Adsorption of trace elements from poultry litter by montmorillonite clay

Poultry litter (PL) is used as fertilizer on agricultural lands because of its high nutrient content. However, the litter also contains trace elements such as As, Cd, Cu, Pb, and Zn. On land application of PL, these trace elements may be absorbed by crops, leach into groundwater, or enter the aquatic system as run-off. The objective of this research was to study the effect of the addition of montmorillonite clay-mineral (CM) in reducing the release of trace elements from PL. Cd, Cu, and Zn showed significant decreases of 29, 34, and 22%, respectively, in PL aqueous leachate (compared with the control-PL without CM) on mixing with 0.05 g CM but no change in As, Co, and Cr concentrations was observed. Lead showed a significant increase in PL aqueous leachate on mixing with 0.2 g CM but Pb concentration was two orders of magnitude less than in CM aqueous leachate alone. On washing, the settled precipitate (PL+CM) in the centrifuge tubes with water (desorption study) most of the adsorbed metals (Cd 85%, Cu 61%, and Zn 100%) were released. The results of this study show that the addition of CM resulted in significant adsorption of Cd and Cu from PL.     

Biodegradation of 2,4-dinitrotoluene using poultry litter leachate

Various micro-organisms are known to degrade 2,4-dinitrotoluene (DNT) through pathways involving intermediates. Addition of nutrients stimulates the biodegradation process. Poultry litter has a consortia of micro-organisms along with many nutrients. The objective was to study the DNT biodegradation using poultry litter in an aqueous medium. Complete biodegradation of 10-50 ppm 2,4-DNT solutions was observed after two days interaction with poultry litter leachate without the formation of any intermediates. No degradation was observed using autoclaved litter leachate.     

In situ stabilization of toxic metals in polluted soils using phosphates: theoretical prediction and experimental verification

The in situ (in place) immobilization of toxic metals, using inexpensive "reactive" amendments, is considered as a simple and cost-effective approach for the treatment of soils, contaminated by the presence of heavy metals, when these soils are difficult or costly to be removed and treated ex situ. Several application studies have demonstrated that the stabilization of contaminated soils and groundwaters by the addition of apatite minerals has the potential to be a successful and widely applicable remediation strategy for the case of Pb, Cd, as well as for other toxic metals, existing in polluted soils. On the other hand, the specific immobilization mechanism(s) of these toxic metals remains rather elusive. The present work involves an interdisciplinary theoretical and experimental approach, designed to gain at the fundamental (molecular) level the understanding of respective mechanisms, considering the immobilization of Pb and Cd by the addition of apatites. The theoretical analysis of stability, regarding the apatite/Pb or apatite/Cd systems and the relevant results of sorption experiments, pointed out two different mechanisms for the immobilization of Pb or Cd by the use of apatites. The possible practical consequences of these findings for the selection/application of natural apatites for the remediation of contaminated soils by the presence of heavy metals have been also discussed.     

Removal of some heavy metals by CKD leachate

In this study, Cu(II), Ni(II), and Zn(II) ions were precipitated from synthetic aqueous solutions as hydroxides by using CKD leachate. Precipitation tests were carried out batch wise in agitated flasks with single-metal solutions (each solution contained 100 mg/l of one of the three metals), and a multi-metal solution that contained 50 mg/l of each of the three elements. The results showed that high removal efficiencies, approaching 100%, of these heavy metals were attained and the leachate of the solid waste CKD, therefore, can be used for removing heavy metals from aqueous solutions.     

