Effect of reducing conditions on sludge melting process

The objective of this study was to compare the effects of CO/CO(2) reducing conditions with those of air oxidizing conditions on the pouring temperature of the sludge melting process and the heavy metal leachability of the resultant sludge slag. Synthetic sludge ash composed of SiO(2), CaO and Al(2)O(3), as well as sewage sludge ash generated from a laboratory incinerator was employed. The experimental results indicated that the pouring temperatures are significantly reduced under the reducing conditions of CO/CO(2), or 24 and 77 degrees C lower than under air conditions for synthetic and sludge ash, respectively. The heavy metal leaching tests further indicate lower heavy metal concentrations present in the leachate under the reducing conditions, notably an order of magnitude lower in Zn. However, X-ray diffractogram indicates similar peaks for these two slags produced under different conditions.     

Laboratory studies of dissipation of 14C‐DDT from soil and plywood surfaces

Abstract

The effects of temperature and solar radiation on dissipation of ¹⁴C‐p,p'‐DDT from a latosol soil were studied under laboratory conditions. Volatilization was measured by trapping organic volatiles during 6 weeks and was found to increase with rise of temperature from 3.8% of initial amount at ambient temperature to 5.9% at 45°C.

Studies on the effect of solar radiation using quartz tubes under sterilized and non‐sterilized conditions have shown that volatilized organics were highest in quartz tubes, with soil microflora presumably playing a very minor role in volatilization. Mineralization was shown to be low in sterilized systems and highest in non‐sterilized quartz systems. Studies on binding suggest that soil bioactivity may be involved in the formation of a portion of the bound residue. These laboratory experiments seem to support data from the field, where it is maintained that volatilization is a major mechanism for dissipation. Degradation in soil and to a lesser extent solar irradiation contribute also substantially to the dissipation mechanisms. Radiocarbon dissipated from plywood surfaces under indoor conditions in a biphasic fashion. Loss of 50% occurred after 5.5 weeks while the remainder dissipated at a very slow rate.     

Uptake of terbuthylazine and its medium polar metabolites into maize plants

The uptake of terbuthylazine and its medium polar metabolites into maize plants under outdoor conditions is investigated. For this purpose, a dynamical fate model consisting of soil, plant and air is developed. The model calculations are compared with experimental results of outdoor lysimeter tests, carried out with¹⁴C-labelled herbicide applied to sandy agricultural soil at a single application rate of 890 g/ha. Approximately 0.3 % of the applied activity remains in all the plants after the vegetation period. The model predicts that about three times that amount is volatilized from the plants into the air. Activity uptaken from soil and volatilized from plant surface into air is predominately associated with metabolites. During the whole vegetation period the fraction of unchanged terbuthylazine in the plants is very small (less than 1 % of the extractable activity).     

Studies of the effects of temperatures and solar radiation on volatilization,mineralization and binding of 14c‐DDT in soil under laboratory conditions

Abstract

The effects of temperatures and solar radiation on the dissipation of ¹⁴C‐p,p'‐DDT from a loam soil was studied by quantifying volatilization, mineralization and binding. The major DDT loss occurred by volatilization, which was 1.8 times more at 45^oC than at ambient temperature (30°C). Mineralization of DDT slowly increased with time but it decreased slightly with increase in temperature. Binding of DDT to soil was found to be less at higher temperatures (35 and 45°C) as compared to ambient temperature. Degradation of DDT to DDE was faster at higher temperatures.

Exposure of non‐sterilized and sterilized soils treated with ¹⁴C‐DDT to sunlight in quartz and dark tubes for 6 weeks resulted in significant losses. Volatilization and mineralization in quartz tubes were more as compared to dark tubes. The volatilized organics from the quartz tubes contained larger amounts of p,p'‐DDE than the dark tubes. Further, higher rates of volatilization were found in non‐sterilized soils than in sterilized soils. The results suggest that faster dissipation of DDT from soil under local conditions relates predominantly to increased volatilization as influenced by high temperature and intense solar radiation.     

