Mercury reduction studies to facilitate the thermal decontamination of phosphor powder residues from spent fluorescent lamps

This work investigates the thermal release of mercury from phosphor powder of spent fluorescent lamps. The treatment conditions and the ability of various reducing agents (primarily sodium borohydride) to lower the overall heating temperature required to improve the release of Hg have been evaluated. Hg species in samples were monitored in a thermal desorption atomic absorption spectrometer system, and total mercury was analyzed in a cold vapor atomic absorption spectrometer. Sodium borohydride was the best reducing agent among the ones studied. However, citric acid presented a high capacity to weaken mercury bonds with the matrix. When the sample was crushed with sodium borohydride for 40min in a mass ratio of 10:1 (sample:reducing agent) and submitted to thermal treatment at 300 degrees C for 2h, the concentration of mercury in a phosphor powder sample with 103mgkg(-1) of mercury reached 6.6mgkg(-1).     

Determination of mercury distribution inside spent compact fluorescent lamps by atomic absorption spectrometry

In this study, spent compact fluorescent lamps were characterized to determine the distribution of mercury. The procedure used in this research allowed mercury to be extracted in the vapor phase, from the phosphor powder, and the glass matrix. Mercury concentration in the three phases was determined by the method known as cold vapor atomic absorption spectrometry. Median values obtained in the study showed that a compact fluorescent lamp contained 24.52±0.4ppb of mercury in the vapor phase, 204.16±8.9ppb of mercury in the phosphor powder, and 18.74±0.5ppb of mercury in the glass matrix. There are differences in mercury concentration between the lamps since the year of manufacture or the hours of operation affect both mercury content and its distribution. The 85.76% of the mercury introduced into a compact fluorescent lamp becomes a component of the phosphor powder, while more than 13.66% is diffused through the glass matrix. By washing and eliminating all phosphor powder attached to the glass surface it is possible to classified the glass as a non-hazardous waste.     

Characteristics of mercury emission from linear type of spent fluorescent lamp

In order to recycle the linear type of SFL (spent fluorescent lamp), mercury from SFL should be controlled to prevent leaking into the environment. For mercury emission from SFL, mercury concentration is estimated in the parts of SFL such as glass tube, phosphor powder, and base cap using the end-cutting unit. It is also evaluated mercury emission in the effluent gas in the end-cutting unit with changing flow rate. From the results of mercury emission from SFLs, phosphor powder has greater than 80% of mercury amount in SFL and about 15% of mercury amount contained in glass tube. The initial mercury concentration in vapor phase is almost decreased linearly with increasing airflow rate from 0.7 L/min to 1.3 L/min. It is desirable that airflow rate should be high until the concentration of mercury vapor will be stable because the stabilized concentration becomes to be low and the stabilized time goes to be short as increased airflow rate. From KET and TCLP results, finally, phosphor powder should be managed as a hazardous waste but base-cap and glass are not classified as hazardous wastes.     

Investigation on the heavy-metal content of zinc-air button cells

Within the framework of a German government project (initiated by the Federal Environment Agency) to check the compliance of commercially available batteries with the German Battery Ordinance concerning their heavy metal contents, 18 different types of commercially available zinc-air button cells were analysed for their cadmium, lead and mercury contents. After microwave assisted dissolution with aqua regia, Cd and Pb were determined using inductively coupled plasma mass spectrometry (ICP-MS), and Hg was determined using inductively coupled plasma optical emission spectrometry (ICP OES) and atomic absorption spectrometry. Cd contents were found to be much lower than the permitted limits; Pb contents were also found to be below the limits. Hg contents were found to be near the limits, and in one case the limit was exceeded.     

