Competitive adsorption behavior of selected heavy metals in three soil types of India amended with fly ash and sewage sludge

Laboratory batch experiments were carried out to study the competitive sorption behavior of metals in three types of Indian soils, differing in their physicochemical properties: acid laterite (SL1), red alfisol (SL2) and black vertisol (SL3) treated with different proportions of fly ash and sewage sludge mixture. Representative samples were equilibrated with 10 to 200 µM L ^-1 concentrations of metals simultaneously containing Cd, Cu, Ni, Pb and Zn in 5 mM of Ca(NO ₃) ₂ solution. In most of the cases the affinity sequence of metals was Pb>Cu>Zn>Ni>Cd based on their amount of sorption, which varied little with either metal equilibrating concentrations or the soil/mixture type. The observed metal affinity sequences in different soils amended with mixtures were compared to the predicted affinity sequences based on metal properties and a good match was found with those predicted by metal hydrolysis constants. This indicated that formation and subsequent sorption of metal hydrolysis products on soil surface is the predominant mechanism for sorption. In all the cases, Pb and Cu showed higher affinity followed by Zn, Ni or Cd. The increase in the metal additions further enhanced the competition among metals for exchange sites. Adsorption isotherms showed that metal sorption was linearly related to its concentration in the equilibrium solution. The distribution coefficients (K _D) computed from the slopes of linear regression for different metals were higher in SL3 than in both SL2 and SL1. All the mixture amended soils produced higher K _D values than their respective controls. Selectivity between metals resulted in the following affinities based on their K _D values—Pb>Cu>Zn>Ni or Cd—which was in line with the value of the hydrolysis constant of the metals under study.     

垃圾填埋场污泥灰改性黏土衬垫的强度特性及微观结构

为评价污泥灰改性黏土作为填埋场衬垫防渗材料的可行性,分析污泥灰改性黏土强度特性及孔隙结构,针对受垃圾渗沥液腐蚀的纯黏土与污泥灰掺量为1%～5%的改性黏土,采用直接剪切试验分析其抗剪强度变化规律,采用低温氮气吸附试验分析剪切变形后试样的孔隙结构组成。结果表明,改性黏土属于VI型等温线,并存在H3型滞后环,且2～6 nm介孔的数量占比较大。受垃圾渗沥液腐蚀后,黏土抗剪强度大幅下降,黏聚力与内摩擦角分别下降60.12%和19.17%;黏土的最大氮气吸附量降低16.19%,且孔隙分布双肩峰发育不完全;随污泥灰添加量的增加,改性黏土抗剪强度增大,且孔隙分布逐渐恢复双肩峰形式,总孔容增大。     

Soil improvement with coal ash and sewage sludge: a field experiment

A field experimental study was carried out successfully to improve the quality of the sandy soil by adding coal ash and sewage sludge. One ha of barren sandy soil field was chosen for the experiment in Shanghe County, Shandong Province, China. For soil amelioration and tree planting, two formulas of the mixture:coal ash, sewage sludge and soil, in ratios of 20:10:70 and 20:20:60, respectively, were used. Poplar trees were planted in pits filled with soils with additives (mixture of ash and sludge) as well as in the original sandy soil. In the 19th months after the trees were planted, the soils with additives were sampled and analyzed. The results show that the barren sandy soil was greatly improved after mixing with coal ash and sludge. The improved soils have remarkably higher nutrient concentrations, better texture, smaller bulk density, higher porosity and mass moisture content, and higher content of fine-grained minerals. During the first 22 months after planting, the annual increase in height of the trees grown in the soil with additives (4.78 m per year) was 55% higher than that of the control group (3.07 m per year), and the annual increase in diameter at the breast height (1.3 m) was 33 % higher (43.03 vs. 32.36 mm). Trees planted in soils with additives appeared healthier and shed leaves later than those in the control group. As the volume of the additives (30–40% in both formulas) is less than that of the sandy soil in and around the tree pits, it appears that the use of coal ash and sludge for tree planting and soil amelioration is environmentally safe even though the additives have relatively high heavy metal concentrations.     

