Impacts of pH and ammonia on the leaching of Cu(II) and Cd(II) from coal fly ash

Many coal-fired power plants are implementing ammonia-based technologies to reduce NO(x) emissions. Excess ammonia in the flue gas often deposits on the coal fly ash. Ammonia can form complexes with many heavy metals and change the leaching characteristics of these metals. This research tends to develop a fundamental understanding of the ammonia impact on the leaching of some heavy metals, exemplified by Cu(II) and Cd(II), under different pH conditions. Batch results indicated that the adsorption is the main mechanism controlling Cu(II) and Cd(II) leaching, and high concentrations of ammonia (>5,000 mg/l) can increase the release of Cu(II) and Cd(II) in the alkaline pH range. Based on the chemical reactions among fly ash, ammonia, and heavy metal ion, a mathematical model was developed to quantify effects of pH and ammonia on metal adsorption. The adsorption constants (logK) of Cu(2+), Cu(OH)(+), Cu(OH)(2), and Cu(NH(3))(m)(2+) for the fly ash under investigation were respectively 6.0, 7.7, 9.6, and 2.9. For Cd(II), these constants were respectively 4.3, 6.9, 8.8, and 2.6. Metal speciation calculations indicated that the formation of less adsorbable metal-ammonia complexes decreased metal adsorption, therefore enhanced metal leaching.     

Isotope dilution analysis of polychlorinated biphenyls (PCBs) in transformer oil and global commercial PCB formulations by high resolution gas chromatography-high resolution mass spectrometry

Special polychlorinated biphenyls (PCBs) standards (native and isotope labeled) were analyzed by isotope dilution method using HRGC-HRMS. Multiple analysis of special PCBs standards by three different laboratories produced the relative response factors (RRFs) and relative standard deviations (RSDs %) was in the average of 0.979 and 3.86, respectively. Additionally, inter-laboratory analysis of various forms of transformer oil revealed the PCBs concentrations were in the following order; PCBs fortified transformer oil (940-1300 ng/g)>PCB polluted transformer oil (490-680 ng/g)>chemically degraded-transformer oil (480-490 ng/g) and PCBs free oil (ND-17 ng/g). Chemical degradation resulted in an order of magnitude decrease in the PCB concentrations. Specifically, higher chlorinated PCBs degraded into lower chlorinated PCBs. Also, composition of PCBs have been determined in PCB formulations from Japan (Kanechlor), Germany (Clophen), USA (Aroclor), Russia (Sovol) and Poland (Chlorofen). Major PCBs (24-PCB congeners) contributed 54-67%, 55-68%, 16-69%, 71% and 72% in Kanechlor, Clophen, Aroclor, Sovol and Chlorofen, respectively to total PCBs. The homologue pattern of Kanechlor, Aroclor and Clophen in technical fromulation was similar (e.g., Kanechlor-300 resembled to those of Clophen A-30 and Aroclor-1242). Furthermore, congener-specific distributions of major PCBs/dioxin-like PCBs and toxic equivalency quantities (TEQ) were calculated. Based on our tentative assumption calculations, cumulative production of five different technical PCB formulations, WHO-TEQ emission was estimated to be approximately 16.05 tons.     

Potential application of synchronous fluorescence spectroscopy to determine benzo[a]pyrene in soil extracts

Benzo[a]pyrene (BaP) is a significant environmental pollutant and rapid, accurate methods to quantify this compound in soil for both research and environmental investigation purposes are required. In this work, solvent extracts from five contrasting soils spiked with four different polycyclic aromatic hydrocarbons (PAHs) were rapidly analysed by using a synchronous fluorescence spectroscopy (SFS) method. The SFS method was validated using HPLC with ultraviolet detection. A good correlation for the quantification of BaP in soil extracts by the two methods was observed. The detection limit of the SFS method was 1.6 x 10(-9) g/ml in CTAB micellar medium (7.8 mmol/l). The work demonstrates that SFS has potential as a sensitive, accurate, rapid, simple and economic methodology and an efficient alternative to HPLC for fast confirmation and quantification of BaP in complex soil extracts.     

Production of activated carbons from waste tire--process design and economical analysis

The process design and economic analysis of process plants to produce activated carbons from waste tires and coal have been performed. The potential range of products from each process has been considered, namely for waste tire--pyro-gas, active carbon, carbon black and pyro-oil; for coal--pyro-gas and active carbons. Sensitivity analyses have been carried out on the main process factors; these are product price, production capacity, total production cost, capital investment and the tipping fee. Net present values for the two plants at various discount factors have been determined and the internal rates of return have been determined as 27.4% and 18.9% for the waste tire plant and the coal plant, respectively.     