Study of the SRF-derived ashes melting behavior and the effects generated by the optimization of their composition on the furnaces energy efficiency in the incineration plants

As regards the incineration process of the urban solid waste, the composition correct management allows not only the valorization of precise civil and industrial groups of waste as alternative fuels but also a considerable increase of the furnace work temperature leading to a remarkable improvement of the related energy efficiency. In this sense, the study of the melting behavior of ashes deriving from several kinds of fuels that have to be processed to heat treatment is really important. This approach, indeed, ensures to know in depth the features defining the melting behavior of these analyzed samples, and as a consequence, gives us the necessary data in order to identify the best mixture of components to be incinerated as a function of the specific working temperatures of the power plant. Firstly, this study aims to find a way to establish the softening and melting temperatures of the ashes because they are those parameters that strongly influence the use of fuels. For this reason, in this work, the fusibility of waste-derived ashes with different composition has been investigated by means of the heating microscope. This instrument is fundamental to prove the strict dependence of the ashes fusion temperature on the heating rate that the samples experienced during the thermal cycle. In addition, in this work, another technological feature of the instrument has been used allowing to set an instantaneous heating directly on the sample in order to accurately reproduce the industrial conditions which characterize the incineration plants. The comparison between the final results shows that, in effect, the achievement of the best performances of the furnace is due to the a priori study of the melting behavior of the single available components.     

A mass balance study of the phytoremediation of perchloroethylene-contaminated groundwater

A mass balance study was performed under controlled field conditions to investigate the phytoremediation of perchloroethylene (PCE) by hybrid poplar trees. Water containing 7–14 mg L^?1 PCE was added to the test bed. Perchloroethylene, trichloroethylene, and cis-dichloroethylene were detected in the effluent at an average of 0.12 mg L^?1, 3.9 mg L^?1, and 1.9 mg L^?1, respectively. The total mass of chlorinated ethenes in the water was reduced by 99%. Over 95% of the recovered chlorine was as free chloride in the soil, indicating near-complete dehalogenation of the PCE. Transpiration, volatilization, and accumulation in the trees were all found to be minor loss mechanisms. In contrast, 98% of PCE applied to an unplanted soil chamber was recovered as PCE in the effluent water or volatilized into the air. These results suggest that phytoremediation can be an effective method for treating PCE-contaminated groundwater in field applications.     

Vaporization of heavy metals during thermal treatment of model solid waste in a fluidized bed incinerator

This paper investigated the volatilization behavior of heavy metals during thermal treatment of model solid waste in a fluidized bed reactor. Four metal chlorides (Cd, Pb, Cu and Zn) were chosen as metal sources. The influence of redox conditions, water and mineral matrice on heavy metal volatilization was investigated. In general, Cd shows significant vaporization especially when HCl was injected, while Cu and Pb vaporize moderately and Zn vaporization is negligible. Increasing oxygen concentration can lower heavy metal vaporization. Heavy metal interactions with the mineral matter can result in the formation of stable metallic species thus playing a negative effect on their behavior. However, HCl can promote the heavy metal release by preventing the formation of stable metallic species. The chemical sorption (either physical or chemical) inside the pores, coupled with the internal diffusion of gaseous metal species, may also control the vaporization process. With SO₂ injected, Cd and Pb show a higher volatility as a result of SO₂ reducing characteristics. From the analysis, the subsequent order of heavy metal volatility can be found: Cd > Cu ? Pb ? Zn.     

城市生活垃圾并流竖炉焚烧模拟实验研究

气化熔融焚烧技术能够避免重金属和二恶英的二次污染，被公认为实现零排放和环境友好型的焚烧方法。在这样的背景下提出了生活垃圾并流竖炉气化熔融焚烧工艺。该工艺以竖炉为气化熔融主体设备，垃圾料层与助燃空气在炉内都是至上而下并流流动，从而使垃圾热解气化产生的可燃气体在竖炉下部完全燃烧，以提供灰渣熔融耗热。并流竖炉热态模拟试验表明，并流时垃圾料层中各点的温度明显高于逆流情况，并流时产生的CO₂量明显高于逆流情况。因此说并流竖炉更适合气化熔融焚烧工艺的要求。     

Destruction of polychlorinated naphthalenes by a high-temperature melting treatment (GeoMelt process)

