Volatilization and biodegradation of naphthalene in the vadose zone impacted by phytoremediation

The combined remediation mechanisms of volatilization and biodegradation in the vadose zone were investigated for naphthalene remediation at a creosote-contaminated site where a poplar tree-based phytoremediation system has been installed. Concurrent field and laboratory experiments were conducted to study the transport and biodegradation of naphthalene in the vadose zone. Soil gas sampling showed that more than 90% of the naphthalene vapors were biodegraded aerobically within 5-10 cm above the water table during the summer months. Peak naphthalene soil gas concentrations were observed in the late summer, corresponding with peak naphthalene aqueous concentrations and the minimum saturated zone thickness. An analytical solution was developed for vapor transport where the diffusion coefficient and first-order biodegradation rate vary vertically in two discrete zones. First-order aerobic biodegradation rates in laboratory columns using unsaturated site soil ranged from 5 to 28 days(-1) with a mean rate of 11 days(-1). The observed naphthalene mass flux at the source (3.3-22 microg cm(-2) d(-1)) was enhanced by aerobic biodegradation and was greater than the mean observed flux in the abiotic control column and the maximum theoretical mass flux by factors of 7 and 28, respectively.     

Mechanisms affecting the infiltration and distribution of ethanol-blended gasoline in the vadose zone

One- and two-dimensional experiments were conducted to examine differences in the behavior of gasoline and gasohol (10% ethanol by volume) as they infiltrate through the unsaturated zone and spread at the capillary fringe. Ethanol in the spilled gasohol quickly partitions into the residual water in the vadose zone and is retained there as the gasoline continues to infiltrate. Under the conditions tested, over 99% of the ethanol was initially retained in the vadose zone. Depending on the volume of gasoline spilled and the depth to the water table, this causes an increase in the aqueous-phase saturation and relative permeability, thus allowing the ethanol-laden water to drain into the gasoline pool. Under the conditions tested, the presence of ethanol does not have a significant impact on the overall size or shape of the resulting gasoline pool at the capillary fringe. Residual gasoline saturations in the vadose zone were significantly reduced however because of reduced surface and interfacial tensions associated with high ethanol concentrations. The flux of ethanol in the effluent of the column ranged from 1.4 x 10(-4) to 4.5 x 10(-7) g/(cm2 min) with the LNAPL and from 6 x 10(-3) to 3.0 x 10(-4) g/(cm2 min) after water was introduced to simulate rain infiltration. The experimental results presented here illustrate that the dynamic effects of ethanol partitioning into the aqueous phase in the vadose zone create an initial condition that is significantly different than previously understood.     

Equilibrium partitioning of chlorinated solvents in the vadose zone: low f(oc) geomedia

A series of gas (vapor)-advecting water-unsaturated column experiments using a low organic content (f(oc)) silica sand was conducted to determine mass distributions of chlorinated-volatile hydrophobic organic compounds (C-VHOCs) in a natural sorbent system. C-VHOCs used were trichloroethene (TCE), tetrachloroethene (PCE), chlorobenzene (CB), and 1,3-dichlorobenzene (DCB). Four volumetric water contents (theta(w) = 0.07, 0.12, 0.17, 0.20) and several influent gas-phase C-VHOC (solute) concentrations were considered. The method of temporal first moments was applied to complete breakthrough curve data to determine total C-VHOC gas-phase retardation and associated gas-phase C-VHOC mass fraction. Results were compared to an equilibrium partitioning advective-dispersive formulation of total gas-phase retardation. Literature-derived values of Henry's law constants and independent measurements of gas/water interface areal extent and interface phase adsorption allowed quantification of C-VHOC mass fractions in the aqueous and gas/water interface phases. Unaccounted C-VHOC mass, derived from comparison of measured C-VHOC retardation to independent phase prediction, was attributed to solid-phase sorption. Results indicate that for all conditions tested, gas/water interfacial adsorption exhibited only a small effect on C-VHOC vapor retardation (accounting for < or = 10% of the total C-VHOC distributions). Solid-phase association was the dominant uptake mechanism, accounting for 46-91% of the total C-VHOC mass in the porous system. Evaluation of the solid-phase C-VHOC uptake results in terms of a modified form of the Dubinin-Radushkevich (DR) isotherm equation provided strong evidence supporting the mechanism of pore-filling in this natural, low f(oc) sorbent.     

