Fugitive emissions opacity determination using the digital opacity compliance system (DOCS)

Maintenance of Department of Defense (DoD) weapon systems, conducting battlefield training exercises as well as meeting military construction and/or demolition schedules, invariably generate fugitive air emissions, many of which are visible. Although there is no codified federal method for quantifying fugitive emissions opacity, many state and local air regulatory agencies have instituted enforceable fugitive emission opacity standards at DoD facilities. The current study focused on comparing the performance of the digital opacity compliance system (DOCS) with U.S. Environment Protection Agency Method 9 (Method 9) certified human observers in quantifying the visible opacity associated with fugitive emissions produced using a commercial fog generator. By systematically repositioning both DOCS cameras and Method 9-certified observers during field testing, differences in method performance as a function of observational locations were documented. At both the 30- and 300-ft off-set distances, opacity levels reported by the DOCS technology and Method 9-certified smoke readers were found to be statistically different at the 99% confidence level. Alternatively, at the 90- and 150-ft off-set distances, results suggested that there was an insignificant difference at the 99% confidence level between the two methods. Comparing the magnitude of the each method's standard deviation suggested that, at the 30-ft off-set distance, the DOCS technology was consistently more precise than Method 9-certified readers regardless of the observer's downwind distance. However, at the 90, 150, and 300-ft off-set distances, method precision seemed to vary as a function of both off-set and downwind distance. The primary factor affecting the consistency in opacity measurements appeared to be the impact of ground-level air turbulence on fog plume dispersion and transport. Field observations demonstrated that localized wind shear played a critical and decisive role in how and to what extent fugitive emissions opacity could be determined, regardless of the method selected.     

Chromate transport through columns packed with surfactant-modified zeolite/zero valent iron pellets

Chromate transport through columns packed with zeolite/zero valent iron (Z/ZVI) pellets, either untreated or treated with the cationic surfactant hexadecyltrimethylammonium (HDTMA), was studied at different flow rates. In the presence of sorbed HDTMA, the chromate retardation factor increased by a factor of five and the pseudo first-order rate constant for chromate reduction increased by 1.5-5 times. The increase in rate constant from the column studies was comparable to a six-fold increase in the rate constant determined in a batch study. At a fast flow rate, the apparent delay in chromate breakthrough from the HDTMA modified Z/ZVI columns was primarily caused by the increase in chromate reduction rate constant. In contrast, at a slower flow rate, the retardation in chromate transport from the HDTMA modified Z/ZVI columns mainly originated from chromate sorption onto the HDTMA modified Z/ZVI pellets. Due to dual porosity, the presence of immobile water was responsible for the earlier breakthrough of chromate in columns packed with zeolite and Z/ZVI pellets. The results from this study further confirm the role of HDTMA in enhancing sorption and reduction efficiency of contaminants in groundwater remediation.     

Variations in PCB concentrations between genders of six warmwater fish species in Lake Logan Martin, Alabama, USA

We collected and analyzed 955 individual fish (six species) for sexual differences in PCB bioaccumulations from a southeastern, USA reservoir. Using 2-way ANCOVAs, we found significant differences in fillet PCB concentrations between sexes for channel catfish (Ictalurus punctatus), largemouth bass (Micropterus salmoides) and spotted bass (Micropterus punctulatus). Striped bass (Morone saxatilus), black crappie (Pomoxis nigromaculatus) and freshwater drum (Aplodinotus grunniens) did not display differences between sexes in PCB concentrations. We suspect that sexual differences may be due to biological differences in reproduction, relative motility and lipid deposition. For one species (striped bass), sexual differences in PCB concentrations were inconsistent with a study in the Hudson River suggesting that sexual differences in bioaccumulations can change across ecosystems. Two species which did show sexual differences, largemouth bass and channel catfish, are often chosen as representative species (e.g., "piscivore" and "benthivore") in contaminant monitoring in many USA states indicating human consumption and risk management decisions would be improved if an equal number of male and female fish were included in composite PCBs analysis. This could reduce variability in fish PCBs data from which consumption advisories are based.     