Leaching of contaminants from untreated pine bark in a batch study: chemical analysis and ecotoxicological evaluation

Low cost sorbents have been widely studied in recent years in the search for filter materials that retain contaminants from water. One promising, low cost material is pine bark, a by-product from the forest industry. Many studies have shown that pine bark has great potential for the treatment of metals and organic substances, as a replacement for other commercial sorbents such as active carbon. However, some potential problems are introduced through the use of natural materials and by-products. One such problem that must be addressed is the possibility of leaching of contaminants from the filter material, especially in the initial filtration step or during flushes of lightly contaminated water, e.g. during rainfall for on-site treatment of storm water or landfill leachate. The aim of this preliminary study was therefore to identify potential risks and limitations of using pine bark as a filter material. Leachate from a standardized batch test was analysed for metals, dissolved organic carbon (DOC) and phenols. In addition to these chemical analyses, an ecotoxicological test was conducted using the test organism Daphnia magna. The results showed significant leaching of DOC and some metals. Only a small fraction of the DOC was present as phenols. The leachate was however found to be toxic to the test organism without pH adjustment, and the EC(50) was established at an approximate leachate concentration of 40%. This was concluded to be related to the low pH in the eluate, since no toxicity was observed after pH adjustment before the toxicity tests.     

Heavy metals distribution in soils surrounding an abandoned mine in NW Madrid (Spain) and their transference to wild flora

The present work concerns the distribution and mobility of heavy metals (Fe, Mn, Cu, Zn and Cd) in the surrounding soils of a mine site and their transfer to wild flora. Thus, soils and plants were sampled from a mining valley in NW Madrid (Spain), and total and extractable heavy metals were analysed. Soils affected by mining activities presented total Cd, Cu and Zn concentrations above toxic thresholds. The percentage of extractable element was highest for Cd and lowest for Cu. A highly significant correlation was observed between the total and extractable concentrations of metals in soils, indicating that, among the factors studied, total metals concentration is the most relevant for heavy metals extractability in these soils. (NH(4))(2)SO(4)-extractable metal concentrations in soils are correlated better with metal concentrations in several plant species than total metals in soils, and thus can be used as a suitable and robust method for the estimation of the phytoavailable fraction present in soils. Twenty-five vascular plant species (3 ferns and 22 flowering plants) were analysed, in order to identify exceptional characteristics that would be interesting for soil phytoremediation and/or reclamation. High Cd and Zn concentrations have been found in the aerial parts of Hypericum perforatum (Cd), Salix atrocinerea (Cd, Zn) and Digitalis thapsi (Cd, Zn). The present paper is, to the best of our knowledge, the first report of the metal accumulation ability of the two latter plant species. The phytoremediation ability of S. atrocinerea for Cd and Zn was estimated, obtaining intervals of time that could be considered suitable for the phytoextraction of polluted soils.     

Heavy metal sorption and desorption capacity of soils containing endogenous contaminants

Soils on serpentinites in some regions of northwestern Spain have been the subject of agricultural management practices involving the use of fertilizers and various types of organic waste containing heavy metals. Although such practices have facilitated crop growth, they have also raised the natural contents in heavy metals of the soils. In this work, three ferralic Cambisols and another three mollic Leptosols with high Cr and Ni contents were used to study competitive sorption and desorption of six heavy metals via K(d100), which was employed as a measure of the ability of the soils to adsorb and retain each metal. Lead was found to be the metal sorbed and retained to the greatest extent, and Cd, Ni and Zn those sorbed and retained in the smallest amounts. Although the ferralic Cambisols were found to contain greater amounts of natural heavy metals, they exhibited an increased ability to adsorb and retain the body of metals relative to the mollic Leptosols by effect of their increased contents in clay and Fe, Mn and Al oxides, in addition to their higher ion-exchange capacity. Based on the results, Pb and Cu are strongly bound, and Zn, Cd and Ni weakly bound, to the soils. The ferralic Cambisols exhibited an increased capacity to adsorb and retain Cd, Ni, Zn and--especially--Cr than the mollic Leptosols; the latter, however, proved more effective in adsorbing and retaining Cu and Pb by virtue of their increased organic matter contents. Copper sorption and retention, and Pb retention, were found to be correlated with the content in organic matter and that in vermiculite--which was only present in the mollic Leptosols--in the clay fraction.     

