Beryllium-7 Measurements in the Houston and Phoenix Urban Areas: An Estimation of Upper Atmospheric Ozone Contributions

Abstract

Natural radionuclides have been proposed as a means of assessing the transport of ozone (O₃) and aerosols in the troposphere. Beryllium-7 (⁷Be) is produced in the upper troposphere and lower stratosphere by the interaction of cosmogenic particles with atmospheric nitrogen and oxygen. ⁷Be has a 53.29-day half-life (478 keV γ) and is known to attach to fine particles in the atmosphere once it is formed. It has been suggested that O₃ from aloft can be transported into rural and urban regions during stratospheric–tropospheric folding events leading to increased background levels of O₃ at the surface. ⁷Be can be used as a tracer of upper atmospheric air parcels and the O₃ associated with them. Aerosol samples with a 2.5-µm cutoff were collected during 12-hr cycles (day/night) for a 30-day period at Deer Park, TX, near Houston, in August– September of 2000, and at Waddell, AZ, near Phoenix, in June–July of 2001. A comparison of ⁷Be levels with 12-hr O₃ averages and maxima shows little correlation. Comparison of nighttime and daytime O₃ levels indicate that during the day, when mixing is anticipated to be higher, the correlation of ⁷Be with O₃ in Houston is approximately twice that observed at night. This is consistent with mixing and with the anticipated loss of O₃ by reaction with nitric oxide (NO) and dry deposition. At best, 30% of the O₃ variance can be explained by the correlation with ⁷Be for Houston, less than that for Phoenix where no significant correlation was seen. This result is consistent with the intercept values obtained for ⁷Be correlations with either O₃ 24-hr averages or O₃ 12-hr maxima and is also in the range of the low O₃ levels (25 ppb) observed at Deer Park during a tropical storm event where the O₃ is attributable primarily to background air masses. That is, maximum background O₃ level contributions from stratospheric sources aloft are estimated to be in the range of 15–30 ppb in the Houston, TX, and Phoenix, AZ, area, and levels above these are because of local tropospheric photochemical production.     

A Question of Boundaries: The Importance of “Revenuesheds” for Watershed Protection1

Patterson, Lauren A., Jeffrey Hughes, Glenn Barnes, and Stacey I. Berahzer, 2012. A Question of Boundaries: The Importance of “Revenuesheds” for Watershed Protection. Journal of the American Water Resources Association (JAWRA) 48(4): 838‐848. DOI: 10.1111/j.1752‐1688.2012.00655.x Abstract: Watersheds transcend jurisdictional boundaries; raising important questions of who should pay for watershed protection, and how can watershed governance be funded? The responsibility and cost for watershed protection has progressively devolved to local governments, resulting in additional negative externalities and financing challenges. Watershed governance structures have formed at the scale of the watershed, but they often lack the financing mechanisms needed to achieve policy goals. Financing mechanisms via local governments provide a reliable source of revenue and the flexibility to address watershed specific issues. We develop a “revenueshed” approach to access the initial challenges local governments face when seeking to finance trans‐jurisdictional watershed governance. The revenueshed approach engages local governments into discussion and implementation of financial strategies for collaborative watershed governance. Legislation places water quality regulations primarily on local governments inside the watershed. The revenueshed approach extends the financial and stewardship discussion to include local governments outside the watershed that benefit from the watershed. We applied the revenueshed approach to the Mills River and Upper Neuse watersheds in North Carolina. Mills River had a partnership governance seeking revenue for specific projects, whereas the Upper Neuse sought long‐term financial stability to meet new water quality legislation.     

Second-order chlorine decay and trihalomethanes formation in a pilot-scale water distribution systems

It is well known that model-building of chlorine decay in real water distribution systems is difficult because chlorine decay is influenced by many factors (e.g., bulk water demand, pipe-wall demand, piping material, flow velocity, and residence time). In this paper, experiments were run to investigate the kinetic model of chlorine decay and the formation model of trihalomethanes (THMs) in pilot-scale water distribution systems. Experimental results show that the rate constants of chlorine decay, including wall decay and bulk decay, increasing with temperature. Moreover, the kinetic model of chlorine decay and the formation model of THMs describe experiment data of pilot-scale water distribution systems. The effect of different piping material on chlorine decay and THMs formation were also investigated. The rate constants of chlorine decay are ranked in order: stainless steel pipe, ductile iron pipe, and last, polyethelene pipe because wall decay is the largest in stainless steel pipe than that in other piping material. Correspondingly, the rate of THMs formation follows the order of stainless steel pipe, ductile iron pipe, and last, polyethelene pipe because of less chlorine in bulk water reacting with the trihalomethane formation potential (THMFP).     

