Antimony smelting process generating solid wastes and dust：Characterization and leaching behaviors

A large amount of solid waste has been produced by the antimony smelting process in the＂World Capital of Antimony＂, Xikuangshan area in China. This study comprehensively investigated the physical and chemical characteristics of the various solid wastes, as well as the leaching behavior of the solid wastes, which included water-quenched slag,arsenic-alkali residue, desulfurized slag and blast furnace dust. These four types of waste were enriched in a variety of heavy metals and metalloids and more specifically with As and Sb levels up to 8.6 × 104 and 3.16 × 105mg/kg, respectively, in arsenic-alkali residue. For desulfurized slag and water-quenched slag, the leaching concentration of Sb significantly exceeded the acceptable limits during the leaching tests using the toxicity characteristic leaching procedure and the synthetic precipitation leaching procedure. In addition, As leaching in arsenic-alkali residue was extraordinarily hazardous, being three orders of magnitude higher than the regulatory level of As. According to the results of the extraction tests, all the tested wastes were classified as hazardous waste.     

Detoxifying PCDD/Fs and heavy metals in fly ash from medical waste incinerators with a DC double arc plasma torch

Medical waste incinerator (MWI) fly ash is regarded as a highly toxic waste because it contains high concentrations of heavy metals anddioxins, including polychlorinateddibenzo-p-dioxins (PCDDs) and polychlorinateddibenzofurans (PCDFs). Therefore fly ash from MWI must be appropriately treated before beingdischarged into the environment. A melting process based on adirect current thermal plasma torch has beendeveloped to convert MWI fly ash into harmless slag. The leaching characteristics of heavy metals in fly ash and vitrified slag were investigated using the toxicity characteristic leaching procedure, while the content of PCDD/Fs in the fly ashes and slags was measured using method 1613 of the US EPA. The experimental results show that thedecomposition rate of PCDD/Fs is over 99% in toxic equivalent quantity value and the leaching of heavy metals in the slag significantlydecreases after the plasma melting process. The produced slag has a compact and homogeneous microstructure withdensity of up to2.8 g/cm3 .     

Investigation of basic properties of fly ash from urban waste incinerators in China

Basic properties of fly ash samples from different urban waste combustion facilities in China were analyzed using as X-ray fluorescence （XRF）, scanning electron microscopy （SEM）, X-ray diffraction （XRD）. The leaching toxicity procedure and some factors influencing heavy metals distribution in fly ash were further investigated. Experimental results indicate that the fly ash structures are complex and its properties are variable. The results of XRF and SEM revealed that the major elements （〉10000 mg/kg, listed in decreasing order of abundance） in fly ash are O, Ca, Cl, Si, S, K, Na, Al, Fe and Zn. These elements account for 93% to 97%, and the content of Cl ranges from 6.93% to 29.18 %, while that of SiO2 does from 4.48% to 24.84%. The minor elements （1000 to 10000 mg/kg） include Cr, Cu and Pb. Primary heavy metals in fly ash include Zn, Pb, Cr, Cu etc. According to standard leaching test, heavy metal leaching levels vary from 0 to 163.10 mg/L （Pb） and from 0.049 to 164.90 mg/L （Zn）, mostly exceeding the Chinese Identification Standard for hazardous wastes. Morphology of fly ash is irregular, with both amorphous structures and polycrystalline aggregates. Further research showed that heavy metals were volatilized at a high furnace temperature, condensed when cooling down during the post-furnace system and captured at air pollution control systems. Generally, heavy metals are mainly present in the forms of aerosol particulates or tiny particulates enriched on surfaces of fly ash particles. The properties of fly ash are greatly influenced by the treatment capacities of incinerators or the variation of waste retention time in chamber. Fly ash from combustors of larger capacities generally has higher contents of volatile component and higher leaching toxicity, while those of smaller capacities often produce fly ash containing higher levels of nonvolatile components and has lower toxicity. The content of heavy metals and leaching toxicity maybe have no convincing correlation, and high alkali content of CaO greatly contribute to leaching toxicity of heavy metal and acid neutralization capacity against acid rain.     

