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.     

Investigation on the heavy metal content of zinc-carbon and alkaline manganese dry cells

The objective of this work was to test the compliance of commercially available batteries with the German Battery Ordinance, a project of the German government that was initiated by the Federal Environment Agency. Different types of commercially available dry cells were analysed for their cadmium, lead and mercury contents. The dry cells underwent mechanical pre-treatment, separation of the different components and microwave-assisted digestion before determination of the heavy metals. Mercury is sometimes added to prevent the generation of gaseous hydrogen from the electrochemical process. Lead could be present since it is sometimes used as an alloying element of zinc. Cadmium has no technical importance and is an undesirable impurity. None of the batteries contained higher heavy metal mass fractions than the permissible limits.     

Century Perspective of Heavy Metal Use in Urban Areas. A Case Study in Stockholm

The inflow and stock (amount in use) of heavy metals (cadmium(Cd), chromium (Cr), copper (Cu), lead (Pb), mercury (Hg), nickel (Ni) and zinc (Zn)) in goods in 1995 have been quantifiedin the anthroposphere of Stockholm, Sweden. Statistics on national, regional and local level were used. Contacts were established with representatives from production and constructionin the industrial sector and with authorities. The results show that the stock of Cd is 0,2 kg per capita. For the other heavymetals the corresponding result per capita is: Cr 8, Cu 170, Hg 0,01, Ni 4, Pb 73 and Zn 40 kg. The inflow varies between2–8%of the stock indicating the importance of the stock. The lowestlevels are for Cu and Pb. Heavy metal levels in solid waste are high, between 15–45% of the amount in the inflow (Hg excluded), the lowest values were for Cu and Pb. Thus, recyclingis incomplete. Long life expectancy goods form the majority of the stock but there is a tendency that short life expectancy goods increase their importance in the inflow. Concealedgoods are also more frequent in inflow than in the stock.     

The BATINTREC process for reclaiming used batteries

The Integrated Battery Recycling (BATINTREC) process is an innovative technology for the recycling of used batteries and electronic waste, which combines vacuum metallurgical reprocessing and a ferrite synthesis process. Vacuum metallurgical reprocessing can be used to reclaim the mercury (Hg) in the dry batteries and the cadmium (Cd) in the Ni-Cd batteries. The ferrite synthesis process reclaims the other heavy metals by synthesizing ferrite in a liquid phase. Mixtures of manganese oxide and carbon black are also produced in the ferrite synthesis process. The effluent from the process is recycled, thus significantly minimizing its discharge. The heavy metal contents of the effluent could meet the Integrated Wastewater Discharge Standard of China if the ratio of the crushed battery scrap and powder to FeSO4.7H2O is set at 1:6. This process could not only stabilize the heavy metals, but also recover useful resource from the waste.     

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。     

Regional Variability of Cd,Hg, Pb and C Concentrations in Different Horizons of Swedish Forest Soils

Contents of cadmium (Cd), mercury (Hg), lead (Pb) and carbon(C) in the O, B and C horizons of podzolized forest soils inSweden were surveyed. Concentrations and storage of Cd, Hg andPb in the O and B horizons were high in southern Sweden and gradually decreased towards the north, though with considerablelocal variability. This pattern reflects the influence of anthropogenic emissions of these metals, as well as the effectsof soil-forming processes. Parent till material, as representedby the C horizon concentration of the respective metal, accountedfor little of the variation in metal concentration in the O horizon. For Cd and Pb, the correlations were not significant orslightly negative (R² = 0.12 and 0.09 respectively) depending on region, while for Hg the correlation was not significant or slightly positive (R² = 0.03 and 0.08). Furthermore, parent till material accounted for more of the variation in metal concentrations in the B horizons in the northern part of Sweden than in the middle and southernmost parts, where the concentration of total carbon had more influence. The correlation between the metal concentrationsin the B and C horizon was strongest for Pb (R² = 0.63 and 0.36 in the two northernmost regions), lower for Cd (R² = 0.19 and 0.16) and not significant for Hg. For allsoil horizons, total C concentration accounted for much of thevariation in Hg concentration in particular (O-horizon R² = 0.15–0.69, B horizon R² = 0.36–0.50, C horizon R² = 0.23–0.50 and ns in one region). Ratios of metal concentrations between the B and C horizons were highest for Hg(maximum value of 30), indicating a relatively larger addition or retention of Hg compared to Cd and Pb (maximum value of 10)in the B horizon. This study indicate that factors other than parent material account for the large scale variation in O horizon concentrationsof metals but patterns correspond well with those of atmosphericdeposition of heavy metals and acidifying substances. Furthermore, the study highlights the importance of soil organicmatter and the intensity of pedogenic processes for the content and distribution of metals throughout the soil horizons.     

