Use of clay mineral (montmorillonite) for reducing poultry litter leachate toxicity (EC50)

Poultry litter (PL) has useful nutrients and is therefore used as manure. In addition to N, P and K, PL also contains some heavy metals (As, Cd, Cu, Mn, Pb and Zn), antibiotics, antioxidants, mold inhibitors and other organic compounds. Poultry litter aqueous leachate (PLL) has been shown to be toxic to many organisms; PLL is more toxic than the aqueous leachate of other animal manures used on agricultural soils. Clayey soils are known to retain toxic heavy metals. The objective of this study was to measure the change in toxicity (EC50) of PLL on the addition of clay mineral--montmorillonite. A significant reduction (124%) in toxicity of the clay poultry litter leachate (CLL) after 7 days was observed compared to the toxicity of the PLL alone after 1 day. This indicates that some of the toxic components of the litter were adsorbed by the clay.     

Trace elements partitioning during co-firing biomass with lignite in a pilot-scale fluidized bed combustor

This study describes the partitioning of 18 trace elements (As, Ba, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, P, Pb, Sb, Se, Sn, Tl, V, Zn) and 9 major and minor elements (Al, Ca, Fe, K, Mg, Na, S, Si, Ti) during co-firing of olive residue, hazelnut shell and cotton residue with high sulfur and ash content lignite in 0.3 MW(t) Middle East Technical University (METU) Atmospheric Bubbling Fluidized Bed Combustor (ABFBC) test rig with limestone addition. Concentrations of trace elements in coal, biomass, limestone, bottom ash, cyclone ash and filter ash were determined by inductively coupled plasma optical emission and mass spectroscopy (ICP-OES and ICP-MS). Partitioning of major and minor elements are influenced by the ash split between the bottom ash and fly ash and that the major proportion of most of the trace elements (As, Ba, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Tl, V and Zn) are recovered in fly ash when firing lignite only. Co-firing lignite with biomass enhances partitioning of these elements to fly ash. Co-firing also shifts the partitioning of Cd, P, Sb and Sn from bottom to fly ash.     

多氨基改性蔗渣对水溶液中Pb~(2+)、Zn~(2+)、Cd~(2+)、Cu~(2+)吸附性能的研究

蔗渣经多氨基改性处理后,得到多氨基改性蔗渣吸附剂。考察了多氨基改性蔗渣吸附剂对模拟废水中Pb2+、Zn2+、Cd2+、Cu2+的吸附性能,主要包括吸附时间、溶液pH值和温度对吸附量的影响以及吸附等温式的研究。研究表明,在实验范围内,Pb2+的吸附平衡时间为12h,适宜吸附Pb2+的pH值范围在4～5,Pb2+的最大吸附量为34.96mg/g;Zn2+的吸附平衡时间为20h,适宜吸附Zn2+的pH值在6.2左右,Zn2+的最大吸附容量为2.24mg/g;Cd2+的吸附平衡时间为20h,适宜吸附Cd2+的pH值在5.0左右,Cd2+的最大吸附容量为10.40mg/g;Cu2+的吸附平衡时间为20h;适宜吸附Cu2+的pH值在5.0左右;Cu2+在不同温度下的最大吸附容量为2.60mg/g。多氨基改性蔗渣对Pb2+、Zn2+、Cd2+、Cu2+的吸附均可用Freundlich方程和Langmuir方程描述。     

Ion-exchange of Pb2+, Cu2+, Zn2+, Cd2+, and Ni2+ ions from aqueous solution by Lewatit CNP 80