Leaching of metals on stabilization of metal sludge using cement based materials

Toxicity characteristic leaching procedure(TCLP) of zinc plating sludge was carried out to assess the leaching potential of the sludge and the leachates were analyzed for heavy metals. The concentration of zinc, chromium, and lead in the leachate were 371.5 mg/L, 1.95 mg/L and 1.99 mg/L respectively. Solidification of zinc sludge was carried out using four different binder systems consisting of cement mortar, fly ash, clay and lime and cured for 28 d, The ratio of sludge added varied from 60% to 80% by volume. The solidified products were tested for metal fixing efficiency and physical strength. It was observed that the volume of sludge added that resulted in maximum metal stabilization was 60% for all the combinations, above which the metal fixation efficiency decreased resulting in high values of zinc in the leachate. Addition of 5% sodium silicate enhanced the chemical fixation of metals in all the binder systems. Among the four fixing agents studied, mixture of fly ash: lime, and cement mortar: lime stabilized zinc and other metals in the sludge effectively than other combinations. Addition of lime increased the stabilization of zinc whereas cement mortar increased the strength of the solidified product.     

Leaching behavior of Pb and Zn in air pollution control residues and their modeling prediction

Increasing attention has been paid to air pollution control （APC） residues in China recently due to the rising proportion of waste incineration and the hazardous characteristics of the residues, among which heavy metal leaching toxicity plays an important role. Leaching behavior and potential risk of Pb and Zn in the APC residues from a Shanghai municipal solid waste （MSW） incinerator was studied, based on the leaching tests under different conditions and theoretical calculation using a geochemical thermodynamic equilibrium model MINTEQA2. Results showed that, extractant species and liquid to solid （L/S） ratio predominantly controlled the leaching toxicity of Pb and Zn, while ionic strength, vibration method and leaching time had less effect on the metals release. Leachate/final pH determined the metal leaching behavior, which changed the speciation of heavy metals in the extraction system. The equilibrium aqueous speciation, precipitation-dissolution of Pb and Zn was investigated according to the model computation, which was well in agreement with the experimental results.     

Chemical speciation and mobility of heavy metals in municipal solid waste incinerator fly ash

Chemical speciation is a significant factor that govems the toxicity and mobility of heavy metals in municipal solid waste incinerator fly ash. Sequential extraction procedure is applied to fractionate heavy metals( Pb, Zn, Cd, Cu, and Cr) into five defined groups: exchangeable, carbonate, Fe-Mn oxide, organic, and residual fractions. The mobility of heavy metals is also investigated with the aid of toxicity characteristic leaching procedure. In the fly ash sample, Pb is primarily presented in the carbonate (51%) and exchangeable(20% ) fractions; Cd and Zn mainly exist as the exchangeable(83% and 49% respectively) ; Cu is mostly contained in the last three fractions(totally 87% ) ; and Cr is mainly contained in the residual fraction(62% ). Pb, Zn and Cd showed the high mobility in the investigation, thus might be of risk to the natural environment when municipal solid waste incinerator fly ash is landfilled or reutilized.     

Effect of chemical and thermal activations on the properties of rice husk ash-based solidified wastes

Strength development,leachability and microstructure of heavy metals from the solidified waste using synthesis rice husk ash (sRHA) and lime blended at the weight ratio of 1:1 were used as binders.The heavy metal-containing sludge was used at the level of 0 wt.%,30 wt.%,and 50 wt.% dry weight,respectively.The sample specimens with and without 1.5 wt.% of sodium silicate (SiO 2 /Na 2 O=1.0) were cured under the ambient condition and elevated temperature curing at 50°C for 24 hr.Experimental results showed that the introduction of sodium silicate solution and elevated temperature curing to sRHA-based solidified waste containing 30 wt.% of heavy metal sludge gave one day strength of 20 kg/cm 2 compared to 0.9 kg/cm2 for the control sample.XRD patterns indicated that most metal-sulfides present in the sludge were appeared in the solidified waste and SEM coupled with EDX techniques reveal these metal-sulfide particles were trapped within the lime-sRHA matrices.In addition,cumulative leaching behavior by tank test (EA NEN 7375:2004) showed that solidified waste containing up to 30 wt.% of heavy metal sludge was suitable to dispose in a secured landfill.     

