Effect of lipids on sorption/desorption hysteresis in natural organic matter

The chemical composition and physical conformation of natural organic matter (NOM) play a major role in regulating its capacity to retain hydrophobic organic compounds. Naphthalene and phenanthrene were used to study the correlations between sorption/desorption isotherm nonlinearity and compositional data obtained from quantitative ¹³C solid-state DPMAS NMR spectroscopy for soil and peat organic matter with or without lipids. Sorption experiments were conducted using a batch equilibration method. Desorption experiments were carried out immediately following the sorption experiments by three successive decant-refill cycles. Hysteresis was observed in all samples. Nonlinear sorption behavior was increased by removal of lipids from the NOM. The hysteresis index, obtained from the ratio of the Freundlich exponents (N values) for the desorption and sorption isotherms, was lower in the lipid-extracted NOM samples than in the same samples without lipid extraction. The relationship between the extent of hysteresis and the characteristics of the ¹³C DPMAS NMR spectra indicates that altering NOM composition through lipid extraction not only increased the proportion of aromatic-C content, but also increased sorption/desorption hysteresis. Our data also suggest that the hysteresis index is negatively related to aromaticity.     

A mathematical model for the interactive behavior of sulfate-reducing bacteria and methanogens during anaerobic digestion

Anaerobic degradation of waste involves different classes of microorganisms, and there are different types of interactions among them for substrates, terminal electron acceptors, and so on. A mathematical model is developed based on the mass balance of different substrates, products, and microbes present in the system to study the interaction between methanogens and sulfate-reducing bacteria (SRB). The performance of major microbial consortia present in the system, such as propionate-utilizing acetogens, butyrate-utilizing acetogens, acetoclastic methanogens, hydrogen-utilizing methanogens, and SRB were considered and analyzed in the model. Different substrates consumed and products formed during the process also were considered in the model. The experimental observations and model predictions showed very good prediction capabilities of the model. Model prediction was validated statistically. It was observed that the model-predicted values matched the experimental data very closely, with an average error of 3.9%.     

Road deicing salt irreversibly disrupts osmoregulation of salamander egg clutches

It has been postulated that road deicing salts are sufficiently diluted by spring rains to ameliorate any physiological impacts to amphibians breeding in wetlands near roads. We tested this conjecture by exposing clutches of the spotted salamander (Ambystoma maculatum) to three chloride concentrations (1 mg/L, 145 mg/L, 945 mg/L) for nine days, then transferred clutches to control water for nine days, and measured change in mass at three-day intervals. We measured mass change because water uptake by clutches reduces risks to embryos associated with freezing, predation, and disease. Clutches in controls sequestered water asymptotically. Those in the moderate concentrations lost 18% mass initially and regained 14% after transfer to control water. Clutches in high concentration lost 33% mass and then lost an additional 8% after transfer. Our results suggest that spring rains do not ameliorate the effects of deicing salts in wetlands with extremely high chloride concentrations.     

Interinstrument comparison of remote-sensing devices and a new method for calculating on-road nitrogen oxides emissions and validation of vehicle-specific power

Emissions of nitrogen oxides (NOx) by vehicles in real driving environments are only partially understood. This has been brought to the attention of the world with recent revelations of the cheating of the type of approval tests exposed in the dieselgate scandal. Remote-sensing devices offer investigators an opportunity to directly measure in situ real driving emissions of tens of thousands of vehicles. Remote-sensing NO₂ measurements are not as widely available as would be desirable. The aim of this study is to improve the ability of investigators to estimate the NO₂ emissions and to improve the confidence of the total NOx results calculated from standard remote-sensing device (RSD) measurements. The accuracy of the RSD speed and acceleration module was also validated using state-of-the-art onboard global positioning system (GPS) tracking. Two RSDs used in roadside vehicle emissions surveys were tested side by side under off-carriageway conditions away from transient pollution sources to ascertain the consistency of their measurements. The speed correlation was consistent across the range of measurements at 95% confidence and the acceleration correlation was consistent at 95% confidence intervals for all but the most extreme acceleration cases. VSP was consistent at 95% confidence across all measurements except for those at VSP ≥ 15 kW t^?1, which show a small underestimate. The controlled distribution gas nitric oxide measurements follow a normal distribution with 2σ equal to 18.9% of the mean, compared to 15% observed during factory calibration indicative of additional error introduced into the system. Systematic errors of +84 ppm were observed but within the tolerance of the control gas. Interinstrument correlation was performed, with the relationship between the FEAT and the RSD4600 being linear with a gradient of 0.93 and an R² of 0.85, indicating good correlation. A new method to calculate NOx emissions using fractional NO₂ combined with NO measurements made by the RSD4600 was constructed, validated, and shown to be more accurate than previous methods.

Implications: Synchronized remote-sensing measurements of NO were taken using two different remote-sensing devices in an off-road study. It was found that the measurements taken by both instruments were well correlated. Fractional NO₂ measurements from a prior study, measurable on only one device, were used to create new NO_x emission factors for the device that could not be measured by the second device. These estimates were validated against direct measurement of total NO_x emission factors and shown to be an improvement on previous methodologies. Validation of vehicle-specific power was performed with good correlation observed.     

