pH-Dependent fate and transport of NTA-complexed cobalt through undisturbed cores of fractured shale saprolite

The codisposal of toxic metals and radionuclides with organic chelating agents has been implicated in the facilitated transport of the inorganic contaminants away from primary waste disposal areas. We investigated the transport of Co(II)NTA through undisturbed cores of fractured shale saprolite. Experiments were conducted across the pH range 4 to 8 by collecting cores from different locations within the weathering profile. Aqueous complexation, adsorption, dissociation and oxidation reactions influenced Co(II)NTA transport. The suite of reaction products identified in column effluent varied with experimental pH. At low pH and in the presence of abundant exchangeable aluminum, Co transport occurred predominantly as the Co2+ ion. At higher pH, Co was transported primarily as Co(II)NTA and the Co(III) species Co(III)(HNTA)2 and Co(III)(IDA)2. The formation of the geochemical oxidation products (Co(III) species) has far reaching implications as these compounds are kinetically and thermodynamically stable, are transported more rapidly than Co(II)NTA, and are resistant to biodegradation. These results demonstrate that natural minerals, in the physical structure encountered naturally, can be more important in the formation of mobile, stable contaminant forms than they can be for the retardation and dissociation of the contaminants.     

Response of Ceriodaphnia dubia to ionic silver: discrepancies among model predictions, measured concentrations and mortality

Silver thiosulfate, often a waste product of photoprocessing, is less bioavailable or toxic to aquatic organisms than is ionic silver. We conducted duplicate 48-h Ceriodaphnia dubia tests in reconstituted laboratory water using treatments of 92.7 nM Ag+ with various concentrations of thiosulfate. Expected Ag+ concentrations were generated for thiosulfate treatment levels using MINEQL + chemical equilibrium modeling. Ag+ concentrations in treatments were determined using a novel silicon-based sensor. Based on predicted Ag+ and published 48-h LC50 values for C. dubia, we did not expect to observe adverse effects. Yet, 100% mortality was observed at low thiosulfate treatments, whereas > 85% and > 95% survival was observed at higher thiosulfate treatment levels, respectively. Our results indicate that biotic responses match the sensor-based Ag+ concentrations. However, there is a discrepancy between these empirical results and responses expected to occur with Ag+ concentrations as predicted by MINEQL + chemical modeling. By correlating silicon sensor data with toxicity results obtained from our laboratory, our work clearly relates a specific chemical form (Ag+) to toxicity results.     

Correlation of human olfactory responses to airborne concentrations of malodorous volatile organic compounds emitted from swine effluent

Direct multicomponent analysis of malodorous volatile organic compounds (VOCs) present in ambient air samples from 29 swine (Sus scrofa) production facilities was used to develop a 19-component artificial swine odor solution that simulated olfactory properties of swine effluent. Analyses employing either a human panel consisting of 14 subjects or gas chromatography were performed on the air stream from an emission chamber to assess human olfactory responses or odorant concentration, respectively. Analysis of the olfactory responses using Fisher's LSD statistics showed that the subjects were sensitive to changes in air concentration of the VOC standard across dilutions differing by approximately 16%. The effect of chemical synergisms and antagonisms on human olfactory response magnitudes was assessed by altering the individual concentration of nine compounds in artificial swine odor over a twofold concentration range while maintaining the other 18 components at a constant concentration. A synergistic olfactory response was observed when the air concentration of acetic acid was increased relative to the concentration of other VOC odorants in the standard. An antagonistic olfactory response was observed when the air concentration of 4-ethyl phenol was increased relative to the other VOC odorants in the standard. The collective odorant responses for nine major VOCs associated with swine odor were used to develop an olfactory prediction model to estimate human odor response magnitudes to swine manure odorants through measured air concentrations of indicator VOCs. The results of this study show that direct multicomponent analysis of VOCs emitted from swine effluent can be applied toward estimating perceived odor intensity.     

Vapor flammability above aqueous solutions of flammable liquids

The flammability of vapors above aqueous solutions of ethanol and acetonitrile was studied experimentally in a 20-L combustion apparatus. No liquid was present in the apparatus, but the vapor concentrations were adjusted to correspond to the vapor in equilibrium with a specified aqueous solution. The experimental results for these two systems show that

• As water is added to the vapor, the lower boundary of the flammability zone decreases. For ethanol, the lower flammability limits (LFL) decreases from 3.7% for pure vapor to 3.2% with saturated water vapor. For acetonitrile, the decrease is from 4.2% to 3.8%. Thus, to a good approximation, the water vapor can be treated as an inert, enabling the data to be displayed on a single flammability triangle diagram. This provides a very simplified method for estimating the flammable behavior for aqueous solutions.

• The upper boundary of the flammability zone is unchanged with the addition of water.

• The limiting oxygen concentration (LOC) is essentially constant for all concentrations of aqueous solutions. The LOC for the pure solvent may be used as a universal LOC for all solvent concentrations.

• The vapor mixture above the aqueous solution is not flammable below a certain liquid mol fraction of flammable. The flammable concentration at which this occurs can be called the maximum safe solvent concentration (MSSC). A method is presented to determine the MSSC from experimental flammability data.

• The oxygen concentration defining the flammable boundary for the vapor decreases rapidly from the MSSC and then increases as the liquid solvent concentration increases.

