Utilization of ICP/OES for the determination of trace metal binding to different humic fractions

In this study, the use of inductively coupled plasma/optical emission spectrometry (ICP/OES) to determine multi-metal binding to three biomasses, Sphagnum peat moss, humin and humic acids is reported. All the investigations were performed under part per billion (ppb) concentrations. Batch pH profile experiments were performed using multi-metal solutions of Cd(II), Cu(II), Pb(II), Ni(II), Cr(III) and Cr(VI). The results showed that at pH 2 and 3, the metal affinity of the three biomasses exposed to the multi-metal solution that included Cr(III) presented the following order: Cu(II), Pb(II)>Ni(II)>Cr(III)>Cd(II). On the other hand, when Cr(VI) was in the heavy metal mixture, Sphagnum peat moss and humin showed the following affinity: Cu(II), Pb(II)>Ni(II)>Cr(VI)>Cd(II); however, the affinity of the humic acids was: Cu(II)>Pb(II), Cr(VI)>Ni(II)>Cd(II). The results demonstrated that pH values of 4 and 5 were the most favorable for the heavy metal binding process. At pH 5, all the metals, except for Cr(VI), were bound between 90 and 100% to the three biomasses. However, the binding capacity of humic acids decreased at pH 6 in the presence of Cr(VI). The results showed that the ICP/OES permits the determination of heavy metal binding to organic matter at ppb concentration. These results will be very useful in understanding the role of humic substances in the fate and transport of heavy metals, and thus could provide information to develop new methodologies for the removal of low concentrations of toxic heavy metals from contaminated waters.     

Determination of the elemental composition of molasses and its suitability as carbon source for growth of sulphate-reducing bacteria

Bioremediation of arsenic-contaminated water could be a cost-effective process provided a cheap carbon source is used. In this work molasses was tested as a possible source of carbon for the growth of sulphate-reducing bacteria (SRB). Its elemental composition and the tolerance of SRB toward different arsenic species (As (III) and As (V)) were also investigated. Batch studies were carried out to assess the suitability of 1, 2.5 and 5 g/l molasses concentrations for SRB growth. The results indicated that molasses does support SRB growth, the level of response being dependant on the concentration. The percentage of sulphate reduction with molasses at 1, 2.5 and 5 g/l was not significantly different. However, growth on molasses was not as good as that obtained when lactate was used as carbon source. Molasses contained the heavy metals Al, As, Cu, Fe, Mn and Zn in concentrations of 0.54, 0.24, 8.7, 0.35, 11.1 and 19.7 microg/g, respectively. Arsenic tolerance, growth response and sulphate-reducing activity of the SRB were investigated using arsenite and arsenate solutions at final concentrations of 1, 5 and 20 mg/l for each species. The results revealed that very little SRB growth occurred at concentrations of 20 mg/l As(III) or As(V). At lower concentrations (1 mg/l) the SRB grew better with As(V) than with As(III). Arsenic pollution in most groundwater sources is below this level (1 mg/l).     

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).     

The bonding of heavy metals on nitric acid-etched coal fly ashes functionalized with 2-mercaptoethanol or thioglycolic acid

Coal fly ash is a waste by-product of the coal fire industry, which generates many environmental problems. Alternative uses of this material would provide efficient solutions for this by-product. In this work, nitric acid-etched coal fly ash labelled with 2-mercaptoethanol or thioglycolic acid was assessed for retention of Al(III), As(III), Cu(II), Cd(II), Fe(III), Mn(II), Hg(II), Ni(II), Pb(II) and Zn(II) ions. The bonding characteristics between the organic compounds with the solid support, as well as with the metal ions, were evaluated using various surface analytical techniques. Visualization of the organically-functionalized coal fly ash particle was possible using scanning electron microscopy (SEM), while the elemental composition of the functionalized material, before and after retention of the metal ions, was obtained by energy dispersive (ED)-X ray spectrometry (XRS) and electrothermal atomic absorption spectrometry (ETAAS). Fourier transform infrared (FT-IR) spectrometry and Raman spectrometry were used to obtain information about the functional groups. It was found that some metal(oid) ions (As, Ni, Pb, Zn) were coordinated through the mercaptan group, while other metal(oid)s (Al, Cd, Cu, Fe, Hg, Mn) were apparently bonded to oxygen atoms. A low-cost and effective solid phase retention system for extraction of heavy metals from aqueous solutions was thus developed.     

