Sorption and bioreduction of hexavalent uranium at a military facility by the Chesapeake Bay

Directly adjacent to the Chesapeake Bay lies the Aberdeen Proving Ground, a U.S. Army facility where testing of armor-piercing ammunitions has resulted in the deposition of >70,000 kg of depleted uranium (DU) to local soils and sediments. Results of previous environmental monitoring suggested limited mobilization in the impact area and no transport of DU into the nation's largest estuary. To determine if physical and biological reactions constitute mechanisms involved in limiting contaminant transport, the sorption and biotransformation behavior of the radionuclide was studied using geochemical modeling and laboratory microcosms (500 ppb U(VI) initially). An immediate decline in dissolved U(VI) concentrations was observed under both sterile and non-sterile conditions due to rapid association of U(VI) with natural organic matter in the sediment. Reduction of U(VI) to U(IV) occurred only in non-sterile microcosms. In the non-sterile samples, intrinsic bioreduction of uranium involved bacteria of the order Clostridiales and was only moderately enhanced by the addition of acetate (41% vs. 56% in 121 days). Overall, this study demonstrates that the migration of depleted uranium from the APG site into the Chesapeake Bay may be limited by a combination of processes that include rapid sorption of U(VI) species to natural organic matter, followed by slow, intrinsic bioreduction to U(IV).     

Demolition of high-rise public housing increases particulate matter air pollution in communities of high-risk asthmatics

Public housing developments across the United States are being demolished, potentially increasing local concentrations of particulate matter (PM) in communities with high burdens of severe asthma. Little is known about the impact of demolition on local air quality. At three public housing developments in Chicago, IL, PM with an aerodynamic diameter < 10 microm (PM10) and < 2.5 microm were measured before and during high-rise demolition. Additionally, size-selective sampling and real-time monitoring were concurrently performed upwind and downwind of one demolition site. The concentration of particulates attributable to demolition was estimated after accounting for background urban air pollution. Particle microscopy was performed on a small number of samples. Substantial increases of PM10 occurred during demolition, with the magnitude of that increase varying based on sampler distance, wind direction, and averaging time. During structural demolition, local concentrations of PM10 42 m downwind of a demolition site increased 4- to 9-fold above upwind concentrations (6-hr averaging time). After adjusting for background PM10, the presence of dusty conditions was associated with a 74% increase in PM10 100 m downwind of demolition sites (24-hr averaging times). During structural demolition, short-term peaks in real-time PM10 (30-sec averaging time) occasionally exceeded 500 microg/m(3). The median particle size downwind of a demolition site (17.3 microm) was significantly larger than background (3 microm). Specific activities are associated with realtime particulate measures. Microscopy did not identify asbestos or high concentrations of mold spores. In conclusion, individuals living near sites of public housing demolition are at risk for exposure to high particulate concentrations. This increase is characterized by relatively large particles and high short-term peaks in PM concentration.     

Kinetics of chromate adsorption on goethite in the presence of sorbed silicic acid

The adsorption of chromate on mineral surfaces has received much attention due to its toxicity in natural systems. Spectroscopic studies have demonstrated that chromate forms inner-sphere complexes on variable-charge surfaces. However, in natural systems chromate has been observed to be fairly mobile, which has been explained by the presence of naturally occurring ligands competing with chromate for mineral surface sites. Silicic acid is a ubiquitous ligand in soil and water environments and also sorbs strongly to variable-charge surfaces. Yet little research has examined its influence on chromate adsorption to variable-charge surfaces such as goethite. This study examined the influence of silicic acid (0.10 and 1.0 mM) on the adsorption kinetics of chromate (0.05 and 0.10 mM) on goethite over a range of common soil pH values (4, 6, and 8). The rate and total quantity of chromate adsorption decreased in all the experiments except at a pH value of 4 and a chromate concentration of 0.05 mM. The inhibition of chromate adsorption ranged from 3.1% (pH = 4, Si = 0.10 mM, chromate = 0.10 mM) to 83.3% (pH = 8, Si = 1.0 mM, chromate = 0.05 mM). The rate of chromate adsorption decreased with an increase in pH and silicic acid concentration. This was attributed to a reduction in the surface potential of goethite on silicic acid adsorption as well as a competition for surface sites. The presence of naturally occurring ligands such as silicic acid may be responsible for the enhanced mobility of chromate in natural systems and demonstrates the importance of competitive adsorption for evaluating the mobility of trace elements.     