Presence of fluoroquinolones and sulfonamides in urban sewage sludge and their degradation as a result of composting

The concentrations of some widely used pharmaceuticals, namely fluoroquinolones (ciprofloxacin C₁₇ H₁₈FN₃O₃, norfloxacin C₁₇ H₁₈FN₃O₃ and ofloxacin C₁₈ H₂₀FN₃O₄ and sulfonamides (sulfadimethoxine C₁₂ H₁₄N₄O₄s and sulfamethoxazole C₁₀ H₁₁N₃O₃S were determined in urban sewage sludge utilized for making compost. The levels of degradation of these pharmaceuticals resulting from sludge treatment were assessed. The concentrations of the studied pharmaceuticals sufficiently varied both in sewage sludge and in compost and due to this phenomenon the possible danger resulting from the presence of pharmaceuticals in sewage sludge, used for composting, can not be ignored. The concentrations of the studied pharmaceuticals were lower in compost, if compared to the relevant concentrations in sewage sludge. The highest pharmaceutical concentration in sewage sludge — 426 μg/kg — was detected in the case of ciprofloxacin. The highest concentrations present in compost were 22 μg/kg of norfloxacin and 20 μg/kg of ciprofloxacin. Results show that before using the sewage sludge for making compost or before using the compost a fertilizer for food plants, they should be carefully tested against the content of commonly used pharmaceuticals.     

Comparison of the effects of conventional organic amendments and biochar on the chemical, physical and microbial properties of coal fly ash as a plant growth medium

The bulk of fly ash (an inorganic waste of coal-fired power generation) produced is deposited in disposal areas where it needs to be revegetated. The effects of addition of three conventional organic amendments (biosolids, poultry manure, green waste compost), or poultry manure-derived biochar, to coal fly ash (at two rates) on some key chemical, physical and microbial properties and on growth of Rhodes grass (Chloris gayana) was studied in a laboratory incubation/greenhouse study. Addition of all amendments, including biochar, increased concentrations of extractable Mg, K, Na and P and CEC_{(pH 7.0)}. Additions of poultry manure, and particularly biosolids, also greatly increased levels of extractable NH₄ ⁺ and NO₃ ⁻-N. Addition of biosolids, green waste compost and biochar resulted in a decrease in macroporosity, a concomitant increase in mesoporosity and, at the high rate of addition, an increase in available water-holding capacity. Basal respiration was very low in fly ash and was increased by addition of all amendments; metabolic quotient was markedly greater in control than amended treatments. Biosolids, poultry manure and green waste compost additions all increased microbial biomass C. Growth of Rhodes grass was extremely low under unfertilized conditions in control, biochar and, to a lesser extent, green waste compost treatments but addition of poultry manure and the lower rate of biosolids resulted in large increases in yields. Although biochar additions increased extractable Ca, K, P, Cu, Zn and Mn, CEC, mesoporosity and water-holding capacity, they had a little or no stimulatory effect on the size of the soil microbial community, N fertility or plant growth. This was attributable to the lack of metabolisable C and an insignificant N-supplying capacity.     

高钙粉煤灰固化重金属污染土的工程性质试验研究

高钙粉煤灰是燃煤电厂排出的固体废物,其堆放不仅需占用大量土地,而且对周围环境存在严重威胁。通过系统的室内试验,着重研究了高钙粉煤灰固化铅与锌污染土的工程性质,揭示了其作用机制,探讨了利用高钙粉煤灰固化重金属污染土的可行性。试验结果表明,土体受到重金属离子污染后其无侧限抗压强度降低,掺入高钙粉煤灰可提高土体强度,并能抑制重金属离子的滤出;污染物浓度较低时,固化污染土中的Pb2+和Zn2+均能得到有效固化,污染物浓度较高时,Zn2+的固化效果优于Pb2+。干湿循环试验结果表明,高钙粉煤灰固化污染土的强度随干湿循环次数的增加,先增大后减小;固化土体中重金属离子浓度较低时,滤出液中金属离子浓度随干湿循环次数增加而增大;重金属离子浓度较高时,滤出液中金属离子浓度基本保持不变。     

The iron-coating role on the oxidation kinetics of a pyritic sludge doped with fly ash