MSW fly ash stabilized with coal ash for geotechnical application

The solidification and stabilization of municipal solid waste (MSW) fly ash for the purpose of minimizing the geo-environmental impact caused by toxic heavy metals as well as ensuring engineering safety (strength and soaking durability) are experimentally evaluated. The mixtures of MSW fly ash stabilized with cement and fluidized bed combustion coal fly ash (FCA) were used for unconfined compressive strength tests, leachate tests, and soaking tests. The behavior of soluble salts contained in the MSW fly ash significantly affects strength development, soaking durability, and the hardening reaction of the stabilized MSW fly ash mixtures. The cement stabilization of the MSW fly ash does not have enough effect on strength development and soaking durability. The addition of cement only contributes to the containment of heavy metals due to the high level of alkalinity. When using FCA as a stabilizing agent for MSW fly ash, the mixture exhibits high strength and durability. However, the Cd leachate cannot be prevented in the early stages of curing. Using a combination of cement and FCA as a MSW fly ash stabilizer can attain high strength, high soaking durability, and the containment of heavy metals. The stabilized MSW fly ash with cement and FCA can be practically applied to embankments.     

Use of fly ash,phosphogypsum and red mud as a liner material for the disposal of hazardous zinc leach residue waste

Increasing amounts of residues and waste materials coming from industrial activities in different processes have become an increasingly urgent problem for the future. The release of large quantities of heavy metals into the environment has resulted in a number of environmental problems. The present study investigated the safe disposal of the zinc leach residue waste using industrial residues such as fly ash, phosphogypsum and red mud. In the study, leachability of heavy metals from the zinc leach residue has been evaluated by mine water leaching procedure (MWLP) and toxicity characteristic leaching procedure (TCLP). Zinc removal from leachate was studied using fly ash, phosphogypsum and red mud. The adsorption capacities and adsorption efficiencies were determined. The adsorption rate data was analyzed according to the pseudo-second-order kinetic, Elovich kinetic and intra-particle diffusion kinetic models. The pseudo-second-order kinetic was the best fit kinetic model for the experimental data. The results show that addition of fly ash, phosphogypsum and red mud to the zinc leach residue drastically reduces the heavy metal content in the leachate and could be used as liner materials.     

Evaluation of the effectiveness of various amendments on trace metals stabilization by chemical and biological methods

We evaluated the effects of five different kinds of amendments on heavy metals stabilization. The five amendments were: zero valent iron, limestone, acid mine drainage treatment sludge, bone mill, and bottom ash. To determine bioavailability of the heavy metals, different chemical extraction procedures were used such as, extraction with (Ca(NO(3))(2), DTPA; toxic characteristic leaching procedure (TCLP), physiologically based extraction test (PBET) that simulates gastric juice, and sequential extraction test. Bioavailability was also determined by measuring uptake of the heavy metals by lettuce (Lactuca sativa L.) and earthworms (Eisenia fetida). In addition, dehydrogenase activity was measured to determine microbial activity in the soil with the different amendments. The addition of amendments, especially limestone and bottom ash, resulted in a significant reduction in extractable metal contents. Biological assays using lettuce, earthworm, and enzyme activity were found as appropriate indicators of available metal fraction after in situ stabilization of heavy metals. In conclusion, TCLP and sequential extraction test appear to be promising surrogate measure of metal bioavailability in soils for several environment endpoints.     

Removal and recovery of lead(II) from single and multimetal (Cd, Cu, Ni, Zn) solutions by crop milling waste (black gram husk)

The study reports removal of heavy metals when present singly or in binary and ternary systems by the milling agrowaste of Cicer arientinum (chickpea var. black gram) as the biosorbent. The biosorbent removed heavy metal ions efficiently from aqueous solutions with the selectivity order of Pb>Cd>Zn>Cu>Ni. The biosorption of metal ions by black gram husk (BGH) increased as the initial metal concentration increased. Biosorption equilibrium was established within 30 min, which was well described by the Langmuir and Freundlich adsorption isotherms. The maximum amount of heavy metals (qmax) adsorbed at equilibrium was 49.97, 39.99, 33.81, 25.73 and 19.56 mg/g BGH biomass for Pb, Cd, Zn, Cu and Ni, respectively. The biosorption capacities were found to be pH dependent and the maximum adsorption occurred at the solution pH 5. Efficiency of the biosorbent to remove Pb from binary and ternary solutions with Cd, Cu, Ni and Zn was the same level as it was when present singly. The presence of Pb in the binary and ternary solutions also did not significantly affect the sorption of other metals. Breakthrough curves for continuous removal of Pb from single, binary and ternary metal solutions are reported for inlet-effluent equilibrium. Complete desorption of Pb and other metals in single and multimetal solutions was achieved with 0.1 M HCl in both shake flask and fixed bed column studies. This is the first report of removal of the highly toxic Pb, Cd, and other heavy metals in binary and ternary systems based on the biosorption by an agrowaste. The potential of application for the treatment of solutions containing these heavy metals in multimetal solutions is indicated.     

