Modelling gas release event behaviour in hazardous waste tanks

Certain radioactive waste storage tanks at the United States Department of Energy Hanford facilities continuously generate gases as a result of radiolysis and chemical reactions. The congealed sludge in these tanks traps the gases beneath it and causes the level of the waste within the tanks to rise. The waste level continues to rise until the sludge loses its buoyancy and rolls over, changing places with fluid on top. During a rollover, the trapped gases are released, resulting in a sudden drop in the waste level. This is known as a gas release event (GRE). After a GRE, the waste re-congeals and gas again accumulates, leading to another GRE. We are interested in the time between consecutive GREs. Understanding the probabilistic behaviour of the time between consecutive GREs is important because the hydrogen and nitrous oxide gases released during a GRE are flammable and the ammonia that is released is a health risk. From a safety perspective, activity around such waste tanks should be halted when a GRE is imminent. With a credible probability model for the time between consecutive GREs, we can establish time windows in which waste tank research and maintenance activities can be safely performed. We discuss the application of non-linear time series models to this problem.     

Fishery Enhancement Reef Building Exercise

The constructive use of coal-fired power station waste products for building artificial reefs is being explored for the first time in the U.K. at present, the practice of sea dumping of raw pulverised fuel ash (PFA) from coal combustion is under review and the use of consolidated PFA blocks offers a possible alternative. the planned fitting of flue gas desulphurisation (FGD) plant in the U.K. will additionally produce large quantities of gypsum. to test the environmental compatability of such materials in marine structures, an experimental reef has been constructed off the central south coast of the U.K. Fifty tonnes of blocks made from different combinations of PFA, gypsum, FGD waste water sludge, cement and gravel using standard concrete as the control material, were deployed. the site selected is remote from prominent sea bed features in an area of flat sand with limited species variety.The preliminary studies leading to the licensing of this project included bioassay experiments with diatom cultures, field trials with test tiles and trace metal bioaccumulation studies the stages of consultation and licensing of the project are outlined.

Colonisation of the reef has been rapid, initially by shoaling fish, particularly by bib (Trisopterus luscus) then, within the first month, by representatives of the commercial crab and lobster species typical of the local natural rocky coast. After three months the epifauna and flora were well established. at this stage some 80 species of flora and fauna have been identified in association with the reef with no differentiation in colonisation apparent between the PFA/gypsum mixtures and the concrete control. the number of species far exceeds that of PFA powder dumping grounds. Analyses for heavy metal ions in the reef blocks after 2 months immersion have not shown any significant difference from the original composition.     

A chemical mechanism for dry deposition—the role of biogenic hydrocarbon (Terpene) emissions in the dry deposition of O3, SO2 and NOx in forest areas

Terpenes react quite rapidly with ambient ozone and lead via ozonides to highly oxidizing radicals and consecutive products forming aerosols. In the presence of SO₂ sulphur containing compounds, mainly as sulphate, are formed. By means of gas chromatography/mass spectrometry and by comparison with known spectra the main products of the reaction of ß‐pinene (as a model compound) with ozone and sulphur dioxide could be identified.

Reaction of terpenes with NO₃‐radicals, which build up in the atmosphere at night‐time, leads to the formation of organic nitrates that form aerosols. The kinetics as well as the products of the reaction between NO₃‐radicals and ß‐pinene have been studied by FTIR and MS.     

Sulphur isotope mass balance of dissolved sulphate ion in a freshwater dam reservoir

We show that sulphur isotopic composition can be a useful tool to discriminate between various sources of sulphate and a tool for better understanding of the sulphur cycling and mass balance. Our investigations, carried out in a dam reservoir, demonstrate differences in sulphur biogeochemistry between different seasons, caused by recharge water supply in spring and intensive sulphate reduction in summer. In the riverine-affected part of the reservoir δ³⁴S(SO₄ ²⁻) varied from 4.7 to 5.9‰ in spring, and from 4.1 to 4.6‰ in summer. In the lacustrine-affected part δ³⁴S(SO₄²⁻) varied from 4.0 to 5.0‰ in spring, and from 4.5 to 5.4‰ in summer. Diurnal variations of δ³⁴S(SO₄ ²⁻) were negligible as compared to seasonal variations.     