The present study examines the processes that control the oxidation attenuation of a pyrite-rich sludge (72 wt% pyrite) from the Iberian Pyrite Belt by the buffer capacity of a fly ash from Los Barrios power station (S Spain), using saturated column experiments. In addition, in order to understand the behaviour of both materials inside these experiments, a fly-ash leaching test and flow-through experiments with pyritic sludge were carried out. The fly-ash leaching test showed that after leaching this material with a slightly acid solution (Millipore MQ water; pH 5.6) the pH raised up to 10.2 and that the metals released by the fly-ash dissolution did not increase significantly the metal concentrations in the output solutions. The flow-through experiments with the pyritic sludge were performed at pH 9, 22 °C and O₂ partial pressure of 0.21 atm, to calculate the dissolution rate of this residue simulating the fly-ash addition. In the experiments Fe bearing oxyhydroxides precipitated as the sludge dissolved. In two non-stirred experiments the iron precipitates formed Fe-coatings on the pyrite surfaces preventing the interaction between the oxidizing agents and the pyrite grains, halting pyrite oxidation (this process is known as pyrite microencapsulation), whereas in two stirred experiments, stirring hindered the iron precipitates to coat the pyrite grains. Thus, based on the release of S (aqueous sulphate) the steady-state pyritic sludge dissolution rate obtained was 9.0 ± 0.2 × ⁻¹¹ mol m⁻² s⁻¹.In the saturated column experiments, the sludge dissolution was examined at acidic and basic pH at 22 °C and oxygen-saturated atmosphere. In a saturated column experiment filled with the pyritic sludge, pyrite oxidation occurred favourably at pH approx. 3.7. As the leachates of the fly ash yielded high basic pH, in another saturated column, consisting of an initial thick layer of fly-ash material and a layer of pyritic sludge, the pyrite dissolution took place at pH approx. 10.45. In this experiment, iron was depleted completely from the solution and attenuation of the sludge oxidation was produced in this conditions. The attenuation was likely promoted by precipitation of iron-bearing phases upon the pyritic surface forming Fe-coatings (of ferrihydrite and/or Fe(III) amorphous phases) that halted the pyrite oxidation (as in non-stirred flow-through experiments). Results suggest that buffering capacity of fly ash can be used to attenuate the pyrite-rich sludge oxidation.     

粉煤灰和二灰对桂林红黏土力学性质的影响

为了研究粉煤灰和二灰掺量及养护时间对桂林红黏土的改良效果,进行了直剪试验、固结试验以及电镜扫描试验。试验结果表明,粉煤灰的掺入提高了红黏土的抗剪强度,但超过一定量（18%粉煤灰掺量）反而会降低红黏土黏聚力,各掺量粉煤灰红黏土随养护龄期的延长,抗剪强度呈先增后缓趋势。二灰改良红黏土,在早期强度剧增,且强度随养护时间增长而大幅增加,一定龄期内,二灰红黏土黏聚力随二灰掺量呈先增后减趋势。粉煤灰和二灰的掺入均增大了红黏土的压缩模量,且随养护时间的延长而逐渐增大。红黏土中随粉煤灰、石灰的加入,发生一系列物理化学反应,从微观结构分析得知土中孔隙减少,结构性较素红黏土好。     

漓江源头大溶江流域土壤理化性质

文章采用ArcGIS和SPSS22.0软件分析珠江三级支流漓江上游大溶江流域内土壤pH、电导率、粒度、土壤总氮(TN)、土壤有机碳(TOC)、土壤无机碳(TIC)及其在空间上的分布特征,结果显示:(1)研究区土壤pH平均值在土下20 cm处为4.04～6.23,土下50 cm处为4.02～6.53,体现出土壤的地带性特...     