Heavy metals removal from automobile shredder residues (ASR)

The fate of heavy metals during a separation process for automobile shredder residues (ASR) was investigated. A washing method to remove heavy metals from the ASR was also investigated. Although the separation process was not designed for removal of heavy metals, but for the recovery of reusable materials, the heavy metal content in the ASR was efficiently decreased. The concentrations of Pb, Cr and Cd in ASR were effectively reduced by a nonferrous metals removal process, and the As concentration was reduced by the removal of light dusts during the separation process. Five heavy metals (As, Se, Pb, Cr, Cd) remaining in the ASR after the separation process satisfied the content criteria of the Environmental Quality Standards for Soil (EQSS), while the concentrations of As, Se, Pb in the leachate from the remaining ASR did not satisfy the elution criteria of the EQSS. After additional washing of the remaining ASR with a pH 1 acid buffer solution, the As, Se, and Pb concentrations satisfied the EQSS for elution. These results indicate that an ASR residue can be safely recycled after a separation process, followed by washing at acidic pH.     

Effect of humic substances on Cu(II) solubility in kaolin-sand soil

The type and amount of organic matter present in industrially contaminated soils will influence the risk they pose. Previous studies have shown the importance of humic and fulvic acids (FAs) (important components of soil organic matter) in increasing the solubility of toxic metals but were not carried out using toxic metal levels and the pH range typical of industrially contaminated soils. This study investigated the influence of three humic substances (HSs: humates, fulvates and humins) on the solubility of copper(II) ions in kaolinitic soil spiked with Cu at levels representative of industrially contaminated soil. Humates, fulvates and humin were extracted from Irish moss peat, and controlled pH batch leaching tests were conducted on an artificial kaolin-sand soil that was spiked with each. Further leaching tests were conducted on soil spiked with each HS and copper nitrate. Dissolved organic contents were determined by titration and total and free aqueous copper concentrations in the leachate were measured using AAS and ion selective electrode (ISE) potentiometry respectively (dissolved complexed copper levels were determined by difference). It was found that humates and fulvates are partially sorbed by the soil, probably by chemisorption on positively charged gibbsite (Al-hydroxide) sites in the kaolinite. The addition of 340 mg/kg Cu(II) ions did not significantly affect the amount of humate or fulvate sorbed. Dissolved humates and fulvates form soluble complexes with copper over the pH range 3-11. However, in the presence of kaolinite, soluble copper humates and fulvates are unable to compete with the kaolinite for Cu ions at pH 6-7. Above pH 8, humate and fulvate complexes are the only forms of dissolved Cu. Humin is largely insoluble and has little effect on Cu mobility between pH 2 and 12. The implication of this study is that measurement of total soil organic content and water leaching tests should be a standard part of contaminated site investigation.     

Assessment of heavy metal contamination and its mobilization from municipal solid waste open dumping site

Influence of heavy metals was investigated by conducting various tests on the samples collected from Nonthaburi dumpsite in Thailand. The heavy metal concentration in the solid waste and its mobility potential based on its binding forms was studied. The sequential extraction method was used to determine the binding forms of metals. From the analysis, Zn was found to be highest concentrated heavy metal compared to Mn, Cu, Cr, Cd, Pb, Ni and Hg in the solid waste. From the sequential extraction, Mn, Zn and Cd mostly found in reducible form, showed its susceptibility to be leached easily. Cu and Cr were found predominantly in oxidizable form and stable under anaerobic condition. Pb and Ni were present in residual form, which is inert. The estimated individual contamination factor (C(f)(i)), showed Zn with highest affinity to leach. The concentration level of all the heavy metals in the leachate except for Cr was noticed to be below the National effluent standards. Though, indicated to be safe for disposal, its effect in any concentration proved toxic to the plant life from the seed germination toxicity test using synthetic chelate ethylene diamine tetraacetic acid (EDTA).     