Characterization and recovery of mercury from spent fluorescent lamps

Fluorescent lamps rely on mercury as the source of ultraviolet radiation for the production of visible light. Partitioning of mercury among vapor phase, loose phosphor powders produced during breaking and washing steps, glass matrices, phosphor powders attached on the glass and aluminum end caps was examined from simulated laboratory lamp recycling tests for different types of spent and new fluorescent lamps. Mercury concentrations in lamp glasses taken from commercial lamp recyclers were also analyzed for comparison with the simulated results of spent and new lamps of different types. The mercury content of the glass from spent lamps was highly variable depending on the lamp type and manufacturer; the median values of the mercury concentration in glasses for spent 26- (T8) and 38-mm (T12) diameter fluorescent lamps were approximately 30 and 45 microg/g, respectively. The average mercury concentration of samples taken from recycler A was 29.6 microg/g, which was about 64% of median value measured from the spent T12 lamps. Over 94% of total mercury in lamps remained either as a component of phosphor powders attached inside the lamp or in glass matrices. New T12 lamps had a higher partitioning percentage of elemental mercury in the vapor phase (0.17%) than spent T12 lamps (0.04%), while spent lamps had higher partitioning percentages of mercury resided on end-caps and phosphor powders detached from the breaking and washing steps. The TCLP values of simulated all lamp-glasses and samples obtained from recyclers were higher than the limit of LDR standard (0.025 mg/L). After investigating acid treatment and high temperature treatment as mercury reclamation techniques, it was found that heating provided the most effective mercury capture. Although the initial mercury concentrations of individual sample were different, the mercury concentrations after 1 h exposure at 100 degrees C were below 4 mug/g for all samples (i.e., <1% remaining). Therefore, it is recommended that heating be used for recovering mercury from spent fluorescent lamps.     

Comparison of methods for leaching heavy metals from composts

This paper presents the determination of total iron, copper, zinc, chromium, nickel, lead, cadmium and mercury contents in the compost obtained from sorted municipal organic solid waste applying the following methods of sample mineralization: 40% hydrofluoric acid with preliminary incineration of a sample, a mixture of concentrated nitric(V) and chloric(VII) acids with preliminary incineration of organic matter and a mixture of nitric(V) and chloric(VII) acids without sample incineration. The speciation analysis of Tessier was used to estimate the bioavailability of the metals. Elution degrees of the mobile forms of the metals from the compost with 10% nitric(V) acid and 1 mol/dm(3) hydrochloric acid were compared. The contents of the elements in the eluates were determined applying atomic absorption spectrometry.     

Microscopic synchrotron X-ray analysis of mercury waste in simulated landfill experiments

Mercury enters into the environment or waste streams because it is present as an impurity in natural minerals. Mercury must be appropriately managed as an hazardous waste. In this study, a waste layer of artificial mercury sulfide mixed with incinerator ash and sewage sludge compost in a simulated landfill experiment for 5 years was analyzed using microscopic synchrotron X-ray to obtain basic knowledge of mercury behavior in a landfill. Mapping by synchrotron X-ray revealed the distribution of mercury-containing particles in the waste layer. In most cases, the movement of mercury sulfide was not considered significant even within a microscopic range; however, water flows could enhance the movement of mercury sulfide particles. When disposing of mercury sulfide, “concentrated placement” or solidification, rather than mixing with other wastes, was more effective at preventing mercury leaching in lysimeters. The chemical form of mercury sulfide in each lysimeter was confirmed by X-ray absorption fine structure (XAFS) analysis, which showed that most of the mercury was present as metacinnabar and had not undergone any changes, indicating that it was extremely stable. The microscopic synchrotron X-ray analysis proved very useful for studying the behavior of mercury waste in a simulated landfill experiment.

     

Sulfur polymer solidification/stabilization of elemental mercury waste

Elemental mercury, contaminated with radionuclides, presents a waste disposal problem throughout the Department of Energy complex. In this paper we describe a new process to immobilize elemental mercury wastes, including those contaminated with radionuclides, in a form that is non-dispersible, will meet EPA leaching criteria, and has low mercury vapor pressure. In this stabilization and solidification process, elemental mercury is combined with an excess of powdered sulfur polymer cement (SPC) and sulfide additives in a mixing vessel and heated to approximately 40 degrees C for several hours, until all of the mercury is converted into mercuric sulfide (HgS). Additional SPC is then added and the temperature of the mixture raised to 135 degrees C, resulting in a molten liquid which is poured into a mold where it cools and solidifies. The final treated waste was characterized by powder X-ray diffraction and found to be a mixture of the hexagonal and orthorhombic forms of mercuric sulfide. The Toxicity Characteristic Leaching Procedure was used to assess mercury releases, which for the optimized process averaged 25.8 microg/l, with some samples being well below the new EPA Universal Treatment Standard of 25 microg/l. Longer term leach tests were also conducted, indicating that the leaching process was dominated by diffusion. Values for the effective diffusion coefficient averaged 7.6x10(-18) cm2/s. Concentrations of mercury vapor from treated waste in equilibrium static headspace tests averaged 0.6 mg/m3.     

