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The use of a high-FeO olivine rock as a redox buffer in a nuclear waste repository.

Due to the higher stability of the spent nuclear fuel (mainly composed of UO2) under reducing conditions, and in order to enhance the retention/retardation of some key radionuclides, the olivine rock from the Lovasjärvi intrusion has been proposed as a potential redox-active backfill-additive in deep high-level nuclear waste (HLNW) repositories. In this work, two different approaches have been undertaken in order to establish the redox buffer capacity of olivine rock: (1) The capacity of the rock to respond to changes in pH or pe has been demonstrated and the final (pH, pe) coordinates agree with the control exerted by the system Fe(II)/Fe(III). (2) The rate of consumption of oxygen has been determined at different pH values. These rates are higher than the ones reported in the literature for other solids, what would point to the possibility of using this rock as an additive to the backfill material in a HLNW.

Buffers↗

Numerical simulation of reactive processes in an experiment with partially saturated bentonite.

Bentonites are preferred materials for use as engineered barriers for high-level nuclear waste repositories. Simulation of geochemical processes in bentonite is therefore important for long-term safety assessment of those repositories. In this work, the porewater chemistry of a bentonite sample subject to simultaneous heating and hydration, as studied by Cuevas et al. [Cuevas, J., Villar, M., Fernández, A., Gómez, P., Martín, P., 1997. Porewaters extracted from compacted bentonite subjected to simultaneous heating and hydration. Applied Geochemistry 12, 473-481.], was assessed with a non-isothermal reactive transport model by coupling the geochemical software PHREEQC2 with the object-oriented FEM simulator GeoSys/RockFlow. Reactive transport modelling includes heat transport, two-phase flow, multicomponent transport and geochemical reactions in the liquid phase, i.e. ion exchange, mineral dissolution/precipitation and equilibrium reactions. Simulations show that the easily soluble minerals in bentonite determine the porewater chemistry. Temperature affects both two-phase flow and geochemical reactions. Porosity change due to dissolution/precipitation is low during the experiment. However, changes of the effective porosity caused by bentonite swelling can be very large. The simulated results agree well with the experimental data.

Bentonite↗

Mechanism for the destruction of carbon tetrachloride and chloroform DNAPLs by modified Fenton's reagent.

The destruction of a carbon tetrachloride DNAPL and a chloroform DNAPL was investigated in reactions containing 0.5 mL of DNAPL and a solution of modified Fenton's reagent (2M H2O2 and 5mM iron(III)-chelate). Carbon tetrachloride and chloroform masses were followed in the DNAPLs, the aqueous phases, and the off gasses. In addition, the rate of DNAPL destruction was compared to the rate of gas-purge dissolution. Carbon tetrachloride DNAPLs were rapidly destroyed by modified Fenton's reagent at 6.5 times the rate of gas purge dissolution, with 74% of the DNAPL destroyed within 24h. Use of reactions in which a single reactive oxygen species (hydroxyl radical, hydroperoxide anion, or superoxide radical anion) was generated showed that superoxide is the reactive species in modified Fenton's reagent responsible for carbon tetrachloride DNAPL destruction. Chloroform DNAPLs were also destroyed by modified Fenton's reagent, but at a rate slower than the rate of gas purge dissolution. Reactions generating a single reactive oxygen species demonstrated that chloroform destruction was the result of both superoxide and hydroxyl radical activity. Such a mechanism of chloroform DNAPL destruction is in agreement with the slow but relatively equal reactivity of chloroform with both superoxide and hydroxyl radical. The results of this research demonstrate that modified Fenton's reagent can rapidly and effectively destroy DNAPLs of contaminants characterized by minimal reactivity with hydroxyl radical, and should receive more consideration as a DNAPL cleanup technology.

Carbon Tetrachloride↗

Analysis of a gas-phase partitioning tracer test conducted in an unsaturated fractured-clay formation.

