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.     

Mercury speciation in fluorescent lamps by thermal release analysis

In this work, mercury speciation in phosphorus powder matrices and soda lime glass waste from new and spent fluorescent lamp wastes has been studied by thermo-desorption/atomic absorption spectrometry (TDAAS), X-ray diffraction (XRD), cold vapor-atomic absorption (CV-AAS) and atomic emission spectrometry/inductively coupled plasma (ICP/AES). TDAAS results show the presence of oxidized forms of mercury, i.e., Hg(1+) and Hg(2+), especially in wastes with high mercury concentration. Such forms are mobile, and therefore represent a potential hazard waste material. Glass TD profiles of spent fluorescent lamps suggested the presence of mercury strongly linked to the matrix, which desorbs only at high temperatures.     

汞矿区汞污染土壤的淋洗修复

以贵州省铜仁市汞矿区汞污染土壤为研究对象,分别采用KI、Na_2S_2O_3、乙二胺四乙酸、柠檬酸、酒石酸、十二烷基硫酸钠溶液对其进行淋洗修复,筛选出合适的淋洗剂,优化了淋洗条件,并探索了淋洗液的处理方法。实验结果表明:对该土壤淋洗效果最好的淋洗剂为Na_2S_2O_3,最佳淋洗条件为Na_2S_2O_3浓度0.01 mol/L、固液比(g/m L)1∶5、淋洗时间4 h、淋洗次数1次,在此条件下土壤中总汞的淋洗率为13.41%,有效态汞含量可降至原来的61.54%;Na2S对淋洗液中的汞具有较好的去除效果,每升淋洗液加入0.6 g Na_2S处理后,即可满足GB8978—1996《污水综合排放标准》。     

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.     

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.     

Thermogravimetric and XRD study of the effects of chloride salts on the thermal decomposition of mercury compounds

In this paper, the effects of chloride salt (MgCl₂, CaCl₂ or NaCl) addition on the thermal decomposition of five inorganic mercury compounds (HgCl₂, HgS, Hg(NO₃)₂·H₂O, HgO, and HgSO₄) were investigated by thermogravimetric analysis. Mercury-contaminated soil samples collected from Inner Mongolia were used to verify the results. The desorption temperatures of the mercury compounds increased in the following order: HgCl = HgCl₂ < HgS < Hg(NO₃)₂·H₂O < HgO < HgSO₄. Among the chloride salts, MgCl₂ had the greatest effect on thermal desorption of the mercury compounds, with the greatest reduction in the initial temperature of thermal desorption. After MgCl₂ treatment, the mercury removal rates for the soil were 65.67–81.35 % (sample A), 70.74–84.91 % (sample B), and 69.08 % (sample C). The increase in the mercury removal rate for sample C with addition of MgCl₂ was particularly large (34.96–69.08 %). X-Ray diffraction analysis of white crystals from the thermal desorption with MgCl₂ indicated that MgCl₂ promoted conversion of the mercury compounds in the soil to mercury(II) chloride and dimercury dichloride. This transformation is beneficial for applying thermal desorption to remedy mercury-contaminated soils and treat of mercury containing waste.     

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).     

万山汞矿区土壤重金属污染特征及来源解析

以万山汞矿区土壤为研究对象,采用电感耦合等离子体质谱仪和原子荧光光谱仪测定土壤中的重金属含量,分别运用内梅罗综合污染指数（NPI）法和潜在生态风险指数（RI）法评价土壤重金属污染和潜在生态风险,并应用相关性分析、主成分分析和聚类分析对土壤重金属来源进行分析。结果表明：土壤Hg、Cd、As、Pb、Cu、Ni和Zn出现不同程度累积,分别达贵州省背景值的263.61、2.31、1.28、2.11、1.70、1.01和3.52倍;土壤重金属平均NPI为188.00,属于严重污染水平,Hg是主要污染因子;土壤重金属平均RI为10 655.70,属于极强潜在生态风险水平,Hg是主要潜在生态风险因子;土壤中Cu、Ni、Cr主要源于自然活动,As、Pb、Zn主要源于燃煤和交通运输污染,Cd主要源于农业污染,Hg主要源于汞冶炼污染。     

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.     