Hydrogen-rich synthesis gas production from waste wood via gasification and reforming technology for fuel cell application

The purpose of this study was to establish a fuel process for an advanced power generation system in which hydrogen-rich synthesis gas, as the fuel for the molten carbonate fuel cell (MCFC), can be extracted from biomass via gasification and reforming technologies. Experiments on waste wood gasification were performed using a bench-scale gasification system. The main factors influencing hydrogen generation in the noncatalytic process and in the catalytic process were investigated, and temperature was identified as the most important factor. At 950°C, without employing a catalyst, hydrogen-rich synthesis gas containing about 54 vol% hydrogen was extracted from feedstock with appropriately designed operation parameters for the steam/carbon ratio and the equivalence ratio. However, by employing a commercial steam reforming catalyst in the reforming process, similar results were obtained at 750°C.     

Improving the TMDL Process Using Watershed Risk Assessment Principles

Ecological risk assessment (ERA) evaluates potential causal relationships between multiple sources and stressors and impacts on valued ecosystem components. ERAs applied at the watershed scale have many similarities to the place-based analyses that are undertaken to develop Total Maximum Daily Loads (TMDLs), in which linkages are established between stressors, sources, and water quality standards, including support of designated uses. TMDLs focus on achieving water quality standards associated with attainment of designated uses. In attempting to attain the water quality standard, many TMDLs focus on the stressor of concern rather than the ecological endpoint or indicators of the designated use that the standard is meant to protect. A watershed ecological risk assessment (WERA), at least in theory, examines effects of most likely stressors, as well as their probable sources in the watershed, to prioritize management options that will most likely result in meeting environmental goals or uses. Useful WERA principles that can be applied to TMDL development include: development and use of comprehensive conceptual models in the Problem Identification step of TMDLs; use of a transparent process for selecting Numeric Targets for TMDLs based on assessment endpoints derived from the management goal or designated use under consideration; analysis of co-occurring stressors likely to cause beneficial use impairment based on the conceptual model; use of explicit uncertainty analyses in the Linkage Analysis step of TMDL development; and frequent stakeholder interactions throughout the process. WERA principles are currently most applicable to those TMDLs in which there is no numeric standard and, therefore, indicators and targets need to be developed, such as many nutrient or sediment TMDLs. WERA methods can also be useful in determining TMDL targets in situations where simply targeting the water quality standard may re-attain the numeric criterion but not the broader designated use. Better incorporation of problem formulation principles from WERA into the TMDL development process would be helpful in improving the scientific rigor of TMDLs.     

Crusting of stored dairy slurry to abate ammonia emissions: pilot-scale studies

Storage of cattle slurry is a significant source of ammonia (NH3) emissions. Emissions can be reduced by covering slurry stores, but this can incur significant costs, as well as practical and technical difficulties. In this pilot-scale study, slurry was stored in small tanks (500 L) and the effectiveness of natural crust development for reducing NH3 emissions was assessed in a series of experiments. Also, factors important in crust development were investigated. Measurements were made of crust thickness and specially adapted tank lids were used to measure NH3 emissions. Slurry dry matter (DM) content was the most important factor influencing crust formation, with no crust formation on slurries with a DM content of <1%. Generally, crusts began to form within the first 10 to 20 d of storage, at which time NH3 emission rates would decrease. The formation of a natural crust reduced NH3 emissions by approximately 50%. The type of bedding used in the free stall barn did not influence crust formation, nor did ambient temperature or air-flow rate across the slurry surface. There was a large difference in crust formation between slurries from cattle fed a corn (Zea mays L.) silage-based diet and those fed a grass silage-based diet, although dietary differences were confounded with bedding differences. The inclusion of a corn starch and glucose additive promoted crust formation and reduced NH3 emission. The maintenance of a manageable crust on cattle slurry stores is recommended as a cost-effective means of abating NH3 emissions from this phase of slurry management.     

AN ANALYSIS OF REGION‐OF‐INFLUENCE METHODS FOR FLOOD REGIONALIZATION IN THE GULF‐ATLANTIC ROLLING PLAINS1

ABSTRACT: Region‐of‐influence (RoI) approaches for estimating stream flow characteristics at ungaged sites were applied and evaluated in a case study of the 50‐year peak discharge in the Gulf‐Atlantic Rolling Plains of the southeastern United States. Linear regression against basin characteristics was performed for each ungaged site considered based on data from a region of influence containing the n closest gages in predictor variable (PRoI) or geographic (GRoI) space. Augmentation of this count based cutoff by a distance based cutoff also was considered. Prediction errors were evaluated for an independent (split‐sampled) dataset. For the dataset and metrics considered here: (1) for either PRoI or GRoI, optimal results were found when the simpler count based cutoff, rather than the distance augmented cutoff, was used; (2) GRoI produced lower error than PRoI when applied indiscriminately over the entire study region; (3) PRoI performance improved considerably when Rol was restricted to predefined geographic subregions.     

