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

Chemical speciation is a significant factor that governs 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.

The Chemical Speciation and Behavior of Mercury and Selenium in the Insoluble Fraction of Striped Dolphin Liver

Most of the mercury and selenium exist in the insoluble fraction of dolphin liver. After the insoluble fraction was digested by alkaline protease in the presence of 1%SDS, approximately 50% of Hg and Se consisted in the supernatant and the others in the residue. Gel filtration chromatography of the hydrolysate showed that 96% of Hg and 87% of Se were combined with the high molecular weight proteins stably, which cannot be substituted by the complex reagents. Mercury and selenium in the residue were confirmed as HgSe crystal.

Characteristics of Chemical Speciation in PM_(1)in Six Representative Regions in China

A better knowledge of aerosol properties is of great significance for elucidating the complex mechanisms behind frequently occurring haze pollution events.In this study,we examine the temporal and spatial variations in both PM_(1)and its major chemical constituents using three-year field measurements that were collected in six representative regions in China between 2012 and 2014.Our results show that both PM_(1)and its chemical compositions varied significantly in space and time,with high PM_(1)loadings mainly observed in the winter.By comparing chemical constituents between clean and polluted episodes,we find that the elevated PM_(1)mass concentration during pollution events should be largely attributable to significant increases in organic matter(OM)and inorganic aerosols like sulfate,nitrate,and ammonium(SNA),indicative of the critical role of primary emissions and secondary aerosols in elevating PM_(1)pollution levels.The ratios of PM_(1)/PM2.5 are found to be generally high in Shanghai and Guangzhou,while relatively low ratios are seen in Xi’an and Chengdu,indicating anthropogenic emissions were more likely to accumulate in forms of finer particles.With respect to the relative importance of chemical components and meteorological factors quantified via statistical modeling practices,we find that primary emissions and secondary aerosols were the two leading factors contributing to PM_(1)variations,though meteorological factors also played important roles in regulating the dispersion of atmospheric PM.

Low-temperature dry reforming of methane tuned by chemical speciations of active sites on the SiO_(2) and γ-Al_(2)O_(3) supported Ni and Ni-Ce catalysts

The cognition of active sites in the Ni-based catalysts plays a vital role and remains a huge challenge in improving catalytic performance of low temperature CO_(2) dry reforming of methane(LTDRM).In this work,typical catalysts of SiO_(2) and γ-Al_(2)O_(3) supported Ni and Ni-Ce were designed and prepared.Importantly,the difference in the chemical speciations of active sites on the Ni-based catalysts is revealed by advanced characterizations and further estimates respective catalytic performance for LTDRM.Results show that larger[Ni0-]particles mixed with[Ni-O-Sin])species on the Ni/SiO_(2)(R)make CH_(4) excessive decomposition,leading to poor activity and stability.Once the Ce species is doped,however,superior activity(59.0%CH_(4) and 59.8%CO_(2) conversions),stability and high H_(2)/CO ratio(0.96)at 600℃ can be achieved on the Ni-Ce/SiO_(2)(R),in comparison with other catalysts and even reported studies.The improved performance can be ascribed to the formation of integral([Ni0_(n))]-[CeⅢ-□-CeⅢ])species on the Ni-Ce/SiO_(2)(R)catalyst,containing highly dispersed[Ni]particles and rich oxygen vacancies,which can synergistically establish a new stable balance between gasification of carbon species and CO_(2) dissocia-tion.With respect to Ni-Ce/γ-Al_(2)O_(3)(R),the Ni and Ce precursors are easily captured by extra-framework Al_(n)-OH groups and further form stable isolated([Ni0_(n))]-[Ni-O-Al_(n)])and[CeⅢ-O-Al_(n)]species.In such a case,both of them preferentially accelerate CO_(2) adsorption and dissociation,causing more car-bon deposition due to the disproportionation of superfuous CO product.This deep distinguishment of chemical speciations of active sites can guide us to further develop new efficient Ni-based catalysts for LTDRM in the future.

