Characterization of controlled-release KMnO4 (CRP) barrier system for groundwater remediation: a pilot-scale flow-tank study

Release and spreading of permanganate (MnO(4)(-)) in the well-based controlled-release potassium permanganate (KMnO(4)) barrier system (CRP system) was investigated by conducting column release tests, model simulations, soil oxidant demand (SOD) analyses, and pilot-scale flow-tank experiments. A large flow tank (L x W x D=8m x 4m x 3m) was constructed. Pilot-scale CRP pellets (OD x L=0.05 m x1.5m; n=110) were manufactured by mixing approximately 198 kg of KMnO(4) powders with paraffin wax and silica sands in cylindrical moulds. The CRP system (L x W x D=3m x 4m x 1.5m) comprising 110 delivery wells in three discrete barriers was constructed in the flow tank. Natural sands (organic carbon content=0.18%; SOD=3.7-11 g MnO(4)(-)kg(-1)) were used as porous media. Column release tests and model simulations indicated that the CRP system could continuously release MnO(4)(-) over several years, with slowly decreasing release rates of 2.5 kg d(-1) (day one), 109 g d(-1) (day 100), 58 g d(-1) (year one), 22 g d(-1) (year five), and 12 g d(-1) (year 10). Mean MnO(4)(-) concentrations within the CRP system ranged from 0.5 to 6 mg l(-1) during the 42 days of testing period. The continuously releasing MnO(4)(-) was gradually removed by SOD limiting the length of MnO(4)(-) zone in the porous media. These data suggested that the CRP system could create persistent and confined oxidation zone in the subsurface. Through development of advanced tools for describing agent transport and facilitating lateral agent spreading, the CRP system could provide new approach for long-term in situ treatment of contaminant plumes in groundwater.     

A new multipollutant, no-threshold air quality health index based on short-term associations observed in daily time-series analyses

Air quality indices currently in use have been criticized because they do not capture additive effects of multiple pollutants, or reflect the apparent no-threshold concentration-response relationship between air pollution and health. We propose a new air quality health index (AQHI), constructed as the sum of excess mortality risk associated with individual pollutants from a time-series analysis of air pollution and mortality in Canadian cities, adjusted to a 0-10 scale, and calculated hourly on the basis of trailing 3-hr average pollutant concentrations. Extensive sensitivity analyses were conducted using alternative combinations of pollutants from single and multipollutant models. All formulations considered produced frequency distributions of the daily maximum AQHI that were right-skewed, with modal values of 3 or 4, and less than 10% of values at 7 or above on the 10-point scale. In the absence of a gold standard and given the uncertainty in how to best reflect the mix of pollutants, we recommend a formulation based on associations of nitrogen dioxide, ozone, and particulate matter of median aerodynamic diameter less than 2.5 microm with mortality from single-pollutant models. Further sensitivity analyses revealed good agreement of this formulation with others based on alternative sources of coefficients drawn from published studies of mortality and morbidity. These analyses provide evidence that the AQHI represents a valid approach to formulating an index with the objective of allowing people to judge the relative probability of experiencing adverse health effects from day to day. Together with health messages and a graphic display, the AQHI scale appears promising as an air quality risk communication tool.     

Measuring the flux at the interface of coal-tar impacted sediment and river water near a former MGP site

Determining water movement through contaminated sediment is critical for characterizing transport of chemicals from the sediment to the overlying water. Field studies to characterize the water flow across the sediment-water interface within a river adjacent to a former manufactured gas plant site were conducted. For this purpose, a new design of an interfacial flow meter was developed and tested. The in situ components of the system consisted of: a cylinder with an interfacial area of 2342 cm2; a dome attached to the cylinder; and a flow tube that allows water to flow from inside the dome to the river at the rate equal to the specific discharge across the sediment-water boundary. A 'heat-pulse' method was used to measure flow by heating the center of the flow tube for a brief time period and measuring the temperature profile within the tube over time. The system was calibrated to measure volumetric flux in the range 1.5-4.0 cm d(-1), however using a flow-addition method, the measurement of lower velocities also was accomplished, and calibration at higher fluxes is possible. From the groundwater flow at the interface of the coal-tar impacted sediment and information on the sediment pore water concentrations of several PAHs (poly-cyclic aromatic hydrocarbons), the mass flux of these PAHs to the river were estimated. Information on PAH mass flux at the sediment-water interface is useful for site assessment, including the evaluation of remediation alternatives and longer term site characterization.     