Airborne emissions of mercury from municipal solid waste. I: new measurements from six operating landfills in Florida

Mercury-bearing material enters municipal landfills from a wide array of sources, including fluorescent lights, batteries, electrical switches, thermometers, and general waste; however, the fate of mercury (Hg) in landfills has not been widely studied. Using automated flux chambers and downwind atmospheric sampling, we quantified the primary pathways of Hg vapor releases to the atmosphere at six municipal landfill operations in Florida. These pathways included landfill gas (LFG) releases from active vent systems, passive emissions from landfill surface covers, and emissions from daily activities at each working face (WF). We spiked the WF at two sites with known Hg sources; these were readily detected downwind, and were used to test our emission modeling approaches. Gaseous elemental mercury (Hg(O)) was released to the atmosphere at readily detectable rates from all sources measured; rates ranged from approximately 1-10 ng m(-2) hr(-1) over aged landfill cover, from approximately 8-20 mg/hr from LFG flares (LFG included Hg(O) at microg/m3 concentrations), and from approximately 200-400 mg/hr at the WF. These fluxes exceed our earlier published estimates. Attempts to identify specific Hg sources in excavated and sorted waste indicated few readily identifiable sources; because of effective mixing and diffusion of Hg(O), the entire waste mass acts as a source. We estimate that atmospheric Hg releases from municipal landfill operations in the state of Florida are on the order of 10-50 kg/yr, substantially larger than our original estimates, but still a small fraction of current overall anthropogenic losses.     

COVID-19: the impact of a global crisis on sustainable development teaching

Environment, Development and Sustainability - The COVID-19 pandemic has caused a global crisis, one which also influences the ways sustainability is being taught at universities. This paper...     

The effects of throughfall manipulation on soil leaching in a deciduous forest

The effects of changing precipitation on soil leaching in a deciduous forest were examined by experimentally manipulating throughfall fluxes in the field. In addition to an ambient treatment (AMB), throughfall fluxes were reduced by 33% (DRY treatment) and increased by 33% (WET treatment) using a system of rain gutters and sprinklers on Walker Branch Watershed, Tennessee. Soil leaching was measured with resin lysimeters in the O horizons and with ceramic cup lysimeters in the E (25 cm) and Bt (70 cm) horizons. Large and statistically significant treatment effects on N fluxes were found in the O horizons (lower N fluxes in the DRY and higher N fluxes in the WET treatment). Together with the greater O horizon N content observed in the DRY treatment, this suggested that N was being immobilized at a greater rate in the DRY treatment than in the AMB or WET treatments. No statistically significant treatment effects on soil solution were found in the E horizons with the exception of (Ca2+ + Mg2+) to K+ ratio. Statistically significant treatment effects on electrical conductivity (EC), pH, Ca2+, Mg2+, K+, Na+, SO4(2-), and Cl- were found in the Bt horizons due to differences between the DRY and other treatments. Despite this, calculated fluxes of Ca2+, Mg2+, K+, Na+, SO4(2-), and Cl- were lowest in the DRY treatment. These results suggest that lower precipitation will cause temporary N immobilization in litter and long-term enrichment in soil base cations whereas increased precipitation will cause long-term depletion of soil base cations.     

Reducing crude protein in beef cattle diet reduces ammonia emissions from artificial feedyard surfaces