Removal of trace amounts of heavy metals can be achieved by means of selective ion-exchange processes. The newly developed resins offered a high resin capacity and faster sorption kinetics for the metal ions such as Pb(2+), Cu(2+), Zn(2+), Cd(2+), and Ni(2+) ions. In the present study, the removal of Pb(2+), Cu(2+), Zn(2+), Cd(2+), and Ni(2+) ions from aqueous solutions was investigated. Experimental investigations were undertaken using the ion-exchange resin Lewatit CNP 80 (weakly acidic) and were compared with Lewatit TP 207 (weakly acidic and chelating). The optimum pH range for the ion-exchange of the above mentioned metal ions on Lewatit CNP 80 and Lewatit TP 207 were 7.0-9.0 and 4.5-5.5, respectively. The influence of pH, contact time, metal concentration and amount of ion-exchanger on the removal process was investigated. For investigations of the exchange equilibrium, different amounts of resin were contacted with a fixed volume of Pb(2+), Cu(2+), Zn(2+), Cd(2+), and Ni(2+) ion containing solution. The obtained sorption affinity sequence in the presented work was Ni(2+)>Cu(2+)>Cd(2+)>Zn(2+)>Pb(2+). The metal ion concentrations were measured by AAS methods. The distribution coefficient values for metal ions of 10(-3)M initial concentration at 0.1mol/L ionic strength show that the Lewatit CNP 80 was more selective for Ni(2+), Cu(2+) than it was for Cd(2+), Zn(2+) and Pb(2+). Langmuir isotherm was applicable to the ion-exchange process and its contents were calculated. The uptake of metal ions by the ion-exchange resins was reversible and thus has good potential for the removal of Pb(2+), Cu(2+), Zn(2+), Cd(2+), and Ni(2+) from aqueous solutions. The amount of sorbed metal ion per gram dry were calculated as 4.1, 4.6, 4.7, 4.8, and 4.7mequiv./g dry resin for Pb(2+), Cu(2+), Zn(2+), Cd(2+), and Ni(2+), respectively. Selectivity increased in the series: Cd(2+)>Pb(2+)>Cu(2+)>Ni(2+)>Zn(2+). The results obtained showed that Lewatit CNP 80 weakly acidic resin had shown better performance than Lewatit TP 207 resin for the removal of metals. The change of the ionic strength of the solution exerts a slight influence on the removal of Pb(2+), Cu(2+), Zn(2+), Cd(2+), and Ni(2+). The presence of low ionic strength or low concentration of NaNO(3) does not have a significant effect on the ion-exchange of these metals by the resins. We conclude that Lewatit CNP 80 can be used for the efficient removal of Pb(2+), Cu(2+), Zn(2+), Cd(2+), and Ni(2+) from aqueous solutions.     

海芒果树叶中氨基酸和微量元素的分析

采用高效液相色谱法和等离子发射光谱法,分析测定了红树植物海芒果Cerberamanghas树叶中氨基酸和微量元素成分。结果表明,叶子提取液中含有16种氨基酸,其中6种为必需氨基酸,2种为半必需氨基酸,其中必需氨基酸占总氨基酸的33.20%;15种微量元素,分别为Al、As、Ba、Ca、Cd、Cr、Cu、Fe、Mg、Mn、Ni、Pb、Sr、Ti、Zn。     

Chemometric studies on relationship between trace elements and three species of sulfur in coal

Based on the determination of several trace elements in coal particulate with different specific gravities using three-variable regression equations, the correlation of the contents of trace elements Be, Cd, Co, Pb, Cu, Ni, As and three species of sulfur in coal were well established. For elements Cd, Co, Pb, Cu and Ni, the regression equations were successfully used for prediction of these trace elements in individual parts of coal with different specific gravities. Factor analysis was also used to analyze the data sets. The results showed that a three-factor model can interpret the data sets reasonably. Trace elements Cd, Co, Pb, Cu, Ni, inorganic sulfide and total sulfur (TS) in coal are highly correlated with the first factor. Trace element Be, sulfate and organic sulfide (OS) are highly correlated with the second factor and trace elements Cr and As are highly correlated with the third factor. The factors can be interpreted by the chemical properties of these elements.     

