Source Apportionment of Phoenix PM2.5 Aerosol with the Unmix Receptor Model

Abstract

The multivariate receptor model Unmix has been used to analyze a 3-yr PM_2.5 ambient aerosol data set collected in Phoenix, AZ, beginning in 1995. The analysis generated source profiles and overall average percentage source contribution estimates (SCEs) for five source categories: gasoline engines (33 ± 4%), diesel engines (16 ± 2%), secondary SO₄ ^2? (19 ± 2%), crustal/soil (22 ± 2%), and vegetative burning (10 ± 2%). The Unmix analysis was supplemented with scanning electron microscopy (SEM) of a limited number of filter samples for information on possible additional low-strength sources. Except for the diesel engine source category, the Unmix SCEs were generally consistent with an earlier multivariate receptor analysis of essentially the same data using the Positive Matrix Factorization (PMF) model. This article provides the first demonstration for an urban area of the capability of the Unmix receptor model.     

SITE Demonstration of Slurry-Phase Biodegradation of PAH Contaminated Soil

This paper summarizes a joint Superfund Innovative Technology Evaluation (SITE) project on slurry-phase biodegradation and a project to collect information for the data base on Best Demonstrated Available Technologies (BOAT). In this 12-week study, a creosote contaminated soil from the Burlington Northern Superfund site in Brainerd, Minnesota was used to evaluate the effectiveness of the bioslurry reactors. During the demonstration, five 64-liter stainless steel bioreactors, equipped with agitation, aeration and temperature controls were used. The pilot scale study employed a 30 percent slurry, an inoculum of indigenous polynuclear aromatic hydrocarbon (PAH) degraders, and inorganic nutrients.

Total PAH degradation averaged 93.4 ± 3.2 percent over all five operating reactors in the 12 weeks with 97.4 percent degradation of the 2- and 3-ring PAHs and 90 percent degradation of the 4- to 6-ring PAHs. A study of the air emissions, both semivolatile compounds such as naphthalene, anthracene, and phenanthrene and volatile compounds such as toluene, xylene, and benzene, from the units showed that the greatest amount of emissions occurred during the loading of the reactors and during the first few days of operation. Therefore, it may not be cost-effective to require elaborate emissions controls unless there are significant quantities of volatile compounds present in the soil or water to be treated in a bioslurry reactor system.     

Aerosol Filtration by Sorbent Beds

Fixed beds of sorbent media are used for the evaluation of poiynuclear aromatic hydrocarbons (PAH) present in air. Twostage sampling and separate extraction and analyses of PAH associated with aerosol particles and those present in the vapor state are usually performed. The ability of commonly used sorbents to retain particulate matter introduces a potential for reducing the time and cost of PAH evaluation procedures.

The filtration efficiency of three sorbent media, Florisil, XAD-2, and polyurethanefoam (PUF), for particles in 0.1 to 1 µm size range was studied using airflow rates from 4 to 2501 /mm through a PS 1 sorbent cartridge. Theoretical considerations were used to identify the principal filtration mechanisms and to assess the predictability of the aerosol filtration performance of sorbent filters. The results of this study indicate XAD-2 to be an efficient filtration medium owing to the electrostatic enhancement of capturing and retaining aerosol particles.

As a result of theoretical considerations, Brownian diffusion and inertial deposition were found to be major filtration mechanisms accompanied by electrostatic effects. While the efficiency of the diffusional deposition mechanism was reasonably well predicted with available theories, modeling of submicron particle impaction at higher fluid velocities appeared to be inadequate. Further developments are suggested to improve our understanding of filtration phenomena in sorbent beds under high flow rate conditions.     

Comparison of summer and winter California central valley aerosol distributions from lidar and MODIS measurements

Aerosol distributions from two aircraft lidar campaigns conducted in the California Central Valley are compared in order to identify seasonal variations. Aircraft lidar flights were conducted in June 2003 and February 2007. While the ground PM_2.5 (particulate matter with diameter ≤ 2.5 μm) concentration was highest in the winter, the aerosol optical depth (AOD) measured from the MODIS and lidar instruments was highest in the summer. A multiyear seasonal comparison shows that PM_2.5 in the winter can exceed summer PM_2.5 by 68%, while summer AOD from MODIS exceeds winter AOD by 29%. Warmer temperatures and wildfires in the summer produce elevated aerosol layers that are detected by satellite measurements, but not necessarily by surface particulate matter monitors. Temperature inversions, especially during the winter, contribute to higher PM_2.5 measurements at the surface. Measurements of the mixing layer height from lidar instruments provide valuable information needed to understand the correlation between satellite measurements of AOD and in situ measurements of PM_2.5. Lidar measurements also reflect the ammonium nitrate chemistry observed in the San Joaquin Valley, which may explain the discrepancy between the MODIS AOD and PM_2.5 measurements.     

