Chemical speciation of PM2.5 and PM10 in south Phoenix, AZ, USA

Phoenix, AZ, experiences high particulate matter (PM) episodes, especially in the wintertime. The spatial variation of the PM concentrations and resulting differences in exposure is of particular concern. In this study, PM2.s (PM with aerodynamic diameter <2.5 microm) and PM10 (PM with aerodynamic diameter <10 microm) samples were collected simultaneously from the east and west sides of South Phoenix and at a control site in Tempe and analyzed for trace elements and bulk elemental and organic carbon. Measurements showed that although PM2.5 concentrations had similar trends in temporal scale across all sites, concentrations of PM10 did not. The difference in PM10 concentrations and fluctuation across the three sites suggest effects of a local soil source as evidenced by high concentrations of Al, Ca, and Fe in PM10. K and anthropogenic elements (e.g., Cu, Pb, and Zn) in PM2.5 samples on January 1 were strikingly high, suggesting the influence of New Year's fireworks. Concentrations of toxic elements (e.g., Pb) in the study presented here are not different from similar studies in other U.S. cities. Application of principal component analysis indicated two broad categories of emission sources--soil and combustion--together accounting for 80 and 90% of variance, respectively, in PM2.5 and PM10. The soil and combustion components explained approximately 60 and 30% of the variance in PM10, respectively, whereas combustion sources dominated PM2.5 (>50% variance). Many elements associated with anthropogenic sources were highly enriched, with enrichment factors in PM2.5 an order of magnitude higher than in PM10 relative to surface soil composition in the study area.     

An analysis of flaring and venting activity in the Alberta upstream oil and gas industry

Alberta, Canada, is an important global producer of petroleum resources. In association with this production, large amounts of gas (1.14 billion m3 in 2008) are flared or vented. Although the amount of flaring and venting has been measurably reduced since 2002, data from 2005 reveal sharp increases in venting, which have important implications in terms of resource conservation and greenhouse gas emissions (which exceeded 8 million tonnes of carbon dioxide equivalent in 2008). With use of extensive monthly production data for 18,203 active batteries spanning the years 2002-2008 obtained in close cooperation with the Alberta Energy Resources Conservation Board, a detailed analysis has been completed to examine activity patterns of flaring and venting and reasons behind these trends in the Alberta upstream oil and gas industry. In any given year, approximately 6000 batteries reported flaring and/or venting, but the distribution of volumes flared and vented at individual sites was highly skewed, such that small numbers of sites handled large fractions of the total gas flaring and venting in the Province. Examination of month-to-month volume variability at individual sites, cast in terms of a nominal turndown ratio that would be required for a compressor to capture that gas and direct it into a pipeline, further revealed that volumes at a majority of sites were reasonably stable and there was no evidence that larger or more stable sites had been preferentially reduced, leaving potential barriers to future mitigation. Through linking of geospatial data with production data coupled with additional statistical analysis, the 31.2% increase in venting volumes since 2005 was revealed to be predominantly associated with increased production of heavier oils and bitumen in the Lloydminster region of the Province. Overall, the data suggest that quite significant reductions in flaring and venting could be realized by seeking mitigation solutions for only the largest batteries in the Province.     

Aluminum water treatment residuals as permeable reactive barrier sorbents to reduce phosphorus losses

Two aluminum water treatment residuals (Al-WTRs) from water treatment plants in Manatee County, FL and Punta Gorda, FL were evaluated as potential permeable reactive barrier (PRB) media to reduce groundwater phosphorus (P) losses. Short-term (<24 h) P sorption kinetics and long-term P sorption capacity were determined using batch equilibration studies. Phosphorus desorption was characterized following P loadings of 10, 20, 30, 40 and >70 g kg⁻¹. Sorption and desorption studies were conducted on the <2.0 mm material and three size fractions within the <2.0 mm material. The effect of dissolved organic carbon (DOC) on P retention was determined by reacting Al-WTRs with P-spiked groundwater samples of varying initial DOC concentrations. Phosphorus sorption kinetics were rapid for all size fractions of both Al-WTRs (>98% P sorption effectiveness at shaking times ?2 h). The effect of DOC was minimal at <150 mg DOC L⁻¹, but modest reductions (<22%) in P sorption effectiveness occurred at 587 mg DOC L⁻¹. The P sorption capacities of the Manatee and Punta Gorda Al-WTRs (<2.0 mm) are ∼44 g kg⁻¹ and >75 g kg⁻¹, respectively, and the lifespan of an Al-WTR PRB is likely many decades. Desorption was minimal (<2% of the P sorbed) for cumulative P loadings <40 g kg^-l, but increased (<9% of the P sorbed) at cumulative P loads >70 g kg⁻¹. The <2.0 mm Manatee and Punta Gorda Al-WTRs are regarded as ideal PRB media for P remediation.     

Tetracycline photolysis in natural waters: loss of antibacterial activity

Previous work has shown that tetracycline undergoes direct photolysis in the presence of sunlight, with the decomposition rate highly dependent on conditions such as water hardness and pH. The purpose of this study was to examine the potential long-term significance of photoproducts formed when tetracycline undergoes photodegradation under a range of environmentally relevant conditions. Tetracycline was photolyzed in nine different natural and artificial water samples using simulated sunlight. The pH values of the samples ranged from 5 to 9. Total hardness values (combined Ca²⁺ and Mg²⁺ concentrations) varied from 30 to 450 ppm. Assays based on growth inhibition of two bacterial strains, Escherichia coli DH5α and Vibrio fischeri, were used to determine the antibacterial activity of tetracycline’s photoproducts in these water samples. In all tested conditions, it was determined that the photoproducts retain no significant antibacterial activity; all observed growth inhibition was attributable to residual tetracycline. This suggests that tetracycline photoproducts formed under a wide range of pH and water hardness conditions will not contribute to the selection of antibiotic-resistant bacteria in environmental systems.     

