Distributions of radionuclide sorption coefficients (Kd) in sub-surface sediments and the implications for transport calculations

The effect of the spatial variability of K_d on calculations of contaminant travel time in the vadose zone was determined. Depth discrete measurements of K_d were made for a suite of radionuclides (¹⁰⁹Cd, ⁵⁷Co, ⁶⁰Co, ⁸⁵Sr, ¹³⁷Cs, and ⁸⁸Y) utilizing a sediment core from the E-Area at the Savannah River Site. The K_d’s were ordered as ⁸⁵Sr²⁺ < ¹³⁷Cs⁺ < ¹⁰⁹Cd²⁺ < ⁵⁷Co²⁺ = ⁶⁰Co²⁺ << ⁸⁸Y³⁺ and the values generally fell below or near the lowest quartile of values reported in the literature. Correlations were generally weak between soil properties and K_d values. Most importantly, all of the K_d distributions could be reasonably approximated as log-normal. Deterministic and stochastic calculations of contaminant travel time to the water table were made. The deterministic calculations were based on each of three conceptual models of the vadose zone: complete stratification (17 strata, each with a different K_d), two strata (two sections of the vadose zone, each characterized by a single, average K_d), and unstratified (a single zone with an average K_d). Stochastic calculations were based on log-normal fits to the K_d data. The two strata model generally yielded travel times 2× greater than those in the completely stratified model. The unstratified model yielded travel times that were between 3 and 5 times greater than the completely stratified model. The stochastic mean travel times were comparable to those of the two strata model.     

Aerosol speciation and mass prediction from toluene oxidation under high NOx conditions

A kinetically based gas-particle partitioning box model is used to highlight the importance of parameter representation in the prediction of secondary organic aerosol (SOA) formation following the photo-oxidation of toluene. The model is initialized using experimental data from York University's indoor smog chamber and provides a prediction of the total aerosol yield and speciation. A series of model sensitivity experiments were performed to study the aerosol speciation and mass prediction under high NO_x conditions (VOC/NO_x = 0.2). Sensitivity experiments indicate vapour pressure estimation to be a large area of weakness in predicting aerosol mass, creating an average total error range of 70 μg m^?3 (range of 5–145 μg m^?3), using two different estimation methods. Aerosol speciation proved relatively insensitive to changes in vapour pressure. One species, 3-methyl-6-nitro-catechol, dominated the aerosol phase regardless of the vapour pressure parameterization used and comprised 73–88% of the aerosol by mass. The dominance is associated with the large concentration of 3-methyl-6-nitro-catechol in the gas-phase. The high NO_x initial conditions of this study suggests that the predominance of 3-methyl-6-nitro-catechol likely results from the cresol-forming branch in the Master Chemical Mechanism taking a significant role in secondary organic aerosol formation under high NO_x conditions. Further research into the yields and speciation leading to this reaction product is recommended.     

Elevated carbon dioxide does not offset loss of soil carbon from a corn-soybean agroecosystem

The potential for storing additional C in U.S. Corn Belt soils - to offset rising atmospheric [CO₂] - is large. Long-term cultivation has depleted substantial soil organic matter (SOM) stocks that once existed in the region's native ecosystems. In central Illinois, free-air CO₂ enrichment technology was used to investigate the effects of elevated [CO₂] on SOM pools in a conservation tilled corn-soybean rotation. After 5 and 6 y of CO₂ enrichment, we investigated the distribution of C and N among soil fractions with varying ability to protect SOM from rapid decomposition. None of the isolated C or N pools, or bulk-soil C or N, was affected by CO₂ treatment. However, the site has lost soil C and N, largely from unprotected pools, regardless of CO₂ treatment since the experiment began. These findings suggest management practices have affected soil C and N stocks and dynamics more than the increased inputs from CO₂-stimulated photosynthesis.     

Toward a robust analytical method for separating trace levels of nano-materials in natural waters: cloud point extraction of nano-copper(II) oxide