Soil column evaluation of factors controlling biodegradation of DNT in the vadose zone

High concentrations of 2,4-dinitrotoluene (2,4-DNT) and 2,6-dinitrotoluene (2,6-DNT) are present in vadose zone soils at many facilities where explosives manufacturing has taken place. Both DNT isomers can be biodegraded under aerobic conditions, but rates of intrinsic biodegradation observed in vadose zone soils are not appreciable. Studies presented herein demonstrate that nutrient limitations control the onset of rapid 2,4-DNT biodegradation in such soils. In column studies conducted at field capacity, high levels of 2,4-DNT biodegradation were rapidly stimulated by the addition of a complete mineral medium but not by bicarbonate-buffered distilled deionized water or by phosphate-amended tap water. Biodegradation of 2,6-DNT was not observed under any conditions. Microcosm studies using a DNT-degrading culture from column effluent suggest that, after the onset of 2,4-DNT degradation, nitrite evolution will eventually control the extent of degradation achieved by two mechanisms. First, high levels of nitrite (40 mM) were found to strongly inhibit 2,4-DNT degradation. Second, nitrite production reduces the solution pH, and at pH levels below 6.0, 2,4-DNT degradation slows rapidly. Under conditions evaluated in laboratory-scale studies, 2,4-DNT biodegradation enhanced the rate of contaminant loss from the vadose zone by a factor of 10 when compared to the washout due to leaching.     

Influence of sources on plutonium mobility and oxidation state transformations in vadose zone sediments

Well-defined solid sources of Pu(III) (PuCl3), Pu(IV) (Pu (NO3)4 and Pu (C2O4)2), and Pu(VI) (Pu02(NO3)2) were placed in lysimeters containing vadose zone sediments and exposed to natural weather conditions for 2 or 11 years. The objective of this study was to measure the release rate of Pu and the changes in the Pu oxidation states from these Pu sources with the intent to develop a reactive transport model source-term. Pu(III) and Pu(IV) sources had identical Pu concentration depth profiles and similar Pu release rates. Source release data indicate that PuIV(C2O4)2 was the least mobile, whereas Pu(VI)O2(NO3)2 was the most mobile. Synchrotron X-ray fluorescence (SXRF) revealed that Pu was very unevenly distributed on the sediment and Mn concentrations were too low (630 mg kg(-1)) and perhaps of the wrong mineralogy to influence Pu distribution. The high stability of sorbed Pu(IV) is proposed to be due to the formation of a stable hydrolyzed Pu(IV) surface species. Plutonium X-ray absorption near-edge spectroscopy (XANES) analysis conducted on sediment recovered at the end of the studyfrom the Pu(IV)(NO3)4- and Pu(III)(III)Cl3-amended lysimeters contained essentially identical Pu distributions: approximately 37% Pu(III), 67% Pu(IV), 0% Pu(V), and 0% Pu(VI). These results were similar to those using a wet chemistry Pu oxidation state assay, except the latter method did not detect any Pu(III) present on the sediment but instead indicated that 93-98% of the Pu existed as Pu(IV). This discrepancy was likely attributable to incomplete extraction of sediment Pu(III) by the wet chemistry method. Although Pu has been known to exist in the +3 oxidation state under microbially induced reducing conditions for decades, to our knowledge, this is the first observation of steady-state Pu(III) in association with natural sediments. On the basis of thermodynamic considerations, Pu(III) has a wide potential distribution, especially in acidic environments, and as such may warrant further investigation.     

Small-volume releases of gasoline in the vadose zone: impact of the additives MTBE and ethanol on groundwater quality

A controlled gasoline spill experiment was performed under outdoor conditions typical for winter in temperate regions to study the fate of methyl tert-butyl ether (MTBE), ethanol, benzene, and selected other petroleum hydrocarbons. Artificial gasoline containing MTBE and ethanol (5% w/w of each) was placed at a defined depth into a 2.3 m thick unsaturated zone of alluvial sand overlying a gravel aquifer in a lysimeter. During an initial period of 41 days without recharge, MTBE and hydrocarbon vapors migrated by vapor-phase diffusion to groundwater, while ethanol vapors were naturally attenuated. In a subsequent period of 30 days with 5-mm daily recharge, all soluble compounds including ethanol were transported to the groundwater. Ethanol disappeared concomitantly with benzene and all other petroleum hydrocarbons except isooctane from the aerobic groundwater due to biodegradation. MTBE persisted for longer than 6 months at concentrations larger than 125000 microg L(-1). No evidence for MTBE biodegradation was found, whereas > 99.6% of ethanol removal from the lysimeter was due to biodegradation. It is concluded that MTBE-free gasoline would be less harmful for groundwater resources and that ethanol is an acceptable substitute.     