Dioxins and furans in emissions from medical waste incinerators

Dioxins and furans were detected in emissions from eight medical waste incinerators tested in California. Total uncontrolled emissions ranged from 363 to 11, 811 nanograms per dry standard cubic meter. The most effective of three wet scrubbers achieved an emissions control efficiency of 95 percent for total PCDD and PCDF. A baghouse was less than 30 percent efficient in removing PCDD and PCDF from the incinerator emissions.     

Miscible fluid displacement stability in unconfined porous media:: Two-dimensional flow experiments and simulations

In situ flushing groundwater remediation technologies, such as cosolvent flushing, rely on the stability of the interface between the resident and displacing fluids for efficient removal of contaminants. Contrasts in density and viscosity between the resident and displacing fluids can adversely affect the stability of the displacement front. Petroleum engineers have developed techniques to describe these types of processes; however, their findings do not necessarily translate directly to aquifer remediation. The purpose of this laboratory study was to investigate how density and viscosity contrasts affected cosolvent displacements in unconfined porous media characterized by the presence of a capillary fringe. Two-dimensional flow laboratory experiments, which were partially scaled to a cosolvent flushing field experiment, were conducted to determine potential implications of flow instabilities in homogeneous sand packs. Numerical simulations were also conducted to investigate the differential impact of fluid property contrasts in unconfined and confined systems. The results from these experiments and simulations indicated that the presence of a capillary fringe was an important factor in the displacement efficiency. Buoyant forces can act to carry a lighter-than-water cosolvent preferentially into the capillary fringe during displacement of the resident groundwater. During subsequent water flooding, buoyancy forces can act to effectively trap the cosolvent in the capillary fringe, contributing to the inefficient removal of cosolvent from the aquifer.     

Exposure to polychlorinated biphenyls from an overheated transformer

A Polychlorinated Biphenyl (PCB) containing transformer released approximately 50 gallons of askarel oil. No polychlorinated dibenzofurans (PCDF) or polychlorinated dibenzodioxins (PCDD) were detected in a sample of the askarel (analytical limit of detection of 40 parts per billion per isomer group). Skin irritation, unusual tiredness, and headaches occurred in approximately 20% of the individuals at the scene of the incident. Serum PCB levels, and mean values for blood and urine tests were within normal ranges.     

Effects of elevated CO2 concentration on the polyamine levels of field-grown soybean at three O3 regimes

Effects of increased ozone (O3) and carbon dioxide (CO2) on polyamine levels were determined in soybean (Glycine max L. Merr. cv. Clark) grown in open-top field chambers. The chamber treatments consisted of three O3 regimes equal to charcoal filtered (CF), non-filtered (NF), and non-filtered plus 40 nl litre(-1) O3 and CO2 treatments equal to 350, 400 and 500 microl litre(-1) for a total of nine treatments. Leaf samples were taken at three different times during the growing season. Examination of growth and physiological characteristics, such as photosynthesis, stomatal resistance, and shoot weight, revealed that increasing CO2 ameliorated the deleterious effects of increased O3. Results from the initial harvest, at the pre-flowering growth stage (23 days of treatment), showed that increasing O3 at ambient CO2 caused increases in putrescine (Put) and spermidine (Spd) of up to six-fold. These effects were lessened with increased CO2. Elevated CO2 increased polyamines in plants treated with CF air, but had no effect in the presence of ambient or enhanced O3 levels. Leaves harvested during peak flowering (37 days of treatment) showed O3-induced increases in Put and Spd at ambient CO2 concentrations. However, increased CO2 levels inhibited this response by blocking the O3-induced polyamine increase. Leaves harvested during the pod fill stage (57 days of treatment) showed no significant O3 or CO2 effects on polyamine levels. Our results demonstrate that current ambient O3 levels induce the accumulation of Put and Spd early in the growing season and that further increases in O3 could result in even greater polyamine increases. These results are consistent with a possible antiozonant function for polyamines. The ability of increased CO2 to protect soybeans from O3 damage, however, does not appear to involve polyamine accumulation.     

Effects of ultraviolet radiation and contaminant-related stressors on arctic freshwater ecosystems

Climate change is likely to act as a multiple stressor, leading to cumulative and/or synergistic impacts on aquatic systems. Projected increases in temperature and corresponding alterations in precipitation regimes will enhance contaminant influxes to aquatic systems, and independently increase the susceptibility of aquatic organisms to contaminant exposure and effects. The consequences for the biota will in most cases be additive (cumulative) and multiplicative (synergistic). The overall result will be higher contaminant loads and biomagnification in aquatic ecosystems. Changes in stratospheric ozone and corresponding ultraviolet radiation regimes are also expected to produce cumulative and/or synergistic effects on aquatic ecosystem structure and function. Reduced ice cover is likely to have a much greater effect on underwater UV radiation exposure than the projected levels of stratospheric ozone depletion. A major increase in UV radiation levels will cause enhanced damage to organisms (biomolecular, cellular, and physiological damage, and alterations in species composition). Allocations of energy and resources by aquatic biota to UV radiation protection will increase, probably decreasing trophic-level productivity. Elemental fluxes will increase via photochemical pathways.