Cloud point extraction (CPE) factors, namely Triton X-114 (TX-114) concentration, pH, ionic strength, incubation time, and temperature, were optimized for the separation of nano-sized copper(II) oxide (nCuO) in aqueous matrices. The kinetics of phase transfer was studied using UV–visible spectroscopy. From the highest separation rate, the most favorable conditions were observed with 0.2 %?w/v of TX-114, pH?=?9.0, ionic strength of 10 mM NaCl, and incubation at 40 °C for 60 min, yielding an extraction efficiency of 89.2?±?3.9 % and a preconcentration factor of 86. The aggregate size distribution confirmed the formation of very large nCuO–micelle assemblies (11.9 μm) under these conditions. The surface charge of nCuO was also diminished effectively. An extraction efficiency of 91 % was achieved with a mixture of TX-100 and TX-114 containing 30 wt.% of TX-100. Natural organic and particulate matters, represented by humic acid (30 mg/L) and micron-sized silica particles (50 mg/L), respectively, did not significantly reduce the CPE efficiency (<10 %). The recovery of copper(II) ions (20 mg/L) in the presence of humic acid was low (3–10 %). The spiked natural water samples were analyzed either directly or after CPE by inductively coupled plasma mass spectrometry following acid digestion/microwave irradiation. The results indicated the influence of matrix effects and their reduction by CPE. A delay between spiking nCuO and CPE may also influence the recovery of nCuO due to aggregation and dissolution. A detection limit of 0.04 μg Cu/L was achieved for nCuO.     

An Analysis of Ozone Generation in Irradiated Houston Air

Ambient ozone measurements in the United States and many other countries are traceable to a National Institute of Standards and Technology Standard Reference Photometer (NIST SRP). The NIST SRP serves as the highest level ozone reference standard in the United States, with NIST SRPs located at NIST and at many U.S. Environmental Protection Agency (EPA) laboratories. The International Bureau of Weights and Measures (BIPM) maintains a NIST SRP as the reference standard for international measurement comparability through the International Committee of Weights and Measures (CIPM). In total, there are currently NIST SRPs located in 20 countries for use as an ozone reference standard. A detailed examination of the NIST SRP by the BIPM and NIST has revealed a temperature gradient and optical path-length bias inherent in all NIST SRPs. A temperature gradient along the absorption cells causes incorrect temperature measurements by as much as 2 °C. Additionally, the temperature probe used for temperature measurements was found to inaccurately measure the temperature of the sample gas due to a self-heating effect. Multiple internal reflections within the absorption cells produce an actual path length longer than the measured fixed length used in the calculations for ozone mole fractions. Reflections from optical filters located at the exit of the absorption cells add to this effect. Because all NIST SRPs are essentially identical, the temperature and path-length biases exist on all units by varying amounts dependent upon instrument settings, laboratory conditions, and absorption cell window alignment. This paper will discuss the cause of, and physical modifications for, reducing these measurement biases in NIST SRPs. Results from actual NIST SRP bias upgrades quantifying the effects of these measurement biases on ozone measurements are summarized.

Implications: NIST SRPs are maintained in laboratories around the world underpinning ozone measurement calibration and traceability within and between countries. The work described in this paper quantifies and shows the reduction of instrument biases in NIST SRPs improving their overall agreement. This improved agreement in all NIST SRPs provides a more stable baseline for ozone measurements worldwide.     

Use of fugacity model to analyze temperature-dependent removal of micro-contaminants in sewage treatment plants

Effluents from sewage treatment plants (STPs) are known to contain residual micro-contaminants including endocrine disrupting chemicals (EDCs) despite the utilization of various removal processes. Temperature alters the efficacy of removal processes; however, experimental measurements of EDC removal at various temperatures are limited. Extrapolation of EDC behavior over a wide temperature range is possible using available physicochemical property data followed by the correction of temperature dependency. A level II fugacity-based STP model was employed by inputting parameters obtained from the literature and estimated by the US EPA’s Estimations Programs Interface (EPI) including EPI’s BIOWIN for temperature-dependent biodegradation half-lives. EDC removals in a three-stage activated sludge system were modeled under various temperatures and hydraulic retention times (HRTs) for representative compounds of various properties. Sensitivity analysis indicates that temperature plays a significant role in the model outcomes. Increasing temperature considerably enhances the removal of β-estradiol, ethinyestradiol, bisphenol, phenol, and tetrachloroethylene, but not testosterone with the highest biodegradation rate. The shortcomings of BIOWIN were mitigated by the correction of highly temperature-dependent biodegradation rates using the Arrhenius equation. The model predicts well the effects of operating temperature and HRTs on the removal via volatilization, adsorption, and biodegradation. The model also reveals that an impractically long HRT is needed to achieve a high EDC removal. The STP model along with temperature corrections is able to provide some useful insight into the different patterns of STP performance, and useful operational considerations relevant to EDC removal at winter low temperatures.     