Effects of sulfur on variations in the chemical speciation of heavy metals from fly ash glass

This work designed a new CaO-Al_(2)O_(3)-SiO_(2)-SO3 glass for the immobilization of multiple heavy metals found in dechlorinated fly ash having high amounts of calcium and sulfur. Increasing the (CaO + SO3)/SiO_(2) mass ratio (M(CS/S)) from 0.28 to 0.85 was found to lower the proportions of Mn, Ni and Zn in an unstable state, while an M(CS/S) ratio of 0.51 gave the lowest proportions of unstable Cr and Pb. Decreasing the degree of polymerization of the glassy network increased the proportions of Mn, Cr, Ni, Pb and Zn in the carbonate bound state. The leaching out of metals in this state was the primary cause of degradation of Q^(3) structural units in the glassy network. The amount of Mn in the iron-manganese oxide bound state was increased by increasing the number of Q^(2) units in the silicate network. Decreasing the CaO/SiO_(2) mass ratio (M(C/S)) raised the proportions of Mn, Ni and Zn in the unstable state. An M(C/S) value of 0.43 lowered the proportions of unstable Cr and Pb. A principal components analysis determined that the leaching of toxic heavy metals from the glass was primarily related to the proportions of these metals in the unstable state while there were no evident correlations between leaching and the proportions in stable states.

Chemical speciation,bioavailability and risk assessment of potentially toxic metals in soils around petroleum product marketing company as environmental degradation indicators

The study aims at investigating chemical speciation,bioavailability and risk assessment of some selected metals in soils around refined petroleum depot using the concentrations of the metals as variables to ascertain the impacts of the activities within the petroleum depot.Surface-soils(0e15 cm)were collected from within the premises of Pipelines and Product Marketing Company,Ibadan,Nigeria,while control samples were collected at 200 m away from the study location.Electrical conductivity and pH were measured using a calibrated dual purpose meter,while elemental analysis was done using Atomic absorption spectroscopy analytical technique.The results showed that the soils exhibited low ecological risk;minor enrichment for Mn,moderately severe enrichment for Ni and Co,severe enrichment for Cr and extremely severe enrichment for Pb,Zn and Cd.There was low contamination factor for Pb,Ni,Mn,Cr,Co,and Fe and moderate contamination by Zn and Cd.Geo-accumulation index results indicated unpolluted with Ni,Mn,Cr,Co,and Fe,unpolluted to moderately polluted with Pb and Zn and moderately to strongly polluted with Cd.Inter-element clustering results indicated chemical affinity and/or similar genetic origin among the elements.Speciation analysis suggested that Fe,Co,Cr,Cd,and Ni occurred in the residual fraction;Pb,and Zn in the carbonate fraction,while Mn have its highest percentage in the Fe eMn oxides fraction.Percentage mobility and bioavailability showed that most of the metals are immobile and non-bioavailable.Study concluded that the oil-impacted soils were contaminated with most of the metals,but with low ecological risk.

The chemical stability of heavy metals in a natural water system

A comprehensive investigation of heavy metal pollutants in Xiangjiang river was accomplished to evaluate their chemical stability through three different ways: (1) Chemical speciation by direct measurements; (2) Chemical equilibrium model simulation; (3) Sediment extraction experiments. All the results demonstrated that the directly bioavailable fraction was in a very limited amount. The metal bound to organic ligands, adsorbed particles and precipitated species presented a buffer for solution species. The majority of metals occured in the residues as solid particulates. It was inferred that the heavy metal pollutants in this aquatic system exhibited a high chemical stability. The critical limits of discharging load and pH values were suggested.

MSWI Fly Ash Based Novel Solidification/Stabilization Matrices for Heavy Metals

The possibilities of MSWI fly ash as a major constituent of novel solidification/stabilization matrices for secure landfill were investigated by mixing MSWI fly ash with rich aluminum components, which was added as bauxite cement or metakaolinite instead, to form Friedel and Ettringite phases with high fixing capacities for heavy metals. The physical properties, heavy metals-fixing capacity, mineral phases and its vibration bands in the novel matrices were characterized by compressive strength, TCLP（toxic characteristic leaching procedure）, XRD （x-ray diffraction） , DTG （derivative thermogravimetry）, and FTIR （fourier transform infrared spectroscopy）, respectively. The Tessier＇s five-step sequential extraction procedure was used to analyze the fractions of chemical speciation for Pb, Cd and Zn ions. The experimental results indicate that Friedel-Ettringite based novel solidification/stabilization matrices can incorporate Pb, Cd and Zn ions effectively by physical encapsulation and chemical fixation, and it exhibits a great potential in co-landfill treatment of MSWI fly ash with some heavy metals-bearing hazardous wastes.