土壤理化参数的反射光谱分析

土壤可见光和近红外波段(400~2 500 nm)反射光谱信息包含了大量土壤物理化学参数,土壤反射光谱测量简单、快速,无需破坏样品,而且还可以通过高光谱遥感方法制图。文中使用江苏国土生态地球化学调查中获取的大量土壤样品,研究了土壤阳离子交换量(CEC)、有机质含量、pH值、铁氧化物类型、铁铝硅等常量元素含量等重要土壤生态地球化学参数的光谱反应。结果显示,土壤CEC是进行光谱预测非常成功的参数,1 400、1 900和2 200 nm附近一阶导数光谱(FD)值或短波方向反射率值均可以很好地反映土壤CEC的大小;土壤有机质含量、铁氧化物类型、铁铝硅含量均可以在反射率光谱或其一阶导数(FD)值找到相关波段;土壤导数光谱存在的A、B、C和D峰使反射光谱方法不仅能够定量铁氧化物总量,还能鉴别铁氧化物矿物类型(针铁矿和赤铁矿)及其相对含量;江都土壤光谱的656 nm附近FD值与pH有很大相关性,但是江苏样品显示pH值光谱经验预测具有区域依赖性,可能与土壤类型有关,说明pH与光谱参数之间的关系并非一般的线性关系,而有更复杂的机制。     

Geotechnical properties of a chemically stabilized soil from Malaysia with rice husk ash as an additive

Summary The stabilization of Malaysian soil by mixing with rice husk ash, a locally available waste material, to improve its engineering properties is described. Stabilizing agents, i.e. cement and lime, were added to produce the reaction products which are responsible for the enhancement of the engineering properties. Based on the strength development, it seems that lime is the more effective stabilizing agent. However, the cheap waste material can be used as partial replacement for the more expensive cement in the cement-treatment of the soil. A durability study was carried out to evaluate the effectiveness of this stabilization method.     

Relationship of chemical fractions of heavy metals with microbial and enzyme activities in sludge and ash-amended acid lateritic soil from India

The influence of metals, Cd, Cr, Cu, Ni, Pb and Zn, on the microbial biomass and enzyme activities of an amended acid lateritic soil were investigated under field conditions receiving a one-time application of 52 t ha^–1 of sludge, coal ash and their mixtures at 1:3, 1:1 and 3:1 proportions, and including control and chemical fertilizer treatment at crop-specific recommended doses. Paddies and peanuts were grown in the experimental plots and soil was sampled twice after 6 months and 1 year after amendment application. The heavy metals in the soil were fractionated using sequential extraction and the increments in their concentrations in amended soil with respect to the control were determined. Concentrations of Cd, Ni and Zn were determined to have increased in their mobile fractions and were more pronounced in soil collected during the second sampling, which was associated with a decrease in soil organic carbon. The size of the microbial biomass carbon and the soil enzyme activities increased with the addition of an amendment and was highest at equal proportions of coal ash and sludge. Further increase in the proportion of sludge resulted in a significant decrease in biomass carbon. Simple correlation revealed significant and strong negative relations of mobile fractions of Cd and Ni with the ratio between microbial biomass C and organic carbon in soil, while the organic carbon content and the pH were positively correlated. The microbial activities were determined to be sensitive to the concentrations of some heavy metals in mobile fractions and therefore indicated possibilities of being useful as indicators for evaluation of toxic effects of sludge-borne metals on soil organisms.     

Changes in soil physical and chemical properties during reversal of desertification in Yanchi County of Ningxia Hui autonomous region,China

Using field surveys and laboratory analysis, soil physical and chemical properties were studied at a site exhibiting the reversal of desertification in Yanchi County of China’s Ningxia Hui autonomous region. The dominant soil particle size changed from coarse-fine sand to a combination of very fine sand and silt + clay, and corresponding levels of each soil nutrient increased. The content of coarse-fine sand (2–0.1 mm) was significantly and negatively correlated with soil nutrient contents, whereas nutrient contents were significantly and positively correlated with the contents of very fine sand (0.1–0.05 mm) and silt + clay (<0.05 mm). The increasingly fine soil texture and the nutrient enrichment both facilitated rehabilitation of desertified land. The silt + clay content contributed the most to the increasing soil nutrient contents, and thus appears to be the key factor in reversal of desertification. Soil nutrient concentrations in the bulk soil increased with increasing content of soil nutrients with different particle fractions, and there were significant positive correlations between them. The nutrients in all particle size classes jointly decided the effect of soil nutrient contents on the reversal process. Principal-components analysis (PCA) revealed that the soil quality tended to increase during the reversal process, and that nutrient factors were more significant than particle size (i.e., were the dominant factor that influenced soil quality). Available nutrients and soil organic matter (SOM) were the most important nutrient factors. Silt + clay were the most important particle factors.     