The calculated adiabatic flame temperature (CAFT) method qualitatively predicts the same behavior as the experimental data.     

Laboratory-scale investigation of UV treatment of ammonia for livestock and poultry barn exhaust applications

The feasibility of using deep ultraviolet (UV) treatment for abatement of ammonia (NH(3)) in livestock and poultry barn exhaust air was examined in a series of laboratory-scale experiments. These experiments simulated moving exhaust air through an irradiation chamber with variables of UV wavelength and dose, NH(3) concentrations, humidity, and presence of hydrogen sulfide (H(2)S). Ammonia, initially at relevant barn exhaust concentrations in air, was substantially or completely reduced by irradiation with 185 nm light. Reactions were monitored using chemiluminescence detection, gas chromatography with mass spectrometry detection, and Fourier transform infrared spectrometry, of which the latter was found to be the most informative and flexible. Detected nitrogen-containing products included N(2)O, NH(4)NO(3), and HNO(3). It was presumed that atomic oxygen is the primary photochemical product that begins the oxidative cascade. The data show that removal of NH(3) is plausible, but they highlight concerns over pollution swapping due to formation of ozone and N(2)O.     

Improvements to lawn and garden equipment emissions estimates for Baltimore, Maryland

Lawn and garden equipment are a significant source of emissions of volatile organic compounds (VOCs) and other pollutants in suburban and urban areas. Emission estimates for this source category are typically prepared using default equipment populations and activity data contained in emissions models such as the U.S. Environmental Protection Agency's (EPA) NONROAD model or the California Air Resources Board's (CARB) OFFROAD model. Although such default data may represent national or state averages, these data are unlikely to reflect regional or local differences in equipment usage patterns because of variations in climate, lot sizes, and other variables. To assess potential errors in lawn and garden equipment emission estimates produced by the NONROAD model and to demonstrate methods that can be used by local planning agencies to improve those emission estimates, this study used bottom-up data collection techniques in the Baltimore metropolitan area to develop local equipment population, activity, and temporal data for lawn and garden equipment in the area. Results of this study show that emission estimates of VOCs, particulate matter (PM), carbon monoxide (CO), carbon dioxide (CO2), and nitrogen oxides (NO(x)) for the Baltimore area that are based on local data collected through surveys of residential and commercial lawn and garden equipment users are 24-56% lower than estimates produced using NONROAD default data, largely because of a difference in equipment populations for high-usage commercial applications. Survey-derived emission estimates of PM and VOCs are 24 and 26% lower than NONROAD default estimates, respectively, whereas survey-derived emission estimates for CO, CO2, and NO(x) are more than 40% lower than NONROAD default estimates. In addition, study results show that the temporal allocation factors applied to residential lawn and garden equipment in the NONROAD model underestimated weekend activity levels by 30% compared with survey-derived temporal profiles.     

Fire effects on stable isotopes in a Sierran forested watershed

This study tested the hypothesis that stable C and N isotope values in surface soil and litter would be increased by fire due to volatilization of lighter isotopes. The hypothesis was tested by: (1) performing experimental laboratory burns of organic and mineral soil materials from a watershed at combinations of temperature ranging 100 to 600 degrees C and duration ranging from 1 to 60 min; (2) testing field samples of upland soils before, shortly after, and 1 yr following a wildfire in the same watershed; and (3) testing field soil samples from a down-gradient ash/sediment depositional area in a riparian zone following a runoff event after the wildfire. Muffle furnace results indicated the most effective temperature range for using stable isotopes for tracing fire impacts is 200 to 400 degrees C because lower burn temperatures may not produce strong isotopic shifts, and at temperatures>or=600 degrees C, N and C content of residual material is too low. Analyses of field soil samples were inconclusive: there was a slightly significant effect of the wildfire on delta15N values in upland watershed analyses 1 yr postburn, while riparian zone analyses results indicated that delta13C values significantly decreased approximately 0.71 per thousand over a 9 mo post-fire period (p=0.015), and ash/sediment layer delta13C values were approximately 0.65 per thousand higher than those in the A horizon. The lack of field confirmation may have been due to overall wildfire burn temperatures being <200 degrees C and/or microbial recovery and vegetative growth in the field. Thus, the muffle furnace experiment supported the hypothesis, but it is as yet unconfirmed by actual wildfire field data.     

The effectiveness of forecast-based humanitarian assistance in anticipation of extreme winters: a case study of vulnerable herders in Mongolia

This paper presents evidence relating to a forecast-based cash and non-food item distribution among vulnerable herder households during the 2017–18 dzud (extreme winter) season in Mongolia, and analyses the results of a quasi-experimental study evaluating its impacts. An innovative approach in disaster risk reduction, forecast-based financing (FbF) can have short- and long-term benefits to vulnerable households but remains understudied. The paper contributes information on a multimodal FbF programme offering one-off cash grants and in-kind veterinary kits. The data found significant effects of reduced mortality and increased offspring survival in some types of livestock, and that the timing of FbF assistance is crucial, as reported early assistance correlated to positive outcomes in terms of reduced animal mortality. These findings can be used to design more effective FbF interventions, to understand better the appropriateness of FbF designs, and to use early warnings and early actions to help people prepare and withstand disasters such as dzuds.