Feasibility of ultraviolet-light-emitting diodes as an alternative light source for photocatalysis

The objective of this study was to determine whether ultraviolet-light-emitting diodes (UV-LEDs) could serve as an efficient photon source for heterogeneous photocatalytic oxidation (PCO). An LED module consisting of 12 high-power UV-A (lambda max = 365 nm) LEDs was designed to be interchangeable with a UV-A fluorescent black light blue (BLB) lamp for a bench scale annular reactor packed with silica-titania composite (STC) pellets. Lighting and thermal properties of the module were characterized to assess its uniformity and total irradiance. A forward current (I(F)) of 100 mA delivered an average irradiance of 4.0 mW cm(-2) at a distance of 8 mm, which is equivalent to the maximum output of the BLB, but the irradiance of the LED module was less uniform than that of the BLB. The LED and BLB reactors were tested for the oxidization of ethanol (50 ppm(v)) in a continuous-flow-through mode with 0.94 sec residence time. At the same average irradiance, the UV-A LED reactor resulted in a lower CO2 production rate (19.8 vs. 28.6 nmol L(-1) s(-1)), lower ethanol removal (80% vs. 91%), and lower mineralization efficiency (28% vs. 44%) than the UV-A BLB reactor. Ethanol mineralization was enhanced with the increase of the irradiance at the catalyst surface. This result suggests that reduced ethanol mineralization in the LED reactor relative to the BLB reactor at the same average irradiance could be attributed to the nonuniform irradiance over the photocatalyst, that is, a portion of the catalyst was exposed to less than the average irradiance. The potential of UV-A LEDs may be fully realized by optimizing the light distribution over the catalyst and utilizing their instantaneous "on" and "off" feature for periodic irradiation. Nevertheless, our results also showed that the current UV-A LED module had the same wall plug efficiency (WPE) of 13% as that of the UV-A BLB, demonstrating that UV-A LEDs are a viable photon source both in terms of WPE and PCO efficiency.     

A Brief Overview of Carbon Sequestration Economics and Policy

This article provides an overview of the issues and challenges involved in analyzing the costs and program design for carbon sequestration. The first section examines some of the pitfalls of comparing the results of carbon sequestration cost studies and suggests some simple ways in which analysts could make their results more useful. The pitfalls in comparing studies include different definitions for the summary statistic dollars per ton, differences in the type of costs that are estimated, and differences in underlying assumptions regarding program design and implementation. Future cost studies will benefit from improved treatment of leakage, general equilibrium interactions, and public finance interactions. The second section reviews issues related to the implementation of a carbon sequestration program, including which policy tools are available and which have received the most attention, some of the challenges for using those policy tools, and one alternative that has received little attention, but may become necessary. The discussion also provides an overview and analysis of the bills introduced in the last two congresses and considers the general policy implications of those proposals.     

Trends in water quality in LEASEQ rivers and streams (northwestern Ohio), 1975-1995. Lake Erie Agricultural Systems for Environmental Quality

Trends in water quality in four northwest Ohio rivers over the period 1975-1995 were identified using datasets of daily concentrations containing 4500 to 6800 observations per river during the study period. Concentrations were log-transformed prior to analysis, and adjusted for flow using a locally weighted scatterplot smoother (LOWESS) fit between log(concentration) and log(flow). Seasonality was modeled using one- and two-cycle sinusoidal oscillations and monthly additive constants. Substantial decreases in total and soluble reactive phosphorus were documented at all stations. Smaller but highly significant decreases in total Kjeldahl nitrogen were documented at all stations, and significant decreases in total suspended solids were documented at three of the four stations. Nitrate did not show significant trends at the two stations draining major watersheds, and showed significant trends in opposite directions at the two stations on smaller watersheds. Comparisons using nonparametric, nonlinear trend fits (LOWESS) suggest that changes in fertilizer and manure application rates are the most important cause of trends in phosphorus and total Kjeldahl nitrogen; point sources are insufficient to account for the phosphorus trends. The conflicting trends for nitrate are enigmatic, but may reflect diverging land use in the two smaller watersheds.     