Using Lichen Chemistry to Assess Airborne Tungsten and Cobalt in Fallon, Nevada

This paper describes the use of lichen chemistry to assess airborne tungsten and cobalt in Fallon, Nevada, where a cluster of childhood leukemia has been on going since 1997. Lichens and their rock substrates were collected from Rattlesnake Hill within Fallon as well as from four different rock outcrops located north, east, south, and west of Fallon and at least 20 km away from the town center. In the lichens themselves, W and Co are significantly higher within Fallon than in the combined control site outside of Fallon. In the rock substrates of the lichens, no differences exist in W and Co. The W and Co differences in lichens cannot be attributed to substrate geochemistry. Fallon is distinctive in west central Nevada for high airborne W and Co, and given its cluster of childhood leukemia, it stands to reason that additional biomedical research is in order to test directly the leukogenicity of combined airborne W and Co.     

Estimated Variability of National Atmospheric Deposition Program/Mercury Deposition Network Measurements Using Collocated Samplers

The National Atmospheric Deposition Program/Mercury Deposition Network (MDN) provides long-term, quality-assured records of mercury in wet deposition in the USA and Canada. Interpretation of spatial and temporal trends in the MDN data requires quantification of the variability of the MDN measurements. Variability is quantified for MDN data from collocated samplers at MDN sites in two states, one in Illinois and one in Washington. Median absolute differences in the collocated sampler data for total mercury concentration are approximately 11% of the median mercury concentration for all valid 1999–2004 MDN data. Median absolute differences are between 3.0% and 14% of the median MDN value for collector catch (sample volume) and between 6.0% and 15% of the median MDN value for mercury wet deposition. The overall measurement errors are sufficiently low to resolve between NADP/MDN measurements by ±2 ng·l⁻¹ and ±2 μg·m⁻²·year⁻¹, which are the contour intervals used to display the data on NADP isopleths maps for concentration and deposition, respectively.     

A near real-time system for continuously monitoring airborne subtilisin-type enzymes in the industrial atmosphere

We describe the development and validation of a portable system comprising an air sampler coupled to an automated flow injection analysis device. The system is able to monitor airborne concentrations of subtilisin-type enzymes in the workplace atmosphere on a continuous basis. Sampling is in two stages: using a sampling head that is designed to mimic human respiration at approx. 1 m s(-1) at a sampling rate of 600 l min(-1). In the second stage, the captured particles are deposited by impaction from the air stream onto the inner surface of a cyclone that is continuously washed with a jet of buffer solution. Deposited particles are then washed into a reservoir from which samples are taken every 5-6 min and injected automatically into a continuous flow injection analysis system. Proteolytic enzyme in the sample passes through a bioreactor maintained at about 40 degrees C. This contains a cellulose solid phase matrix on which is covalently immobilised Texas Red-labelled gelatin as substrate. The passing enzyme partially digests the substrate releasing fluorophore that is detected down stream in a flow cell coupled to a fluorimeter. The system is calibrated using enzyme standards and the intensity of the resulting peaks from the ex-air samples is converted to airborne concentrations using a mathematical model programmed into a PC. The system has a limit of detection of 4.8 ng m(-3) and a dynamic range of 5-60 ng m(-3). The within assay precision (RSD) is 6.3-9.6% over this range. The within batch precision is 20.3% at 20 ng m(-3) and the corresponding between batch value is 19.5%. The system has been run for periods up to 8 h in the laboratory and for up to 4 h at a factory site and the values obtained compared with time-averaged values obtained from a conventional Galley sampler and in-house analysis when reasonable agreement of the results was observed. The stability of the system over 21 days of continuous use with standards injected periodically was studied. Linearity was observed for all the standard plots throughout. At the end of 21 days, after a total exposure equivalent to 2395 ng ml(-1) of Savinase, the signal due to the 5.0 ng ml(-1) standard was still easily detectable.     

Removal of added nitrate in the single, binary, and ternary systems of cotton burr compost, zerovalent iron, and sediment: Implications for groundwater nitrate remediation using permeable reactive barriers