Accumulation and partitioning of seven trace metals in mangroves and sediment cores from three estuarine wetlands of Hainan Island, China

Trace metals in mangrove tissues (leaf, branch, root and fruit) of nine species and sediments of ten cores collected in 2008 from Dongzhai Harbor, Sanya Bay and Yalong Bay, Hainan Island, were analyzed. The average concentrations of Cu, Pb, Zn, Cd, Cr, Hg and As in surface sediments were 14.8, 24.1, 57.9, 0.17, 29.6, 0.08 and 9.7 μg g(-1), whereas those in mangrove tissues were 2.8, 1.4, 8.7, 0.03, 1.1, 0.03, and 0.2 μg g(-1), respectively. Compared to those from other typical mangrove wetlands of the world, the metal levels in Hainan were at low- to median-levels, which is consistent with the fact that Hainan Island is still in low exploitation and its mangroves suffer little impact from human activities. Metal concentrations among different tissues of mangroves were different. In general, Zn and Cu were enriched in fruit, Hg was enriched in leaf, Pb, Cd and Cr were enriched in branch, and As was enriched in root. The cycle of trace metals in mangrove species were estimated. The biota-sediment accumulation factors (BSAFs) followed the sequence of Hg (0.43)>Cu (0.27)>Cd (0.22)>Zn (0.17)>Pb (0.07)>Cr (0.06)>As (0.02).     

Removal of metals from landfill leachate by sorption to activated carbon, bone meal and iron fines

Sorption filters based on granular activated carbon, bone meal and iron fines were tested for their efficiency of removing metals from landfill leachate. Removal of Al, As, Ca, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Mo, Ni, Pb, Sr and Zn were studied in a laboratory scale setup. Activated carbon removed more than 90% of Co, Cr, Cu, Fe, Mn and Ni. Ca, Pb, Sr and Zn were removed but less efficiently. Bone meal removed over 80% of Cr, Fe, Hg, Mn and Sr and 20-80% of Al, Ca, Cu, Mo, Ni, Pb and Zn. Iron fines removed most metals (As, Ca, Co, Cr, Cu, Fe, Mg, Mn, Pb, Sr and Zn) to some extent but less efficiently. All materials released unwanted substances (metals, TOC or nutrients), highlighting the need to study the uptake and release of a large number of compounds, not only the target metals. To remove a wide range of metals using these materials two or more filter materials may need to be combined. Sorption mechanisms for all materials include ion exchange, sorption and precipitation. For iron fines oxidation of Fe(0) seems to be important for metal immobilisation.     

Managing trace elements in Portland cement – Part I: Interactions between cement paste and heavy metals added during mixing as soluble salts

The aim of this work is to investigate the effect of the addition of Cu, Cd, Ni, Pb and Zn nitrate salts on the compressive strength of a CEM I Portland cement. Concentrations of 0.018 or 0.18 mol/kg of cement of each trace element were tested. After 2 days age, the compressive strength was reduced by various extents by addition of heavy metals, with the exception of Ni. This difference is due to a delay in tricalcium silicate hydration (C₃S) as shown by an isothermal calorimetry test. Trace elements also influence the 28-days compressive strength, whereas the measured degree of hydration of these cement pastes is the same. As shown by scanning electron microscopy and X-ray diffraction, Cu and Pb are predominantly absorbed in the calcium silicate hydrate gel (C–S–H) while Cd, Ni and Zn are mainly precipitated as hydroxides within the intergranular porosity. Thus, trace elements precipitated as hydroxides have only a slight effect on the compressive strength. In contrast, Cu and Pb cause an increase in mechanical resistance by changing the C–S–H nanometric assembly and its density.     

On-site treatment and landfilling of MSWI air pollution control residues

Air pollution control (APC) residues from municipal solid waste incineration (MSWI) are difficult to landfill due to substantial leaching of trace metals. An on-site pretreatment prior to landfilling of APC-residues was investigated in terms of bench-scale experiments with a semidry APC-residue and a fly ash. The treatment involved mixing of the residues with a ferrous sulphate solution and subsequent oxidation of the suspension. Afterwards, the suspension was spread on a dedicated landfill section and allowed to drain by gravity through the drainage system of the landfill. The wastewater from the process, collected through the drainage system, contained large concentrations of salts (Cl: 14-30 g/l, Na: 4-9 g/l, K: 5-11 g/l, Ca: 2-12 g/l) but low concentrations of trace metals (e.g. Pb: 14-100 microg/l, Cd: <2-7 microg/l). The treated residues left in the landfills were later subject to leaching by simulated rainfall. The leachate contained low concentrations of trace metals (Pb: <120 microg/l, Cd: <2 microg/l, Cr: <485 microg/l). The leachate concentrations from the treated APC-residues were substantially reduced compared to concentrations in leachate from untreated APC-residues. Particularly in the early stages of the leaching, concentrations of trace metals were reduced by up to four orders of magnitude.     