The gas-phase partitioning tracer method was used to estimate non-aqueous phase liquid (NAPL), water, and air saturations in the vadose zone at a chlorinated-solvent contaminated field site in Tucson, AZ. The tracer test was conducted in a fractured-clay system that is the confining layer for the underlying regional aquifer. Three suites of three tracers were injected into wells located 14, 24, and 24 m from a single, central extraction well. The tracers comprised noble gases (traditionally thought to be nonsorbing), alkanes (primarily water partitioning), perfluorides (primarily NAPL partitioning), and halons (both NAPL and water partitioning). Observations of vacuum response were consistent with flow in a fractured system. The halon tracers exhibited the greatest amount of retardation, and helium and the perfluoride tracers the least. The alkane tracers were unexpectedly more retarded than the perfluoride tracers, indicating low NAPL saturations and high water saturations. An NAPL saturation of 0.01, water saturation of 0.215, and gas saturation of 0.775 was estimated based on analysis of the suite of tracers comprising helium, perfluoromethylcyclohexane and dibromodifluoromethane, which was considered to be the most robust set. The estimated saturations compare reasonably well to independently determined values.

Air Movements↗

Quantification of potassium permanganate consumption and PCE oxidation in subsurface materials.

A series of laboratory scale batch slurry experiments were conducted in order to establish a data set for oxidant demand by sandy and clayey subsurface materials as well as to identify the reaction kinetic rates of permanganate (MnO(4)(-)) consumption and PCE oxidation as a function of the MnO(4)(-) concentration. The laboratory experiments were carried out with 31 sandy and clayey subsurface sediments from 12 Danish sites. The results show that the consumption of MnO(4)(-) by reaction with the sediment, termed the natural oxidant demand (NOD), is the primary reaction with regards to quantification of MnO(4)(-) consumption. Dissolved PCE in concentrations up to 100 mg/l in the sediments investigated is not a significant factor in the total MnO(4)(-) consumption. Consumption of MnO(4)(-) increases with an increasing initial MnO(4)(-) concentration. The sediment type is also important as NOD is (generally) higher in clayey than in sandy sediments for a given MnO(4)(-) concentration. For the different sediment types the typical NOD values are 0.5-2 g MnO(4)(-)/kg dry weight (dw) for glacial meltwater sand, 1-8 g MnO(4)(-)/kg dw for sandy till and 5-20 g MnO(4)(-)/kg dw for clayey till. The long term consumption of MnO(4)(-) and oxidation of PCE can not be described with a single rate constant, as the total MnO(4)(-) reduction is comprised of several different reactions with individual rates. During the initial hours of reaction, first order kinetics can be applied, where the short term first order rate constants for consumption of MnO(4)(-) and oxidation of PCE are 0.05-0.5 h(-1) and 0.5-4.5 h(-1), respectively. The sediment does not act as an instantaneous sink for MnO(4)(-). The consumption of MnO(4)(-) by reaction with the reactive species in the sediment is the result of several parallel reactions, during which the reaction between the contaminant and MnO(4)(-) also takes place. Hence, application of low MnO(4)(-) concentrations can cause partly oxidation of PCE, as the oxidant demand of the sediment does not need to be met fully before PCE is oxidised.

Aluminum Silicates↗

An overview and analysis of site remediation technologies.

This paper presents an analysis of the site restoration techniques that may be employed in a variety of contaminated site cleanup programs. It is recognized that no single specific technology may be considered as a panacea for all contaminated site problems. An easy-to-use summary of the analysis of the important parameters that will help in the selection and implementation of one or more appropriate technologies in a defined set of site and contaminant characteristics is also included.

Environmental Pollution↗

Natural materials for treatment of industrial effluents: comparative study of the retention of Cd, Zn and Co by calcite and hydroxyapatite. Part I: batch experiments.