重金属螯合剂TMT-15处理高含汞气田废水

选用重金属螯合剂TMT-15处理高含汞气田废水(COD=1 560 mg/L,SS=210 mg/L,pH=2.5~3.0,汞质量浓度为340 mg/L),考察了TMT-15投加量,废水pH,与氢氧化物、硫化物联用等因素对汞去除效果的影响,分析了TMT-15与汞的螯合产物的稳定性。实验结果表明:TMT-15能与汞强力螯合并沉淀,投加量低,pH适用范围广;絮凝剂聚合硫酸铝与TMT-15的联用可提高除汞效果,但作用有限;TMT-15与氢氧化物联用时的汞的去除效果提升显著,在氢氧化钠、三聚硫氰酸、汞元素的摩尔比为0.5:0.5:1和废水pH为3.0的条件下,汞去除率可达99.99%,剩余汞浓度低于GB 8978—1996中规定的汞排放浓度;螫合产物具有很高的热稳定性,且在较高浓度的酸碱环境中溶解率低,对环境造成二次污染的风险小。     

用改性海泡石处理含磷废水

以海泡石为原料,经盐酸活化、水热活化,再加入氯化镁、氯化铁复合制得除磷剂原粉;再用聚氯乙烯将除磷剂原粉黏合成粒状除磷剂。用粒状除磷剂对废水中的磷（PO4^3-）进行吸附、洗脱,考察除磷剂的循环使用性能。实验结果表明：除磷剂对废水中磷的吸附容量可达92m g/g以上;以碳酸钠为洗脱剂,磷的洗脱率可达90%以上;除磷剂可重复使用,且性能优良。     

锌冶炼烟气制酸废水中汞的测定

采用冷原子吸收光度法测定经石灰乳和铁盐处理后的锌冶炼烟气制酸废水中汞的浓度时,可按废水中汞浓度与其pH的关系,从试样pH的高低大致估计其汞浓度范围,由此确定其稀释倍数和取样量。试样用KBrO3-KBr消解法消解,用直接法稀释,这样可以减少操作步骤、缩短测定周期、减少样品中汞的损失、提高监测结果的可靠性和准确性,同时可减少人力、物力浪费,降低监测成本。     

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.     

Urban Metabolism of Mercury Turnover,Emissions and Stock in Stockholm 1795–1995

This article accounts for the use of mercury (Hg) in differentactivities in Stockholm during the time period 1795–1995.Turnover of Hg is estimated to 122–440 tons, amounts recycled: 27–50 tons and total emissions of Hg are estimated to 90–390 tons. The stock was approximately 4.4–8.1 tons in 1995. 19th century handicraft occupations and medical treatment emitted alarge part of the Hg, emission sources that hitherto have beenunknown in Sweden. Emissions peaked around 1960, thereafter theemissions plummeted, being the result of decreased use of Hg fordental fillings and in products such as batteries, while recycling efforts had a limited effect on reducing total emissions. Based on this finding, the current focus on collectionof Hg containing products for long term storage in bedrock is questioned. If the aim is to reduce the potential for environmental hazards because of Hg it might be better to focusmore attention on the already emitted amounts since these are nearly 30 times greater than the amount of Hg in stock.     

Laboratory waste minimization by recovery of silver as nano-silver colloidal dispersion from waste silver chloride

The use of cyclic experiments, where the product of one reaction becomes the starting material for the next experiment, was proposed as an effective protocol for waste minimization in an educational lab. A simple, cheap and pollution-free method was developed for recovering silver as nano-silver colloidal dispersion from waste silver chloride in the laboratories of the Faculty of Health, Safety and Environment. Silver nanoparticles of the size 5–18 nm were recovered in the presence of sodium borohydride as a reducing agent and polyvinylpyrrolidone as a stabilizer agent. The nano-silver particles were studied for their formation, structure, stability and size using UV–Vis spectroscopy, transmission electron microscopy and dynamic light scattering techniques. The antibacterial assays of nanoparticles showed satisfactory results for Escherichia coli ATCC25922, Staphylococcus aureus ATCC 29213, and Acinetobacter baumanii (Clinical isolate). A laboratory experiment was designed in which students synthesize yellow colloidal silver solution from chemical waste silver chloride and estimate particle size using visible spectroscopy.     