Zinc,lead, and cadmium tolerance and accumulation in Cistus libanotis,Cistus albidus,and Cistus salviifolius: Perspectives on phytoremediation

Heavy metal contamination is of particular concern for human health and the environment. Phytoremediation is an emerging cost‐effective strategy to remediate heavy metal contaminated soil. However, this technique is limited by the small number of plants that are tolerant to heavy metals and are also accumulators. This study assayed zinc, lead, and cadmium tolerance and accumulation in Cistus libanotis, Cistus albidus, and Cistus salviifolius. The plants were cultivated in hydroponic conditions and exposed to different concentrations of Pb(NO₃)₂ (100 and 200 µM), ZnSO₄ (100 and 200 µM), or CdCl₂ (10 and 20 µM) for 3 weeks. Plant biomass and metal accumulation in roots and aboveground parts varied greatly among the species. All three species appeared to be sensitive to Zn. However, C. albidus displayed strong tolerance to Pb and accumulated large quantities of Pb and Cd in its roots. C. libanotis accumulated large quantities of Pb and Cd in its aboveground parts. C. libanotis can thus be classified as a Pb and Cd accumulator species. The study results show that C. albidus is suitable for phytostabilization of Pb‐contaminated soils, while C. libanotis can be used for phytoextraction of both Pb and Cd.     

Atmospheric Metal Pollutants-Archives, Methods, and History

Pollution of the atmosphere with cadmium (Cd), mercury (Hg), and lead (Pb) is a consequence of human activities. Natural archives are necessary to reconstruct the long-term history of metal deposition because accurate measurement of atmospheric deposition is a recent accomplishment. Reconstructions require: (1) accurate determination of concentrations of elements and isotopes, (2) accurate chronology of archives, and (3) archives that faithfully record atmosphere deposition. The most useful long-term archives are accumulations of ice and snow, peat, and lake sediment. Quantification of Cd deposition is uncommon because of its low concentration and substantial chemical mobility. Nonetheless, trends in peat and lake sediment are similar to those of Hg and Pb since ca. 1800 a.d. Both Hg and Pb are relatively chemically immobile and thus the peat and lake archives are believed to record historic trends of atmospheric deposition. Isotopic and concentration studies of Pb indicate a history of northern hemisphere atmospheric pollution extending back prior to 0 a.d. Although measurements of Hg concentration are now routine, isotopic measurements are in their infancy. Some Hg pollution sources have unique isotopic ratios, thereby contributing unique signals to the total Hg. Maximum accumulation rates of Hg and Pb occur up to 10 years later than for Cd (1970s versus 1960s in eastern North America, perhaps slightly later in Europe). By 2004, deposition of Cd, Hg, and Pb had declined from peak values in eastern North America more than 75, 75, and 90%, respectively.     

Microbial Activity in Relation to Small Scale Patterns of Heavy Metals and Substrate Quality in Spruce Mor Layers (Of) in Southern Sweden

The within-site correlations between soil respiration rates,lead (Pb), mercury (Hg) and cadmium (Cd) concentrations andorganic matter quality variables were investigated at four sites in southern Sweden. The aim was to study whether the within-site variation in heavy metal concentrations could beused to monitor biological effects of regional deposition of heavy metals. Two sites in the south-west, one in the mid-southof the country, and one in south-east were investigated. At the south-eastern, least contaminated, site there were no correlations between soil respiration rate, and either organicmatter quality variables or heavy metal concentrations. At the remaining sites, negative correlations were found between Pb andsoil respiration rate. However, at two of these three sites there was a covariation with cellulose that could account for these correlations. The within-site variation of pH and total nitrogen (N) was low, and did not show any correlative general trends with either respiration rate or heavy metals. Meta analysis showed that negative correlations between Pb or Hg, on the one hand, and cellulose or hemicellulose on the other weregenerally found in within-site investigations. However, this does not necessarily explain the correlation between Pb and soil respiration, as was shown for the southernmost site. A PLS model of soil respiration rates at this site, using allmeasured variables, including heavy metals, explained more variation than a model developed using only mor layer thickness,pH, carbohydrate, ash and nitrogen concentrations, as independent variables. Thus there is a risk of toxic effects from Pb even at the levels found in south-western Sweden today(>120 g Pb * g dw^-1). However, since the correlationsbetween heavy metals and cellulose were not significantly different at the different sites, random sampling variation could not be ruled out as an explanation of the different results for the different sites. The causes of the correlationbetween organic matter quality and heavy metals have not yet been clarified. Analysis of mor samples incubated in thelaboratory for 2 yr with 1200 g Pb * g dw^-1 or 5 gHg * g dw^-1 did not show any differences in carbohydrate composition, compared to control samples. This shows that within-site studies of correlations between respiration rate and heavy metals have to be combined with studies of metal additions to soils and analysis of organic matter quality beforeany valid conclusions can be made.     