This work explores the heavy metal retention capacity of materials developed from minerals that are abundant in nature, with low cost and minimum environmental impact. To accomplish this objective we have: (a) characterized commercial samples of calcite (CA) and hydroxyapatite (HAP)--including their surface properties (BET area, electrophoretic mobility, SEM, and X-ray energy dispersive spectroscopy); and, (b) qualified and quantified the interaction of Cd, Zn and Co with calcite (CaCO3) and hydroxyapatite [Ca5(PO4)3OH] through batch experiments, in a range of metal concentrations (4 Zn>Co and Cd>Zn approximately Co, respectively. Retention increased with pCa and pH and could be modeled by: (a) a non-ideal ion exchange mechanism (Me/Ca) for the adsorption of Cd, Zn and Co onto CA; and, (b) a mechanism of non-ideal ion exchange and specific adsorption (Me/Ca and identical with PO4O-Me) in the case of HAP. The pH dependence is indirect in CA and is related to its solubility changes (pCa increases with pH, and so does sorption of Cd, Zn and Co). Both materials, HAP and CA, can be used for heavy metal retention. The former has better performance for water treatment due to its greater efficiency for the retention of Cd, Zn and Co (over two orders of magnitude per gram of material) and its lower solubility in a wide range of pH (6<pH<9).

Adsorption↗

Evaluation of broiler litter transportation in northern Alabama, USA.

The profitability of using broiler litter as a source of crop nutrients was calculated using a phosphorus-consistent litter application rule. A ton of litter can cost effectively be transported up to 164 miles from the production facility. A cost-minimizing phosphorus-consistent transportation model developed to meet the nutrient needs of 29 counties in northern Alabama revealed that not all of the litter can be utilized in the region. The total cost increased when transportation of the litter out of the heavily surplus counties was prioritized. Total litter use was minimally affected by changes in chemical fertilizer prices. Shadow prices indicated the robustness of the model.

Animals↗

Cleaner production in the ammonia-soda industry: an ecological and economic study.

Five methods to reduce the negative influence of soda ash factories on the natural environment are presented: 1. obtaining calcium-magnesium phosphates by treating the suspension from raw brine purification with orthophosphoric acid (H(3)PO(4)), 2. production of precipitated chalk from soda processing waste, 3. production of gypsum and semi-brine, 4. desulphurisation of fume gases from the factory power plant, 5. utilization of distiller waste. The tests, accomplished on a laboratory scale, showed the high efficiency of these methods. Economic analysis has proved that only four out of the five presented processes can have a positive financial effect on soda ash factories, as well as being well justified economically. The value of two of the innovations presented is confirmed by their implementation in factories.

Ammonia↗

Sulfur, chromium, and selenium accumulated in Chinese cabbage under direct covers.

Currently, pollution of our agricultural soils and waters is increasing and is often associated with many human health ailments. Soils contaminated with low levels of heavy metals and other trace elements are frequently used for growing vegetable crops and in such a situation, these toxic contaminants often accumulate in the edible portions of these agricultural plants and thereby enter the human food chain. In 3 consecutive years of field experiments (1994-1996), two different crop-covering treatments--T (50 microm perforated polyethylene), and T2 (17 gm(-2) non-woven polypropylene)--were used to modify the environmental conditions for the growth of Chinese cabbage 'Nagaoka 50' [Brassica rapa L. (Pekinensis group)]. Open-air plots (T(0)) were used as controls. Analytical determinations of chromium (Cr), selenium (Se), two forms of sulfur (total-S and sulfate-S), and amino acids (Isoleucine, leucine, lysine, methionine, serine, threonine, and valine) were performed utilizing plant shoots for analysis. The T1 and T2 treated plants contained concentrations of lysine, methionine, serine, and threonine higher than in T(0). Under T1, the extent of Cr and Se removal in the field was more favorable. Direct covers could be used in contaminated agricultural zones for a variety of plant species, not just for use with those plants previously reported to be efficient at bio-accumulating toxic elements because the thermal effect created by the covers favors phytoextraction processes. However, it is clear that the accumulation of these toxic substances in the plants (Cr) would deem the plant material unsuitable for human consumption and use as animal fodder.

Amino Acids↗

An efficient technology to treat heavy metal--lead--contaminated soil by microwave radiation.