Resilience of Norovirus GII.4 to Freezing and Thawing: Implications for Virus Infectivity

Genogroup II.4 norovirus (NoV) remains the predominant NoV strain in food- and water-borne outbreaks. Capsid integrity as well as viral RNA persistence were determined for GII.4 NoV by real-time RT-PCR after 1?C14 freeze/thaw (F/T) cycles (?80?°C/+22?°C) or after ?80?°C storage for up to 120?days. In both cases, capsid integrity and viral RNA titers remained stable. RNase was exogenously added after 1?C14 F/T cycles, but did not alter the amount of genomic NoV RNA detected, indicating that capsids remained intact. Presumptive NoV infectivity was evaluated in functional studies by a porcine gastric mucin binding assay. Viruses frozen and thawed up to 14× bound similarly to porcine mucin, suggesting no reduction in virus infectivity. Overall, this study shows that a) NoV particles retain their integrity for at least 14 F/T cycles, b) long-term (120?day) frozen storage does not decrease NoV RNA titers, and c) capsid binding to receptor-like glycoprotein moieties remains unaltered after 14 F/T cycles. This work indicates that freezing and thawing of foods or beverages would not be a practical processing intervention to reduce NoV contamination. Likewise, repeated freezing and thawing, as might be encountered during winter months, is not expected to inactivate NoV in the environment. Results do show that laboratory samples destined for molecular biological analyses or for use as positive controls may be repeatedly frozen and thawed without any anticipated reduction in NoV RNA titers. This study documents the cryostability of NoV capsids and RNA to freezing and thawing and to the possible retention of virus infectivity.     

An on-farm survey of spatial and temporal stratifications of 17β-estradiol concentrations

17β-estradiol (E2) is a natural estrogenic hormone found in animal manure and urine, which may cause endocrine disruption in sensitive organisms. 17β-Estradiol has been widely detected in the environment, and animal agriculture may be an important source. The objectives of this study were to investigate the potential sources and/or spatial and temporal characteristics contributing to detections of E2 at the farm-scale. Soil cores, segmented into 0.15 m increments, were taken down to the water table from four locations (three potential E2 sources and one control) at or around a swine (Sus scrofa domesticus) farm on five different dates between 2006 and 2007. Estradiol was quantified in the soil-water extracts using liquid chromatography-with tandem mass spectrometry (LC/MS/MS) analysis. Estradiol detections were widespread and found in 128 out of 345 extractions (37%). Concentrations ranged from 0 to 1910 ng L⁻¹ (porewater equivalents). A location that received field application of manure had significantly lower E2 concentrations compared to other locations. Also, the spring 2007 E2 concentrations were significantly higher than all other sample dates, perhaps related to climatic and hydrological events. Results suggested E2 was not directly related to manure sources, but was widespread in this environment. Where E2 was detected, highest concentrations favored the upper profile, while the greatest frequency of detections was in the lower profile and near the water table. Detections of E2 were associated with high organic mater contents in the upper profile and high sand contents in the lower profile. The study suggests that E2 is widespread in some soil environments, raising questions as to the source and mechanisms that facilitate its transport and mobility.     

Relationships between soil physicochemical, microbiological properties, and nutrient release in buffer soils compared to field soils

The retention of nutrients in narrow, vegetated riparian buffer strips (VBS) is uncertain and underlying processes are poorly understood. Evidence suggests that buffer soils are poor at retaining dissolved nutrients, especially phosphorus (P), necessitating management actions if P retention is not to be compromised. We sampled 19 buffer strips and adjacent arable field soils. Differences in nutrient retention between buffer and field soils were determined using a combined assay for release of dissolved P, N, and C forms and particulate P. We then explored these differences in relation to changes in soil bulk density (BD), moisture, organic matter by loss on ignition (OM), and altered microbial diversity using molecular fingerprinting (terminal restriction fragment length polymorphism [TRFLP]). Buffer soils had significantly greater soil OM (89% of sites), moisture content (95%), and water-soluble nutrient concentrations for dissolved organic C (80%), dissolved organic N (80%), dissolved organic P (55%), and soluble reactive P (70%). Buffer soils had consistently smaller bulk densities than field soils. Soil fine particle release was generally greater for field than buffer soils. Significantly smaller soil bulk density in buffer soils than in adjacent fields indicated increased porosity and infiltration in buffers. Bacterial, archaeal, and fungal communities showed altered diversity between the buffer and field soils, with significant relationships with soil BD, moisture, OM, and increased solubility of buffer nutrients. Current soil conditions in VBS appear to be leading to potentially enhanced nutrient leaching via increasing solubility of C, N, and P. Manipulating soil microbial conditions (by management of soil moisture, vegetation type, and cover) may provide options for increasing the buffer storage for key nutrients such as P without increasing leaching to adjacent streams.     