Laboratory study on the behaviour of spent AA household alkaline batteries in incineration

The quantitative evaluation of emissions from incineration is essential when Life Cycle Assessment (LCA) studies consider this process as an end-of-life solution for some wastes. Thus, the objective of this work is to quantify the main gaseous emissions produced when spent AA alkaline batteries are incinerated. With this aim, batteries were kept for 1h at 1273K in a refractory steel tube hold in a horizontal electric furnace with temperature control. At one end of the refractory steel tube, a constant air flow input assures the presence of oxygen in the atmosphere and guides the gaseous emissions to a filter system followed by a set of two bubbler flasks having an aqueous solution of 10% (v/v) nitric acid. After each set of experiments, sulphur, chlorides and metals (As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Tl and Zn) were analyzed in both the solutions obtained from the steel tube washing and from the bubblers. Sulphur, chlorides and metals were quantified, respectively, using barium sulfate gravimetry, the Volhard method and atomic absorption spectrometry (AAS). The emissions of zinc, the most emitted metal, represent about 6.5% of the zinc content in the batteries. Emissions of manganese (whose oxide is the main component of the cathode) and iron (from the cathode collector) are negligible when compared with their amount in AA alkaline batteries. Mercury is the metal with higher volatility in the composition of the batteries and was collected even in the second bubbler flask. The amount of chlorides collected corresponds to about 36% of the chlorine in the battery sleeve that is made from PVC. A considerable part of the HCl formed in PVC plastic sleeve incineration is neutralized with KOH, zinc and manganese oxides and, thus, it is not totally released in the gas. Some of the emissions are predictable through a thermodynamic data analysis at temperatures in the range of 1200-1300K taking into account the composition of the batteries. This analysis was done for most of potential reactions between components in the batteries as well as between them and the surrounding atmosphere and it reasonably agrees the experimental results. The results obtained show the role of alkaline batteries at the acid gases cleaning process, through the neutralization reactions of some of their components. Therefore, LCA of spent AA alkaline batteries at the municipal solid waste (MSW) incineration process must consider this contribution.     

Enrichment of elements in industrial waste incineration bottom ashes obtained from three different types of incinerators,as studied by ICP-AES and ICP-MS

The elemental composition of the industrial waste incineration bottom ash (IWIBA) samples collected from three different types of incinerator with different kinds of wastes were compared. The major-to-ultratrace elements in the IWIBA samples were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). As a result, ca. 40 elements in the concentration range from milligrams per gram to submicrograms per gram could be determined with relative standard deviations of less than 5%. The IWIBA sample from petrochemical wastes contained lower concentrations of the elements, because fewer mineral constituents were contained in the input waste materials. On the contrary, the elemental concentrations in the IWIBA sample from industrial solid wastes provided the highest values for most elements, while the elemental compositions of the IWIBA sample from food wastes were similar to those of municipal solid waste incineration bottom ash. In addition, it was found from the analytical results that the levels of various heavy metals such as Cr, Mn, Fe, Ni, Cu, As, Zr, Mo, Sb, Ba, and Pb were higher in the IWIBA samples than in municipal solid waste incineration bottom ash. The enrichment factors of the elements in the IWIBA samples were estimated from the analytical results to compare the elemental distributions in incineration bottom ashes in relation to their mining influence factors, which are the indices for human use of the elements.     