Long-Term Community Dynamics of Small Landbirds with and Without Exposure to Extensive Disturbance from Military Training Activities

Military training activities are known to impact individual species, yet our understanding of how such activities influence animal communities is limited. In this study, we used long-term data in a case study approach to examine the extent to which the local small landbird community differed between a site in northeast Kansas that experienced intensive disturbance from military training activities (Ft. Riley Military Installation) and a similar, nearby site that experienced minimal human disturbance (Konza Prairie Biological Station). In addition, we characterized how the regional pool of potential colonizers influenced local community dynamics using Breeding Bird Survey data. From 1991 to 2001, most species of small terrestrial landbirds (73%) recorded during breeding surveys were found at both sites and the mean annual richness at Ft. Riley (39.0 ± 2.86 [SD]) was very similar to that of Konza Prairie (39.4 ± 2.01). Richness was maintained at relatively constant levels despite compositional changes because colonizations compensated local extinctions at both sites. These dynamics were driven primarily by woodland species that exhibited stochastic losses and gains and were present at a low local and regional abundance. Our results suggest that military training activities may mimic natural disturbances for some species in this area because the small landbird community did not differ markedly between sites with and sites without extensive human disturbance. Although our results suggest that military training is not associated with large changes in the avian community, additional studies are needed to determine if this pattern is found in other ecological communities.     

Equilibration time scales of organic aerosol inside thermodenuders: Evaporation kinetics versus thermodynamics

The interpretation of thermodenuder (TD) data often relies on the assumption that thermodynamic equilibrium is reached inside the instrument. We modeled the evaporation of three organic aerosol types (adipic acid, α-pinene SOA and aged OA) inside a thermodenuder with a mass transfer model, and calculated equilibration time scales for these systems at realistic conditions. The equilibrium times varied from less than a second to several hours, decreasing with increasing aerosol concentrations, decreasing particle sizes, decreasing volatilities and increasing mass accommodation coefficients. The results indicate that generally TDs measure particle evaporation rates rather than equilibria, and time-dependent modeling of the evaporation is usually needed to interpret the data. Measurements at varying residence times and temperatures, on the other hand, are desirable to investigate the equilibration of the studied aerosol and decouple the kinetic effects from the effects caused by the thermodynamic properties of the aerosol. Organic aerosol is likely to be further from equilibrium under typical field conditions compared with laboratory data. When determining the aerosol properties from TD data, assuming incorrectly equilibrium results in under-prediction of the vaporization enthalpy of the evaporating species. Similar under-estimation is predicted if multicomponent aerosols are approximated with single-component properties.     

Pollutants and the health of green sea turtles resident to an urbanized estuary in San Diego, CA

Rapid expansion of coastal anthropogenic development means that critical foraging and developmental habitats often occur near highly polluted and urbanized environments. Although coastal contamination is widespread, the impact this has on long-lived vertebrates like the green turtle (Chelonia mydas) is unclear because traditional experimental methods cannot be applied. We coupled minimally invasive sampling techniques with health assessments to quantify contaminant patterns in a population of green turtles resident to San Diego Bay, CA, a highly urbanized and contaminated estuary. Several chemicals were correlated with turtle size, suggesting possible differences in physiological processes or habitat utilization between life stages. With the exception of mercury, higher concentrations of carapace metals as well as 4,4′-dichlorodiphenyldichloroethylene (DDE) and γ chlordane in blood plasma relative to other sea turtle studies raises important questions about the chemical risks to turtles resident to San Diego Bay. Mercury concentrations exceeded immune function no-effects thresholds and increased carapace metal loads were correlated with higher levels of multiple health markers. These results indicate immunological and physiological effects studies are needed in this population. Our results give insight into the potential conservation risk contaminants pose to sea turtles inhabiting this contaminated coastal habitat, and highlight the need to better manage and mitigate contaminant exposure in San Diego Bay.     

Cadmium and lead in tissues of Mallards (Anas platyrhynchos) and Wood Ducks (Aix sponsa) using the Illinois River (USA)

Cadmium and lead concentrations were determined in the tissues of Mallards and Wood Ducks collected from two waterfowl management areas along the Illinois River, USA, during the autumn and late winter of 1997-1998. Lead concentrations in livers of Mallards were lower than previously reported, and, along with those in a small sample of Wood Duck livers, were within background levels (<2.0 microg/g wet weight). Mean concentrations of cadmium in the kidneys of Wood Ducks utilizing the Illinois River were four times greater than in after-hatch-year Mallards, and 14 times greater than in hatch-year Mallards. Concentrations of cadmium in the kidneys of Wood Ducks were comparable with those of specimens dosed with cadmium or inhabiting contaminated areas in previous studies. Wood Ducks utilizing wetlands associated with the Illinois River, and presumably other portions of the lower Great Lakes region, may be chronically exposed to cadmium.     