A series of treatment experiments were carried out to evaluate the applicability of a high-temperature melting treatment (GeoMelt process) to the destruction of polychlorinated naphthalene (PCN) formulation. We started with 10-kg-scale experiments in which a small melting furnace was used and then scaled up to a 1-t-scale experiment in which a melting furnace that resembled an actual treatment system was used. These runs were evaluated whether destruction efficiency (DE) of total PCNs was more than 99.999 % and whether concentrations of PCNs and polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDDs/DFs) in vitrified materials, emission gas, and scrubber water were below the target levels. Because DE values and the target levels of PCNs and PCDDs/DFs in these runs were satisfactory, then we carried out a demonstrative experiment using the actual treatment system and confirmed destruction of PCNs. Based on good results of the demonstrative experiment, stock of PCN formulation was successfully treated continuously.     

Characterization of spent nickel–metal hydride batteries and a preliminary economic evaluation of the recovery processes

Valuable metal materials can be recovered from spent nickel–metal hydride (NiMH) batteries. However, little attention has been paid to the metal compositions of individual components of NiMH batteries, although this is important for the selection of the appropriate recycling process. In this study, NiMH batteries were manually disassembled to identify the components and to characterize the metals in each of these. A preliminary economic analysis was also conducted to evaluate the recovery of valuable metals from spent NiMH batteries using thermal melting versus simple mechanical separation. The results of this study show that metallic components account for more than 60% of battery weight. The contents of Ni, Fe, Co, and rare earth elements (REEs) (i.e., valuable metals of interest for recovery) in a single battery were 17.9%, 15.4%, 4.41%, and 17.3%, respectively. Most of the Fe was in the battery components of the steel cathode collector, cathode cap, and anode metal grid, while Ni (>90%) and Co (>90%) were mainly in the electrode active materials (anode and cathode metal powders). About 1.88 g of REEs (Ce, La, and Y) could be obtained from one spent NiMH battery. The estimated profits from recovering valuable metals from spent NiMH batteries by using thermal melting and mechanical processes are 2,329 and 2,531 USD/ton, respectively, when including a subsidy of 1,710 USD/ton. The findings of this study are very useful for further research related to technical and economic evaluations of the recovery of valuable metals from spent NiMH batteries. Implications: The spent nickel–metal hydride (NiMH) batteries were manually disassembled and their components were identified. The metals account for more than 60% of battery weight, when Ni, Fe, Co, and rare earth elements (REEs) were 17.9%, 15.4%, 4.41%, and 17.3%, respectively, in a single battery. The estimated profits of recovering valuable metals from NiMH batteries by using thermal melting and mechanical processing are 2,329 and 2,531 USD/ton, respectively, when including a subsidy of 1,710 USD/ton. These findings are very useful to develop or select the recovery methods of valuable metals from spent NiMH batteries.     

Determination of PCDDs,PCDFs, PCBs and HCB emissions from the metallurgical sector in Poland

Background The aim of the project was to measure the actual emissions of PCDD/F, PCBs and HCB from 20 selected metallurgical installations in Poland, in order to update the national inventory of dioxin emission from metallurgical industry for developing a strategy for dioxins and furans emission abatement from the subject facilities (UNEP 2005). Methods Sampling methodology used in this work was developed at the Cracow University of Technology because of the complexity of simultaneous sampling and determining PCDFs, PCDDs, PCB and HCB. For the determination a GC-MS/MS system was used. Results and Discussion Results from the work indicate that the highest dioxins and PCB concentrations were recorded for iron ore sintering plants at 1.10–1.32 ng total¹ TEQ/Nm³ followed by aluminium scrap melting at 0.03–0.66 ng total TEQ/Nm³. The highest HCB concentrations at 613–1491 ng/Nm³ were also recorded for iron ore sintering plants, whereas at aluminium plants the HCB concentrations were in the range of only 10.1–22.7 ng/Nm³. Conclusions The above investigations indicate that secondary aluminium production is the most significant dioxins source, if calculated as emission factor values. However, iron ore sintering plants are operating at much higher production capacity, causing this process to become the major source of dioxins, PCB and HCB pollution to the atmosphere in Poland. Recommendations and Perspectives Based on the performed tests and the environmental reviews of selected plants several recommendations were formulated for the reduction of generation or of emission of these pollutants from iron ore sintering plants, electric arc furnace steel production processes, hot-blast furnace operations, secondary aluminium smelting and primary zinc production from zinc cathodes.     