Review: Automation and meat quality-global challenges.

The global meat industry has seen significant changes in the methods used to harvest and process fresh meat over the past century. Increased use of automation has led to significant increases in line speed for beef, pork, sheep, poultry and fish operations. For example, currently the fastest line observed has been broilers at 13,500/h. Such developments have required in-depth understanding of the pre and post rigor processes to prevent defects. Procedures such as maturation chilling and electrical stimulation are now common in red meat and poultry processing; allowing shorter time to deboning, while harvesting high quality meat. Robots designed to cut meat are also appearing on the market, and replacing traditional manual operations. This is a challenge, because high speed equipment is not necessarily sensitive to variations in size/quality issues, and requires development of unique sensors and control systems. Also, progress in breeding and genetics is contributing to greater product uniformity and quality; helping in operating automated equipment.     

New field method: gas push-pull test for the in-situ quantification of microbial activities in the vadose zone

Quantitative information on microbial processes in the field is important. Here we propose a new field method, the "gas push-pull test" (GPPT) for the in-situ quantification of microbial activities in the vadose zone. To evaluate the new method, we studied microbial methane oxidation above an anaerobic, petroleum-contaminated aquifer. A GPPT consists of the injection of a gas mixture of reactants (e.g., methane, oxygen) and nonreactive tracer gases (e.g., neon, argon) into the vadose zone and the subsequent extraction of the injection gas mixture together with soil air from the same location. Rate constants of gas conversion are calculated from breakthrough curves of extracted reactants and tracers. In agreement with expectations from previously measured gas profiles, we determined first-order rate constants of 0.68 h(-1) at 1.1 m below soil surface and 2.19 h(-1) at 2.7 m, close to the groundwater table. Co-injection of a specific inhibitor (acetylene) for methanotrophs showed that the observed methane consumption was microbially mediated. This was confirmed by increases of stable carbon isotope ratios in methane by up to 42.6 %. In the future, GPPTs should provide useful quantitative information on a range of microbial processes in the vadose zone.     

News: EPA near completion of "natural attenuation" remediation policy

Technology.     

Density-modified displacement for DNAPL source zone remediation: density conversion and recovery in heterogeneous aquifer cells

Low interfacial tension (IFT) displacement (mobilization) of nonaqueous phase liquids (NAPLs) offers potential as an efficient remediation technology for contaminated aquifer source zones. However, displacement of dense NAPLs (DNAPLs) is problematic due to the tendency for downward migration and redistribution of the mobilized DNAPL. To overcome this limitation, a density-modified displacement method (DMD) was developed, which couples in situ density conversion of DNAPLs via alcohol partitioning with low IFT NAPL displacement and recovery. The objective of this work was to evaluate the DMD method for two representative DNAPLs, chlorobenzene (CB) and trichloroethene (TCE). Laboratory-scale experiments were conducted in a two-dimensional (2-D) cell, configured to represent a heterogeneous unconfined aquifer system containing low permeability lenses. After release and redistribution of either CB- or TCE-NAPL, the 2-D aquifer cells were flushed with a 6% (wt) n-butanol aqueous solution to achieve DNAPL to light NAPL conversion, followed by a low IFT surfactant solution consisting of 4% (4:1) Aerosol MA/Aerosol OT + 20% n-butanol + 500 mg/L CaCl2. Visual observations and experimental measurements demonstrated that in situ density conversion and immiscible displacement of both CB and TCE were successful. Effluent NAPL densities ranged from 0.96 to 0.90 g/mL for CB and from 0.95 to 0.92 g/mL for TCE, while aqueous phase densities remained above 0.96 g/L. Density conversion of CB and TCE was achieved after flushing with 1.2 and 4.9 pore vol of 6% n-butanol solution, respectively. Recoveries of 90% CB and 85% TCE were realized after flushing with 1.2 pore vol of the low IFT surfactant solution, which was followed by a 1 pore vol posttreatment water flood. Surfactant and n-butanol recoveries ranged from 75 to 96% based on effluent concentration data. The observed minimal mobilization during the n-butanol density conversion preflood and near complete mobilization during the low IFT displacement flood were consistent with total trapping number calculations. The results reported herein demonstrate the potential efficiency of the DMD technology as a means of DNAPL source zone restoration.     