Optimization using central composite design (CCD) for the biosorption of Cr(VI) ions by cross linked chitosan carbonized rice husk (CCACR)

The presence of heavy metals in aqueous streams arising from the discharge of industrial effluents into water bodies is one of the most important environmental issues because of their toxic nature and its removal is highly essential. This paper deals with the adsorption studies for the removal of hexavalent chromium ions from aqueous solutions using Schiff based chitosan activated carbonized rice husk composites as adsorbent. The activation and surface properties of the adsorbent were characterized by Scanning Electron Microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and Brauner Emmet and Teller (BET) analyzer. Central Composite Design (CCD) was used to optimize the process variables such as initial metal ion concentration, adsorbent dosage and pH of the solution on the performance of percentage removal and adsorption capacity. The experimental data were validated with different isotherms and kinetic models to evaluate the solute interaction behavior and nature of adsorption.     

The removal of arsenic(V) from acidic solutions

The residual concentrations of dissolved arsenic(V) in 1.5% sulphuric acid solutions treated with iron salts and alkaline earth metal compounds have been measured. The results are plotted on triangular composition diagrams covering the composition ranges As 0.2% to 1.2%, Fe 1.0% to 4.0%, alkaline earth metal 3.0% to 6.5%. The results indicate that ferrous iron and lime are the most effective in removing 99.9% of the arsenic over a wide composition range to give residual dissolved arsenic concentrations of ca. 0.5 ppm. Ferric iron is more effective when used in conjunction with mixed calcium and magnesium hydroxides than with lime alone. Ferric iron and dolomite offered the least effective treatment.The effect of lime particle size on the residual dissolved arsenic concentration following ferrous iron-lime treatment was studied. The optimum lime particle size range for arsenic removal was 50–100 μm.Leaching tests were carried out on samples of arsenic bearing sludge from the ferrous iron and lime treatment process mixed with sand chalk and clay soils. The presence of 5,000 ppm of acetic acid in the aqueous leachant did not appear to significantly affect the leaching test results and, after passage through contaminated and uncontaminated soils arsenic concentrations in the leachate were generally below 0.05 ppm. Ferrous iron and lime appeared to be suitable for treating the arsenic solutions and the resulting sludge seemed to be suitable for land disposal.     

Adsorption of copper and zinc from aqueous solutions by using natural clay

In this study, removal of copper (Cu(2+)) and zinc (Zn(2+)) from aqueous solutions is investigated using Cankiri bentonite, a natural clay. During the removal process, batch technique is used, and the effects of pH, clay amount, heavy metal concentration and agitation time on adsorption efficiency are studied. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherms are applied in order to determine the efficiency of natural clay used as an adsorbent. Results show that all isotherms are linear. It is determined that adsorption of Cu(2+) and Zn(2+) is well-fitted by the second order reaction kinetic. In addition, calculated and experimental heavy metal amounts adsorbed by the unit clay mass are too close to each other. It is concluded that natural clay can be used as an effective adsorbent for removing Cu(2+) and Zn(2+) from aqueous solutions.     

Characterization of aqueous lead removal by phosphatic clay: equilibrium and kinetic studies