Microwave (MW) technology can be used to vitrify contaminated soil wastes and immobilize heavy metal ions in soils. More than 93% of the Pb(II)-contaminated soil was vitrified to a glass/ceramic formation after 30 min of MW radiation. In a 6-year study, the Pb(II) concentration of the vitrified soil in the leaching test was less than 1.0 mg/l, which is substantially below the USEPA regulatory limit of 5.0 mg/l.

Carbon↗

Treatment of lead mine waste by a Mozley multi-gravity separator (MGS).

Increasing environmental awareness and pressure is focusing attention on metal removal leading to the accelerated development of contaminated land reclamation technologies. The majority of wastes associated with base metal mining activity are fine tailings. Depending on the age and history of the metals, their characteristics vary considerably and each deposit requires individual characterisation. This paper investigates the treatment of lead-zinc mine wastes by the multi-gravity separator, a novel mineral processing machine. A laboratory study was carried out to find the most effective conditions using parameters such as drum angle and size fraction. A material and mass balance for the laboratory system has demonstrated that approximately 12% of the Pb can be removed in the form of concentrate with 12% Pb content.

Decontamination↗

Impacts of land use conversion on bankfull discharge and mass wasting.

Mass wasting and channel incision are widespread in the Nemadji River watershed of eastern Minnesota and northwestern Wisconsin. While much of this is a natural response to glacial rebound, sediment coring and tree ring data suggest that land use has also influenced these erosional processes. We characterized land use, inventoried mass wasting, surveyed stream channels and collected discharge data along segments of five streams in the Nemadji River watershed. Due to natural relief in this region, wetlands and agricultural lands are concentrated in the flatter terrain of the uplands of the Nemadji watershed, while forestland (coniferous or deciduous) is concentrated in the deeply incised (50-200% slope) stream valleys. Bankfull discharge was higher where forests had been converted from coniferous to deciduous forests and where there were fewer wetlands. Mass wasting increased exponentially with bankfull flows. While mass wasting was not correlated with forest type conversion and agricultural land use, it was negatively dependent upon wetland extent in headwater areas. Interactions between the spatial distribution of land use and terrain obfuscate any clear cause-and-effect relationships between land use, hydrology and fluvial processes.

Agriculture↗

Electroosmotic dewatering of dredged sediments: bench-scale investigation.

The Indiana Harbor (Indiana, USA) has not been dredged since 1972 due to lack of a suitable disposal site for dredged sediment. As a result of this, over a million cubic yards of highly contaminated sediment has accumulated in the harbor. Recently, the United States Army Corps of Engineers (USACE) has selected a site for the confined disposal facility (CDF) and is in the process of designing it. Although dredging can be accomplished rapidly, the disposal in the CDF has to be done slowly to allow adequate time for consolidation to occur. The sediment possesses very high moisture content and very low hydraulic conductivity, which cause consolidation to occur slowly. Consolidation of the sediment is essential in order to achieve adequate shear strength of sediments and also to provide enough air space to accommodate the large amount of sediment that requires disposal. Currently, it has been estimated that if a one 3-foot (0.9-m) thick layer of sediment was disposed of at the CDF annually, it would take approximately 10 years to dispose of all the sediment that is to be dredged from the Indiana Harbor. This study investigated the feasibility of using an electroosmotic dewatering technology to accelerate dewatering and consolidation of sediment, thereby allowing more rapid disposal of sediment into the CDF. Electroosmotic dewatering essentially involves applying a small electric potential across the sediment layer, thereby inducing rapid flow as a result of physico-chemical and electrochemical processes. A series of bench-scale electrokinetic experiments were conducted on actual dredged sediment samples from the Indiana Harbor to investigate dewatering rates caused by gravity alone, dewatering rates caused by gravity and electric potential, and the effects of the addition of polymer flocculants on dewatering of the sediments. The results showed that electroosmotic dewatering under an applied electric potential of 1.0VDC/cm could increase the rate of dewatering and consolidation by an order of magnitude as compared to gravity drainage alone. Amending the sediment with polymers at low concentrations (0.5-1% by dry weight) will enhance this dewatering process; however, the optimal polymer concentration and the cost-effectiveness of using polymers should be investigated further.