Concentrated animal feeding operations are major sources of ammonia to the atmosphere. Control methods to reduce emissions include acidifying amendments, urease inhibitors, and absorbents. For beef cattle, decreasing crude protein (CP) in diets may be the most practical and cost-effective method to reduce ammonia emissions. Our objective was to quantify the effect of reducing CP in beef cattle diet on ammonia emissions. Two groups of steers were fed diets with either 11.5 or 13.0% CP and all urine and feces were collected. Manures from the two diet treatments were applied in a replicated laboratory chamber experiment, and ammonia emission was quantified using acid gas washing. In four seasonal field trials, manures from the two diet treatments were applied to two 10-m-diameter, circular, artificial feedyard surfaces, and ammonia emission was quantified using the integrated horizontal flux method. Manure from steers fed 11.5% CP diet had less urine, less urinary N, and a lesser fraction of total N in urine, compared with the 13.0% CP diet. Decreasing crude protein in beef cattle diets from 13 to 11.5% significantly decreased ammonia emission by 44% (p < 0.01) in the closed chamber laboratory experiment, and decreased mean daily ammonia flux by 30% (p = 0.10), 52% (p = 0.08), and 29% (p < 0.01) in summer, autumn, and spring field trials, respectively. No difference was observed in winter. On an annual basis, decreasing crude protein reduced daily ammonia flux by 28%. Reducing crude protein in beef cattle diets may provide the most practical and cost-effective way to reduce ammonia emissions from feedyards.     

Perchlorate retention and mobility in soils

Adsorption and release of perchlorate in a variety of soils, minerals, and other media were studied when the solid media were exposed to low and high aqueous solutions of perchlorate salts. Low level ClO4- exposure was investigated by subjecting triplicate 5.0 g portions of a solid medium (38 different soils, minerals, or dusts) to 25 mL of an aqueous ammonium perchlorate (NH4ClO4) solution containing 670 ng mL(-1) (6.8 microM) perchlorate. This corresponds to a perchlorate-to-soil ratio of 3.4 microg g(-1) (34 nmol g(-1)). At this level of exposure, more than 90% of the perchlorate was recovered in the aqueous phase, as determined by ion chromatography. In some cases, more than 99% of the perchlorate remained in the aqueous phase. In some cases, the apparent loss of aqueous perchlorate was not clearly distinguishable from the variation due to experimental error. The forced perchlorate anion exchange capacities (PAECs) were studied by soaking triplicate 5.0 g portions of the solid media in 250 mL of 0.20 M sodium perchlorate (NaClO4) followed by repeated deionized water rinses (overnight soaks with mixing) until perchlorate concentrations fell below 20 ng mL(-1) in the rinse solutions. The dried residua were leached with 15.0 mL of 0.10 M sodium hydroxide. The leachates were analyzed by ion chromatography and the perchlorate concentrations thus found were subsequently used to calculate the PAECs. The measurable PAECs of the insoluble and settleable residua ranged from 4 to 150 nmol g(-1) (micromol kg(-1)), with most in the 20-50 nmol g(-1) range. In some soils or minerals, no sorption was detectable. The mineral bentonite was problematic, however. Overall, the findings support the widely accepted idea that perchlorate does not appreciably sorb to soils and that its mobility and fate are largely influenced by hydrologic and biologic factors. They also generally support the idea that intrasoil perchlorate content is depositional rather than sorptive. On the other hand, sorption (anion replacement) of perchlorate appears to occur in some soils. Therefore, the measurement of perchlorate in soils requires accounting for ion exchange phenomena; leaching with water alone may give inaccurate results. If perchlorate anion exchange is confirmed to be negligible, then leaching procedures may be simplified accordingly.     

Alternative method of groundwater sparging for petroleum hydrocarbon remediation

An alternative method of in-situ groundwater sparging, termed density-driven convection (patent pending), is presented. This method has been successfully used to remediate eight underground storage tank releases involving a wide distillation range of petroleum hydrocarbons (gasoline to waste oil) and in a variety of site soils (clay to sandy gravel). Application of the density-driven convection method is detailed in a case study. The system, installed to remediate a gasoline and diesel release from an underground storage tank, was operated and monitored for a period of one year. Monitoring data indicate reductions in total petroleum hydrocarbon concentrations in groundwater and in soil. Concentrations of aromatic hydrocarbons (benzene, toluene, ethylbenzene, xylenes, and naphthalene) also decreased in both media. Stimulation of natural biodegradation, the primary mechanism of removal, occurred rapidly. Natural biological activity gradually declined over the subsequent 150 days. After one year of operation, the sparging system has achieved or is rapidly approaching the regulatory cleanup goals for both soil and groundwater, including reduction of dissolved concentrations below maximum contaminant levels established under the Safe Drinking Water Act.