Immobilization of heavy metals from contaminated environments is an emerging field of interest from both resource conservation and environmental remediation points of view. This study investigated the feasibility of using phosphatic clay, a waste by-product of the phosphate mining industry, as an effective sorbent for Pb from aqueous effluents. The major parameters controlling aqueous Pb removal, viz. initial metal ion concentrations, solution pH, sorbent amounts, ionic strength and presence of both inorganic and organic ligands were evaluated using batch experiments. Results demonstrated that aqueous Pb removal efficiency of phosphatic clay is controlled mainly by dissolution of phosphatic clay associated fluoroapatite [Ca(10)(PO(4))(5)CaCO(3)(F,Cl,OH)(2)], followed by subsequent precipitation of geochemically stable pyromorphite [Pb(10)(PO(4))(6)(F,Cl,OH)(2)], which was confirmed by both X-ray diffraction (XRD) and scanning electron microscopic (SEM) analysis. Lead removal efficiency of phosphatic clay increased with increasing pH, sorbent amount and decreasing ionic strength. It also depends on the nature of complexing ligands. Formation of insoluble calcium oxalate and lead oxalate in the presence of oxalic acid explained high uptake of Pb by phosphatic clay from aqueous solution. However, Pb sorption kinetics onto phosphatic clay were biphasic, with initially fast reactions followed by slow and continuous Pb removal reactions. The slow reactions may include surface sorption, co-precipitation and diffusion. The exceptional capability of phosphatic clay to remove aqueous Pb demonstrated its potential as a cost effective way to remediate Pb-contaminated water, soils and sediments.     

Heavy metal leaching from aerobic and anaerobic landfill bioreactors of co-disposed municipal solid waste incineration bottom ash and shredded low-organic residues

In this study, heavy metal leaching from aerobic and anaerobic landfill bioreactor test cells for co-disposed municipal solid waste incineration (MSWI) bottom ash and shredded low-organic residues has been investigated. Test cells were operated for 1 year. Heavy metals which were comparatively higher in leachate of aerobic cell were copper (Cu), lead (Pb), boron (B), zinc (Zn), manganese (Mn) and iron (Fe), and those apparently lower were aluminum (Al), arsenic (As), molybdenum (Mo), and vanadium (V). However, no significant release of heavy metals under aerobic conditions was observed compared to anaerobic and control cells. Furthermore, there was no meaningful correlation between oxidation-reduction potential (ORP) and heavy metal concentrations in the leachates although some researchers speculate that aeration may result in excessive heavy metal leaching. No meaningful correlation between dissolved organic carbon (DOC) and leaching of Cu and Pb was another interesting observation. The only heavy metal that exceeded the state discharge limits (10mg/l, to be enforced after April 2005) in the aerobic cell leachate samples was boron and there was no correlation between boron leaching and ORP. Higher B levels in aerobic cell should be due to comparatively lower pH values in this cell. However, it is anticipated that this slightly increased concentrations of B (maximum 25mg/l) will not create a risk for bioreactor operation; rather it should be beneficial for long-term stability of the landfill through faster washout. It was concluded that aerobization of landfills of heavy metal rich MSWI bottom ash and shredded residues is possible with no dramatic increase in heavy metals in the leachate.     

Stabilization of cadmium contaminated soils using synthesized zeolite

This research investigates the effect of synthesized zeolite on stabilizing Cd-contaminated soil, using 0.01 M CaCl₂ leaching solution in batch and column experiments. The zeolite was synthesized from fly ash obtained from a Coal-Fired Power Plant, by adding 2 N NaOH and subjecting to 90°C for 24 h. The experiment used two groups of soil samples: (1) addition of Cd to four series of background soils: Pinchen, Jente, Erlin and Chengchung; (2) actual contaminated soils from Chungsing and Tsasta sites. The result of the batch experiment indicates that the addition of zeolite reduces Cd leaching from all types of contaminated soils. The more zeolite added, the lower Cd concentrations were detected in the leaching solution. The stabilized Cd in soils in the presence of zeolite is also demonstrated in the column experiments; the leachate contains insignificant Cd, and Cd depth analysis of the soil columns shows little Cd migration. For example, for Pinchen and Jente soils, after 12 and 49 pore volumes of leaching solution, the remaining Cd levels in the soils were 12% and 35%, respectively, of the original Cd values with no zeolite added, as compared to 96% and 99% in the presence of 16% zeolite. The higher cation exchange capacity of the zeolite/soil mixtures and higher pH are responsible for stabilizing Cd in soils. The effect is most useful in application to the acidic sandy soils to prevent contaminated heavy metals from leaching.