Assessing soil heavy metal pollution in the water-level-fluctuation zone of the Three Gorges Reservoir, China

The water-level-fluctuation zone (WLFZ) between the elevations of 145-175 m in China's Three Gorges Reservoir has experienced a novel hydrological regime with half a year (May-September) exposed in summer and another half (October-April) submerged in winter. In September 2008 (before submergence) and June 2009 (after submergence), soil samples were collected in 12 sites in the WLFZ and heavy metals (Hg, As, Cr, Cd, Pb, Cu, Zn, Fe, and Mn) were determined. Enrichment factor (EF), factor analysis (FA), and factor analysis-multiple linear regression (FA-MLR) were employed for heavy metal pollution assessment, source identification, and source apportionment, respectively. Results demonstrate spatial variability in heavy metals before and after submergence and elements of As, Cd, Pb, Cu, and Zn are higher in the upper and low reaches. FA and FA-MLR reveal that As and Cd are the primary pollutants before submergence, and over 45% of As originates from domestic sewage and 59% of Cd from industrial wastes. After submergence, the major contaminants are Hg, Cd, and Pb, and traffic exhaust contributes approximately 81% to Hg and industrial effluent accounts about 36% and 73% for Cd and Pb, respectively. Our results suggest that increased shipping and industrial wastes have deposited large amounts of heavy metals which have been accumulated in the WLFZ during submergence period.     

Partitioning behavior of trace elements during pilot-scale fluidized bed combustion of high ash content lignite

This study describes the partitioning of 20 trace elements (As, B, Ba, Cd, Co, Cr, Cu, Hg, Li, Mn, Mo, Ni, P, Pb, Sb, Se, Sn, Tl, V, Zn) and eight major and minor elements (Al, Ca, Fe, K, Mg, Na, Si, Ti) during the combustion of high ash content lignite. The experiments were carried out in the 0.3 MW(t) Middle East Technical University (METU) atmospheric bubbling fluidized bed combustor (ABFBC) test rig with and without limestone addition. Inert bed material utilized in the experiments was bed ash obtained previously from the combustion of the same lignite without limestone addition in the same test rig. Concentrations of trace elements in coal, limestone, bottom ash, cyclone ash and filter ash were determined by inductively coupled plasma optical emission spectroscopy (ICP-OES). Partitioning of major and minor elements are influenced by the ash split between the bottom ash and fly ash and that the major proportion of most of the trace elements (As, Ba, Cr, Hg, Li, Mo, Ni, Sn, V, Zn) are recovered in fly ash. Limestone addition shifts the partitioning of Ba, Cr, Mo, Ni, Sn, V, Zn from bottom ash to fly ash.     

Determination of heavy metals by ICP-OES and F-AAS after preconcentration with 2,2'-bipyridyl and erythrosine

The applicability of 2,2'-bipyridyl and erythrosine co-precipitation method for the separation and preconcentration of some heavy metals, such as Cd, Co, Cu, Ni, Pb and Zn in actual samples for their determination by ICP-OES and F-AAS was studied. Experimental conditions influencing the recovery of the investigated metals, such as pH, molar ratio of 2,2'-bipyridyl to erythrosine, the effect of time on co-precipitation were optimized. The analytical characteristics of the method (e.g. limit of detection, sensitivity, linear range and preconcentration factor) were obtained. The limits of detection LOD (ng mL(-1)) of the ICP-OES (F-AAS) method were: Cd: 4.0 (7.75), Co: 3.1 (57.2), Cu: 18 (10.3), Ni 21.3 (32.8), Pb: 35.9 (29.2) and Zn: 10.2 (6.90). The recovery of all the elements tested was more than 93%. The influence of inorganic matrix was examined. The proposed method was applied to determination of Cd, Co, Cu, Ni, Pb and Zn in vegetables and certified reference material (NCS ZC85006 Tomato).     