Distribution and bioavailability of mercury in size-fractioned atmospheric particles around an ultra-low emission power plant in Southwest China

Ultra-low emission(ULE)technology retrofits significantly impact the particulate-bound mercury(Hg)emissions from coal-fired power plants(CFPPs);however,the distribution and bioavailability of Hg in size-fractioned particulate matter(PM)around the ULE-retrofitted CF-PPs are less understood.Here,total Hg and its chemical speciation in TSP(total suspended particles),PM_(10)(aerodynamic particle diameter≤10μm)and PM_(2.5)(aerodynamic particle diameter≤2.5μm)around a ULE-retrofitted CFPP in Guizhou Province were quantified.Atmospheric PM_(2.5)concentration was higher around this ULE-retrofitted CFPP than that in the intra-regional urban cities,and it had higher mass Hg concentration than other sizefractioned PM.Total Hg concentrations in PM had multifarious sources including CFPP,vehicle exhaust and biomass combustion,while they were significantly higher in autumn and winter than those in other seasons(P<0.05).Regardless of particulate size,atmospheric PM-bound Hg had lower residual fractions(<21%)while higher HCl-soluble fractions(>40%).Mass concentrations of exchangeable,HCl-soluble,elemental,and residual Hg in PM_(2.5)were higher than those in other size-fractioned PM,and were markedly elevated in autumn and winter(P<0.05).In PM_(2.5),HCl-soluble Hg presented a significantly positive relationship with elemental Hg(P<0.05),while residual Hg showed the significantly positive relationships with HCl-soluble Hg and elemental Hg(P<0.01).Overall,these results suggested that atmospheric PM-bound Hg around the ULE-retrofitted CFPP tends to accumulate in finer PM,and has higher bioavailable fractions,while has potential transformation between chemical speciation.

Migration and distribution characteristics of soil heavy metal(loid)s at a lead smelting site

Heavy metal(loid)s contamination is a constant issue at smelting sites.It is essential to investigate the spatial distribution and migration characteristics of heavy metal(loid)s in the soil for environmental management and remediation strategies of non-ferrous smelting sites.In this study,203 soil samples from 57 sites were collected in a typical lead smelting site.The findings demonstrated that there were significant Pb,Zn,Cd,and As contamination in soil samples.The spatial distribution of heavy metal(loid)s showed strong spatial heterogeneity,the contaminated soil areas of Pb,As,Cd,and Zn were 99.5%,98.9%,85.3%,and 72.4%,respectively.Pb,Cd,and As contamination of the soil reached a depth of 5 m,which migrated from the surface to deep soil layers.The leaching contents of Zn,Pb,and As decreased obviously in 3-4 m soil layer,but the leaching content of Cd was still high,which indicated the high migration of Cd.With the increase of depth,the proportion of acid soluble fraction of heavy metal(loid)s decreased,and the residual fraction increased.The acid soluble fraction of Cd accounted for a higher proportion,and As mainly existed in reducible and residual fractions in soil.According to the calculation of the migration factor,the migration of heavy metal(loid)s in soils were ordered as Cd>Zn>Pb>As.The outcomes are advantageous for risk reduction and site remediation for non-ferrous metal smelting sites.

Distribution and Speciation of Chromium and Cadmium in an Organic and Inorganic Fertilized Chernozem

Fertilizers are widely applied in agricultural practice to improve crop yield and quality.However, they can also alter the behavior of soil pollutants.A field experiment was conducted on a chernozem in Heilongjiang Province, China.Various proportions of inorganic nitrogen(N), phosphorus(P), and organic(manure) fertilizers were applied.Soil samples were collected four times over 2 years, and the total concentrations and speciation of chromium(Cr) and cadmium(Cd) were analyzed.Inorganic fertilizer addition had little effect on the total concentration of Cr and Cd, while organic fertilizer addition reduced the total concentrations of both Cr and Cd.Inorganic fertilizers increased the concentration of Cr in the exchangeable form, but decreased that of the residual form(P < 0.05).Addition of inorganic or organic fertilizer alone decreased concentrations of exchangeable Cd(P < 0.05), but the combination of inorganic and organic fertilizers had the opposite effect.High concentration of total Cd exceeding the upper limits of the Environmental Quality Standard for Soils proposed by the Ministry of Environmental Protection of China could result in an environmental risk, and fertilizer application could lower that risk.Results of risk assessment code calculated as the percentage of the sum of metal concentrations in the exchangeable and carbonate-associated form in total metal concentration showed that Cr and Cd risks were lowered when organic fertilizer was applied alone or in combination with inorganic fertilizers.Our study highlighted that organic fertilizer should be applied alone or in combination with inorganic fertilizers to lower the environmental risks of Cr and Cd pollution in the chernozem.