Thermal Encapsulation of Metals in Superfund Soils

Abstract

Superfund sites frequently contain both heavy metals and organic hazardous waste. If not properly controlled, the metals may be changed to a more leachable form and may also be emitted to the atmosphere via the exhaust stack. This paper documents a batch kiln R&D test program to solve these metal-related problems. It was performed under the U.S. EPA’s SITE (Superfund Innovative Technology Evaluation) Emerging Technology Program. Allis Mineral Systems has developed the Thermal Encapsulation Process. Metals with limits set by EPA’s TCLP (Toxicity Characteristic Leaching Procedure) test and BIF (boiler and industrial furnace) stack emission regulations, such as cadmium, chromium, and lead, are the initial target of this process. This process, while unproven in these areas, may also apply to mixed waste (EPA hazardous waste/low-level radioactive wastes) and may also benefit commercial hazardous waste or Superfund thermal treatment systems. The results of the SITE tests were positive: strong, durable nodules were produced with excellent crush strength and improved resistance to leaching. Feed preparation, particularly control of moisture content, was found to be a key element in initiation of agglomeration. A good correlation was found between decreasing TCLP metals leachate levels and increasing crush strength.     

Solubilization, solution equilibria, and biodegradation of PAH's under thermophilic conditions

Biodegradation rates of PAHs are typically low at mesophilic conditions and it is believed that the kinetics of degradation is controlled by PAH solubility and mass transfer rates. Solubility tests were performed on phenanthrene, fluorene and fluoranthene at 20 degrees C, 40 degrees C and 60 degrees C and, as expected, a significant increase in the equilibrium solubility concentration and of the rate of dissolution of these polycyclic aromatic hydrocarbons (PAHs) was observed with increasing temperature. A first-order model was used to describe the PAH dissolution kinetics and the thermodynamic property changes associated with the dissolution process (enthalpy, entropy and Gibb's free energy of solution) were evaluated. Further, other relevant thermodynamic properties for these PAHs, including the activity coefficients at infinite dilution, Henry's law constants and octanol-water partition coefficients, were calculated in the temperature range 20-60 degrees C. In parallel with the dissolution studies, three thermophilic Geobacilli were isolated from compost that grew on phenanthrene at 60 degrees C and degraded the PAH more rapidly than other reported mesophiles. Our results show that while solubilization rates of PAHs are significantly enhanced at elevated temperatures, the biodegradation of PAHs under thermophilic conditions is likely mass transfer limited due to enhanced degradation rates.     

Improving the effectiveness of angular dispersion in plant neighbourhood models

Spatial arrangement can be an important factor affecting competition among plants. We evaluated three ways to improve the effectiveness of angular dispersion (AD) for describing spatial arrangement in plant neighbourhood models. First, we modified Zar's (1974) AD formula by weighting each neighbour by its competitive influence. We calculated this using two different competition indices to derive an AD of competitive influence, rather than of equally weighted plant locations, around a subject plant. Secondly, we constrained the effect of AD on the neighbourhood model using an optimised parameter that defines the minimum value that AD can adopt. Thirdly, we included the direction in which competition is concentrated (the mean azimuth of the weighted AD) in the growth models. These developments were evaluated within a radial growth model of Scots pine and birch growing in semi-natural, spatially heterogeneous forest. Weighted AD resulted in significant improvements in predicted radial growth of target trees over the traditional measure of AD. The optimised parameter that defines the minimum value of AD consistently evolved values significantly higher than zero. This suggests that clumped and dispersed neighbourhoods do not differ in their negative effects on a subject tree as much as expected. The inclusion of directional components of the weighted AD did not improve the accuracy of the growth models. Weighting of the angular dispersion of neighbours improved the performance of local competition models.