Recent research has shown that carbonaceous solid materials and zerovalent iron (Fe(0)) may potentially be used as media in permeable reactive barriers (PRBs) to degrade groundwater nitrate via heterotrophic denitrification in the solid carbon system, and via abiotic reduction and autotrophic denitrification in the Fe(0) system. Questions arise as whether the more expensive Fe(0) is more effective than the less expensive carbonaceous solid materials for groundwater nitrate remediation, and whether there is any synergistic effect of mixing the two different types of materials. We carried out batch tests to study the nature and rates of removal of added nitrate in the suspensions of single, binary, and ternary systems of cotton burr compost, Peerless Fe(0), and a sediment low in organic carbon. Cotton burr compost acted as both organic carbon source and supporting material for the growth of indigenous denitrifiers. Batch tests showed that cotton burr compost alone removed added nitrate at a greater rate than did Peerless Fe(0) alone on an equal mass basis with a pseudo-first-order rate constant k=0.0830+/-0.0031 h(-1) for cotton burr compost and a k=0.00223+/-0.00022 h(-1) for Peerless Fe(0); cotton burr compost also removed added nitrate at a faster rate than did cotton burr compost mixed with Peerless Fe(0) and/or the sediment. Furthermore, there was no substantial accumulation of ammonium ions in the cotton burr compost system, in contrast to the systems containing Peerless Fe(0) in which ammonium ions persisted as major products of nitrate reduction. It is concluded that cotton burr compost alone may be used as an excellent denitrification medium in a PRB for groundwater nitrate removal. Further study is needed to evaluate performance of its field applications.     

Sorption of organic contaminants by biopolymers: role of polarity, structure and domain spatial arrangement

Sorption behavior of hydrophobic organic contaminants (HOCs) (i.e., pyrene, phenanthrene and naphthalene) by native and chemically modified biopolymers (lignin, chitin and cellulose) was examined. Lignins (native and treated) showed nonlinear sorption for all compounds studied, emphasizing their glassy character. Chitins and celluloses had linear isotherms for phenanthrene and naphthalene, illustrating the dominance of partitioning, while pyrene yielded nonlinear isotherms. Sorption capacity (K(oc)) of HOCs was negatively correlated with the polarity [(O+N)/C] of the biopolymers. Aromatic and alkyl+aromatic C percentages, rather than alkyl C content, demonstrated a better correlation with K(oc) values, indicating the importance of aromatic structures for HOC affinity. Hydrophobicity (K(ow))-normalized K(oc) values decreased sharply with increasing percentage of O-alkyl C versus total aliphatic C (O-alkyl C/total aliphatic C) or with polar C/(alkyl+aromatic C) ratio of the biopolymers until their values reached 80% and 4, respectively, illustrating the effect of surrounding polar groups on reducing affinity for HOCs. Overall, the results of this study highlight the role of spatial arrangement of domains within biopolymers in sorption of HOCs, and point to sorbent properties, such as functionality, polarity and structure, jointly regulating the sorption of HOCs in biopolymers.     

Age and seasonal variability of polybrominated diphenyl ethers in free-ranging East Greenland polar bears (Ursus maritimus)

Polybrominated diphenyl ethers (PBDEs) were analysed in adipose tissue from 92 East Greenland polar bears (Ursus maritimus) sampled during 1999-2001. Mean SigmaPBDE concentrations were 70 ng/g lipid weight (lw) (range: 22-192 ng/g lw) and showed no relationship with age or sex. Of the 32 analysed PBDE congeners; BDE47, BDE153, BDE99 and BDE100 dominated, and comprised 99.6% of the SigmaPBDE concentration. The SigmaPBDE concentration had a highly significant correlation with SigmaPCB, SigmaCHL, dieldrin, HCB and SigmaHCH concentrations. We found a seasonal pattern of median SigmaPBDE concentration with 1.2 to 1.8 times higher concentrations in March to July than the rest of the year. The seasonal variation also provides a clue to the seasonal exposure, bio-availability, toxic exposure and degradation. We suggest that future geographical PBDE data comparisons may not need corrections for sex or age, but such data sets should be corrected for seasonal variability, using the presented correctional trigonometric regression.     

Managing scuba divers to meet ecological goals for coral reef conservation

Marine protected areas increasingly are challenged to maintain or increase tourism benefits while adequately protecting resources. Although carrying capacity strategies can be used to cope with use-related impacts, there is little understanding of divers themselves, their management preferences, and how preferences relate to conservation goals. By using a stated preference choice modeling approach, we investigated the choices divers make in selecting diving trips to marine protected areas as defined by use level, access, level of supervision, fees, conservation education, and diving expectations. Logit models showed that divers preferred a more restrictive management scenario over the status quo. Divers favored reductions in the level of site use and increased levels of conservation education. Divers did not favor fees to access protected areas, having less access to the resource, or extensive supervision. Finally, divers were much more willing to accept increasingly restrictive management scenarios when they could expect to see increased marine life.