Sequence of the main geochemical controls on the Cu and Zn fractions in the Yangtze River estuarine sediments

Metal speciation can provide sufficient infor- mation for environmental and geochemical researches. In this study, based on the speciation determination of Cu and Zn in the Yangtze Estuary sediments, roles of eight geochemical controls （i.e., total organic carbon （TOC）, clay, Fe/Mn in five chemical fractions and salinity） are fully investigated and sequenced with correlation analysis （CA） and principal components analysis （PCA）. Results show that TOC, clay and Fe/Mn oxides are key geochemical factors affecting the chemical speciation distributions of Cu and Zn in sediments, while the role of salinity appears to be more indirect effect. The influencing sequence generally follows the order： TOC 〉 clay 〉 Mn oxides 〉 Fe oxides 〉 salinity. Among the different fractions of Fe/Mn oxides, residual and total Fe content, and exchangeable and carbonate Mn exert the greatest influences, while exchangeable Fe and residual Mn show the poorest influences.

Chemical composition and Zn bioavailability of the soil solution extracted from Zn amended variable charge soils

A study on variable charge soils （volcanic Italian and podzolic Scottish soils） was performed to investigate the influence of soil properties on the chemical composition of soil solution. Zinc speciation, bioavallability and toxicity in the soil solution were examined. The soils were spiked with increasing amounts of Zn （0, 100, 200, 400 and 1000 mg/kg） and the soil solutions were extracted using rhizon soil moisture samplers. The pH, total organic carbon （TOC）, base cations, anions, total Zn and free Zn^2＋ in soil solution were analysed. A rapid bioassay with the luminescent bacterium Escherichia coli HB 101 pUCD607 was performed to assess Zn toxicity. The influence of soil type and Zn treatments on the chemical composition of soil solution and on Zn toxicity was considered and discussed. Different trends of total and free Zn concentrations, base cations desorption and luminescence of E. coli HB 101 pUCD607 were observed. The soil solution extracted from the volcanic soils had very low total and free Zn concentrations and showed specific Zn^2＋/Ca^2＋ exchange. The soil solution from the podzolic soil had much higher total and free Zn concentrations and showed no evidence of specific Zn^2＋/Ca^2＋ exchange. In comparison with the subalkaline volcanic soils, the acidic podzol showed enhanced levels of toxic free Zn^2＋ and consequently stronger effects on E. coli viability.

Pisco grape pomace:Iron/copper speciation and antioxidant properties,towards their comprehensive utilization

The pisco and wine industry produces hundreds of tons of grape pomace each year in Chile,generating environmental problems,and demanding urgent strategies for its management.The aim of this work was to study the pisco grape pomace based on a physicochemical characterization,an iron/copper speciation analysis,and the optimization for polyphenols recovery,establishing the polyphenolic profile,antioxidant properties,and the Fe^(2+)/Cu^(2+) chelating activity,to promote their revalorization as an ingredient with potential application in the food industry.The chemical characterization showed mainly high values for crude protein(15.36%dw)and potassium(9240.66 mg/kg).The Fe/Cu speciation depicted that iron and copper soluble forms in pisco pomace flour represented 70.57%and 52.18%,respectively,regarding total content.The optimized extract showed mainly pyrogallol,catechin and epicatechin,with concentrations of 1078.43±60.14μg/g,883.20±7.57μg/g and,751.76±23.04μg/g,respectively,with a relevant antioxidant capacity by Oxygen Radical Absorbance Capacity(ORAC)of 1402.15μmol TE/g dw GPE and,a better chelating ability to complex Fe^(2+) than Cu^(2+).The pisco pomace was for the first time chemically characterize,showing it as a potential source of minerals and antioxidant biocompounds,making it a good candidate for nutritional applications,as a rich source of organic matter or even could be potentially utilized to produce value-added commodities,toward a circular economy.

Fate of mercury in flue gas desulfurization gypsum determined by Temperature Programmed Decomposition and Sequential Chemical Extraction

A considerable amount of Hg is retained in flue gas desulfurization（FGD） gypsum from Wet Flue Gas Desulfurization（WFGD） systems. For this reason, it is important to determine the species of Hg in FGD gypsum not only to understand the mechanism of Hg removal by WFGD systems but also to determine the final fate of Hg when FGD gypsum is disposed. In this study, Temperature Programmed Decomposition（TPD） and Sequential Chemical Extraction（SCE） were applied to FGD gypsum to identify the Hg species in it. The FGD gypsum samples were collected from seven coal-fired power plants in China, with Hg concentrations ranging from 0.19 to 3.27 μg/g. A series of pure Hg compounds were used as reference materials in TPD experiments and the results revealed that the decomposition temperatures of different Hg compounds increase in the order of Hg_2Cl_2〈 HgCl_2〈 black HgS 〈 Hg_2SO_4〈 red HgS 〈 HgO 〈 HgSO_4. The Hg compounds existing in FGD gypsums identified by TPD included HgCl_2, Hg_2Cl_2, Hg_2SO_4, black HgS and red HgS, of which mercury sulfides were the primary compounds. The results of SCE indicated that Hg was mainly distributed in the strongly complexed phase. The low Hg content in FGD gypsum increases the ambiguity of assigning extraction fractions to certain Hg species by SCE. The fact that the primary compounds in FGD gypsum are HgS phases leads the leaching of Hg in the natural environment to be quite low, but a considerable amount of Hg may be released during the industrial heating process.

