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(P...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.展开更多
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...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.展开更多
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 ...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.展开更多
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 i...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.展开更多
The concentration and chemical speciation of heavy metals including REEs （rare earth elements）, Th （thorium） and U （uranium） in domestic sludge and electroplating sludge were investigated, and those of the domes...The concentration and chemical speciation of heavy metals including REEs （rare earth elements）, Th （thorium） and U （uranium） in domestic sludge and electroplating sludge were investigated, and those of the domestic sludge were compared with those of natural soil. Removal of heavy metals in electroplating sludge was studied with bio-surfactants （saponin and sophorolipid） by batch and column experiments. The results suggested that heavy metals have greater concentrations and exist as more relatively unstable fraction in sludge than those in Natural soil. Nonionic saponin is more efficient than sophorolipid for the removal of heavy metals from the electroplating sludge, and mainly reacts with carbonate state （i.e., F3） and Fe-Mn oxide state （i.e., F5） fractions. The recovery efficiency of heavy metals in leachates from the electroplate sludge was attained 88%-97%. Saponin can be reused and be a promising and cost-effective material for the removal of heavy metals in sludge.展开更多
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) m...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.展开更多
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 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.展开更多
The occurrence of geogenic arsenic(As)in groundwater is a global public health concern.However,there remain large gaps in groundwater As data,making it difficult to identify non-compliant domestic wells,partly due to ...The occurrence of geogenic arsenic(As)in groundwater is a global public health concern.However,there remain large gaps in groundwater As data,making it difficult to identify non-compliant domestic wells,partly due to lack of low-cost methods capable of rapid As analysis.Therefore,the development of high through-put and reliable on-site determination methods for inorganic As is essential.Herein,a portable automated analyzer was developed for the determination of arsenite(As(Ⅲ)),arsenate(As(Ⅴ))and phosphate in As contaminated groundwater based on a previously adapted method for molybdenum blue spectrophotometry.After the optimization of the chemical reactions and flow manifold,the system demonstrated a high sample through-put(4.8/h for As(Ⅲ),As(Ⅴ)and phosphate analysis),allowing this system to screen 125 samples in 24 h.Other advantages include low operational costs(0.3 CNY per sample),appropriate sensitivity for contaminated groundwater(detection limits of 4.7μg/L,8.3μg/L and 5.4μg/L for As(Ⅲ),As(Ⅴ)and phosphate,respectively),good linearity(R^(2)>0.9996 at As concentrations up to 1600μg/L)and high precision(relative standard deviations of 3.5% and 2.8% for As(Ⅲ)and As(Ⅴ),respectively).The portable system was successfully used for As speciation analysis in 5 groundwater samples collected from multi-level wells at Yinchuan Plain,northwestern China,with total As concentrations ranging from 75.7 to 295.0μg/L,independently assessing As speciation,providing a promising novel method for the rapid on-site screening of As in tens of millions of domestic wells worldwide.展开更多
Fractionation of metals in acid sandy loam soil amended withalkaline-stabilised sewage sludge biosolids was conducted in order toassess metal bioavailability and environmental mobility. Soilsolution was extracted by a...Fractionation of metals in acid sandy loam soil amended withalkaline-stabilised sewage sludge biosolids was conducted in order toassess metal bioavailability and environmental mobility. Soilsolution was extracted by a centrifugation and filtration technique.Meal speciation in the soil solution was determined by a cationexchange resin method. Acetic acid and EDTA extracting solutions wereused for extraction of metals in soil solid surfaces. Metaldistribution in different fractions of soil solid phase wasdetermined using a three-step sequential extraction scheme.展开更多
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 Pr...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.展开更多
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) Chemi...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.展开更多
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, bioavallab...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.展开更多
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 on...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.展开更多
Modified potential ecological risk index （MRI） was proposed based on the potential ecological risk index （RI） and risk assessment code （RAC） by modifying an index. The modified index was relevant to the chemical...Modified potential ecological risk index （MRI） was proposed based on the potential ecological risk index （RI） and risk assessment code （RAC） by modifying an index. The modified index was relevant to the chemical speciation of heavy metals. Xiawan Port, a typical region contaminated by industrial production, was selected as a case study area. The total concentrations and chemical speciation of heavy metals in sediments of Xiawan Port were analyzed. The experimental data indicate that Xiawan Port is seriously polluted by heavy metals, especially by Cd. The risks of heavy metals are evaluated by RI, RAC and MRI, respectively. The resluts of MRI show that the risks of heavy metals are in the decreasing order of Cd〉Pb〉Cu〉Zn. Comparison of results by different methods reveals that MRI integrates the characters of RI and RAC. MRI is recognized to be useful for risk managemnt of heavy metals in sediments.展开更多
