplicate tubes (<7%) and duplicate canisters (≤10%) for BTEX, perchloroethylene, and styrene. The tubes yielded statistically significantly higher concentrations than canisters for benzene, toluene, ethylbenzene, and m,p-xylene. However, all differences were estimated to be <0.1 ppbv. No concentration differences among the four Whiting sites were found for any of the VOCs.

Implications: Recently enacted EPA Methods 325A/B use passive-diffusive tube samplers to measure benzene at refinery fenceline locations. This pilot study presents VOC data applying a modified version of EPA Method 325 A/B and its comparison to EPA Compendium Method TO-15 canister samplers at four refinery fenceline sites. The findings from this study provide additional confidence in application of the tube method at refineries to ascertain VOC source influence since tube and canister samplers were comparable and good precision was obtained from duplicate sampling for both methods. No overall difference in these reported VOC concentrations was found between Whiting sites for tubes or canisters.     

Distribution and partitioning of depleted uranium (DU) in soils at weapons test ranges - investigations combining the BCR extraction scheme and isotopic analysis

Depleted uranium (DU) has become a soil contaminant of considerable concern in many combat zones and weapons-testing sites around the world, including locations in Europe, the Middle East and the USA, arising from its dispersion via the application of DU-bearing munitions. Once DU is released into the environment its mobility and bioavailability will, like that of other contaminants, largely depend on the type of associations it forms in soil and on the nature of the soil components to which it binds. In this study we used the BCR sequential extraction scheme to determine the partitioning of DU amongst soil fractions of texturally varying soils from locations affected by weapons-testing activities. Isotopic analyses (MC-ICP-MS and alpha-spectrometry) were performed to verify the presence of DU in whole soils and soil fractions and to determine any preferential partitioning of the contaminant. Results identified soil organic matter as being consistently the most important component in terms of DU retention, accounting for 30-100% of DU observed in the soils examined. However, at greater distances from known contamination points, DU was also found to be largely associated with the exchangeable fraction, suggesting that DU can be mobilised and transported by surface and near-surface water and does remain in an exchangeable (and thus potentially bioavailable) form in soils.