Products of denitrification by a marine bacterium as revealed by gas chromatography

Gas chromatography was used to analyse the gases released by growing cultures of the denitrifying marine bacterium Pseudomonas perjectomarinus. When nitrate was provided as final oxidant, CO₂ was the first detectable gas released. Following the peak rate of release of CO₂ at approximately 16 h, N₂ liheration began and peaked at 30 h. When N₂O was provided as terminal oxidant, CO₂ and N₂ release began within a few hours and the rate of liberation of both increased for 45 to 50 h before leveling. Cell-free extracts of bacteria from denitrifying cultures of P. perfectomarinus were incubated anaerobically with nitrate, malic acid and electron transfer cofactors provided, and the gases in the atmosphere above the reaction mixtures were analysed. NO was found to be present transiently, and N₂O was discerned after prolonged incubation. The applicability of gas chromatography to analyses of marine ecosystems and the need for better means of sampling the atmosphere above enzymatic reaction mixtures were disoussed.     

Sulphur compounds—their environmental aspect and their elimination from waste water

The sulphur content of domestic waste water is similar to its phosphorus and nitrogen content. In conventional treatment processes sulphur compounds are converted to sulphate, thus all reaching the recipients and the oceans. In the aquatic metabolic cycle sulphate then acts as a catalyst towards anaerobiosis. Therefore, besides its efforts for removal of other nutrients, waste water technology should look for possibilities of minimizing the discharge of sulphurous effluents into the water course. Here, a new treatment process for sulphur elimination is introduced, the Root Zone method.     

Fishery Enhancement Reef Building Exercise

The constructive use of coal-fired power station waste products for building artificial reefs is being explored for the first time in the U.K. at present, the practice of sea dumping of raw pulverised fuel ash (PFA) from coal combustion is under review and the use of consolidated PFA blocks offers a possible alternative. the planned fitting of flue gas desulphurisation (FGD) plant in the U.K. will additionally produce large quantities of gypsum. to test the environmental compatability of such materials in marine structures, an experimental reef has been constructed off the central south coast of the U.K. Fifty tonnes of blocks made from different combinations of PFA, gypsum, FGD waste water sludge, cement and gravel using standard concrete as the control material, were deployed. the site selected is remote from prominent sea bed features in an area of flat sand with limited species variety.The preliminary studies leading to the licensing of this project included bioassay experiments with diatom cultures, field trials with test tiles and trace metal bioaccumulation studies the stages of consultation and licensing of the project are outlined.

Colonisation of the reef has been rapid, initially by shoaling fish, particularly by bib (Trisopterus luscus) then, within the first month, by representatives of the commercial crab and lobster species typical of the local natural rocky coast. After three months the epifauna and flora were well established. at this stage some 80 species of flora and fauna have been identified in association with the reef with no differentiation in colonisation apparent between the PFA/gypsum mixtures and the concrete control. the number of species far exceeds that of PFA powder dumping grounds. Analyses for heavy metal ions in the reef blocks after 2 months immersion have not shown any significant difference from the original composition.     