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.     

Changes in Atmospheric Deposition Rates of Heavy Metals in Sweden A Summary of Nationwide Swedish Surveys in 1968/70 – 1995

The Swedish nationwide surveys of atmospheric heavy metal deposition in 1968/70 – 1995 using bryophytes (carpet-forming mosses) as monitors are reviewed. Considered are cadmium (Cd), copper (Cu), iron (Fe), lead (Pb), mercury (Hg), nickel (Ni), vanadium (V), and zinc (Zn). The close agreement between data obtained with deposition (precipitation) collectors and moss carpet analysis is documented briefly, as well as measures of quality control and assessment of reproducibility. Since 1968/70, the deposition rate of the heavy metals considered has declined gradually and evenly, particularly in the southern parts of the country, reflecting an improvement of general air quality due to decreasing dust emission from mainly industry and fossil fuel combustion in northern and western Europe. By far the greatest absolute decrease in deposition rate was measured in Fe, which is a main constituent of most man-generated dust particles. However, the greatest per cent decreases in deposition rates were measured for Pb. The Pb concentration of moss carpets in Sweden as a whole in 1995 was only 11% of the value in 1968/70. Corresponding figures for Fe was 20%, Cd 24%, Ni 28%, Hg 31%, V 43%, Zn 51%, and Cu 52%. For Zn the current deposition rate seems to approach a natural baseline, whereas deposition of the other seven elements are still decreasing according to the surveys of 1990 and 1995.     

Assessment of toxic metals in waste personal computers

Considering the enormous production of waste personal computers nowadays, it is obvious that the study of their composition is necessary in order to regulate their management and prevent any environmental contamination caused by their inappropriate disposal. This study aimed at determining the toxic metals content of motherboards (printed circuit boards), monitor glass and monitor plastic housing of two Cathode Ray Tube (CRT) monitors, three Liquid Crystal Display (LCD) monitors, one LCD touch screen monitor and six motherboards, all of which were discarded. In addition, concentrations of chromium (Cr), cadmium (Cd), lead (Pb) and mercury (Hg) were compared with the respective limits set by the RoHS 2002/95/EC Directive, that was recently renewed by the 2012/19/EU recast, in order to verify manufacturers’ compliance with the regulation. The research included disassembly, pulverization, digestion and chemical analyses of all the aforementioned devices. The toxic metals content of all samples was determined using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). The results demonstrated that concentrations of Pb in motherboards and funnel glass of devices with release dates before 2006, that is when the RoHS Directive came into force, exceeded the permissible limit. In general, except from Pb, higher metal concentrations were detected in motherboards in comparison with plastic housing and glass samples. Finally, the results of this work were encouraging, since concentrations of metals referred in the RoHS Directive were found in lower levels than the legislative limits.     

Solubility and Potential Mobility of Heavy Metals in Two Contaminated Urban Soils from Stockholm,Sweden

The solubility and potential mobility of heavy metals (Cd, Cu,Hg, Pb and Zn) in two urban soils were studied by sequential andleaching extractions (rainwater). Compared to rural (arable) soils on similar parent material, the urban soils were highlycontaminated with Hg and Pb and to a lesser extent also with Cd,Cu and Zn. Metal concentrations in rainwater leachates were related to sequential extractions and metal levels reported fromStockholm groundwater. Cadmium and Zn in the soils were mainly recovered in easily extractable fractions, whereas Cu and Pb were complex bound. Concentrations of Pb in the residual fractionwere between two- and eightfold those in arable soils, indicatingthat the sequential extraction scheme did not reflect the solidphases affected by anthropogenic inputs. Cadmium and Zn conc. inthe rainwater leachates were within the range detected in Stockholm groundwater, while Cu and Pb conc. were higher, whichsuggests that Cu and Pb released from the surface soil were immobilised in deeper soil layers. In a soil highly contaminatedwith Hg, the Hg conc. in the leachate was above the median concentration, but still 50 times lower than the max concentration found in groundwater, indicating the possibilityof other sources. In conclusion, it proved difficult to quantitatively predict the mobility of metals in soils by sequential extractions.     