Long-term effects of fertilization on the forms and availability of soil phosphorus in rice paddy

The changes in total P accumulation and P compounds with time in the plough layer in a paddy soil in southern Korea were investigated in relation to the continuous application of chemical fertilizers (NPK), straw based compost (Compost), combination these two (NPK+Compost) for 31 years. Continuous fertilization increased the total and inorganic P contents in plough layers. In NPK, inorganic P fraction did not change with time, but organic P content increased significantly. Long-term application of chemical fertilizer together with compost accelerated the decrease in the organic P fraction, presumably due to promoting microbial activity in the plow layer, and then increased significantly inorganic P fraction. Compost application decreased the residual P and Fe-P fractions and then increased inorganic P fraction, in spite of continuous compost application. Increase in total, inorganic and extractable P with time may be closely related to the increase in the availability of accumulated P for rice growth.     

Catalytic wet oxidation of ammonia: why is N2 formed preferentially against NO3 -?

The role of catalyst and the reason for the preferential formation of N(2) in the catalytic oxidation reaction of ammonia in water over a Ru (3wt.%)/TiO(2) catalyst were elucidated. It was verified that the catalyst in the reaction had no direct relevance to the selective formation of N(2), but was responsible only for the oxidation of aqueous ammonia, NH(3)(aq), finally giving a molecule of nitrous acid. The preferential production of N(2) was experimentally demonstrated due to the homogeneous aqueous phase reaction of the nitrous acid-dissociated NO(2)(-) with NH(4)(+) ions. Even under the highly oxidizing condition, NO(2)(-) was much more likely to react with NH(4)(+) to form N(2) than being oxidized over the catalyst to NO(3)(-) as long as NH(4)(+) was available in solution.     

Hydrochemical Monitoring and Heavy Metal Contaminations at the Narim Mine Creek in the Sulcheon District, Republic of Korea

The Narim gold mine is located approximately 200km southeast of Seoul within the Sulcheon mineralised district in the Yeongnam massif, Korea. In this study, environmental geochemical analyses were undertaken for soil, sediment and water samples collected in April, September and November in 1998 from the Narim mine creek. The mine area consists mainly of granitic gneiss; however, mineral constituents of soil and sediment near the mine were mainly composed of quartz, feldspar, mica, amphibole, some pyrite and clay minerals. Also were found some pyrite, arsenopyrite, chalcopyrite, sphalerite, galena, malachite, goethite, various hydroxide and unidentified secondary minerals. Generally, high concentrations of heavy metals in the soil and sediment are correlated with a high proportion of secondary minerals. Hydrochemical compositions of water samples are characterised by relative significant enrichment of Na⁺+K⁺ and alkali metals in the ground water, whereas the surface and mine waters are relatively enriched in Ca²⁺+Mg²⁺ and heavy metals. Anion contents of the ground waters are typically enriched in HCO₃ ^–, NO₃ ^– and Cl^–, whereas the surface and mine waters are highly enriched in HCO₃ ^– and SO₄ ^2–. The pH and EC values of the surface water from the non-mine creek are relatively lower compared with those of the surface water around the mine and waste dump. The range of D and ¹⁸O values (d parameters) of the water samples are shown in distinct two groups for the April waters of 10.1–13.1, and for the November waters of 5.8–7.9, respectively. This range variation indicates that two group water were composed of distinct waters because of seasonal difference. Geochemical modelling showed that mostly heavy toxic metals may exist largely in the form of free metal (M²⁺) and metal-sulphate (MSO₄ ^2–), and SO₄ ^2– concentration influenced the speciation of heavy metals in the mine water. These metals in the ground water could be formed of CO₃ ^– and OH^– complex ions. Using a computer program, saturation indices of albite, calcite, dolomite in mostly surface water show undersaturated and progressively evolved toward the saturation state, however, ground and mine waters are nearly saturated. The gibbsite, kaolinite and smectite are supersaturated in the surface and ground water, respectively. Calculated water-mineral reaction and stabilities suggest that the weathering of silicate minerals may be stable kaolinite. The clay minerals of K-illite and Na-smectite will be transformed to more stable kaolinite owing to the continuous reaction.     