Treatment of tunnel wash waters – experiments with organic sorbent materials. Part II: Removal of toxic metals

In the first part of the article, the column and the bag experiments concerning removal of polycyclic aromatic hydrocarbons (PAHs) and nonpolar oil (NPO) from tunnel wash waters using organic sorbent materials have been described. This part presents the results of removal of toxic metals. The metals of concern (Al, As, Cd, Cr, Cu, Fe, Pb, Mo, Ni, and Zn) were selected based on the priority toxicant pollutants defined in surface water quality criteria. Concentrations of these metals in the collected effluent...     

Metals in sediment/pore water in Chaohu Lake: Distribution, trends and flux

Nine metals, Cd, Cu, Ni, Pb, As, Cr, Zn, Fe, and Mn in sediment and pore water from 57 sampling sites in Chaohu Lake (Anhui Province, China) were analyzed for spatial distribution, temporal trends and diffuse flux in 2010. Metals in the surface sediment were generally the highest in the western lake center and Nanfei-Dianbu River estuary, with another higher area of As, Fe, and Mn occurring in the Qiyang River estuary. Metal contamination assessment using the New York sediment screening criteria showed that the sediment was severely contaminated in 44% of the area with Mn, 20% with Zn, 16% with Fe, 14% with As, and 6% with Cr and Ni. An increasing trend of toxic metals (Cd, Cu, Ni, Pb, As, Cr, Zn) and Mn with depth was shown in the western lake. Compared with metal content data from the sediment survey conducted in 1980s, the metal content of surface sediment in 2010 was 2.0 times that in the 1980s for Cr, Cu, Zn, and As in the western lake, and less than 1.5 times higher for most of the metals in the eastern lake. Among the metals, only Mn and As had a widespread positive diffuse flux from the pore water to overlying water across the whole lake. The estimated flux in the whole lake was on average 3.36 mg/(m². day) for Mn and 0.08 mg/(m². day) for As, which indicated a daily increase of 0.93 μg/L for Mn and 0.02 μg/L for As in surface water. The increasing concentration of metals in the sediment and the flux of metals from pore water to overlying water by diffusion and other physical processes should not be ignored for drinking-water sources.     

Size distribution, characteristics and sources of heavy metals in haze episod in Beijing

Size segragated samples were collected during high polluted winter haze days in 2006 in Beijing, China. Twenty nine elements and 9 water soluble ions were determined. Heavy metals of Zn, Pb, Mn, Cu, As, Cr, Ni, V and Cd were deeply studied considering their toxic effect on human being. Among these heavy metals, the levels of Mn, As and Cd exceeded the reference values of National Ambient Air Quality Standard （GB3095-2012） and guidelines of World Health Organization. By estimation, high percentage of atmospheric heavy metals in PM2.5 indicates it is an effective way to control atmospheric heavy metals by PM2.5 controlling. Pb, Cd, and Zn show mostly in accumulation mode, V, Mn and Cu exist mostly in both coarse and accumulation modes, and Ni and Cr exist in all of the three modes. Considering the health effect, the breakthrough rates of atmospheric heavy metals into pulmonary alveoli are： Pb （62.1%） 〉 As （58.1%） 〉 Cd （57.9%） 〉 Zn （57.7%） 〉 Cu （55.8%） 〉 Ni （53.5%） 〉 Cr （52.2%） 〉 Mn （49.2%） 〉 V （43.5%）. Positive matrix factorization method was applied for source apportionment of studied heavy metals combined with some marker elements and ions such as K, As, SO42- etc., and four factors （dust, vehicle, aged and transportation, unknown） are identified and the size distribution contribution of them to atmospheric heavy metals are discussed.     