Effect of soil ageing on in vivo arsenic bioavailability in two dissimilar soils

Arsenic (As) bioavailability in spiked soils aged for up to 12 months was assessed using in vitro and in vivo methodologies. Ageing (natural attenuation) of spiked soils resulted in a decline in in vivo As bioavailability (swine assay) of over 75% in soil A (Red Ferrosol) but had no significant effect on in vivo As bioavailability even after 12 months of ageing in soil B (Brown Chromosol). Sequential fractionation, however, indicated that there was repartitioning of As within the soil fractions extracted during the time course investigated. In soil A, the As fraction associated with the more weakly bound soil fractions decreased while the residual fraction increased from 12% to 35%. In contrast, little repartitioning of As was observed in soil B indicating that natural attenuation may be only applicable for As in soils containing specific mineralogical properties.     

Application of an in vivo swine model for the determination of arsenic bioavailability in contaminated vegetables

Considerable information is available in the literature regarding the uptake of arsenic (As) from contaminated soil and irrigation water by vegetables. However, few studies have investigated As speciation in these crops while a dearth of information is available on As bioavailability following their consumption. In this study, the concentration and speciation of As in chard, radish, lettuce and mung beans was determined following hydroponic growth of the vegetables using As-contaminated water. In addition, As bioavailability was assessed using an in vivo swine feeding assay. While As concentrations ranged from 3.0 to 84.2mg As kg(-1) (dry weight), only inorganic As (arsenite and arsenate) was detected in the edible portions of the vegetables. When As bioavailability was assessed through monitoring blood plasma As concentrations following swine consumption of As-contaminated vegetables, between 50% and 100% of the administered As dose was absorbed and entered systemic circulation. Arsenic bioavailability decreased in the order mung beans>radish>lettuce=chard.     

Extensive biodegradation of polychlorinated biphenyls in Aroclor 1242 and electrical transformer fluid (Askarel) by natural strains of microorganisms indigenous to contaminated African systems

Evidence for substantial aerobic degradation of Aroclor 1242 and Askarel fluid by newly characterized bacterial strains belonging to the Enterobacter, Ralstonia and Pseudomonas genera is presented. The organisms exhibited degradative activity in terms of total PCB/Askarel degradation, degradation of individual congeners and diversity of congeners attacked. Maximal degradation by the various isolates of Askarel ranged from 69% to 86% whereas, Aroclor 1242, with the exception of Ralstonia sp. SA-4 (9.7%), was degraded by 37% to 91%. PCB analysis showed that at least 45 of the representative congeners in Aroclor 1242 were extensively transformed by benzoate-grown cells without the need for biphenyl as an inducer of the upper degradation pathway. In incubations with Aroclor 1242, no clear correlation was observed between percentage of congener transformed and the degree of chlorination, regardless of the presence or absence of biphenyl. Recovery of significant but nonstoichiometric amounts of chloride from the culture media showed partial dechlorination of congeners and suggested production of partial degradation products. Addition of biphenyl evidently enhanced dechlorination of the mixture by some isolates. With the exception of Ralstonia sp. SA-5, chloride released ranged from 24% to 60% in the presence of biphenyl versus 0.35% to 15% without biphenyl.     

Comparison of naphthalene bioavailability determined by whole-cell biosensing and availability determined by extraction with Tenax

A rapid biological method for the determination of the bioavailability of naphthalene was developed and its value as an alternative to extraction-based chemical approaches demonstrated. Genetically engineered whole-cell biosensors are used to determine bioavailable naphthalene and their responses compared with results from Tenax extraction and chemical analysis. Results show a 1:1 correlation between biosensor results and chemical analyses for naphthalene-contaminated model materials and sediments, but the biosensor assay is much faster. This work demonstrates that biosensor technology can perform as well as standard chemical methods, though with some advantages including the inherent biological relevance of the response, rapid response time, and potential for field deployment. A survey of results from this work and the literature shows that bioavailability under non-equilibrium conditions nonetheless correlates well with K_oc or K_d. A rationale is provided wherein chemical resistance is speculated to be operative.     

Probing emissions of military cargo aircraft: description of a joint field measurement Strategic Environmental Research and Development Program

To develop effective air quality control strategies for military air bases, there is a need to accurately quantify these emissions. In support of the Strategic Environmental Research and Development Program project, the particulate matter (PM) and gaseous emissions from two T56 engines on a parked C-130 aircraft were characterized at the Kentucky Air National Guard base in Louisville, KY. Conventional and research-grade instrumentation and methodology were used in the field campaign during the first week of October 2005. Particulate emissions were sampled at the engine exit plane and at 15 m downstream. In addition, remote sensing of the gaseous species was performed via spectroscopic techniques at 5 and 15 m downstream of the engine exit. It was found that PM mass and number concentrations measured at 15-m downstream locations, after dilution-correction generally agreed well with those measured at the engine exhaust plane; however, higher variations were observed in the far-field after natural dilution of the downstream measurements was accounted for. Using carbon dioxide-normalized data we demonstrated that gas species measurements by extractive and remote sensing techniques agreed reasonably well.