Emission Control in Coking Operations By Use of Stage Charging

At the Clairton Coke Works of the United States Steel Corporation (the world’s largest coke plant), with coal charges of about 30,000 net tons per day, a system designated as “stage charging” has been developed for charging coal into the coke oven chamber without emissions to the atmosphere. The principles of the system are based on controlled sequential flow of the coal from the charging hoppers, during which the oven chamber is maintained under a very slight negative pressure condition by use of steam aspiration in the offtakes for on-the-main charging. The techniques are basic but require knowledge of the coal characteristics, adequate and properly maintained aspirating systems, including clean offtake piping, control of coal volume in the individual hoppers, and last, and probably most important, adherence by the operating crew to specific charging and leveling practices.     

R&D Activities,Operating Experience Discussed at Fabric Alternatives Forum

ABSTRACT

Previously reported volatile organic compounds (VOC) radiocarbon (¹⁴C) measurements for 1992 summertime Atlanta, GA, have been compared with chromatographic data and emissions inventory predictions. The chromatographic approach that was used provided a more comprehensive VOC characterization than typically achieved, and the emissions inventory was research-grade level (date-, site-, and time-specific). The comparisons are in general agreement that biogenic emissions contribute only modestly (<10%) to the VOC content of the particular ambient samples that were collected and measured. The choices of sampling site (near city-center) and times (early morning and late evening) are major influences on the results, which consequently should not be regarded as representing the average VOC biogenic impact for the Atlanta area.     

Fate and effects of anthropogenic chemicals in mangrove ecosystems: a review

The scientific literature for fate and effects of non-nutrient contaminant concentrations is skewed for reports describing sediment contamination and bioaccumulation for trace metals. Concentrations for at least 22 trace metals have been reported in mangrove sediments. Some concentrations exceed sediment quality guidelines suggesting adverse effects. Bioaccumulation results are available for at least 11 trace metals, 12 mangrove tissues, 33 mangrove species and 53 species of mangrove-habitat biota. Results are specific to species, tissues, life stage, and season and accumulated concentrations and bioconcentration factors are usually low. Toxicity tests have been conducted with 12 mangrove species and 8 species of mangrove-related fauna. As many as 39 effect parameters, most sublethal, have been monitored during the usual 3 to 6 month test durations. Generalizations and extrapolations for toxicity between species and chemicals are restricted by data scarcity and lack of experimental consistency. This hinders chemical risk assessments and validation of effects-based criteria.     

Detection of antibacterial-like activity on a silica surface: fluoroquinolones and their environmental metabolites