Distribution of atmospheric SF6 near a large urban area as recorded in the vadose zone

Local emissions of SF6 are of interest for studying their impact on the use of SF6 as a groundwater-dating tool near source regions as well as for investigating the spatial distributions of (inert) gaseous compounds spreading from urban or industrial centers. A precondition for the use of SF6 in such studies is the capability to document the temporal and spatial evolution of SF6 in and around source regions with sufficient resolution. Here we present a time series of SF6 measurements in soil air at a site (Sparkill, NY) about 25 km north of New York City carried out between May 2000 and January 2002. The data show that, below about 2 m depth, the vadose zone integrates atmospheric SF6 mixing ratios over time scales greater than 1 month. SF6 mixing ratios in soil air at these depths match averaged high-resolution atmospheric measurements performed at Lamont-Doherty Earth Observatory in Palisades, NY, located about 3 km south of Sparkill. To a first-order approximation, a simple one-dimensional diffusion model reproduces the measured SF6 profiles in the vadose zone, suggesting that the soil indeed acts as a low-pass filter for inert atmospheric gases. These findings indicate that measurements of soil air can be used to determine the spatial pattern of SF6 excess relative to the remote atmosphere for a given region. A transect of soil profiles from Manhattan to the tip of Long Island indicates that emissions from sites close to New York City lead to significant SF6 excesses (ca. 25% or more) above the clean air mixing ratios over distances of the order of 80 km.     

Current situation and future challenges of tobacco control policy in Thailand

In Thailand, the prevalence of smoking has steadily declined over the past 20 years, suggesting an effective tobacco control policy. However, the prevalence has recently stabilised and youth smoking now appears to be on the rise. Tobacco use is the third highest risk factor contributing to the burden of disease in the country. This is an issue of concern and led to the present review of tobacco control measures in Thailand. The present evidence-based review shows that Thailand's tobacco control measures are relatively strong and comply well with the WHO Framework Convention on Tobacco Control in terms of taxation, advertisement through popular media, and warning labels on cigarettes and other tobacco product packages. However, challenges remain in dealing with highly prevalent roll-your-own cigarettes, strict prohibition of tobacco sale to underage youths, household smoking, illicit trade of tobacco products, viable tobacco crop diversification for domestic tobacco growers and liability. If these challenges are met, the prevalence of tobacco consumption could possibly be further reduced.     

Character of environmental harms: overcoming implementation challenges with policy makers and regulators

Policy makers and regulators are charged with the daunting task of comparing incommensurate environmental risks to inform strategic decisions on interventions. Here we present a policy-level framework intended to support strategic decision processes concerning environmental risks within the Department for Environment, Food and Rural Affairs (Defra). The framework provides the structure by which risk-based evidence may be collated and by assessing the value of harm expressed by different environmental policy areas against a consistent objective (e.g., sustainable development), we begin to form a basis for relative comparison. This research integrates the prior art, examples of best practice, and intimate end-user input to build a qualitative assessment informed by expert judgment. Supported by contextual narratives, the framework has proven successful in securing organizational support and stimulating debate about proportionate mitigation activity, resource allocation, and shifts in current risk thinking.     