The pollution characteristics of Pb, Cd, Zn, Cu and Ni in soil of lead-zinc mining area were studied. The results indicate that the contamination degree followed the sequence of Cd〉Pb〉Zn〉Ni〉Cu and concentrations o...The pollution characteristics of Pb, Cd, Zn, Cu and Ni in soil of lead-zinc mining area were studied. The results indicate that the contamination degree followed the sequence of Cd〉Pb〉Zn〉Ni〉Cu and concentrations of Pb, Cd and Zn exceeded corresponding limits of the Chinese National Soil Environmental Quality Standard III. The soil was extremely polluted by Cd（Iego=5.26）, moderately to heavily polluted by Zn（Iego=2.38）, heavily to extremely polluted by Pb（Iego=4.13）. The results of BCR three-step sequential extraction procedure show that the active Cd, Pb and Zn were relatively high and might exert adverse effects on the plants grown in the soil, while Cu and Ni existed in soil with a relatively stable form. Potential ecological risk results indicate that soils were engaging in a high potential ecological risk by pollution of Cd and should be given rise to concern.展开更多
Iron L-edge and sulfur K-edge X-ray absorption near edge structure（XANES） spectroscopy analysis of pyrite leached by extreme thermophilic Archaea strain Acidianus manzaensis（A.manzaensis） was carried out.Leaching ...Iron L-edge and sulfur K-edge X-ray absorption near edge structure（XANES） spectroscopy analysis of pyrite leached by extreme thermophilic Archaea strain Acidianus manzaensis（A.manzaensis） was carried out.Leaching experiments show that the oxidation of pyrite can be accelerated by A.manzaensis.Leaching results show that with the increase of leaching time,pH value in the leaching solution gradually decreases,redox potential increases rapidly from day 0 to day 3,and then increases slowly.The SEM results show that the pyrite surfaces are corroded gradually by A.manzaensis,and the XRD results show that the leaching residues contain new compositions of jarosite and elemental sulfur（S0）.The iron L-edge XANES spectroscopy analysis of pyrite during biooxidation indicates that pyrite is gradually converted to Fe（III）-containing species.The sulfur K-edge XANES spectroscopy analysis indicates that elemental sulfur is produced during bioleaching and maintains mass fractions of 3.2%-5.9%.Sodium thiosulfate was also detected from day 2 to day 4,indicating the existence of thiosulfate during biooxidation of pyrite.展开更多
Soil contamination in the vicinity of the Dabaoshan Mine, Guangdong Province, China, was studied through determi- nation of total concentrations and chemical speciation of the toxic metals, Cu, Zn, Cd, and Pb, using i...Soil contamination in the vicinity of the Dabaoshan Mine, Guangdong Province, China, was studied through determi- nation of total concentrations and chemical speciation of the toxic metals, Cu, Zn, Cd, and Pb, using inductively coupled plasma mass spectrometry. The results showed that over the past decades, the environmental pollution was caused by a combination of Cu, Zn, Cd, and Pb, with tailings and acid mine drainage being the main pollution sources affecting soils. Significantly higher levels （P ≤ 0.05） of Cu, Zn, Cd, and Pb were found in the tailings as compared with paddy, garden, and control soils, with averages of 1486, 2516, 6.42, and 429 mg kg^-1, respectively. These metals were continuously dispersed downstream from the tallings and waste waters, and therefore their concentrations in the paddy soils were as high as 567, 1 140, 2.48, and 191 mg kg^-1, respectively, being significantly higher （P ≤ 0.05） as compared with those in the garden soils. The results of sequential extraction of the above metals from all the soil types showed that the residual fraction was the dominant form. However, the amounts of metals that were bound to Fe-Mn oxides and organic matter were relatively higher than those bound to carbonates or those that existed in exchangeable forms. As metals could be transformed from an inert state to an active state, the potential environmental risk due to these metals would increase with time.展开更多
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 manageme...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.展开更多
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 ...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.展开更多
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 ...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.展开更多
文摘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.
基金financially supported by the National Natural Science Foundation of China (22006059, 21968015)National Engineering Laboratory for Flue Gas Pollutants Control Technology and Equipment (NEL-KF-201905)+1 种基金Applied Basic Research Program of Yunnan Province, China (202101AU070154, 2019FD034)Analysis and Testing Fund of Kunming University of Science and Technology (2020 T20200006)
文摘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.
文摘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.
基金This work was financially supported by National Key R&D Plan(Grant No.2017YFC0210000)National Natural Science Foundation of China(Grant No.41701413)+1 种基金National Key R&D Plan(Grant No.2017YFC0212703)Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB05020401).Meteorological data were acquired from the Meteorological Information Comprehensive Analysis and Process System(air temperature,relative humidity,and wind speed),and ERA-Interim reanalysis(boundary layer height)that was provided by the European Centre for Medium-Range Weather Forecasts.