Oxidative properties of ambient PM2.5 and elemental composition: Heterogeneous associations in 19 European cities

We assessed the extent to which constituents of PM_2.5 (transition metals, sodium, chloride) contribute to the ability to generate hydroxyl radicals (OH) in vitro in PM_2.5 sampled at 20 locations in 19 European centres participating in the European Community Respiratory Health Survey. PM_2.5 samples (n = 716) were collected on filters over one year and the oxidative activity of particle suspensions obtained from these filters was then assessed by measuring their ability to generate OH in the presence of hydrogen peroxide. Associations between OH formation and the studied PM constituents were heterogeneous. The total explained variance ranged from 85% in Norwich to only 6% in Albacete. Among the 20 centres, 15 showed positive correlations between one or more of the measured transition metals (copper, iron, manganese, lead, vanadium and titanium) and OH formation. In 9 of 20 centres OH formation was negatively associated with chloride, and in 3 centres with sodium. Across 19 European cities, elements which explained the largest variations in OH formation were chloride, iron and sodium.     

Nitrogen fertilizer form and associated nitrate leaching from cool-season lawn turf

Various N fertilizer sources are available for lawn turf. Few field studies, however, have determined the losses of nitrate (NO(3)-N) from lawns receiving different formulations of N fertilizers. The objectives of this study were to determine the differences in NO(3)-N leaching losses among various N fertilizer sources and to ascertain when losses were most likely to occur. The field experiment was set out in a completely random design on a turf typical of the lawns in southern New England. Treatments consisted of four fertilizer sources with fast- and slow-release N formulations: (i) ammonium nitrate (AN), (ii) polymer-coated sulfur-coated urea (PCSCU), (iii) organic product, and (iv) a nonfertilized control. The experiment was conducted across three years and fertilized to supply a total of 147 kg N ha(-1) yr(-1). Percolate was collected with zero-tension lysimeters. Flow-weighted NO(3)-N concentrations were 4.6, 0.57, 0.31, and 0.18 mg L(-1) for AN, PCSCU, organic, and the control, respectively. After correcting for control losses, average annual NO(3)-N leaching losses as a percentage of N applied were 16.8% for AN, 1.7% for PCSCU, and 0.6% for organic. Results indicate that NO(3)-N leaching losses from lawn turf in southern New England occur primarily during the late fall through the early spring. To reduce the threat of NO(3)-N leaching losses, lawn turf fertilizers should be formulated with a larger percentage of slow-release N than soluble N.     

Evaluation of catalyzed and electrically heated filters for removal of particulate emissions from diesel-A- and JP-8-fueled engines

In-service diesel engines are a significant source of particulate matter (PM) emissions, and they have been subjected to increasingly strict emissions standards. Consequently, the wide-scale use of some type of particulate filter is expected. This study evaluated the effect of an Engelhard catalyzed soot filter (CSF) and a Rypos electrically heated soot filter on the emissions from in-service diesel engines in terms of PM mass, black carbon concentration, particle-bound polycyclic aromatic hydrocarbon concentration, and size distribution. Both filters capture PM. The CSF relies on the engine's exhaust to reach the catalyst regeneration temperature and oxidize soot, whereas the electrically heated filter contains a heating element to oxidize soot. The filters were installed on several military diesel engines. Particle concentrations and compositions were measured before and after installation of the filter and again after several months of operation. Generally, the CSF removed at least 90% of total PM, and the removal efficiency improved or remained constant after several months of operation. In contrast, the electrical filters removed 44-69% of PM mass. In addition to evaluating the soot filters, the sampling team also compared the results of several real-time particle measurement instruments to traditional filter measurements of total mass.     

Concentration changes for 5 PCDD/F congeners after administration in beef cattle

Ten cattle were treated with daily doses of five PCDD/F congeners, over a 4 week period. Four control animals were not treated. They were subsequently slaughtered as three groups, at 5, 18 and 31 weeks after the first dose. All congeners showed an increase in concentration within animal tissues when sampled at 5 weeks post-dosing. Concentrations had reduced after 18 weeks and there was a further small reduction after 31 weeks. Halflives for each congener were calculated at 13-21 weeks (93-148 days). Concentrations of congeners were different in the various tissues analysed. At 5 weeks after dosing commenced, concentrations in sub-cutaneous fat and in perirenal fat were close to 40 ng/kg (a predicted level based on 50% absorption of the dosed compounds). Concentrations on a fat basis in muscle tissue and liver were, however, about 5 and 10 times higher, respectively. The concentrations found in muscle tissue and liver samples taken at 18 and 31 weeks were approximately twice that found in fat deposits, thus the differences were still apparent, but at a reduced level. It is possible that the distribution phase was incomplete and that PCDD/Fs remained predominantly in association with circulating blood lipids rather than in equilibrium with depot fat. It follows that if livestock were recently exposed to PCDD/Fs (for example, through the consumption of contaminated feed), the analysis of depot fats would not necessarily provide a reliable indicator of the concentrations of PCDD/Fs in edible tissues.