Spectroscopic and diffraction study of uranium speciation in contaminated vadose zone sediments from the Hanford site, Washington state

Contamination of vadose zone sediments under tank BX-102 at the Hanford site, Washington, resulted from the accidental release of 7-8 metric tons of uranium dissolved in caustic aqueous sludge in 1951. We have applied synchrotron-based X-ray spectroscopic and diffraction techniques to characterize the speciation of uranium in samples of these contaminated sediments. UIII-edge X-ray absorption fine structure (XAFS) spectroscopic studies demonstrate that uranium occurs predominantly as a uranium(VI) silicate from the uranophane group of minerals. XAFS cannot distinguish between the members of this mineral group due to the near identical local coordination environments of uranium in these phases. However, these phases differ crystallographically, and can be distinguished using X-ray diffraction (XRD) methods. As the concentration of uranium was too low for conventional XRD to detect these phases, X-ray microdiffraction (microXRD) was used to collect diffraction patterns on approximately 20 microm diameter areas of localized high uranium concentration found using microscanning X-ray fluorescence (microSXRF). Only sodium boltwoodite, Na(UO2)(SiO3OH) x 1.5H20, was observed; no other uranophane group minerals were present. Sodium boltwoodite formation has effectively sequestered uranium in these sediments under the current geochemical and hydrologic conditions. Attempts to remediate the uranium contamination will likely face significant difficulties because of the speciation and distribution of uranium in the sediments.     

Technical challenges involved in implementation of VOC reactivity-based control of ozone

Controlling VOC emissions on the basis of their individual contribution to ozone formation has been subject to extensive discussion and research in past years, and the concept has gained some acceptance in the air pollution community for certain product categories and industrial operations. Despite its potential to decrease ozone formation, there are some technical challenges that still remain before we can confidently apply the concept of reactivity in the most beneficial manner to reduce ozone concentrations. The goal of this paper is to (1) assess how existing science in this area supports the use of reactivity, particularly, the maximum incremental reactivity, for VOC control under a national policy application and (2) identify where uncertainties exist that could affect such a policy. Box model and air quality model results are used to show that there are ways to describe a chemical's reactivity that are relatively robust across large geographic areas. Modeling results also indicate that the choice of metric is important in determining the potential benefits and detriments of a reactivity-based emission control policy.     

Scientific and Technical Aspects of Yogurt Aroma and Taste: A Review

Abstract: Yogurt is a basic dairy product that has been consumed for centuries as a part of the diet, even when its beneficial effects were neither fully known nor scientifically proven. With time, yogurt has been continuously modified to obtain a product with better appeal and nutritional effects. The flavor components of yogurt are affected because of these modifications. The present review article is focused on the influence of the different parameters and modifications on aroma and taste components of yogurt. Extensive work has been done to explore the effect of chemical components as well as the microbial, processing, and storage aspects. The popularity of yogurt as a food component depends mainly on its sensory characteristics, of which aroma and taste are most important. This review also outlines the effects of the different modifications attempted in the composition of yogurt.     

食品中重金属总量及形态分析研究进展

食品中重金属元素含量超标对人体危害较大,对其中的总量及形态分析的研究工作十分重要,因此近年来成为研究热点。本文对重金属总量分析和元素形态分析的方法进行了综述,从前处理方法、分离方法和仪器检测方法三方面进行了归纳总结,就重金属总量分析和元素形态分析的发展方向进行了展望。      

食品中重金属总量及形态分析研究进展

食品中重金属元素含量超标对人体危害较大,对其中的总量及形态分析的研究工作十分重要,因此近年来成为研究热点本文对重金属总量分析和元素形态分析的方法进行了综述,从前处理方法、分离方法和仪器检测方法三方面进行了归纳总结,就重金属总量分析和元素形态分析的发展方向进行了展望.     

Fe(O)/lignitic coal: an efficient and mechanically stable reactive material for purification of water containing heavy metals, radionuclides, and nitroaromatics

Mine water in the former uranium mine of K?nigstein (Saxony, Germany) contains high concentrations of acid, sulfate, iron, aluminum, various heavy metals, radionuclides, and nitroaromatics. Research has been conducted for several years to establish the extent to which reduction of pollutant concentrations can be positively influenced and accelerated by storage of reactive materials in mine cavities. Investigations were made at different scales to test and select materials with respect to maximum fixation of contaminants (underground column tests) to examine hydraulic effects (underground large-scale column tests) and to optimize material properties (laboratory tests). The investigations have shown that a mixture of Fe chips and lignitic coal is capable of efficiently cleaning acid and contaminant-containing mine water. The examined material is easily available and compatible with the environment. A large-scale application of such a reactive barrier is being considered for mine water treatment in the future and is deemed to be a reasonable conception for a safety component after conclusion of the flooding.