Outdoor experiments on enhanced volatilization by venting of kerosene component from soil

The effect of soil properties on the retention of kerosene in soils, at equilibrium and under venting, was studied. Eleven soils were studied, which represent a wide range of chemical properties and mechanical composition. The retention of kerosene in dry soils ranges from 3.5 to 18.1 mL/(100 g), and was related linearly to clay, silt and organic matter (OM) contents. A coarsely-aggregated dry vertisol (2–5 mm aggregates) retained half as much kerosene as its finely-aggregated (<2 mm) counterpart. Moisture content had a strong inverse effect on kerosene retention. The soil factors that inversely affected kerosene retention also enhanced kerosene stripping by venting. Of these, soil aggregation and porosity were the most important. In addition, kerosene volatilized faster and more completely from an initially moist soil, as compared with an initially dry soil. Differential volatilization of lighter components of kerosene changed the chemical composition of the residue in the soil substantially, as compared with the initial composition.     

利用高炉瓦斯泥中的锌制备活性氧化锌的研究

利用高炉炼铁瓦斯泥中的锌,采用火法富集和湿法浸取制取活性氧化锌。考察了温度、时间对火法富集产品中氧化锌含量和原料瓦斯泥中锌挥发率的影响,确定了富集工艺的最佳条件为:在氮气氛围下,温度从常温以10℃/min升温至1 000℃并且在1 000℃下保持1 h,得到的富集产品中氧化锌含量82.24%;瓦斯泥中锌挥发率97%。同时考察了温度、氨水用量、碳酸氢铵用量和液固比等因素对氧化锌浸取率的影响。确定的最佳工艺条件为:浸取温度40℃,氨水用量为理论量的2倍,碳酸氢铵用量为理论量的2倍,液固比4∶1,浸取时间2 h,氧化锌浸取率达99.9%。湿法制得的活性前驱体碱式碳酸锌,经煅烧得到纯度为98.4%的活性氧化锌产品,氧化锌的总回收率达95.3%。     

Emissions and distribution of methyl bromide in field beds applied at two rates and covered with two types of plastic mulches

A field experiment was conducted to compare two plastic mulches and two application rates on surface emissions and subsurface distribution of methyl bromide (MBr) in field beds in Florida. Within 30 minutes after injection of MBr to 30 cm depth, MBr had diffused upward to soil surface in all beds covered with polyethylene film (PE) or virtually impermeable film (VIF) and applied at a high rate (392 kg/ha) and a low rate (196 kg/ha). Due to the highly permeable nature of PE, within 30 minutes after injection, MBr volatilized from the bed surfaces of the two PE-covered beds into the atmosphere. The amount of volatilization was greater for the high rate-treatment bed. On the other hand, volatilization of MBr from the bed surfaces of the two VIF-covered beds were negligible. Volatilization losses occurred from the edges of all the beds covered with PE or VIF and were greater from the high rate-treatment beds. Initial vertical diffusion of MBr in the subsurface of the beds covered with PE or VIF was mainly upward, as large concentrations of MBr were detected from near bed surfaces to 20 cm depth in these beds 30 minutes after injection and little or no MBr was found at 40 cm depth. The two VIF-covered beds exhibited greater MBr concentrations and longer resident times in the root zone (0.5-40 cm depth) than corresponding PE-covered beds. Concentrations of MBr in the root zone of the high rate-treatment beds were 3.6-6.1 times larger than the low rate-treatment beds during the first days after application. In conclusion, VIF promoted retention of MBr in the root zone and, if volatilization loss from bed edges can be blocked, volatilization loss from VIF-covered beds should be negligible.     