Background, scope, and aims

Antibacterial fluoroquinolones (FQs) are third-generation antibiotics that are commonly used as therapeutic treatments of respiratory and urinary tract infections. They are used far less in intensively farmed animal production systems, though their use may be permitted in the veterinary treatments of flocks or in medicated feeds. When used, only a fraction of ingested parent FQ actually reaches the in vivo target site of infection, while the remainder is excreted as the parent FQ and its metabolized products. In many species?? metabolism, enrofloxacin (EF) is converted into ciprofloxacin (CF) while both FQs are classified as parent FQs in human treatments. It is therefore likely that both FQs and their metabolic products will contribute to a common pool of metabolites in biological wastes. Wastes from intensive farming practices are either directly applied to agricultural land without treatment or may be temporarily stored prior to disposal. However, human waste is treated in sewage treatment plants (STPs) where it is converted into biosolids. In the storage or treatment process of STPs, FQs and their in vivo metabolites are further converted into other environmental metabolites (FQEMs) by ex vivo physicochemical processes that act and interact to produce complex mixtures of FQEMs, some of which have antibacterial-like activities. Biosolids are then often applied to agricultural land as a fertilizer amendment where FQs and FQEMs can be further converted into additional FQEMs by soil processes. It is therefore likely that FQ-contaminated biowaste-treated soils will contain complex mixtures of FQEMs, some of which may have antibacterial-like activities that may be expressed on bacteria endemic to the receiving agricultural soil environment. Concern has arisen in the scientific and in the general community that repeated use of FQ-contaminated biowaste as fertilizer amendments of nutrient-impoverished agricultural land may create a selective environment in which FQ-resistant bacteria might grow. The likelihood of this happening will depend, to some extent, on whether bioactive FQEMs are first synthesized from the parent FQs by the action and interaction of in vivo and ex vivo processes producing bioactive FQEMs in biowastes and biosolids. The postulated creation of a selective environment will also depend, in part, on whether such bioactive FQEMs are biologically available to bacteria, which may, in turn, be influenced by soil type, amendment regime, and the persistence of the bioactive FQEMs. Additionally, soil bacteria and soil processes may be affected in different ways or extents by bioactive FQEMs that could possibly act additively or synergistically at ecological targets in these non-target bacteria. This is an important consideration, since, while parent FQs have well-defined ecological targets (DNA gyrase and topoisomerase IV) and modes of bactericidal action, the FQEMs and their possible modes of action on the many different species of soil bacteria is less well studied. It is therefore understandable that there is a lack of conclusive evidence directly attributing biosolid usage to any increase in FQ-resistant bacteria detected in biowaste-amended agricultural soil. However, a lack of evidence may simply imply that a causal relationship between biosolid usage programs and any detection of low levels of FQ-resistant bacteria in soils has yet to be established, rather than an assumption of no relationship whatsoever. Based on results presented in this paper, the precautionary principle should be applied in the usage of FQ-contaminated biosolids as fertilizer amendments of agricultural land. The aim of this research was to test whether any bioactive FQEMs of EF could be synthesized by aerobic fermentation processes using Mycobacterium gilvum (American Tissue Culture Collection) and a mixed culture of microorganisms derived from an agricultural soil. High-performance thin-layer chromatography (HPTLC) and bioautography were tested as screening techniques in the detection and analysis of bioactive FQEMs.

Materials and methods

FQEMs derived from M. gilvum and mixed (soil) culture aerobic ferments were fractionated using preparative HPTLC. A standard strain of Escherichia coli was then used as the reporter organism in a bioautography assay in the detection of bioactive-FQEMs on a mid-section of the HPTLC plate. Plate sections were reassembled, and a photograph was taken under low-intensity ultraviolet (UV) light to reveal regions that contained analytes that had UV chromophores and antibacterial-like activities.

Results and discussion

Many fractionated FQEMs displayed antibacterial-like activity while bound to silica gel HPTLC plates. These results also provide evidence that sufficient quantities of biologically active FQEMs were biologically available from a silica gel surface to prevent the adherent growth of E. coli. Six to seven FQEMs derived from EF using aerobic fermentation processes had antibacterial-like activities, while two FQEMs were also detectable using UV light. Furthermore, similar banding patterns of antibacterial-like activity were observed in both the monoculture (M. gilvum) and mixed culture bioautography assays, indicating that similar processes operated in both aerobic fermentations, either producing similar biologically active FQEMs or biologically active FQEMs that had similar physicochemical properties in both ferments. The simplest explanation for these findings is that the tested agricultural soil also contained mycobacteria that metabolized EF in a similar way to the purchased standard monoculture M. gilvum. Additionally, the marked contrast between the bioautography results and the UV results indicated that the presence of UV chromophores is not a prerequisite for the detection of antibacterial-like activity.

Conclusions

A reliance on spectrophotometric techniques in the detection of bioactive FQEMs in the environment may underestimate component antibacterial-like activity and, possibly, total antibacterial-like activity expressed by EF and its FQEMs. The described bioautography method provides a screening technique with which antibacterial-like activities derived from EF and possibly other FQs can be detected directly on silica gel HPTLC plates.

Recommendations

It is recommended that both bioassay and instrumental analytical techniques be used in any measurement of hazard and risk relating to antibacterial-like activities in the environment that are derived from fluoroquinolone antibiotics and their environmental metabolites.