Microbial physiology-based model of ethanol metabolism in subsurface sediments

Dense non-aqueous phase liquids (DNAPLs) present in the subsurface may contain surface active compounds that impact DNAPL migration and distribution. While a number of studies have revealed the role surface active compounds play in altering the wettability of quartz sand, few have considered the implications for other minerals common to contaminated sites. This study extends understanding of DNAPL/surfactant wettability to iron oxide surfaces. Specifically, quartz and iron oxide-coated sands in a tetrachloroethene (PCE)/water system containing the organic base (an organic molecule that acts as a base) dodecylamine (DDA) were compared at a variety of scales. Wettability of the minerals' surfaces, and the impact of wettability on capillary resistance to DNAPL entry, were assessed as a function of pH through: (i) advancing and receding contact angles, (ii) primary drainage capillary pressure-saturation experiments, and (iii) small, two-dimensional, flow cell experiments. The work revealed that, at neutral pH and under identical boundary capillary pressures, DNAPL invaded quartz sand but not iron oxide-coated sand; however, at low pH, DNAPL invaded both sands equally. These differences were demonstrated to be due to wettability alterations associated with the strength of attractive forces between DDA and the mineral surface, dictated by the isolectric point of the minerals and system pH. Observed differences in DNAPL invasion behavior were consistent with measured intrinsic contact angles and P(c)-S relationships, the latter requiring scaling by the operative contact angle inside the porous medium for a meaningful comparison. This study suggests that the distribution of minerals (and, more specifically, their isoelectric points), as well as the aqueous phase pH at a given site, may have a significant impact on the DNAPL source zone architecture.     

The Role of Observer Variation in Determining Rosgen Stream Types in Northeastern Oregon Mountain Streams1

Abstract: Consistency in determining Rosgen stream types was evaluated in 12 streams within the John Day Basin, northeastern Oregon. The Rosgen classification system is commonly used in the western United States and is based on the measurement of five stream attributes: entrenchment ratio, width‐to‐depth ratio, sinuosity, slope, and substrate size. Streams were classified from measurements made by three monitoring groups, with each group fielding multiple crews that conducted two to three independent surveys of each stream. In only four streams (33%) did measurements from all crews in all monitoring groups yield the same stream type. Most differences found among field crews and monitoring groups could be attributed to differences in estimates of the entrenchment ratio. Differences in entrenchment ratio were likely due to small discrepancies in determination of maximum bankfull depth, leading to potentially large differences in determination of Rosgen’s flood‐prone width and consequent values of entrenchment. The result was considerable measurement variability among crews within a monitoring group, and because entrenchment ratio is the first discriminator in the Rosgen classification, differences in the assessment of this value often resulted in different determination of primary stream types. In contrast, we found that consistently evaluated attributes, such as channel slope, rarely resulted in any differences in classification. We also found that the Rosgen method can yield nonunique solutions (multiple channel types), with no clear guidance for resolving these situations, and we found that some assigned stream types did not match the appearance of the evaluated stream. Based on these observations we caution the use of Rosgen stream classes for communicating conditions of a single stream or as strata when analyzing many streams due to the reliance of the Rosgen approach on bankfull estimates which are inherently uncertain.     

Deep eutectic solvents as green absorbents of volatile organic pollutants

Volatile organic compounds are a major source of air pollutants. Absorption is an effective solution to treat polluted air loaded with volatile organic compounds, but most actual absorbents are often toxic and non-biodegradable. Here, we tested eutectic solvent mixtures for the absorption of volatile organic compounds for the first time. The affinity of solvent mixtures for toluene, acetaldehyde and dichloromethane was determined by measuring vapour–liquid partition coefficients and liquid phase absorption capacities. Results show that the vapour–liquid partition coefficients vary, at 30 °C, from close to zero for acetaldehyde in the mixtures choline chloride:urea, choline chloride:glycerol and tetrabutylphosphonium bromide:glycerol to 0.124 for dichloromethane in the choline chloride:urea eutectic mixture. These values are similar or even superior to those published for ionic liquids and organic solvents. Solvents based on choline chloride, a food additive, and urea, can solubilize up to 500 times more volatile organic compounds compare to water. Moreover, deep eutectic solvents are easier to prepare and more biodegradable than ionic liquids, which are also toxic. Deep eutectic solvents are more biodegradable than silicone oils, which are also expensive. Furthermore, in terms of recycling, the absorption capacities of the tested solvents remained unchanged during five absorption–desorption cycles. These findings are patented.     