Emissions and distribution of methyl bromide in field beds applied at two rates and covered with two types of plastic mulches

A field experiment was conducted to compare two plastic mulches and two application rates on surface emissions and subsurface distribution of methyl bromide (MBr) in field beds in Florida. Within 30 minutes after injection of MBr to 30 cm depth, MBr had diffused upward to soil surface in all beds covered with polyethylene film (PE) or virtually impermeable film (VIF) and applied at a high rate (392 kg/ha) and a low rate (196 kg/ha). Due to the highly permeable nature of PE, within 30 minutes after injection, MBr volatilized from the bed surfaces of the two PE-covered beds into the atmosphere. The amount of volatilization was greater for the high rate-treatment bed. On the other hand, volatilization of MBr from the bed surfaces of the two VIF-covered beds were negligible. Volatilization losses occurred from the edges of all the beds covered with PE or VIF and were greater from the high rate-treatment beds. Initial vertical diffusion of MBr in the subsurface of the beds covered with PE or VIF was mainly upward, as large concentrations of MBr were detected from near bed surfaces to 20 cm depth in these beds 30 minutes after injection and little or no MBr was found at 40 cm depth. The two VIF-covered beds exhibited greater MBr concentrations and longer resident times in the root zone (0.5–40 cm depth) than corresponding PE-covered beds. Concentrations of MBr in the root zone of the high rate-treatment beds were 3.6–6.1 times larger than the low rate-treatment beds during the first days after application. In conclusion, VIF promoted retention of MBr in the root zone and, if volatilization loss from bed edges can be blocked, volatilization loss from VIF-covered beds should be negligible.     

Loss of PM2.5 nitrate from filter samples in central California

Evaporative loss of particulate matter (with aerodynamic diameter < 2.5 microm, [PM2.5]) ammonium nitrate from quartz-fiber filters during aerosol sampling was evaluated from December 3, 1999, through February 3, 2001, at two urban (Fresno and Bakersfield) and three nonurban (Bethel Island, Sierra Nevada Foothills, and Angiola) sites in central California. Compared with total particulate nitrate, evaporative nitrate losses ranged from < 10% during cold months to > 80% during warm months. In agreement with theory, evaporative loss from quartz-fiber filters in nitric acid denuded samplers is controlled by the ambient nitric acid-to-particulate nitrate ratio, which is determined mainly by ambient temperature. Accurate estimation of nitrate volatilization requires a detailed thermodynamic model and comprehensive chemical measurements. For the 14-month average of PM2.5 acquired on Teflon-membrane filters, measured PM2.5 mass was 8-16% lower than actual PM2.5 mass owing to nitrate volatilization. For 24-hr samples, measured PM2.5 was as much as 32-44% lower than actual PM2.5 at three California Central Valley locations.     

Laboratory Scale Thermal Plasma Arc Vitrification Studies of Heavy Metal-Laden Waste

Abstract

Plasma processing has been identified as a useful tool for immobilizing heavy metal-contaminated wastes into safe, leach-resistant slag. Although much effort has gone into developing this technology on a pilot scale, not much information has been published on basic research topics. A laboratory-scale plasma arc furnace located at the University of Illinois was operated in cooperation with the U.S. Army Construction Engineering Research Laboratories in an effort to establish an understanding of the chemical and physical processes (such as metal volatilization and resultant gas evolution) that occur during thermal plasma treatment of metal-spiked samples. Experiments were conducted on nickel and chromium using a highly instrumented furnace equipped with a 75 kW transferred arc plasma torch. The volatility of nickel and chromium was examined as a function of varying oxygen partial pressures. Oxidizing conditions reduced the total dust gathered for both the nickel and chromium samples, although each dust sample was found to be metal-enriched. Plasma treating increased the leach-resistance of the slags by at least one order of magnitude when compared to unprocessed specimens. The leach- resistance of the nickel-containing slags increased in the presence of oxygen, whereas chromium samples remained relatively constant.     

Theoretical versus observed gas-particle partitioning of carbonyl emissions from motor vehicles