Stockhome: A Spreadsheet Model of Urban Heavy Metal Metabolism

Computer models for analysis,visualising and decision support in environmentalresearch have become increasingly popular. TheStockhome project, where the urban metabolism ofheavy metals in Stockholm was studied, resultedin a database with historical data of the use ofgoods containing cadmium (Cd), chromium (Cr),copper (Cu), lead (Pb), mercury (Hg), nickel (Ni)and zinc (Zn). A spreadsheet model was developedto study flows and stocks of the metalconsumption process and emissions. The modelindicates uncertainties of the data, societalaspects such as field of use and rights ofdisposition of the goods. By considering goods asthe drivers of the emissions, the model would bewell suited for policy support.     

Laboratory study on the leaching potential of spent alkaline batteries

Four different leaching tests were carried out with spent alkaline batteries as an attempt to quantify the environmental potential burdens associated with landfilling. The tests were performed in columns filled up with batteries either entire or cross-cut, using either deionized water or nitric acid solution as leachant. In a first set of tests, the NEN 7343 standard procedure was followed, with leachant circulating in open circuit from bottom to top through columns. These tests were extended to another leaching step where leachant percolated the columns in a closed loop process.Leachate solutions were periodically sampled and pH, conductivity, density, redox potential, sulphates, chlorides and heavy metals (As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Tl and Zn) were determined in the samples.The results showed that the total amount of substances leached in tests with cross-cut batteries was higher than with entire ones; zinc and sulphates were the substances found the most in the leachate solutions. In general, the amount of substances dissolved in open circuit is higher than in closed loop due to the effect of solution saturation and the absence of fresh solution addition.Results were compared with metal contents in the batteries and with legal limits for acceptance in landfill (Decision 2003/33/CE and Decree-Law 152/2002). None of the metals were meaningfully dissolved comparatively to its content in the batteries, except Hg. Despite the differences in the experiment procedure used and the one stated in the legislation (mixing, contact time and granulometry), the comparison of results obtained with cross-cut batteries using deionized water with legal limits showed that batteries studied could be considered hazardous waste.     

Fluxes and Loading of Heavy Metals, Benzo[a]pyrene and Oil Products in Vilnius City

The concentrations of heavy metals Pb, Cd, Cu, Zn and Hg, benzo[a]pyrene and oil products (C₁₅–C₂₈) in bulk (wet and dry) atmospheric deposition in Vilnius city in 2005–2006 were analysed. The highest flux to the ground surface of the city residential area, reaching 1,680 mg m^?2 year^?1, was determined for oil products, which in atmospheric bulk deposition was estimated to be mainly in the form of solid sediments. Among heavy metals, the highest flux was determined for Zn (113.5 mg m^?2 year^?1), while the lowest flux was determined for Hg (0.06 mg m^?2 year^?1). The flux of investigated pollutants ranges from a few times, or for some pollutants, up to one order of magnitude higher at the urban sampling site in comparison to residential or background sites. Some hundred tons of oil products, approximately 52 tons of zinc and a considerably lower amount of mercury, benzo[a]pyrene and cadmium deposit yearly to the ground and water surface of Vilnius city. Metallic constructions related to transport and buildings, automobile exhausts, spills of fuel and lubricants are suggested to be the factors which result in the accumulation of high amounts of heavy metals, oil products and other pollutants on the ground surface of the city.     