Emissionen und Minderungspotential von HFKW, FKW und SF6 in Deutschland

The greenhouse gases subject to emission reduction commitments under the UN Climate Convention include the fluorinated compounds sulphur hexafluoride (SF₆), perfluorocarbons (PFCs) and hydrofluorocarbons (HFCs). The present study projects the emissions of these gases in Germany over the 1995–2010 period, with and without additional emission abatement efforts In the business-as-usual scenario, total emissions of the three fluorinated gases rise over the 1995–2010 period from 11,1 to 27.4 million tonnes CO₂ equivalent. This rise is attributable to 72% to HFCs, used above all for refrigeration and stationary air-conditioning, for mobile air-conditioning, for blowing extruded polystyrene (XPS) foam and for one-component polyurethane (PU) foam. Soundproof glazing is the largest SF₆ emission sector. Most PFC emissions come from semiconductor manufacturing and aluminium smelting. The reduction scenario does not achieve a stabilisation of fluorinated gas emissions either. The rate of growth is only slowed, with 11.1 million tonnes CO₂ equivalent in 1995 growing to 14.9 million in 2010. The measures proposed to attenuate emissions growth are: mandatory equipment maintenance in refrigeration and stationary air-conditioning, refrigerant substitution of HFCs by CO₂ in mobile air-conditioning, partial HFC substitution by CO₂ in XPS foam blowing, 95% HFC substitution by flammable hydrocarbons in one-component PU foam. Complete SF₆ phase-out is considered to be feasible in soundproof glazing. The PFC emissions of the semiconductor industry can be cut by 85% by new chamber cleaning technologies.     

Evaluation of acid production potential of mining waste materials

The formation of acidic effluents from mining waste materials is discussed and the chemisry involved explained. The bacteriumThiobacillus ferrooxidans plays an important role in acid production due to its ability to rapidly oxidize reduced forms of iron and sulphur which can result in the generation of H₂SO₄. The sulphide mineral pyrite (FeS₂), often present in waste materials, is generally recognized as the chief source of acid mine drainage.A small-scale test procedure has been developed which rapidly evaluates a waste material's capability to produce an acidic effluent. If the material is assessed as a potential acid producer, then scale-up testing procedures are available which can be used to simulate the characteristics of the effluents produced from a commercial-size waste dump.During periods of little rainfall, localized biological activity may occur in wet areas of a waste dump, resulting in possible accumulation of soluble pollutants. The length of these dry periods greatly affects effluent characteristics during subsequent rainfalls.     

Stability of a Coal Waste Artificial Reef

The feasibility of using U.K. coal-fired power station waste materials for artificial reef production is being examined. in June, 1989, an experimental artificial reef was constructed in Poole Bay, off the central south coast of the U.K., using three different mixtures of pulverised fuel ash (PFA), flue gas desulphurisation (FGD) gypsum and slurry, stabilized with cement and formed into blocks. Fifty tonnes of 40 × 20 × 20 cm blocks were formed into eight conical reef units replicating three different PFA/gypsum mixtures and one concrete control. the reef structure is 10m below chart datum on a flat sandy sea-bed.

Combustion of coal concentrates the heavy metal content in the resultant ash. the purpose of stabilization of the ash as blocks is twofold: to immobilize heavy metals (or other components) and to provide hard substratum for the attachment of organisms. to examine the effectiveness of this stabilization and hence the environmental compatibility of the block materials, heavy metal (Cd, Cr, Cu, Pb, Mn, Ni, Zn) content of the blocks has been monitored routinely over two years, to determine leaching rates. Sectional profiles indicate partial replacement of calcium content by magnesium. Associated with this there has also been some redistribution of heavy metals. Only in the case of cadmium has there been a detectable loss from the surface of blocks. Chromium and manganese concentrations appear to have increased. the metal content of the reef epibiota (including ascidians, Ascidia mentula; hydroids, Halecium spp.; bryozoans, Bugula spp. and red algae) growing on the ash blocks has been compared to that of epibiota attached to the concrete controls and surrounding sea-bed. to date no evidence of excess bioaccumulation of metals has been detected.

The physical integrity of the ash reef blocks has been maintained. There is evidence that the blocks are increasing in compressive strength.

An indication of the fishery enhancement potential of the experimental structure is given by the presence of eight commercially fished species (crustaceans and molluscs) including lobsters (Homarus gammarus).     