Mercury leaching characteristics of waste treatment residues generated from various sources in Korea

In this study, mercury (Hg) leaching characteristics of the waste treatment residues (fly ash, bottom ash, sludge, and phosphor powder) generated from various sources (municipal, industrial, medical waste incinerators, sewage sludge incinerator, oil refinery, coal-fired power plant, steel manufacturing plant, fluorescent lamp recycler, and cement kiln) in Korea were investigated. First, both Hg content analysis and toxicity characteristic leaching procedure (TCLP) testing was conducted for 31 collected residue samples. The Hg content analysis showed that fly ash from waste incinerators contained more Hg than the other residue samples. However, the TCLP values of fly ash samples with similar Hg content varied widely based on the residue type. Fly ash samples with low and high Hg leaching ratios (R_L) were further analyzed to identify the major factors that influence the Hg leaching potential. Buffering capacity of the low-R_L fly ash was higher than that of the high-R_L fly ash. The Hg speciation results suggest that the low-R_L fly ashes consisted primarily of low-solubility Hg compounds (Hg₂Cl₂, Hg⁰ or HgS), whereas the high-R_L fly ashes contain more than 20% high-solubility Hg compounds (HgCl₂ or HgSO₄).     

Mercury flows in a zinc smelting facility in South Korea

To prepare for the international mercury convention, the characteristics of mercury emissions from a zinc smelting facility in South Korea have been reviewed and a material flow analysis (MFA) has been conducted in this research. As inputs into the mercury MFA study, zinc ores and sulfuric acid were examined, whereas wastewater sludge, effluence water, spent catalyst, and emissions from the casting and roasting processes were examined as outputs. Mercury concentrations extracted from end products like zinc ingots, cadmium ingots, and sulfuric acid were then analyzed. Our results showed that the wastewater sludge discharged from the zinc smelting process had a relatively higher concentration of mercury, indicating that the concentration of mercury was further enriched in the wastewater sludge. The wastes discharged through the zinc smelting process should be thoroughly controlled, as results of the MFA showed that approximately 89 % of the mercury contained in the original input was later found in the waste. According to this study, the higher the concentration of mercury within zinc ores at the input stage, the higher is the mercury concentration found in the wastewater sludge at the output stage.     

Determining heavy metals in spent compact fluorescent lamps (CFLs) and their waste management challenges: Some strategies for improving current conditions

From environmental viewpoint, the most important advantage of compact fluorescent lamps (CFLs) is reduction of green house gas emissions. But their significant disadvantage is disposal of spent lamps because of containing a few milligrams of toxic metals, especially mercury and lead. For a successful implementation of any waste management plan, availability of sufficient and accurate information on quantities and compositions of the generated waste and current management conditions is a fundamental prerequisite. In this study, CFLs were selected among 20 different brands in Iran. Content of heavy metals including mercury, lead, nickel, arsenic and chromium was determined by inductive coupled plasma (ICP). Two cities, Tehran and Tabriz, were selected for assessing the current waste management condition of CFLs. The study found that waste generation amount of CFLs in the country was about 159.80, 183.82 and 153.75 million per year in 2010, 2011 and 2012, respectively. Waste generation rate of CFLs in Iran was determined to be 2.05 per person in 2012. The average amount of mercury, lead, nickel, arsenic and chromium was 0.417, 2.33, 0.064, 0.056 and 0.012 mg per lamp, respectively. Currently, waste of CFLs is disposed by municipal waste stream in waste landfills. For improving the current conditions, we propose by considering the successful experience of extended producer responsibility (EPR) in other electronic waste management. The EPR program with advanced recycling fee (ARF) is implemented for collecting and then recycling CFLs. For encouraging consumers to take the spent CFLs back at the end of the products’ useful life, a proportion of ARF (for example, 50%) can be refunded. On the other hand, the government and Environmental Protection Agency should support and encourage recycling companies of CFLs both technically and financially in the first place.     

Leaching behavior of some demolition wastes

Demolition wastes may be used in different civil engineering applications as road constructions, concrete, and embankments or landfill. Regardless its application, leaching tests of the waste should be carried out to assess concentrations of pollutants. Concrete, brick and mixture of concrete, bricks, tiles and ceramics wastes were subject to percolation test—CEN/TS 14405, and batch test—SR EN 12457. The leachates were analyzed with respect to concentration of inorganic elements—arsenic, barium, cadmium, chromium, copper, mercury, molybdenum, nickel, lead, selenium, zinc, fluoride, chloride and sulfate, and organic compounds (phenol index). The concentrations of elements in leachates were compared with the limit values of European regulation for the acceptance of inert wastes at landfills. Generally, the releases of inorganic species in leachates were below limits values. Some waste leachates obtained by percolation and batch test had high values for phenol index.     