Changes in mobility and speciation of heavy metals in clay-amended incinerator fly ash

The generation of municipal solid waste incinerator fly ash (MSWIF) has been increasing significantly over the recent past, and its disposal is problematic and costly due to high concentration of leachable heavy metals present in the material. This study explored a potential stabilization of MSWIF by blending with a natural sorbent material with low permeability, clay, and assessed the potential release of heavy metals from the stabilized mixtures under various simulated subsurface environments. The leachability of heavy metals such as Pb, Cd, Cr, Zn and Cu in the MSWIF-clay mixtures cured for 1 to 360 days was investigated by performing leaching tests and sequential chemical extractions (SCE). Leaching tests were performed at acidic, neutral and alkaline pH values. The leaching test results suggested that the natural clay could turn the MSWIF into non-hazardous material. All the MSWIF-clay mixtures demonstrated leaching behavior different from that of the original MSWIF. SCE results revealed that the acidic and reducing conditions were the most unfavorable to the immobilization of the heavy metals in the stabilized MSWIF-clay matrix. Conversely, the oxidizing and alkaline conditions were not critical to the stabilized MSWIF-clay mixtures. Apparently, clay in the mixtures could function as an adsorptive micro-barrier to retain the heavy metals within the MSWIF-clay matrices.     

冻融循环对二灰和改性聚乙烯醇固化盐渍土力学性能的影响

随季节性变化的冻融循环作用对土体结构有显著的影响。为降低盐渍土对环境温度的敏感性并将其应用于工程中,提出以石灰、粉煤灰和改性聚乙烯醇(MPA)为固化材料的联合固化方法。先通过无侧限抗压强度(UCS)和微观扫描试验评价固化效果,构建固化材料的参数范围,再将抗剪强度(黏聚力和内摩擦角)与正交试验相结合,分析各因素的影响,明确最佳组合参数。结果表明:石灰+粉煤灰+MPA联合固化有助于提高盐渍土的强度,联合固化盐渍土的UCS为1 130.25 kPa,是盐渍土(218 k Pa)的5.18倍;联合固化盐渍土的冻融强度满足工程规范(JTG 3430-2020)要求。冻融循环作用下联合固化盐渍土的UCS稳定值为700k Pa,且3次循环后的波动范围在5%左右。适宜配比下联合固化盐渍土的抗剪强度(黏聚力和内摩擦角)在3次冻融循环后为208.2 kPa和38.56°。各因素的敏感性由高到低依次为养护时间、石灰掺量、MPA掺量、干密度、含盐量和冻融循环次数,随石灰、粉煤灰和MPA掺量的增加,联合固化盐渍土强度增大并趋于稳定,固化参数的优化可有效弱化冻融作用对滨海盐渍土的影响。结合抗压及抗剪强度试验结果,...     

Particle size distribution and dissolution properties of metals in cyclone fly ash

The particles in the examined cyclone fly ash were all smaller than 0.25 mm. in diameter, and particles smaller than 0.075 mm. in diameter accounted for 88.4 % of the ash weight. This result indicates that cyclone fly ash consists of particles with a small diameter. The metals in the cyclone fly ash were enriched in small particles. The highest concentrations for zinc, copper, lead, cadmium and molybdenum in the cyclone fly ash were found in the smallest particle size fraction (< 0.075 mm.) and for Barium, chromium, nickel, Vanadium and Cobalt in the second to smallest particle size fraction (0.075-0.125 mm.). From an environmental and toxicological standpoint, the smallest particles are of the greatest concern when ash is handed at landfill disposal sites (transport and disposal especially in stormy weather conditions), and some studies have reported risks to workers from prolonged exposure to ash. The results of the comparison of various dissolution methods for metals showed that the digestion procedures with nitric acid alone (USEPA 3051) or with a mixture of nitric acid + hydrogen peroxide (USEPA 3050B) slightly underestimated the metal concentrations in the cyclone fly ash. Although the use of hydrofluoric acid is often necessary for the determination of a number of elements associated with siliceous minerals, its use can result in loss of trace elements during dissolution.     