Retention of arsenic on hydrous ferric oxides generated by electrochemical peroxidation

Electrochemical peroxidation (ECP), an emerging remediation technology, with direct electric current applied to steel electrode and small addition of H2O2, was used to remove As(III) from contaminated aqueous solutions. Bench scale experiments were conducted to evaluate the sorption and distribution of arsenic between the soluble and solid state hydrous ferric oxides (HFO) formed as part of the ECP process. ECP was effective in removing arsenic from the aqueous solution, with >98% of the applied As(III) adsorbed on HFO. Removal was complete within 3 min of ECP treatment and apparently independent of the initial pH of the water (3.5-9.5). In the absence of H2O2 more As(III) was adsorbed by solid state iron at pH 9.5 than at 3.5 (2600 vs. 1750 microg l(-1)). Thus H2O2 was crucial to oxidize As(III) to As(V) which is more strongly retained by HFO. Removal of As was not significantly affected by the concentration of H2O2 or by current processing time. The optimal operating conditions were pH < 6.5, H2O2 concentration of 10 mg l(-1) and current process time not exceeding 3 min. X-ray diffraction (XRD), diffuse-reflectance infrared Fourier transform (DRIFT) spectroscopy and transmission electron microscopy (TEM) were applied to study the HFO deposits. The XRD data indicated the prevalence of poorly ordered Fe minerals in the suspended ECP solids with a dominance of 5 line ferrihydrite in the absence of H2O2. At pH 3.5 and with 100 mg H2O2 l(-1), akaganeite was formed, whereas an incipient hematitic phase, reflection at 0.39 nm, occurred at pH 6.5. DRIFT data indicate that both As(III) and As(V) were specifically adsorbed onto HFO at acid and neutral pH. TEM observations indicated the presence of spherical shape ferrihydrite and provided evidence for possible formation of subrounded hematite and acicular shape goethite.     

Polybrominated diphenyl ethers in house dust in Singapore

The use of polybrominated diphenyl ethers (PBDEs) as flame retardants in Singapore is not strictly regulated; therefore these compounds can be readily found in furniture, electronic devices, and building materials. This study was the first of its kind to be conducted in Singapore to measure concentrations of PBDEs in house dust. Samples were collected from 31 homes in various locations across the island-state of Singapore, and a total eight PBDEs congeners were measured. PBDEs were detected in all 31 dust samples and the number of BDE congener detected per home ranged between 3 and 8. The most abundant BDE congeners found were BDE 47, 99 and 209, with a median value of 20 ng g(-1) dust, 24 ng g(-1) dust and 1000 ng g(-1) dust, respectively. BDE 209 contributed 88% to the median of all the congeners, and BDE 47 and 99 contributed 1.8% and 3.5%, respectively. Different congener profiles were observed between this and studies conducted elsewhere, which is consistent with the use of different commercial PBDE around the world. No significant correlations between PBDE dust levels and residential characteristics (number of TVs and computers, floor area or flooring material) were observed. The daily intake of PBDEs via the inhalation pathway was estimated. House dust may be regarded as the most important exposure route of PBDEs for children.     

Refinery evaluation of optical imaging to locate fugitive emissions

Fugitive emissions account for approximately 50% of total hydrocarbon emissions from process plants. Federal and state regulations aiming at controlling these emissions require refineries and petrochemical plants in the United States to implement a Leak Detection and Repair Program (LDAR). The current regulatory work practice, U.S. Environment Protection Agency Method 21, requires designated components to be monitored individually at regular intervals. The annual costs of these LDAR programs in a typical refinery can exceed US$1,000,000. Previous studies have shown that a majority of controllable fugitive emissions come from a very small fraction of components. The Smart LDAR program aims to find cost-effective methods to monitor and reduce emissions from these large leakers. Optical gas imaging has been identified as one such technology that can help achieve this objective. This paper discusses a refinery evaluation of an instrument based on backscatter absorption gas imaging technology. This portable camera allows an operator to scan components more quickly and image gas leaks in real time. During the evaluation, the instrument was able to identify leaking components that were the source of 97% of the total mass emissions from leaks detected. More than 27,000 components were monitored. This was achieved in far less time than it would have taken using Method 21. In addition, the instrument was able to find leaks from components that are not required to be monitored by the current LDAR regulations. The technology principles and the parameters that affect instrument performance are also discussed in the paper.