Effluents and residues from industrial sites for carbon dioxide capture: a review

The adverse effects of climate change calls for the rapid transformation of manufacturing processes to decrease the emissions of carbon dioxide. In particular, a lower carbon footprint can be achieved by capturing carbon dioxide at the site of emission. Here we review the use of industrial effluents, waste and residues to capture carbon dioxide. Waste include steelmaking slag, municipal solid waste incinerator ashes, combustion fly ash, black liquor, paper mill waste, mining waste, cement waste, construction and demolition waste, waste from the organic industry, and flue gas desulfurization gypsum waste. Capture capacities range from 2 to 800 kg of carbon dioxide per ton of waste, depending on processes, waste type and conditions. Cement waste and flue gas desulfurization gypsum waste show the highest capture capacity per ton of waste.

     

Optimal sequestration of carbon dioxide and phosphorus in soils by gypsum amendment

Gypsum has been applied as a natural fertilizer and soil amendment for centuries in agriculture for providing crop nutrients such as Ca and S, and for improving soil physical properties. Recently, gypsum has been tested for sequestrating CO₂ from the air and for capturing soluble phosphates in the soil, through formation of insoluble calcium phosphates and carbonates. However, the environmental factors controlling these sequestration processes have not been systemically studied. Here, we calculate optimal conditions of sequestration using chemical equilibrium modeling. Our results show that CO₂ carbonation is effective at pH higher than 8.5 at atmospheric concentration. The removal of P is higher than 80 % for pH higher than 6.4, when Ca and P are at stoichiometric ratio. Also, placement of gypsum in subsoil is more effective for CO₂ capture than applying it on soil surface since soil pores often contain higher concentrations of CO₂ due to the soil respiration process. Overall, increases in medium pH, gypsum application rate, or CO₂ partial pressure can increase the effectiveness of the amendment.     

Cytotoxic activity of spark‐decomposed sulfur hexafluoride and analysis of cytotoxic contributions of individual spark decomposition products†

Sulfur hexafluoride decomposed by electrical sparks has been found to by cytotoxic to hamster cells when tested in an in vitro cell survival assay, while SF₆ shows no cytotoxic activity. Chemical analysis of spark‐decomposed SF₆ has identified and quantified the following compounds: SOF₂, SO₂F₂, SF₄, SOF₄, SiF₄, SO₂ and HF. Each of these gases, at concentration ranges expected in spark‐decomposed SF₆, were tested for cytotoxic activity toward hamster cells. Of the gases showing cytotoxic activity, SO₂F₂ and SOF₄ were similar in activity, as were SOF₂ and SF₄, while the behavior of SiF₄ was different from the rest. None of these individual gases, at concentrations expected in spark‐decomposed SF₆, has sufficient cytotoxic activity to account for the cytotoxic effect of spark‐decomposed SF₆ observed in our assay system. A four‐component mixture of some of the gases enumerated above (at concentrations overestimating their abundance in spark‐decomposed SF₆) was much less cytotoxic than the spark‐decomposed SF₆ gas. A mathematical simulation of the cytotoxic activity of a mixture of gases at concentrations found in spark‐decomposed SF₆ was made, assuming independent cytotoxic effects from each component. The simulated cytotoxic effect thus computed was less than that seen in spark‐decomposed SF₆. Since individual components or mixtures of the major decomposition products do not account for the observed biological activity of spark‐decomposed SF₆, this suggests there may be one or more components, present in the spark‐decomposed gas at very low concentrations, which may have a very strong cytotoxic activity.     