Municipal solid waste composition determination supporting the integrated solid waste management system in the island of Crete

A one-year survey was conducted in the greater region of Crete (located at the lower region of the Aegean Sea) for the purpose of identifying waste composition (including chemical and physical characterization), as well as any seasonal variation. The investigation was carried out repeatedly at seven landfills and one transfer station in Crete, in four phases. Each sampling phase corresponded to a season (autumn, winter, spring, summer). ASTM D5231-92(2003) standard method and RCRA Waste Sampling Draft Technical Guidance were used. Hand sorting was used for classifying the collected wastes into the following categories: plastics, paper, metals, aluminium, leather-wood-textiles-rubbers, organic wastes, non-combustibles and miscellaneous. Further analysis included proximate and ultimate analysis of combustible materials. Metals such as lead, cadmium and mercury were also investigated. The results show that there has been a significant decrease of organic wastes during the last decade due to the increase of packaging materials, as a result of a change in consumption patterns. Three main waste categories were determined: organic wastes, paper and plastics, which combined represent 76% of the total waste in Crete. Furthermore, a high fraction of glass and a seasonal variation of aluminium indicate a strong correlation of waste composition with certain human activities, such as tourism. There is also a variation between the municipal solid waste (MSW) composition in the region of Crete (2003-2004) and MSW composition suggested in the National Solid Waste Planning (2000) [National Solid Waste Planning, 2000. Completion and particularization of Common Ministerial Act 113944//1944/1997: National Solid Waste Planning, June 2000]. The results of this survey are to be utilized by the regional solid waste authorities in order to establish an integrated waste treatment site, capable of fulfilling the regional waste management demands.     

Recycling and reuse of industrial wastes in Taiwan

Eighteen million metric tons of industrial wastes are produced every year in Taiwan. In order to properly handle the industrial wastes, the Taiwan Environmental Protection Administration (Taiwan EPA) has set up strategic programs that include establishment of storage, treatment, and final disposal systems, establishment of a management center for industrial wastes, and promotion of recycling and reuse of industrial wastes. The Taiwan EPA has been actively promoting the recycling and reuse of industrial wastes over the years. In July 1995 the Taiwan EPA amended and promulgated the Criteria for the Industrial Waste Storage, Collection and Processing Facility, July, 1995 that added articles related to general industrial waste recycling and reuse. In June 1996 the Taiwan EPA promulgated the Non-listed General Industrial Waste Reuse Application Procedures, June, 1996, followed by the Regulations Governing the Permitting of Hazardous Industrial Waste Reuse, June 1996, setting up a full regulatory framework for governing industrial waste reuse. To broaden the recycling and reuse of general industrial wastes, the Taiwan EPA has listed 14 industrial waste items for recycling and reuse, including waste paper, waste iron, coal ash, tempered high furnace bricks (cinder), high furnace bricks (cinder), furnace transfer bricks (cinder), sweetening dregs, wood (whole/part), glass (whole/part), bleaching earth, ceramics (pottery, brick, tile and cast sand), individual metal scraps (copper, zinc, aluminum and tin), distillery grain (dregs) and plastics. As of June 1999, 99 applications for reuse of industrial wastes had been approved with 1.97 million metric tons of industrial wastes being reused.     

Review of environmental aspects and waste management of stone cutting and fabrication industries

Iran is the second largest stockholder of construction stones with 10 % of world production ;and there are more than 4000 stone cutting and fabrication industries (SCFIs). In the processing of raw stones, a considerable part of stone is turned into waste. Generated wastes include excess parts of different stones and sludge. The present paper reviews the state of SCFIs waste management using multiple data sources including site, analysis of effluent and sludge samples, and conducting interviews with people who are involved in 286 SCFIs in Qom and Tabriz. The results revealed that currently almost 35 to 52.5 % of raw stones were converted to solid wastes depending on stone cutting and processing methods, type of stones and their quality, which seemed a high percentage. Also, the effluents between 0.8 and 2.8 m³ were generated per ton of processed stone. Based on the analysis of heavy metals with atomic absorption spectroscopy, sludge samples contained a considerable amount of Pb, Cu, Cr, and Cd. It was also found that the lack of specific recycling, reuse and disposal programs and suitable supervision has led to uncontrolled disposal of stone wastes and sludge in different areas. However, there are good opportunities for reuse and recycling of the SCFIs wastes.     