Distribution of heavy metals in Lakes Doirani and Kerkini, Northern Greece

The distribution of heavy metals in two lakes of high ecological significance, Doirani and Kerkini, located in Northern Greece was studied. Eight metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) were determined in water, total suspended solids, fine and coarse sediments. Moreover, the modified BCR fractionation scheme was employed in sediments and suspended solids to determine soluble, oxidisable, reducible and residual fractions of metals. The Lake Doirani presents higher metal concentrations in aqueous phase than Lake Kerkini; Cd, Cu, Ni, Pb and Zn are above the chronic freshwater quality criteria for aquatic life. In both lakes, Fe and Mn are the most abundant elements in total suspended solids whereas Cd the less abundant. The Lake Kerkini exhibits higher concentrations of all the examined metals in sediments comparing to the Lake Doirani, however the concentrations are lower than the sediment quality guidelines. Cd in sediments is mainly in soluble fraction, Pb and Cu exhibit significant oxidisable fractions whereas, Cr and Fe associated mainly with residual fraction.     

生态水泥中SiO2掺量对焚烧飞灰中重金属固溶特性的影响

按不同SiO2掺量(质量分数)进行垃圾焚烧飞灰的水泥固化试验,研究了SiO2掺量对熟料试样的重金属分布、浸出毒性的影响。结果表明,SiO2掺量低于16%时,提高掺量有利于增加熟料中Cr、Ni、Cu、As固溶率;但SiO2掺量超过16%后,重金属固溶率与其成反比。Cd、Pb、Zn的挥发率随SiO2掺量增加而减少,掺加SiO2能明显抑制Zn的挥发,但基本不影响Hg的挥发。SiO2掺量增加后熟料结构进一步致密化,重金属浸出量减少。     

Sequential extraction for evaluating the leaching behavior of selected elements in municipal solid waste incineration fly ash

A sequential extraction method has been applied for the determination of binding forms of trace elements in the municipal solid waste incineration (MSWI) fly ash and evaluating their leaching behavior in view of their potential environmental impact. The elemental determinations in the different leachates are performed by ICP-AES and ICP-MS, respectively. The morphology and mineralogical phases after extraction step were performed by scanning electron microscopy (SEM). Total of 20 elements in the samples are investigated. A reference material of city waste incineration fly ash (BCR No. 176) is also tested to examine the applicability as well as accuracy of the proposed method. The sum of most elements present in the individual fractions shows a good agreement with the total elemental concentrations. The extraction efficiencies are generally higher than 80% except for that of Cr and V. The extractable data of most elements give information about the binding forms of various elements in both incineration fly ashes. It was found that the elements such as Ca, K, Na, Pb, Zn, Cd, Cu and Sr have exhibited a remarkable mobility in fly ash. More than half of them would be dissolved or exchanged under a mild leaching condition. The toxic elements such as Pb, Cd, Zn and Cu have a great potential to be released into the environment under normal conditions.     

Peat filter performance under changing environmental conditions

Peat is a candidate filter material for in situ treatment of urban runoff, contaminated groundwater and landfill leachates. Until now research has focused on peat sorption in batch experiments and there is a lack of knowledge on peat performance in filter beds. In this project column tests were carried out to evaluate the capacity of peat to remove As, Cd, Cu, Cr, Ni, Pb and Zn in multi-metal solution under a range of environmental conditions that may be encountered in real-life applications (draining, water stagnation, freezing, change in pH and metal concentrations, input of NaCl and elevated DOC). The removal capacity was 91–98% for Cd, Cu, Zn, Ni and Pb and the efficiency was unaffected by the changes of physical factors, but temporarily inhibited for solutions containing NaCl. Leaching of DOC from peat was detected in the initial samples and temporarily decreased metal removal. The peat filters showed high removal rates for Cd, Cu, Zn, Ni and Pb under all experimental conditions and are recommended for treatment of waters containing these elements. In contrast, peat was not found to be efficient for treatment of As and Cr in the multi-metal contaminated water at the pH range (6.7–8.0) studied.     