Acrylic Resins↗

Designing reverse-flow packed bed reactors for stable treatment of volatile organic compounds.

Reverse-flow packed bed reactors can be used to treat gaseous pollutants from chemical plants. This article describes the design and operation of a modified reverse-flow reactor (MRFR) which has a recuperator on each end of the reactor and a reaction zone in the middle. The recuperators have low thermal dispersion and the reaction zone has a high thermal dispersion, obtained by placing metal inserts into the bed, parallel with the gas flow. Performance of the MRFR during extended lean and rich conditions is determined with analytical analysis and compares well with numerical simulations of CO oxidation; however, the theory is expected to be useful for any reaction kinetics. A major advantage of this MRFR design is an extended time for the reactor to extinguish during lean conditions. This work also describes MRFR performance with internal reactor cooling, which can be used as a control mechanism to maintain reactor temperature for proper removal of volatile organic compounds.

Air Pollutants↗

Environmental regulation, productive efficiency and cost of pollution abatement: a case study of the sugar industry in India.

In this paper the input distance function is estimated for the Indian Sugar industry under alternative assumptions of weak and strong disposability of bad outputs. The estimated distance function is used to make the estimates of environmental efficiency, Malmquist productivity index and shadow prices of pollutants. The technical efficiency measure estimated under the assumption of weak disposability of bad outputs is utilized to test the Porter hypothesis. Marginal costs of pollution abatement functions are estimated for different pollutants of water. Pollutant specific taxes are computed using the tax-standards method.

Agriculture↗

Integrated treatment and recycling of stormwater: a review of Australian practice.

With the use of water approaching, and in some cases exceeding, the limits of sustainability in many locations, there is an increasing recognition of the need to utilise stormwater for non-potable requirements, thus reducing the demand on potable sources. This paper presents a review of Australian stormwater treatment and recycling practices as well as a discussion of key lessons and identified knowledge gaps. Where possible, recommendations for overcoming these knowledge gaps are given. The review of existing stormwater recycling systems focussed primarily on the recycling of general urban runoff (runoff generated from all urban surfaces) for non-potable purposes. Regulations and guidelines specific to stormwater recycling need to be developed to facilitate effective design of such systems, and to minimise risks of failure. There is a clear need for the development of innovative techniques for the collection, treatment and storage of stormwater. Existing stormwater recycling practice is far ahead of research, in that there are no technologies designed specifically for stormwater recycling. Instead, technologies designed for general stormwater pollution control are frequently utilised, which do not guarantee the necessary reliability of treatment. Performance modelling for evaluation purposes also needs further research, so that industry can objectively assess alternative approaches. Just as many aspects of these issues may have impeded adoption of stormwater, another impediment to adoption has been the lack of a practical and widely accepted method for assessing the many financial, social and ecological costs and benefits of stormwater recycling projects against traditional alternatives. Such triple-bottom-line assessment methodologies need to be trialled on stormwater recycling projects. If the costs and benefits of recycling systems can be shown to compare favourably with the costs and benefits of conventional practices this will provide an incentive to overcome other obstacles to widespread adoption of stormwater recycling.

Australia↗

Suitability of the vegetation types in Mexico's Tamaulipas state for the siting of hazardous waste treatment plants.

A land suitability study was carried out by applying a multiple-criteria technique to 12 different vegetation types in Mexico's Tamaulipas state to help select potentially suitable sites for hazardous waste treatment plants. Species richness, spatial distribution, and uniqueness were selected as the criteria for estimating a vegetation type's suitability. Using the analytical hierarchy process, we ranked and mapped vegetation types, then compared the results with rankings of the same vegetation types based only on their number of endemic species. The suitabilities of the various vegetation types were ordered in more or less the same way by both methods, except in two cases for which the results were very different. The method proved to be a useful tool despite the availability of only partial (mostly qualitative) information; under such circumstances, expert experience can be incorporated in the evaluation process to a limited degree. The technique described in this paper has a high potential to aid decisions when many opinions and options must be considered simultaneously.

Ecosystem↗