Hydrologic Landscape Classification to Estimate Bristol Bay,Alaska Watershed Hydrology

Hydrologic landscapes (HLs) have proven to be a useful tool for broad scale assessment and classification of landscapes across the United States as they help organize larger geographical areas into areas of similar hydrologic characteristics. We developed a HL classification for the Bristol Bay watershed of southwest Alaska that incorporates indices of annual climate and seasonality, terrain, geology, and the influences of large lakes and glaciers. A HL classification is particularly useful in this large watershed because of its hydrologic and landscape variability, important salmon fishery, variety of environmental and potential anthropogenic stressors, and lack of widespread hydrologic data. Following creation of Bristol Bay basin‐wide HL classes, we compared the HL distributions within watersheds grouped by two calculated runoff parameters derived from available long‐term streamflow records and found HL distributions within these groups provided predictive insight on hydrologic behavior. Using these developed runoff groups, we estimated expected hydrologic behavior in watersheds across the larger Bristol Bay watershed that lacked gauged streamflow records. The HL approach provides a scientific basis for estimating the first‐order hydrologic behavior of watersheds and landscapes that lack detailed hydrologic information.     

Distribution of Selected Soil and Water Conservation Practices in the U.S. as Identified with Google Earth

The proper representation of conservation practices on agricultural lands is an important factor in large‐scale assessments of water quality in the United States. Unfortunately, there are few publicly available data sources at the local level and even fewer at the national scale. In this research, randomly selected points within agricultural lands were examined for selected conservation practices using Google Earth aerial imagery by a team of interpreters. In total, 13,530 points had field boundaries digitized, and were subsequently examined and classified. The presence of terraces, grassed waterways, contour farming, center pivot irrigation, strip cropping, ponds, riparian vegetation, filter strips, and land cover were noted. Subjectivity among interpreters was evaluated using duplicate samples and was found to be similar to image misclassification rates in other research. Conservation practice adoption rates for selected major river basins compared favorably with data collected by the Conservation Effects Assessment Project. The frequency of occurrence of each conservation practice was summarized and presented by ecoregion. To facilitate future research, point level data and software source code developed in this research are available via the web at http://nlet.brc.tamus.edu/Conservation . Aerial imagery was found to be a powerful, inexpensive, and easily accessible tool to assess large‐scale conservation practice implementation for certain conservation practices.     

Dissipation,half-lives,and mass spectrometric identification of chlorpyrifos and its two metabolites on field-grown collard and kale

The persistence and fate of chlorpyrifos and its two metabolites, chlorpyrifos-oxon and the 3, 5, 6-trichloro-2-pyridinol (TCP) break-down product were investigated on kale and collard leaves under field conditions. A simultaneous extraction and quantification procedure was developed for chrorpyrifos and its two main metabolites. Residues of chlorpyrifos, chlorpyrifos oxon, and TCP were determined using a gas chromatograph (GC) equipped with an electron capture detector (GC/ECD). Chlorpyrifos metabolites were detectable up to 23 days following application. Residues were confirmed using a GC equipped with a mass selective detector (GC/MSD) in total ion mode. Initial residues of chlorpyrifos were greater on collard (14.5 µg g^?1) than kale (8.2 µg g^?1) corresponding to half-lives (T_1/2) values of 7.4 and 2.2 days, respectively. TCP, the hydrolysis product, was more persistent on collards with an estimated T_1/2 of 6.5 days compared to kale (T_1/2 of 1.9 days).     

Investigation of the binding and simultaneous quantifications of propanil and bromoxynil herbicide concentrations in human serum albumin