Removal of heavy metals using waste eggshell

The removal capacity of toxic heavy metals by the reused eggshell was studied.As a pretreatment process for the preparation of reused material from waste eggshell,calcination was performed in the furnace at 800℃for 2 h after crushing the dried waste eggshell.Calcination behavior,qualitative and quantitative elemental information,mineral type and surface characteristics before and after calcination of eggshell were examined by thermal gravimetric analysis(TGA),X-ray fluorescence (XRF),X-ray diffraction(XRD) and scanning electron microscopy(SEM),respectively.After calcination,the major inorganic composition was identified as Ca(lime, 99.63%)and K,P and Sr were identified as minor components.When calcined eggshell was applied in the treatment of synthetic wastewater containing heavy metals,a complete removal of Cd as well as above 99% removal of Cr was observed after 10 min. Although the natural eggshell had some removal capacity of Cd and Cr,a complete removal was not accomplished even after 60 min due to quite slower removal rate.However,in contrast to Cd and Cr,an efficient removal of Pb was observed with the natural eggshell rather than the calcined eggshell.From the application of the calcined eggshell in the treatment of real electroplating wastewater, the calcined eggshell showed a promising removal capacity of heavy metal ions as well as had a good neutralization capacity in the treatment of strong acidic wastewater.     

Characterization of changes in extracellular polymeric substances and heavy metal speciation of waste activated sludge during typical oxidation solubilization processes

Biopolymer solubilization is considered to be the rate-limiting stage of anaerobic digestion of waste activated sludge(WAS). Oxidation processes have been proven to be effective in disrupting sludge flocs and causing solubilization of the solid biopolymers. In this study,WAS was treated by NaNO2 or H2 O2 oxidation at p H of 2. The changes in extracellular polymeric substances properties and the speciation of heavy metals were investigated. The results revealed that both NaNO2 and H2 O2 treatments were effective in solubilizing organics in WAS, while the conversion of biopolymers in the two treatment processes was different. Free nitrous acid destroyed the gel network structure of EPS, and organic materials were released from the solid phase to the supernatant. Indigenous peroxidase catalyzed H2 O2 to produce hydroxyl radicals which caused significant solubilization of biopolymers, and the protein-like substances were further degraded into micro-molecule polypeptides or amino acids at high dosages of H2 O2. During the oxidation processes, Zn, Cd and Cu, with excellent mobility, tended to migrate to the supernatant, and thus were easy to remove through the liquid–solid separation process. Ni and As showed moderate migration ability, of which the residual fraction tended to transform into reducible and soluble fractions. With poor mobility, Cr and Pb mainly existed in the forms of residual and oxidizable fractions, which were difficult to dissolve and remove from WAS. Both NaNO2 and H2 O2 treatment resulted in the enhancement of sludge solubilization efficiency and heavy metal mobility in WAS, but different heavy metals showed distinct migration and transformation behaviors.     

Initial identification of heavy metals contamination in Taihu Lake, a eutrophic lake in China

A detailed investigation of seven heavy metals (Cu, Cd, Cr, As, Pb, Zn, Ni) in the water column, interstitial water and surface sediment was conducted to quantify the extent of their contamination in Taihu Lake. Results showed the average total concentrations ranged from 0.93 μg/L for Cd to 47.03 μg/L for Zn. The dissolved concentrations in the overlying water ranged from 0.06 μg/L for Cd to 15.86 μg/L for Zn. The metals in the Taihu Lake surface water were primarily in the particulate phase, especially for Cd, whose particulate concentration represented 94.3% of the total. In the surface sediment, the mean concentrations for Cr, Ni, Cu, Zn, As, Cd and Pb were 41.50, 28.72, 27.82, 65.46, 5.94, 0.82 and 41.17 mg/kg, respectively. The metals in the water column and sediments of Taihu Lake displayed significant spatial variations, and the higher metal concentrations mainly occurred in the north and west of Taihu Lake, especially in Zhushan Bay and West Taihu Lake. A quality assessment indicated that most of the metals in the surface water of Taihu Lake had no or low adverse health effects on organisms, except for Pb and Cu, which may cause chronic toxicity. Compared with the "Consensus-Based Sediment Quality Guidelines", the polluting metals were Cr, Ni and Cd, and the polluted regions were confined to Zhushan Bay, Meiliang Bay and the west of Taihu Lake, especially for north of Zhushan Bay. The polluted areas for Cr, Ni and Cd were 14.36, 34.70 and 13.24 km², respectively. We suggest that Cr, Ni, and Cd in the polluted areas should be addressed and that tissue chemistry and sediment toxicity assessments be performed as soon as possible.     