Oxidation of sulphite originating from flue gas desulphurization waste in soil

The rate of catalyzed oxidation of sulphite originating from flue gas desulphurization (FGD) waste was studied under varying conditions. The pH dependence was examined in aqueous solution at the pH range of 5 to 8, the effect of soil moisture was studied in sieved soil of different moisture contents, and the oxidation of sulphite to a soil as FGD waste, was measured at different depths in a field experiment. The experiments that the half-lives of sulphite in aqueous solution were between 0.5 and 2 hours and that the oxidation rate was highest at the lowest pH. In sieved soil the half-lives of sulphite were in the range of 3 to 20 days with the oxidation rate at the highest moisture content, indication that oxygen availability was the limiting factor. The slowest decrease of the sulphite concentration was found at a soil depth of 8–10 cm which was the where the highest background concentration of sulphite was found in control plots, too.Environmental Geochemistry and Health, 1988,10(1), 26–30     

Sekundärrohstoffe aus Abfall-Lösungen

Every year about 40 000 m³ of waste solutions from photographic fixing and developing processes are produced in Germany. A new method of reclaiming some base chemicals (silver, fixing salt, gypsum and ammonia) from these solutions has been developed for black and white photographic processes. The remaining waste water has a low COD-value and low concentration of dissolved salts. This method is considered further to develop the state-of-the-art technique and is economically feasible.     

Control of hydrogen sulfide emissions using autotrophic denitrification landfill biocovers: engineering applications

Hydrogen sulfide (H₂S) emitted from construction and demolition waste landfills has received increasing attention. Besides its unpleasant odor, longterm exposure to a very low concentration of H₂S can cause a public health issue. In the case of construction and demolition (C&D) waste landfills, where gas collection systems are not normally required, the generated H₂S is typically not controlled and the number of treatment processes to control H₂S emissions in situ is limited. An attractive alternative may be to use chemically or biologically active landfill covers. A few studies using various types of cover materials to attenuate H₂S emissions demonstrated that H₂S emissions can be effectively reduced. In this study, therefore, the costs and benefits of H₂S-control cover systems including compost, soil amended with lime, fine concrete, and autotrophic denitrification were evaluated. Based on a case-study landfill area of 0.04 km², the estimated H₂S emissions of 80900 kg over the 15-year period and costs of active cover system components (ammonium nitrate fertilizer for autotrophic denitrification cover, lime, fine concrete, and compost), ammonium nitrate fertilizer is the most cost effective, followed by hydrated lime, fine concrete, and yard waste compost. Fine concrete and yard waste compost covers are expensive measures to control H₂S emissions because of the large amount of materials needed to create a cover. Controlling H₂S emissions using fine concrete and compost is less expensive at landfills that provide on-site concrete recovery and composting facilities; however, ammonium nitrate fertilizer or hydrated lime would still be more cost effective applications.     

Radon Exhalation Rate of Some Building Materials Used in Egypt

Indoor radon has been recognized as one of the health hazards for mankind. Common building materials used for construction of houses, which are considered as one of the major sources of this gas in indoor environment, have been studied for exhalation rate of radon. Non-nuclear industries, such as coal fired power plants or fertilizer production facilities, generate large amounts of waste gypsum as by-products. Compared to other building materials waste gypsum from fertilizer production facilities (phosphogypsum) shows increased rates of radon exhalation. In the present, investigation solid state alpha track detectors, CR-39 plastic detectors, were used to measure the indoor radon concentration and the radon exhalation rates from some building materials used in Egypt. The indoor radon concentration and the radon exhalation rate ranges were found to be 24–55 Bq m⁻³ and 11–223 mBq m⁻² h⁻¹, respectively. The effective dose equivalent range for the indoor was found 0.6–1.4 mSv y⁻¹. The equilibrium factor between radon and its daughters increased with the increase of relative humidity.     