90Sr, 137Cs and (239,240)Pu concentration surface water time series in the Pacific and Indian Oceans--WOMARS results

Under an IAEA's Co-ordinated Research Project "Worldwide Marine Radioactivity Studies (WOMARS)" 90Sr, 137Cs and (239,240)Pu concentration surface water time series in the Pacific and Indian Oceans have been investigated. The Pacific and Indian Oceans were divided into 17 latitudinal boxes according to ocean circulation, global fallout patterns and the location of nuclear weapons test sites. The present levels and time trends in radionuclide concentrations in surface water for each box were studied and the corresponding effective half-lives were estimated. For the year 2000, the estimated average 90Sr, 137Cs and (239,240)Pu concentrations in surface waters of the Pacific and Indian Oceans varied from 0.1 to 1.5 mBq/L, 0.1 to 2.8 mBq/L, and 0.1 to 5.2 microBq/L, respectively. The mean effective half-lives for 90Sr and 137Cs in surface water were 12+/-1 years for the North, 20+/-1 years for the South and 21+/-2 years for the Equatorial Pacific. For (239,240)Pu the corresponding mean effective half-lives were 7+/-1 years for the North, 12+/-4 years for the South and 10+/-2 years for the Equatorial Pacific. For the Indian Ocean the mean effective half-lives of 137Cs and (239,240)Pu were 21+/-2 years and 9+/-1 years, respectively. There is evidence that fallout removal rates before 1970 were faster than those observed during recent decades. The estimated surface water concentrations of 90Sr, 137Cs and (239,240)Pu in latitudinal belts of the Pacific and Indian Oceans for the year 2000 may be used as the average levels so that any new contribution from nuclear facilities, nuclear weapons test sites, radioactive waste dumping sites and from possible nuclear accidents can be identified.     

Trace Metal Concentrations in an Intensive Agricultural Watershed in British Columbia,Canada1

Abstract: Effects of agricultural intensification and a naturally occurring landslide of asbestos material upon water and sediment quality in a transboundary watershed were investigated. The water and sediments of the Sumas River watershed were analyzed for copper (Cu), zinc (Zn), chromium (Cr), and nickel (Ni) concentrations in 1993/1994 and 2003/2004 and differences within sites over time were examined. Based upon a review of the literature, Cu and Zn were used as indicators of agricultural impacts while Cr and Ni were used as indicators of impacts from an asbestos landslide. Animal unit equivalents (AUEs) were calculated on a per area basis as an indicator of livestock density using detailed statistical census data. Whatman #42 filtered metals, bioavailable metals, and sediment‐bound metals (in the <63 μm fraction) were determined at 22 sites along the mainstem and tributaries, including two reference sites. Temperature, pH, and dissolved organic carbon (DOC) were also measured. The bioavailable metal fraction was determined using the diffusive gradient thin film technique (DGT). Sediment‐bound results were compared with British Columbia’s Interim Sediment Quality Guidelines (ISQGs) and Severe Effects Levels (SELs). A Wilcoxon signed rank test was used to determine if the concentrations of metals changed significantly within sites between 1993/1994 and 2003/2004. Spearman rank correlation analysis was used to determine relationships between trace metals, water quality parameters, and AUEs/hectare. The results indicate that Cu and Zn levels in sediments increased significantly to concentrations above the ISQGs of 35.7 mg/kg and 123 mg/kg, respectively from 1993/1994 to 2003/2004 in streams, where associated land use was dominated by intensive agriculture. Higher AUEs/hectare were significantly correlated with greater bioavailable levels of Zn as well as higher sediment‐bound Zn concentrations. Neither Cu nor Cr were detected by the DGTs on any of the sampling occasions. The Cr and Ni sediment concentrations were highest in Swift Creek, the headwater tributary affected by the natural landslide of asbestos material, and decreased in the Sumas River downstream from the point of input. Cr and Ni concentrations have increased in the mid‐region of the Sumas River since 1993/1994, suggesting downstream movement of the asbestos material over time. DGT results indicated that bioavailable Zn is significantly positively correlated to sediment‐bound Zn and livestock density, and bioavailable Ni is significantly correlated to sediment‐bound Ni.