文摘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.
文摘The concentration and chemical speciation of heavy metals including REEs （rare earth elements）, Th （thorium） and U （uranium） in domestic sludge and electroplating sludge were investigated, and those of the domestic sludge were compared with those of natural soil. Removal of heavy metals in electroplating sludge was studied with bio-surfactants （saponin and sophorolipid） by batch and column experiments. The results suggested that heavy metals have greater concentrations and exist as more relatively unstable fraction in sludge than those in Natural soil. Nonionic saponin is more efficient than sophorolipid for the removal of heavy metals from the electroplating sludge, and mainly reacts with carbonate state （i.e., F3） and Fe-Mn oxide state （i.e., F5） fractions. The recovery efficiency of heavy metals in leachates from the electroplate sludge was attained 88%-97%. Saponin can be reused and be a promising and cost-effective material for the removal of heavy metals in sludge.
基金supported by the National Natural Science Foundation of China(Nos.52070181 and 51934006).
文摘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.
文摘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.
基金supported by the Natural Science Foundation of Fujian Province(No.2020J06008)for Distinguished Young Scholarsthe Fujian Provincial Central Guided Local Science and Technology Development Special Project(No.2022L3078).
文摘The occurrence of geogenic arsenic(As)in groundwater is a global public health concern.However,there remain large gaps in groundwater As data,making it difficult to identify non-compliant domestic wells,partly due to lack of low-cost methods capable of rapid As analysis.Therefore,the development of high through-put and reliable on-site determination methods for inorganic As is essential.Herein,a portable automated analyzer was developed for the determination of arsenite(As(Ⅲ)),arsenate(As(Ⅴ))and phosphate in As contaminated groundwater based on a previously adapted method for molybdenum blue spectrophotometry.After the optimization of the chemical reactions and flow manifold,the system demonstrated a high sample through-put(4.8/h for As(Ⅲ),As(Ⅴ)and phosphate analysis),allowing this system to screen 125 samples in 24 h.Other advantages include low operational costs(0.3 CNY per sample),appropriate sensitivity for contaminated groundwater(detection limits of 4.7μg/L,8.3μg/L and 5.4μg/L for As(Ⅲ),As(Ⅴ)and phosphate,respectively),good linearity(R^(2)>0.9996 at As concentrations up to 1600μg/L)and high precision(relative standard deviations of 3.5% and 2.8% for As(Ⅲ)and As(Ⅴ),respectively).The portable system was successfully used for As speciation analysis in 5 groundwater samples collected from multi-level wells at Yinchuan Plain,northwestern China,with total As concentrations ranging from 75.7 to 295.0μg/L,independently assessing As speciation,providing a promising novel method for the rapid on-site screening of As in tens of millions of domestic wells worldwide.
基金National Natural Science Foundation of China(Nos.49831070 and 40125005)theNational Key Basic Research Support Foundation of China (No. G1999011807)the Jiangsu Provincial Foundation for Young Scientists (No. BQ98050).
文摘Fractionation of metals in acid sandy loam soil amended withalkaline-stabilised sewage sludge biosolids was conducted in order toassess metal bioavailability and environmental mobility. Soilsolution was extracted by a centrifugation and filtration technique.Meal speciation in the soil solution was determined by a cationexchange resin method. Acetic acid and EDTA extracting solutions wereused for extraction of metals in soil solid surfaces. Metaldistribution in different fractions of soil solid phase wasdetermined using a three-step sequential extraction scheme.
基金the National Key Technology R&D Program of China(Nos.2012BAD15B05 and 2013BAD16B01)
文摘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.
文摘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.
文摘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.
基金supported by the National Natural Science Foundation of China (No. 51376109)
文摘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.
基金Projects (51039001, 50978087, 51009063, 50808071) supported by the National Natural Science Foundation of ChinaProject (SX2010-026) supported by State Council Three Gorges Project Construction Committee Executive Office,China+2 种基金Project (2009ZX07212-001) supported by Ministry of Environmental Protection of ChinaProject (BYHGLC-2010-02) supported by Guangzhou Water Authority,ChinaProject (CX2010B157) supported by Hunan Provincial Innovation Foundation for Postgraduate,China
文摘Modified potential ecological risk index （MRI） was proposed based on the potential ecological risk index （RI） and risk assessment code （RAC） by modifying an index. The modified index was relevant to the chemical speciation of heavy metals. Xiawan Port, a typical region contaminated by industrial production, was selected as a case study area. The total concentrations and chemical speciation of heavy metals in sediments of Xiawan Port were analyzed. The experimental data indicate that Xiawan Port is seriously polluted by heavy metals, especially by Cd. The risks of heavy metals are evaluated by RI, RAC and MRI, respectively. The resluts of MRI show that the risks of heavy metals are in the decreasing order of Cd〉Pb〉Cu〉Zn. Comparison of results by different methods reveals that MRI integrates the characters of RI and RAC. MRI is recognized to be useful for risk managemnt of heavy metals in sediments.