Fume emissions during gas metal arc welding

The control of exposure to welding fumes is of increasing importance in promoting a healthy, safe and productive work environment. This article describes the effects of shielding gas composition on the amount and composition of welding fumes produced during gas metal arc welding (GMAW). The amount of fumes generated during welding was measured for steady current over a range of wire-feed speeds and arc voltages using the standard procedures contained in ANSI/AWS F1.2 [American Welding Society. ANSI/AWS F1.2. Laboratory method for measuring fume generation rates and total fume emission of welding and allied processes. Miami, Florida; 1992]. Results of these measurements show that the fume formation rates (FFRs) increase with CO₂ and O₂ in the shielding gas mixture. The lowest FFRs were obtained with the mixtures of Ar?+?2%CO₂ and Ar?+?3%CO₂?+?1%O₂. The highest FFRs were obtained with the mixtures of Ar?+?18%CO₂ and Ar?+?5%CO₂?+?4%O₂. The welding fumes contains mainly iron, manganese, silicon, titanium and sodium under oxide forms. The fume cluster particles have dimensions between 0.5 and 2?µm. The FFR was found to be governed by the transfer modes of molten metal, i.e. the current intensity and arc voltage, as well as by the shielding gas mixtures composition. Thus these parameters have to be taken into consideration before designing a welding process. Whenever possible, users of GMAW should use the lowest current intensity. However, when this is not possible, due to the constraints of process productivity, welders should use higher currents, but with Ar?+?2%CO₂ and Ar?+?3%CO₂?+?1%O₂ shielding mixtures, which will lead to smaller fume emissions.     

Aktuelle und künftige Emissionen treibhauswirksamer fluorierter Verbindungen in Deutschland

The fluorinated compounds sulphur hexafluoride (SF₆), perfluorocarbons (CF₄, C₂F₆) and hydrofluorocarbons (HFCs) are atmospheric trace gases with extremely high global warming potentials (GWP). The study examines the real emissions of these compounds in Germany between 1990 and 1995, and develops projections for the years up to 2020. These projections indicate that annual perfluorocarbon releases will drop between the years 1990 and 2000 from 335 t/34 t to 100 t/10 t due to automation measures at the main source (aluminium smelting). Sulphur hexafluoride emissions, however, will remain in the range between 200 and 300 t per annum until the year 2020. By far the largest emitters are car tyres and sound-insulation glazing, non-electrical swithgear, the latter being relatively well sealed and linked to management and reprocessing concepts for used gas. As concerns hydrofluorocarbons which have only been used since 1990 with the specific intention of substituting chlorofluorocarbons (CFCs), an increasing degree of CFC substitution in stationary and mobile refrigeration technology, in canned PUR foams and in asthma sprays must be expected to lead to steeply rising emissions to levels exceeding 9,700 t/a from the year 2007 onwards, if halogen-free alternatives are not used more strongly. Assuming these trends, the cumulative emissions of the stated fluorinated compounds will correspond to a global warming impact of 25 million t CO₂ (GWP time horizon: 100 years) by the year 2020.     

The use of35S to study sulphur cycling in forests

Estimates of the atmospheric deposition of sulphur compounds to forests can be made from measurements of throughfall and stemflow below the forest canopy if internal cycling of sulphur can be neglected. The use of³⁵SO4 as a tracer isotope to study movement of sulphate from the soil to the tree and subsequent leaching by rain is described, and illustrated by reference to a field experiment in a Scots pine forest. Application of 1.85 GBq of³⁵SO4 to an area of 35 m² of the forest floor resulted in measurable activity in both foliage and throughfall. Activity in foliage continued to increase through the winter after application in June. Activity in throughfall was initially high (20 Bq S mg⁻¹), then fell to a steady value (<2 Bq S mg⁻¹) from August onwards. There was good spatial correlation between activity in the canopy and in throughfall below canopy. The temporal changes showed that complete and rapid equilibration of the isotope with the pool of sulphur in the canopy could not be safely assumed. Laboratory experiments with excised shoots demonstrated a much smaller specific activity (Bq mg⁻1 S) in leached sulphate than in the whole needles. Nevertheless, leaching contributed only a small proportion (<15%) of the sulphate in net throughfall (throughfall + stemflow − rain), except during the period of needle expansion, which coincided with application of the isotope. The results suggest that the errors involved in neglecting internal cycling are of the same order as the uncertainties with which sulphur deposition in throughfall and stemflow can be measured. Such measurements may therefore be used to estimate sulphur deposition to forests with uncertainties comparable to those of current methods based on micrometeorological methods.