The physical, chemical and mineralogical properties of three cemented layers within sulfide-bearing mine tailings

The oxidation and subsequent dissolution of sulfide minerals within mine tailings impoundments releases H⁺, Fe(II), SO₄ and trace elements to the tailings pore water. Subsequent pH-buffering and hydrolysis reactions result in the precipitation of secondary phases such as gypsum, goethite and jarosite. In areas of intense precipitation, cemented layers or “hardpans” often form within the shallow tailings. Three cemented layers within pyrrhotite-bearing mine tailings at the Fault Lake, Nickel Rim and East Mine impoundments located near Sudbury, Canada, were examined. The location of the three cemented layers within the tailings stratigraphy varies as does their location relative to the water table. The morphology, mineralogy and chemical composition of the cemented layers also vary between sites. The bulk density within the three cemented layers all showed an increase relative to the surrounding uncemented tailings ranging from 9% to 29%. The porosity of each cemented layer decreased relative to the surrounding uncemented tailings ranging from an 8% to 18% decrease. The cemented layers also showed relative enrichment of total sulfur, carbon and trace elements relative to the surrounding uncemented tailings. Arsenic concentrations showed an enrichment in the cemented layers of up to 132%, Cd up to 99%, Co up to 84%, Cu up to 144%, Ni up to 693% and Zn up to 145% relative to the surrounding uncemented tailings. All the cemented layers studied show an evolution of the secondary phases with time from a gypsum–jarosite-based cement to a goethite-rich cement. The formation of these layers could potentially have a significant effect on the environmental impacts of sulfide-bearing mine waste.     

Exploitation of gold in a historic sewage sludge stockpile, Werribee, Australia: resource evaluation, chemical extraction and subsequent utilisation of sludge

Sewage sludges are dewatered end products of human sewage waste and are recognised repositories of organic pollutants and heavy metals. They may be considered targets for economic extraction of Au because of the documented Au content of sewage sludges worldwide which are of the order of some ore deposits currently mined for Au. They are also highly nutrient enriched (nitrogen and phosphorus) and therefore amenable to use as agricultural fertiliser or as covers for mine wastes. The sewage of Melbourne, Australia, a city with a current population of 3.3 million, was stockpiled in large, closed, lagoonal tanks from 1898 until 1980. In 1995 Echidna Mining, an Australian gold exploration company, acquired the exploration rights to the ground surrounding the historic sludge reserves and commenced a program of resource evaluation, utilising RNAA, INAA, GFAAS, ICP–MS and FLAAS to determine 31 elements, including Au, Ag, Sb, As, Cd, Hg, Zn, Cu, and Pb. The study was initiated to determine Au, Ag and other metal variations in both space and time and to investigate the economics of chemical extraction of the precious metals. A total of 149 samples from over 50 hand-auger drillholes to a depth up to 4 m have been analysed from the stockpiles, with Au assays yielding remarkably consistent results. Average grades of 0.77 g/t Au and 18.8 g/t Ag have been documented for a measured resource of 770,000 m³ (of an estimated 1.6–2.5 million m³ contained) at a density of 1.0 g/cm³ and an average moisture content of around 40%. Laboratory-based extractive metallurgy of the Werribee sludges has demonstrated that Au, Ag and Zn can be removed with relative ease by heap-leaching using modified conventional technology, albeit with prohibitive reagent consumption. The extraction of the precious metals also results in the variable removal of contaminant metals such as Cd, As, Sb, Hg and Cr which may render the sludges fit for sale as agricultural fertiliser, provided organic pollutants and pathogenic organisms are below governmental environmental protection limits, an area beyond the scope of this paper. Another potential avenue of the exploitation of sewage sludges is discussed: that of the utilisation of sludges to extract contaminant metals from waste water and contaminated mine waters, which we demonstrate on pure aqueous synthetic samples. This paper presents a study of the exploitation of an historic sludge resource for its contained Au and residue post-metal extraction.