喀斯特山区燃煤电厂土壤重金属污染评价

选取地处贵州省喀斯特山区的金沙电厂为研究对象,对电厂周围的表层土壤、蔬菜(莲花白)试样的重金属含量进行了测定,采用模糊数学法对土壤重金属污染进行了评价,采用富集系数法分析了莲花白对重金属的富集能力。实验结果表明:电厂周围表层土壤中Hg,As,Cd,Pb,Cu的平均含量分别达0.70,26.40,0.61,44.83,35.51 mg/kg,其中,Hg和Cd的平均含量分别为GB 15618—1995《土壤环境质量标准》中二级标准的1.40和2.03倍;电厂周围土壤受到较为严重的Hg,As,Cd污染,各个方向的重金属污染程度大小顺序为西北西东南西南东北东,总体趋势为西向大于东向;莲花白对土壤中Cd的富集作用较强,对其他重金属的富集作用较弱。     

Investigation of potentially toxic heavy metals in different organic wastes used to fertilize market garden crops

The benefits of using organic waste as fertilizer and soil amendment should be assessed together with the environmental impacts due to the possible presence of heavy metals (HMs). This study involved analysing major element and HM contents in raw and size-fractionated organic wastes (17 sewage sludges and composts) from developed and developing countries. The overall HM concentration pattern showed an asymmetric distribution due to the presence of some wastes with extremely high concentrations. HM concentrations were correlated with the size of cities or farms where the wastes had been produced, and HM were differentiated with respect to their origins (geogenic: Cr–Ni; anthropogenic agricultural and urban: Cu–Zn; anthropogenic urban: Cd–Pb). Size fractionation highlighted Cd, Cu, Zn and Pb accumulation in fine size fractions, while Cr and Ni were accumulated in the coarsest. HM associations with major elements revealed inorganic (Al, Fe, etc.) bearing phases for Cr and Ni, and sulfur or phosphorus species for Cd, Cu Pb and Zn.     

Heavy Metals in Stockholm Groundwater – Concentrations and Fluxes

Sampling of groundwater in theQuaternary deposits was carried out at 70 sitesin Stockholm for, among other things, metalanalyses. The objectives were to get a notion of the metal content and to get a basis for anestimation of the order of magnitude of thegroundwater transported metal contribution to themain surface water bodies in comparison to otherroutes. Thus, in three watershed areaswithin the Stockholm Town, groundwater flow andmetal concentration propagation were simulatedand metal fluxes were calculated. Theconcentrations of heavy metals were in generalfound to be very high in comparison withgroundwater in forested areas. This was mostpronounced for mercury (Hg) and copper (Cu). Themost remarkable result was a Hg concentration of4.57 g L^-1 in the vicinity of a closed downhospital. The annual contribution of heavy metals(kg) by groundwater to the main surface waterbodies was estimated to: As (2.2), Cd (0.20), Co(4.9), Cr (3.1), Cu (34), Hg (0.06), Ni (28), Pb(2.2) Zn (118). These fluxes are much smallerthan those in forest ecosystems, due to lowergroundwater recharge in urban areas, where agreat part of the runoff is diverted bylandsealing, drainage, tunnels etc. The modelingresults emphasize the importance of the sorptionprocesses indicating that the modeled areas arein a non-steady state condition. It also showsthat the sources generating elevatedconcentrations of the high adsorptive metals Pband Hg are likely to be nearby.     

Characteristics of ashes from different locations at the MSW incinerator equipped with various air pollution control devices

The characteristics of ashes from different locations at a municipal solid waste incinerator (MSWI) equipped with a water spray tower (WST) as a cooling system, and a spray dryer adsorber (SDA), a bag filter (BF) and a selective catalytic reactor (SCR) as air pollution control devices (APCD) was investigated to provide the basic data for further treatment of ashes. A commercial MSWI with a capacity of 100 tons per day was selected. Ash was sampled from different locations during the normal operation of the MSWI and was analyzed to obtain chemical composition, basicity, metal contents and leaching behavior of heavy metals. Basicity and pH of ash showed a broad range between 0.08-9.07 and 3.5-12.3, respectively. Some major inorganics in ash were identified and could affect the basicity. This could be one of the factors to determine further treatment means. Partitioning of hazardous heavy metals such as Pb, Cu, Cr, Hg and Cd was investigated. Large portions of Hg and Cd were emitted from the furnace while over 90% of Pb, Cu and Cr remained in bottom ash. However 54% of Hg was captured by WST and 41% by SDA/BF and 3.6% was emitted through the stack, while 81.5% of Cd was captured by SDA/BF. From the analysis data of various metal contents in ash and leach analysis, such capturing of metal was confirmed and some heavy metals found to be easily released from ash. Based on the overall characteristics of ash in different locations at the MSWI during the investigation, some considerations and suggestions for determining the appropriate treatment methods of ash were made as conclusions.