Modelling the leaching of Pb, Cd, As, and Cr from cementitious waste using PHREEQC

A leaching model was developed using the United States Geological Survey public domain PHREEQC geochemical package to simulate the leaching of Pb, Cd, As, and Cr from cementitious wastes. The model utilises both kinetic terms and equilibrium thermodynamics of key compounds and provides information on leachate and precipitate speciation. The model was able to predict the leaching of Pb, Cd, As, and Cr from cement in the presence of both simple (0.1 and 0.6M acetic acid) and complex municipal landfill leachates. Heavy metal complexation by the municipal landfill leachate was accounted for by the introduction of a monoprotic organic species into the model. The model indicated Pb and As were predominantly incorporated within the calcium silicate hydrate matrix while a greater portion of Cd was seen to exist as discrete particles in the cement pores and Cr (VI) existed mostly as free CrO4(2-) ions. Precipitation was found to be the dominant mechanism controlling heavy metal solubility with carbonate and silicate species governing the solubility of Pb and carbonate, silicate and hydroxide species governing the solubility of Cd. In the presence of acetic acid, at low pH values Pb and Cd acetate complexes were predominant whereas, at high pH values, hydroxide species dominated. At high pH values, the concentration of As in the leachate was governed by the solubility of Ca3(AsO4)2 with the presence of carbonate alkalinity competing with arsenate for Ca ions. In the presence of municipal landfill leachate, Pb and Cd organic complexes dominated the heavy metal species in solution. The reduction of As and Cr in municipal landfill leachate was crucial for determining aqueous speciation, with typical municipal landfill conditions providing the reduced forms of As and Cr.     

Coagulation–flocculation process with metal salts,synthetic polymers and biopolymers for the removal of trace metals (Cu,Pb, Ni,Zn) from municipal wastewater

To ensure compliance with regulatory standards, it is important to examine the potential of treatment technologies to enhance trace metal removal from wastewater. This study investigated the effectiveness of coagulation–flocculation at removing trace metals from humus effluent with ferric chloride (FeCl₃), the synthetic polymer polyethyleneimine (PEI) and the biopolymers chitosan and floculan. Effluent samples were collected from a trickling filter treatment works operating in the UK and contained 21 ± 4 μg/L Cu, 0.8 ± 0.1 μg/L Pb, 4 ± 1 μg/L Ni and 43 ± 9 μg/L Zn. The influence of coagulant dosage and the velocity and time of the slow mixing stage were studied via a series of jar tests. Chitosan and PEI had a moderate effect on the removal of trace metals (≤ 35%). FeCl₃ removed 48% Cu, 56% Pb and 41% Zn at the optimised dose of 0.10 mg/L. At the optimised dose of 0.25 mg/L, floculan removed 77% Cu, 68% Pb and 42% Zn. The dominant mechanism for particle removal by FeCl₃ was enmeshment in the precipitates (i.e. sweep flocculation), whereas, for floculan, inter-particle bridging was the dominant removal mechanism. Overall, FeCl₃ and floculan were found to be most effective at removing trace metals from wastewater.

     

Low Blank Preconcentration Technique for the Determination of Lead, Copper, and Cadmium in Small-Volume Seawater Samples by Isotope Dilution ICPMS

A simple low-blank method is described for the analysis of Pb, Cu, and Cd in seawater using Mg(OH)(2) coprecipitation and isotope dilution inductively coupled plasma mass spectrometry (ICPMS). Here, 20-40 μL of 9 M aqueous NH(3) is mixed into a 1.3 mL seawater sample spiked with enriched isotopes of Pb, Cu, and Cd. After centrifugation, the supernatant is discarded and the Mg(OH)(2) precipitate dissolved in 100 μL of 5% HNO(3) for ICPMS analysis. This method is simple, accurate, and precise, with detection limits of Pb = 1.3 pM, Cu = 39 pM, and Cd = 5.0 pM and blanks of Pb = 0.62 pM, Cu = 27 pM, and Cd = 6.0 pM. The method is demonstrated by oceanographically consistent profiles of these trace metals at an ocean station in the eastern North Atlantic.