Synthesis of hydrogarnet from molten slag and its hydrogen chloride fixation performance at high temperature

Hydrogarnet was synthesized hydrothermally below 200°C using molten slag obtained from municipal solid waste. For comparison, it was also synthesized using pure-phase CaO–Al₂O₃–SiO₂–H₂O, as reported previously. The structural and textural properties of this material were investigated using various analytical and spectroscopic techniques such as X-ray diffraction, X-ray fluorescence spectrometry, atomic absorption spectrometry (AAS), thermogravimetry/differential thermal analysis, Fourier transform infrared spectroscopy, and scanning electron microscopy. The Cl⁻ fixation ability of hydrogarnet was investigated in the temperature range 500–800°C in a fixed-bed flow reactor using a HCl concentration (1000 p.p.m.v.) similar to that of incinerator exhaust gas. Under these experimental conditions, the hydrogarnet was capable of reducing the HCl gas level to less than 1 p.p.m.v. Analysis of the spent catalyst revealed that the hydrogarnet was being transformed into wadalite and CaCl₂ at high temperatures. The elution test for chromium ions in hydrogarnet obtained from slag was also used, and it was found that chromium ions were not eluted from hydrogarnet. Received: January 27, 2001 / Accepted: October 11, 2001     

Management of hazardous waste in Thailand: present situation and future prospects

 This paper deals with the present scenario of hazardous waste management practices in Thailand, and gives some insights into future prospects. Industrialization in Thailand has systematically increased the generation of hazardous waste. The total hazardous waste generated in 2001 was 1.65 million tons. It is estimated that over 300 million kg/year of hazardous waste is generated from nonindustrial, community sources (e.g., batteries, fluorescent lamps, cleansing chemicals, pesticides). No special facilities are available for handling these wastes. There are neither well-established systems for separation, storage, collection, and transportation, nor the effective enforcement of regulations related to hazardous wastes management generated from industrial or nonindustrial sectors. Therefore, because of a lack of treatment and disposal facilities, these wastes find their way into municipal wastewaters, public landfills, nearby dump sites, or waterways, raising serious environmental concern. Furthermore, Thailand does not have an integrated regulatory framework regarding the monitoring and management of hazardous materials and wastes. In addition to the absence of a national definition of hazardous wastes, limited funding has caused significant impediments to the effective management of hazardous waste. Thus, current waste management practices in Thailand present significant potential hazards to humans and the environment. The challenging issues of hazardous waste management in Thailand are not only related to a scarcity of financial resources (required for treatment and disposal facilities), but also to the fact that there has been no development of appropriate technology following the principles of waste minimization and sustainable development. A holistic approach to achieving effective hazardous waste management that integrates the efforts of all sectors, government, private, and community, is needed for the betterment of human health and the environment. Received: February 26, 2001 / Accepted: October 11, 2002     

Pelleted organo-mineral fertilisers from composted pig slurry solids, animal wastes and spent mushroom compost for amenity grasslands

In Ireland, conversion of biodegradable farm wastes such as pig manure spent mushroom compost and poultry litter wastes to pelletised fertilisers is a desirable option for farmers. In this paper, results obtained from the composting of pig waste solids (20% w/w) blended with other locally available biodegradable wastes comprising poultry litter (26% w/w), spent mushroom compost (26% w/w), cocoa husks (18% w/w) and moistened shredded paper (10% w/w) are presented. The resulting 6-mo old 'mature' composts had a nutrient content of 2.3% total N, 1.6% P and 3.1% K, too 'low' for direct use as an agricultural fertiliser. Formulations incorporating dried blood or feather meal amendments enriched the organic N-content, reduced the moisture in mature compost mixtures and aided the granulation process. Inclusion of mineral supplements viz., sulphate of ammonia, rock phosphate and sulphate of potash, yielded slow release fertilisers with nutrient N:P:K ratios of 10:3:6 and 3:5:10 that were suited for amenity grasslands such as golf courses for spring or summer application and autumn dressing, respectively. Rigorous microbiological tests carried out throughout the composting, processing and pelletising phases indicated that the formulated organo-mineral fertilisers were free of vegetative bacterial pathogens.