Survey of mercury,cadmium and lead content of household batteries

The objective of this work was to provide updated information on the development of the potential impact of heavy metal containing batteries on municipal waste and battery recycling processes following transposition of the new EU Batteries Directive 2006/66/EC. A representative sample of 146 different types of commercially available dry and button cells as well as lithium-ion accumulators for mobile phones were analysed for their mercury (Hg)-, cadmium (Cd)- and lead (Pb)-contents. The methods used for preparing the cells and analysing the heavy metals Hg, Cd, and Pb were either developed during a former study or newly developed. Several batteries contained higher mass fractions of mercury or cadmium than the EU limits. Only half of the batteries with mercury and/or lead fractions above the marking thresholds were labelled. Alkaline–manganese mono-cells and Li-ion accumulators, on average, contained the lowest heavy metal concentrations, while zinc–carbon batteries, on average, contained the highest levels.     

Performance evaluation of material separation from spent fluorescent lamps using the thermal end-cutting method

The recovery of valuable materials such as aluminum, phosphor powder, and glass from spent fluorescent lamps (SFLs) is part of the overall recycling process of lamps. In the end-cutting process, an SFL is separated into a base cap and a glass part using thermal shock caused by the temperature difference between the heating unit and the cooling unit. The separation efficiency of the end-cutting system is estimated by measuring the mass of the parts of the SFL. The optimum condition of the end-cutting process with thermal shock was determined to have a temperature difference of 600 °C and moving speed of 2 cm/s. At optimum conditions, the separation efficiency of glass and the end cap from an SFL using the end-cutting method is estimated to be more than about 97 %. In an air injection system, however, the separation efficiency of phosphor powder from glass is less than 50 %. Separation efficiency in the end-cutting system is increased by decreasing the moving speed of the SFL and increasing the temperature difference between the heating unit and the cooling unit. From the results of experiments, it was found that the end-cutting unit has very high performance because the overall separation efficiency is more than 95 %.     

Effects of carbonation and leaching on porosity in cement-bound waste

Porosity is possibly an important parameter with respect to leaching of constituents from cement monoliths. During its lifetime, the pore structure of cementitious matrices changes due to carbonation and leaching. This paper discusses the effects of both accelerated carbonation and continuous leaching on the porosity, and, conversely, how porosity affects leaching properties. Two sample types are investigated: a mortar with MSWI-bottom ash substituting the sand fraction and a cement paste with 30 wt% of the cement substituted by a flue gas cleaning residue. The samples have been intensively carbonated in a 20% CO(2) atmosphere for up to 60 days and were subsequently leached. The porosity was investigated by mercury intrusion porosimetry. Accelerated carbonation decreases total porosity by 12% in the case of 60 days of treatment of bottom ash mortars, whereas continuous leaching during 225 days increases it by 16%. Both carbonation and leaching decrease the amount of smaller capillary pores. Carbonation decreases both porosity and pH. Decreasing porosity diminishes leaching of sodium and potassium, while the decrease in pH increases leaching. However, the former process dominates the latter, resulting in a net decreasing effect of carbonation on the release of sodium and potassium from these cement matrices.     

Mercury cleanup: The commercial application of a new mercury removal/recovery technology

Efficient, economical treatment of mercury-contaminated soils and industrial wastes requires a treatment process that reduces mercury content to near background levels (<1 ppm) and recovers the removed mercury in pure recyclable form without producing liquid, solid, or gaseous secondary wastes. This article reviews the results achieved using a medium-temperature thermal desorption process developed and commercialized by Mercury Recovery Services, Inc. (MRS) that has successfully achieved these goals.     

Elemental analysis of printed circuit boards considering the ROHS regulations

The EU RoHS Directive (2002/95/EC of the European Parliament and of the Council) bans the placing of new electrical and electronic equipment containing more than agreed levels of lead, cadmium, mercury, hexavalent chromium, polybrominated biphenyl (PBB) and polybrominated diphenyl ether (PBDE) flame retardants on the EU market. It necessitates methods for the evaluation of RoHS compliance of assembled electronic equipment. In this study mounted printed circuit boards from personal computers were analyzed on their content of the three elements Cd, Pb and Hg which were limited by the EU RoHS directive. Main focus of the investigations was the influence of sample pre-treatment on the precision and reproducibility of the results. The sample preparation steps used were based on the guidelines given in EN 62321. Five different types of dissolution procedures were tested on different subsequent steps of sample treatment like cutting and milling. Elemental analysis was carried out using ICP-OES, XRF and CV-AFS (Hg). The results obtained showed that for decision-making with respect to RoHS compliance a size reduction of the material to be analyzed to particles ?1.5 mm can already be sufficient. However, to ensure analytical results with relative standard deviations of less than 20%, as recommended by the EN 62321, a much larger effort for sample processing towards smaller particle sizes might be required which strongly depends on the mass fraction of the element under investigation.