A state-of-the-science thermodynamic model describing gas-particle absorption processes was used to predict the gas-particle partitioning of mixtures of approximately 60 carbonyl compounds emitted from low-emission gasoline-powered vehicles, three-way catalyst gasoline-powered vehicles, heavy-duty diesel vehicles under the idle-creep condition (HDDV idle), and heavy-duty diesel vehicles under the five-mode test (HDDV 5-mode). Exhaust was diluted by a factor of 120-580 with a residence time of approximately 43 sec. The predicted equilibrium absorption partitioning coefficients differed from the measured partitioning coefficients by several orders of magnitude. Time scales to reach equilibrium in the dilution sampling system were close to the actual residence time during the HDDV 5-mode test and much longer than the actual residence time during the other vehicle tests. It appears that insufficient residence time in the sampling system cannot uniformly explain the failure of the absorption mechanism to explain the measured partitioning. Other gas-particle partitioning mechanisms (e.g., heterogeneous reactions, capillary adsorption) beyond the simple absorption theory are needed to explain the discrepancy between calculated carbonyl partitioning coefficients and observed partitioning. Both of these alternative partitioning mechanisms imply great challenges for the measurement and modeling of semi-volatile primary organic aerosol (POA) species from motor vehicles. Furthermore, as emitted particle concentrations from newer vehicles approach atmospheric background levels, dilution sampling systems must fundamentally change their approach so that they use realistic particle concentrations in the dilution air to approximately represent real-world conditions. Samples collected with particle-free dilution air yielding total particulate matter concentrations below typical ambient concentrations will not provide a realistic picture of partitioning for semi-volatile compounds.     

Magnetic resonance imaging of nonaqueous phase liquid during soil vapor extraction in heterogeneous porous media

Soil vapor extraction (SVE) is commonly used to remediate nonaqueous phase liquids (NAPLs) from the vadose zone. This paper aims to determine the effect of grain size heterogeneity on the removal of NAPL in porous media during SVE. Magnetic resonance imaging (MRI) was used to observe and quantify the amount and location of NAPL in flow-through columns filled with silica gel grains. MRI is unique because it is nondestructive, allowing three-dimensional images to be taken of the phases as a function of space and time. Columns were packed with silica gel in three ways: coarse grains (250-550 microm) only, fine grains (32-63 microm) only, and a core of fine grains surrounded by a shell of coarse grains. Columns saturated with water were drained under a constant suction head, contaminated with decane, and then drained to different decane saturations. Each column was then continuously purged with water-saturated nitrogen gas and images were taken intermittently. Results showed that at residual saturation, a sharp volatilization front moved through the columns filled with either coarse-grain or fine-grain silica gel. In the heterogeneous columns, the volatilization front in the core lagged just behind the shell because gas flow was greater through the shell and decane in the core diffused outward to the shell. When decane saturation in the core was above residual saturation, decane volatilization occurred near the inlet, the relative decane saturation throughout the core dropped uniformly, and decane in the core flowed in the liquid phase to the shell to replenish volatilized decane. These results indicate that NAPL trapped in low-permeability zones can flow to replenish areas where NAPL is lost due to SVE. However, when residual NAPL saturation is reached, NAPL flow no longer occurs and diffusion limits removal from low-permeability zones.     

Theoretical versus Observed Gas-Particle Partitioning of Carbonyl Emissions from Motor Vehicles

Abstract

A state-of-the-science thermodynamic model describing gas-particle absorption processes was used to predict the gas-particle partitioning of mixtures of approximately 60 carbonyl compounds emitted from low-emission gasoline-powered vehicles, three-way catalyst gasoline-powered vehicles, heavy-duty diesel vehicles under the idle-creep condition (HDDV idle), and heavy-duty diesel vehicles under the five-mode test (HDDV 5-mode). Exhaust was diluted by a factor of 120–580 with a residence time of approximately 43 sec. The predicted equilibrium absorption partitioning coefficients differed from the measured partitioning coefficients by several orders of magnitude. Time scales to reach equilibrium in the dilution sampling system were close to the actual residence time during the HDDV 5-mode test and much longer than the actual residence time during the other vehicle tests. It appears that insufficient residence time in the sampling system cannot uniformly explain the failure of the absorption mechanism to explain the measured partitioning. Other gas-particle partitioning mechanisms (e.g., heterogeneous reactions, capillary adsorption) beyond the simple absorption theory are needed to explain the discrepancy between calculated carbonyl partitioning coefficients and observed partitioning. Both of these alternative partitioning mechanisms imply great challenges for the measurement and modeling of semi-volatile primary organic aerosol (POA) species from motor vehicles. Furthermore, as emitted particle concentrations from newer vehicles approach atmospheric background levels, dilution sampling systems must fundamentally change their approach so that they use realistic particle concentrations in the dilution air to approximately represent real-world conditions. Samples collected with particle-free dilution air yielding total particulate matter concentrations below typical ambient concentrations will not provide a realistic picture of partitioning for semi-volatile compounds.