Biogas productivity of algal residues from bioethanol production

Journal of Material Cycles and Waste Management - The purpose of this study was to investigate biogas productivity of algal residues from bioethanol production. Pre-treatment based on enzyme was...     

Stabilization of Cu-contaminated army firing range soils using waste oyster shells

A stabilization/solidification (S/S) process was used to immobilize Cu in contaminated soils obtained from two army firing ranges sites (A and B) with total Cu concentrations of 520 and 380 mg/kg, respectively. Both waste oyster shells (WOS) and pretreated oyster shells (POS) were used to immobilize Cu in the contaminated soils. Waste oyster shells passing the #10 mesh and #20 mesh were used for the Sites A and B, respectively. WOS- and POS-treated soil samples cured for 28 days were evaluated for Cu leaching by the Korean Standard Leaching Test (KSLT) method. Slurry suspensions were prepared to investigate the Cu immobilization mechanism using X-ray powder diffraction (XRPD) and scanning electron microscopy (SEM) energy dispersive X-ray spectroscopy (EDX) analyses. The treatment results showed that the POS treatment was more effective than the WOS treatment of 28 days. For Site A, 10 wt% WOS and 3 wt% POS dosages were required to pass the Korean warning standard of 50 mg/kg, while 10 wt% WOS and 5 wt% POS dosages were required for the Site B treatment. The XRPD and SEM-EDX results showed that Cu immobilization was strongly linked to both CSH/CAH and ettringite. Overall, the POS treatment was effective at immobilizing the Cu in the contaminated soils, very likely due to its CaO content.     

Modeling toxic compounds from nitric oxide emission measurements

Determining the amount and rate of degradation of toxic pollutants in soil and groundwater is difficult and often requires invasive techniques, such as deploying extensive monitoring well networks. Even with these networks, degradation rates across entire systems cannot readily be extrapolated from the samples. When organic compounds are degraded by microbes, especially nitrifying bacteria, oxides or nitrogen (NO_x) are released to the atmosphere. Thus, the flux of nitric oxide (NO) from the soil to the lower troposphere can be used to predict the rate at which organic compounds are degraded. By characterizing and applying biogenic and anthropogenic processes in soils the rates of degradation of organic compounds. Toluene was selected as a representative of toxic aromatic compounds, since it is inherently toxic, it is a substituted benzene compound and is listed as a hazardous air pollutant under Section 12 of the Clean Air Act Amendments of 1990. Measured toluene concentrations in soil, microbial population growth and NO fluxes in chamber studies were used to develop and parameterize a numerical model based on carbon and nitrogen cycling. These measurements, in turn, were used as indicators of bioremediation of air toxic (i.e. toluene) concentrations. The model found that chemical concentration, soil microbial abundance, and NO production can be directly related to the experimental results (significant at P < 0.01) for all toluene concentrations tested. This indicates that the model may prove useful in monitoring and predicting the fate of toxic aromatic contaminants in a complex soil system. It may also be useful in predicting the release of ozone precursors, such as changes in reservoirs of hydrocarbons and oxides of nitrogen. As such, the model may be a tool for decision makers in ozone non-attainment areas.