Assessment of mercury(II) bioavailability using a bioluminescent bacterial biosensor: Practical and theoretical challenges

Critical methodological challenges in the microbial biosensor approach to assessing Hg（II） bioavailability were evaluated from the perspective of analytical chemists. The main challenge stems from the fact that the chemical speciation of Hg（II） in natural waters exerts a major control on its bioavailability, yet its natural complexation equilibria are extensively altered during conventional bioassays. New data, obtained using a bioluminescent Hg（II）-biosensor, that illustrate these challenges are presented and potential solutions proposed.

Leachability and fractionation of heavy metals in stainless steelmaking plant dusts

The leachability and fractionation of the selected heavy metals （Cr, Cd, Pb and Zn） in the stainless steelmaking plant dusts were studied by the modified HJ/T299-2007 method, the modified TCLP test and a seven-step sequential extraction procedure. The results show that the stainless steelmaking plant dusts are considered as hazardous materials since at least one of the leachable heavy metals exceeds the corresponding limit levels of State Environmental Protection Administration of China. Pb is the most extractable heavy metals by the sequential extraction procedure, while Cr, Cd and Zn mainly presents in the residual fraction bound to spinel phase and silicates. The mobile heavy metals in the dusts, which present as the species of water soluble, exchangeable species and the species bounded to carbonates and hydroxides, can be estimated as 0.08 1.2% of Cr, 7.6% 31.8% of Cd, 34.1% of Pb, 0.052-0.4% of Zn, respectively.

Adsorption of Cadmium and Zinc onto Micaceous Minerals:Effect of Siderophore Desferrioxamine B

The mobility,bioavailability,and environmental fate of heavy metals in soil are controlled by their adsorption onto soil minerals and solid organic matter.The adsorption is strongly affected by the presence of various low-molecular-weight organic acids.In this study,effect of hydroxamate siderophore desferrioxamine B (DFOB) on cadmium (Cd) and zinc (Zn) adsorption onto two micaceous clay minerals,muscovite and phlogopite,was evaluated in batch experiments.Results showed that the presence of DFOB diminished the adsorption of Cd and Zn onto both minerals,particularly under neutral to alkaline pH conditions.For instance,at pH 8.2,the presence of DFOB caused a decrease in the adsorption of Zn onto phlogopite by nearly 50%.The equilibrium adsorption of Cd and Zn was satisfactorily described using Freundlich isotherm.The adsorption isotherms showed that the affinity of Cd and Zn onto the minerals decreased in the presence of DFOB.For example,at pH 8.0,the presence of siderophore caused a decrease in the Freundlich adsorption isotherm coefficient KF for Zn adsorption onto muscovite and phlogopite from 4.60 to 0.07 L g^-1 and from 3.56 to 0.36 L g^-1,respectively.These findings confirm the potential influence of siderophore on the fate of Cd and Zn in arid soils containing substantial contributions of micaceous silicate minerals.

Evolutionary processes and sources of high-nitrate haze episodes over Beijing,Spring

Rare and consecutive high-nitrate haze pollution episodes were observed in Beijing in spring2012. We present detailed characterization of the sources and evolutionary mechanisms of this haze pollution, and focus on an episode that occurred between 15 and 26 April. Submicron aerosol species were found to be substantially elevated during haze episodes, and nitrates showed the largest increase and occupation（average： 32.2%） in non-refractory submicron particles（NR-PM1）, which did not occur in other seasons as previously reported. The haze episode（HE） was divided into three sub-episodes, HEa, HEb, and HEc. During HEa and HEc, a shallow boundary layer, stagnant meteorological conditions, and high humidity favored the formation of high-nitrate concentrations, which were mainly produced by three different processes —daytime photochemical production, gas-particle partitioning, and nighttime heterogeneous reactions — and the decline in visibility was mainly induced by NR-PM1.However, unlike HEa and HEc, during HEb, the contribution of high nitrates was partly from the transport of haze from the southeast of Beijing — the transport pathway was observed at ~800–1000 m by aerosol Lidar —and the decline in visibility during HEb was primarily caused by PM（2.5）. Our results provide useful information for air quality improvement strategies in Beijing during Spring.