Health risks associated with heavy metals in the drinking water of Swat, northern Pakistan

The concentrations of heavy metals such as Cd, Cr, Cu, Mn, Ni, Pb and Zn were investigated in drinking water sources （surface and groundwater） collected from Swat valley, Khyber Pakhtunkhwa, Pakistan. The potential health risks of heavy metals to the local population and their possible source apportionment were also studied. Heavy metal concentrations were analysed using atomic absorption spectrometer and compared with permissible limits set by Pakistan Environmental Protection Agency and World Health Organization. The concentrations of Cd, Cr, Ni and Pb were higher than their respective permissible limits, while Cu, Mn and Zn concentrations were observed within their respective limits. Health risk indicators such as chronic daily intake （CDI） and health risk index （HRI） were calculated for adults and children separately. CDIs and HRIs of heavy metals were found in the order of Cr 〉 Mn 〉 Ni 〉 Zn 〉 Cd 〉 Cu 〉 Pb and Cd 〉 Ni 〉 Mn 〉 Cr 〉 Cu 〉 Pb 〉 Zn, respectively. HRIs of selected heavy metals in the drinking water were less than 1, indicating no health risk to the local people. Multivariate and univariate statistical analyses showed that geologic and anthropogenic activities were the possible sources of water contamination with heavy metals in the study area.     

A novel strategy of tannery sludge disposal –converting into biochar and reusing for Cr(Ⅵ)removal from tannery wastewater

Tannery sludge with high chromium content has been identified as hazardous solid waste due to its potential toxic effects.The safety disposal and valorization of the tannery sludge remains a challenge.In this study,the chromium stabilization mechanism was systematically investigated during chromium-rich tannery sludge was converted to biochar and the removal performance of the sludge biochar (SBC) for Cr(Ⅵ) from tannery wastewater was also investigated.The results showed that increase in pyrolys...     

Insights into metals in individual fine particles from municipal solid waste using synchrotron radiation-based micro-analytical techniques

Excessive inter-contamination with heavy metals hampers the application of biological treatment products derived from mixed or mechanically-sorted municipal solid waste(MSW). In this study, we investigated fine particles of 2 mm, which are small fractions in MSW but constitute a significant component of the total heavy metal content, using bulk detection techniques. A total of 17 individual fine particles were evaluated using synchrotron radiation-based micro-X-ray fluorescence and micro-X-ray diffraction. We also discussed the association, speciation and source apportionment of heavy metals. Metals were found to exist in a diffuse distribution with heterogeneous intensities and intense hot-spots of 10 μm within the fine particles. Zn–Cu, Pb–Fe and Fe–Mn–Cr had significant correlations in terms of spatial distribution. The overlapped enrichment, spatial association, and the mineral phases of metals revealed the potential sources of fine particles from size-reduced waste fractions(such as scraps of organic wastes or ceramics) or from the importation of other particles. The diverse sources of heavy metal pollutants within the fine particles suggested that separate collection and treatment of the biodegradable waste fraction(such as food waste) is a preferable means of facilitating the beneficial utilization of the stabilized products.     

Role of adsorption behavior on metal build-up in urban road dust

Metal pollution of stormwater runoff can cause potential toxic impacts on the receiving water environment and human health. Effective pollution mitigation requires accurate stormwater quality modeling. Even though a significant knowledge base exists on the factors influencing metal build-up on urban roads, very limited studies have investigated how metal–particulate interaction influences metal build-up. This study quantitatively assessed the influence of particulate characteristics, together with vehicular traffic and land use, on the build-up of Zn, Cu, Pb, Cr, Ni and Cd on urban roads. The study outcomes revealed that the variability in metal build-up is highly influenced by the variability associated with metal adsorption to particulates. The percentage contribution from particulate properties influencing metal adsorption in the case of 150 μm size road dust particles was found to be higher(Zn 44%, Cu 52%, Cr 16%, Ni 27% and Cd 45%) when compared to traffic and land use characteristics(Zn 21%, Cu 13%, Cr and Ni 10% and Cd 34%). Similar adsorption behavior was noted for metals associated with 150 μm size road dust particles. Among different particulate properties influencing metal adsorption, effective cation exchange capacity showed a strong positive relationship with the build-up of Cd compared to other metals,highlighting the potential role of Cd in stormwater quality as a readily available metal. The build-up of metals such as Cr and Ni are highly influenced by metal oxides of Al, Fe and Mn and clay forming minerals, indicating that Cr and Ni are relatively stable in nature.     