This study reported the use of UV–visible and fluorescence spectroscopy and partial-least-square (PLS) multivariate regression for accurate and simultaneous quantifications of two widely used herbicides, propanil, 3′,4′-dichloropropionanilide (PPL) and bromoxynil, 3,5-dibromo-4-hydroxybenzonitrile (BXL) in human serum albumin (HSA) at physiological conditions. The binding affinity and thermodynamic properties of PPL-HSA and BXL-HSA complexes were also investigated. Partial-least-square (PLS) regression was used to collate the variability in the absorption or emission spectra of PPL-HSA and BXL-HSA complexes with PPL and/or BXL concentrations in HSA samples. The binding constants of 7.66× 10⁸ M^?1 for PPL-HSA and 4.88× 10⁶ M^?1 for BXL-HSA complexes were calculated at physiological conditions (temperature, 310 K; pH 7.4). Thermodynamic parameter values: enthalpy (ΔH) (13.99 kJ mol^?1), entropy (ΔS) (0.078 kJ mol^?1 K^?1), and Gibbs free energy (ΔG) (?10.19 kJ mol^?1) were determined for PPL-HSA complexation at physiological conditions. However, differences in thermodynamic property values of: ΔH (?214.3 kJ mol^?1), ΔS (?0.563 kJ mol^?1 K^?1), and ΔG (?39.70 kJ mol^?1) were observed for BXL–HSA complexes. The binding constants and negative ΔG values indicated strong binding affinity and thermodynamically favorability of PPL–HSA and BXL–HSA complex formation. Results of the PLS regression calibration showed good linearity (R² ≥ 0.998289), high sensitivity, and impressive low limit-of-detections (LODs) of 1.38× 10^?8 M for PPL and 1.68× 10^?8 M for BXL that are comparable and/or lower than many previously reported LODs for herbicide and pesticide analyses. Most importantly, PLS regression is capable of simultaneous quantifications of PPL and BXL concentrations in HSA samples with good accuracy and low errors of 3.66%. UV–visible spectrophotometers and spectrofluorometers are fairly inexpensive, easy to use, and are readily available in almost every laboratory, making this protocol excellent and affordable for routine analysis of weed/pest control chemical residues in humans. The results of this study are significant and remarkable that will provide critical insight into the binding mechanism of herbicide toxicity in humans and non-target organisms, which are of special interest in the area of biomedical study, environmental risk assessment, and ecotoxicology.     

CeO2 nanoparticle fate in environmental conditions and toxicity on a freshwater predator species: a microcosm study

Environmental Science and Pollution Research - We studied the fate and toxicity of two types of CeO2 NPs (bare or citrate-coated) in environmentally relevant conditions, using large indoor...     

Expected ozone benefits of reducing nitrogen oxide (NOx) emissions from coal-fired electricity generating units in the eastern United States

On hot summer days in the eastern United States, electricity demand rises, mainly because of increased use of air conditioning. Power plants must provide this additional energy, emitting additional pollutants when meteorological conditions are primed for poor air quality. To evaluate the impact of summertime NO_x emissions from coal-fired electricity generating units (EGUs) on surface ozone formation, we performed a series of sensitivity modeling forecast scenarios utilizing EPA 2018 version 6.0 emissions (2011 base year) and CMAQ v5.0.2. Coal-fired EGU NO_x emissions were adjusted to match the lowest NO_x rates observed during the ozone seasons (April 1–October 31) of 2005–2012 (Scenario A), where ozone decreased by 3–4 ppb in affected areas. When compared to the highest emissions rates during the same time period (Scenario B), ozone increased ～4–7 ppb. NO_x emission rates adjusted to match the observed rates from 2011 (Scenario C) increased ozone by ～4–5 ppb. Finally in Scenario D, the impact of additional NO_x reductions was determined by assuming installation of selective catalytic reduction (SCR) controls on all units lacking postcombustion controls; this decreased ozone by an additional 2–4 ppb relative to Scenario A. Following the announcement of a stricter 8-hour ozone standard, this analysis outlines a strategy that would help bring coastal areas in the mid-Atlantic region closer to attainment, and would also provide profound benefits for upwind states where most of the regional EGU NO_x originates, even if additional capital investments are not made (Scenario A).

Implications: With the 8-hr maximum ozone National Ambient Air Quality Standard (NAAQS) decreasing from 75 to 70 ppb, modeling results indicate that use of postcombustion controls on coal-fired power plants in 2018 could help keep regions in attainment. By operating already existing nitrogen oxide (NO_x) removal devices to their full potential, ozone could be significantly curtailed, achieving ozone reductions by up to 5 ppb in areas around the source of emission and immediately downwind. Ozone improvements are also significant (1–2 ppb) for areas affected by cross-state transport, especially Mid-Atlantic coast regions that had struggled to meet the 75 ppb standard.     

Sampling Airborne Solids in a Duct Following a 90° Bend

Present standardized methods (ASME Power Test Code 27, Western Precipitation Bulletin 50, etc.) of stack sampling usually stress sampling under conditions of steady flow (no variation with time) in order to obtain data representative of the source emissions. On many occasions these standardized methods are applied when the velocity and/or the mass flow rate of pollutants do vary with time, thus impairing the accuracy of the sampling results. In addition, it is difficult to evaluate any inaccuracy of the sampling data. This paper classifies these two source variables into four categories and suggests basic sampling approaches for each type of source condition. Several standardized procedures are evaluated and classified according to the source conditions to which the procedure is applicable. The intent of this paper is to show the most accurate sampling approach for each source condition and thus serve as a guide when planning source sampling programs.