基金Project(2012FJ1010)supported by the National Science and Technology Major Project,ChinaProject(2012BAC09B04)supported by the National"Twelfth Five-Year"Plan for Science&Technology,ChinaProject(2012AA06202)supported by the National High-tech Research and Development Program of China
文摘The pollution characteristics of Pb, Cd, Zn, Cu and Ni in soil of lead-zinc mining area were studied. The results indicate that the contamination degree followed the sequence of Cd〉Pb〉Zn〉Ni〉Cu and concentrations of Pb, Cd and Zn exceeded corresponding limits of the Chinese National Soil Environmental Quality Standard III. The soil was extremely polluted by Cd（Iego=5.26）, moderately to heavily polluted by Zn（Iego=2.38）, heavily to extremely polluted by Pb（Iego=4.13）. The results of BCR three-step sequential extraction procedure show that the active Cd, Pb and Zn were relatively high and might exert adverse effects on the plants grown in the soil, while Cu and Ni existed in soil with a relatively stable form. Potential ecological risk results indicate that soils were engaging in a high potential ecological risk by pollution of Cd and should be given rise to concern.
基金Project(51274257)supported by the National Natural Science Foundation of ChinaProject(U1232103)supported by the Joint Funds of National Natural Science Foundation of China and Large Scientific Facility Foundation of Chinese Academy of Sciences+1 种基金Project(CX2014B092)supported by the Hunan Provincial Innovation Foundation For Postgraduate,ChinaProject(VR-12419)supported by Beijing Synchrotron Radiation Facility Public User Program,China
文摘Iron L-edge and sulfur K-edge X-ray absorption near edge structure（XANES） spectroscopy analysis of pyrite leached by extreme thermophilic Archaea strain Acidianus manzaensis（A.manzaensis） was carried out.Leaching experiments show that the oxidation of pyrite can be accelerated by A.manzaensis.Leaching results show that with the increase of leaching time,pH value in the leaching solution gradually decreases,redox potential increases rapidly from day 0 to day 3,and then increases slowly.The SEM results show that the pyrite surfaces are corroded gradually by A.manzaensis,and the XRD results show that the leaching residues contain new compositions of jarosite and elemental sulfur（S0）.The iron L-edge XANES spectroscopy analysis of pyrite during biooxidation indicates that pyrite is gradually converted to Fe（III）-containing species.The sulfur K-edge XANES spectroscopy analysis indicates that elemental sulfur is produced during bioleaching and maintains mass fractions of 3.2%-5.9%.Sodium thiosulfate was also detected from day 2 to day 4,indicating the existence of thiosulfate during biooxidation of pyrite.
基金Project supported by the Guangdong Environmental Protection Bureau of China (No.2001-27)Guangdong Provincial Department of Science and Technology,China (No.2004A30308002)State Key Laboratory of Environment Geochemistry,Chinese Academy of Sciences
文摘Soil contamination in the vicinity of the Dabaoshan Mine, Guangdong Province, China, was studied through determi- nation of total concentrations and chemical speciation of the toxic metals, Cu, Zn, Cd, and Pb, using inductively coupled plasma mass spectrometry. The results showed that over the past decades, the environmental pollution was caused by a combination of Cu, Zn, Cd, and Pb, with tailings and acid mine drainage being the main pollution sources affecting soils. Significantly higher levels （P ≤ 0.05） of Cu, Zn, Cd, and Pb were found in the tailings as compared with paddy, garden, and control soils, with averages of 1486, 2516, 6.42, and 429 mg kg^-1, respectively. These metals were continuously dispersed downstream from the tallings and waste waters, and therefore their concentrations in the paddy soils were as high as 567, 1 140, 2.48, and 191 mg kg^-1, respectively, being significantly higher （P ≤ 0.05） as compared with those in the garden soils. The results of sequential extraction of the above metals from all the soil types showed that the residual fraction was the dominant form. However, the amounts of metals that were bound to Fe-Mn oxides and organic matter were relatively higher than those bound to carbonates or those that existed in exchangeable forms. As metals could be transformed from an inert state to an active state, the potential environmental risk due to these metals would increase with time.
基金supported by the National Key Research and Development Program of China (No.2019YFC1803604)the National Natural Science Foundation of China (No.42177392).
文摘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.
基金funded by Florida Department of Environmental Protection (contract SP507)
文摘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.
基金supported by the National Natural Science Foundation of China(No.50804037)
文摘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.