Distribution, risk and bioavailability of metals in sediments of Lake Yamdrok Basin on the Tibetan Plateau, China

Total contents of metals in soil and sediments on the Tibetan Plateau of China have been widely analyzed, but existing information is insufficient to effectively evaluate metal ecological risk because of a lack of metal bioavailability data. In this study, distribution, potential risk, mobility and bioavailability of metals in sediments of Lake Yamdrok Basin in Tibet of China were explored by combined use of total digestion, sequential extraction and the diffusive gradient in thin-films (DGT). Average concentrations of Cr, Ni, Cu, Zn, As, Cd and Pb in surface sediments were 31.25, 30.31, 22.00, 45.04, 31.32, 0.13 and 13.39 mg/kg, respectively. Higher levels of metals were found near the inflowing rivers. Residual form was dominant in Cr, Ni, Zn, Cd and Pb, and reducible form was dominant in As and Cd. Metals in surface sediments showed a low enrichment degree overall, but Cd and As had higher ecological risk levels than the other metals. Furthermore, there was a larger average proportion of exchangeable form of As (20.4%) and Cd (9.0%) than the other metals (1.7%-3.3%), implying their higher mobility and release risk. Average DGT-labile concentrations of Cr, Ni, Cu, Zn, As, Cd and Pb were 0.5, 4.5, 0.7, 25.1, 60.0, 0.22 and 1.0 µg/L, respectively. The DGT-labile As was significantly correlated with extractable As forms (p< 0.01), suggesting that extractable As in sediments acts as a “mobile pool” for bioavailable As. These results suggest potential risks of As and Cd, especially As, deserve further attention in Lake Yamdrok Basin.     

Heavy-metal contents in suspended solids of Meiliang Bay, Taihu Lake and its environmental significances

Surface water was taken from river mouth to the central area of Meiliang Bay, Taihu Lake, a large shallow eutrophic lake in China. Suspended solids were condensed by centrifugation 25L surface water samples from each selected site. Suspended solids and surface sediments were further freeze-dried and microwave digested before determining the metals by ICP-AES. Among the metals analyzed in suspended solids and sediments, contents of Cr, Cu, Mn, Ni, and Zn in suspended solids were significantly higher than those in sediments while contents of AI, Ba, Be, Ca, Co, Fe, K, Mg, Pb, and V in suspended solids were 10%-30% higher than those in sediments. Sr and Ti contents in suspended solids and sediments were very similar. Na content in suspended solids was lower than that in sediments. Heavy metals were significantly accumulated in suspended solids. From the river mouth to the center of Meiliang Bay, contents of Cr, Cu, Pb, and Zn in suspended solids showed a gradual decreasing trend indicating the river(Zhihugang River) still discharged large quantity of heavy metals to Meiliang Bay. The study suggests that the geochemical behaviors and ecological effects of heavy metals in suspended solids may serve as a good indicator for the pollution of lake.     

Instrumental and bio-monitoring of heavy metal and nanoparticle emissions from diesel engine exhaust in controlled environment

In the present article we characterized the emissions at the exhaust of a Common Rail (CR) diesel engine, representative of lightduty class, equipped with a catalyzed diesel particulate filter (CDPF) in controlled environment. The downstream exhausts were directly analyzed (for PM, CO, CO2, O2, HCs, NOx) by infrared and electrochemical sensors, and SEM-EDS microscope; heavy metals were chemically analyzed using mosses and lichens in bags, and glass-fibre filters all exposed at the engine exhausts. The highest particle emission value was in the 7–54 nm size range; the peak concentration rose until one order of magnitude for the highest load and speed. Particle composition was mainly carbonaceous, associated to noticeable amounts of Fe and silica fibres. Moreover, the content of Cu, Fe, Na, Ni and Zn in both moss and lichen, and of Al and Cr in moss, was significantly increased. Glass-fibre filters were significantly enriched in Al, B, Ba, Cu, Fe, Na, and Zn. The role of diesel engines as source of carbonaceous nanoparticles has been confirmed, while further investigations in controlled environment are needed to test the catalytic muffler as a possible source of silica fibres considered very hazardous for human health.