Removal of Zn(II), Cu(II), Ni(II), Ag(I) and Cr(VI) present in aqueous solutions by aluminium electrocoagulation

The performance of an electrocoagulation system with aluminium electrodes for removing heavy metal ions (Zn2+, Cu2+, Ni2+, Ag+, Cr2O7(2-)) on laboratory scale was studied systematically. Several parameters - such as initial metal concentration, numbers of metals present, charge loading and current density - and their influence on the electrocoagulation process were investigated. Initial concentrations from 50 to 5000 mg L(-1) Zn, Cu, Ni and Ag did not influence the removal rates, whereas higher initial concentrations caused higher removal rates of Cr. Increasing the current density accelerated the electrocoagulation process but made it less efficient. Zn, Cu and Ni showed similar removal rates indicating a uniform electrochemical behavior. The study gave indications on the removal mechanisms of the investigated metals. Zn, Cu, Ni and Ag ions are hydrolyzed and co-precipitated as hydroxides. Cr(VI) was proposed to be reduced first to Cr(III) at the cathode before precipitating as hydroxide.     

Characteristics and accumulation of heavy metals in sediments originated from an electroplating plant

Heavy metals in river water and sediments originated from an electroplating plant in Jiangsu Province of China were studied and analyzed for their environmental impact. The results indicated that the wastewater from the plant degraded the quality of the aquatic environment downstream from the plant. In surface water, considerable concentrations of Cu, Ni, Zn, Mn and Cr were present at the sites near the plant. Unsafe levels of Cu were observed at all sites, and unsafe levels of Ni, Zn, and Cr were present at some sites. Significant accumulation of Ni, Cu, Zn and Cr was identified, and heavy metal longitudinal distribution in sediments was similar to that in water. The contents of Ni, Cu and Cr at all sites and Zn at some sites were likely to result in harmful effects on the environment. The risks posed by Ni, Cu, Zn and Cr in water and sediments decreased with increasing downstream distance. Moreover, a modified sequential extraction procedure was employed to determine exchangeable, carbonate-bound, iron-manganese oxide bound, organic matter bound and residual fractions of metals in sediments. The results showed that Ni was distributed in every fraction except for iron-manganese oxide bound, significant Mn exhibited in exchangeable fractions, and high percentage of Cu was in the organic matter and residual fractions. Residual fraction was the dominant fractions for Pb and Zn. According to RACs, Ni and Mn posed a high risk to the environment, Zn exhibited medium to high risk, Cu had low to high risk, and Pb possessed a low to medium risk.     

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.     

Influence of raw materials and distillation equipment on the heavy metal content of waste from an alcoholic anis-type beverage

This study focused on the heavy metal content waste resulting from the production of an anis-type beverage. Although natural ingredients were used in the production process, the waste contains heavy metals and is considered hazardous. Several metals were found in the waste (Fe, Cu, Ni, Zn, Cr and Cd), with concentrations of Fe to 157.5, Cu to 82.5, Zn to 31 and Ni to 8.5mg/l. To collect information on the source of these metals, the residues of the herbs used for flavoring were examined for processes employing metallic and non-metallic pot stills. Herbs distillation residues were found to contain metals in non-metallic stills, e.g. aniseed residues from glass stills contained Cu up to 1.02 and Ni up to 0.9 mg/l. Fennel residues contained Ni up to 1.2 and Zn up to 6.6mg/l. The main source for the metals was the bronze pot stills. The metals were in complexed form in the solution. The existence of metals in the amorphous phase as shown by a SEM micrograph indicates forming of metal-organic complexes, also verified by HPLC. Complexation data can be used for selecting the proper wash treatment method. The formation of large molecules favors precipitation and chemi-sorption treatment methods.     

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.     

Assessment of single extraction methods for the prediction of bioavailability of metals to Brassica juncea L. Czern. (var. Vaibhav) grown on tannery waste contaminated soil

Various single extractant (DTPA, EDTA, NH(4)NO(3), CaCl(2), and NaNO(3)) was used to evaluate the bioavailability of heavy metals from tannery wastewater contaminated soil and translocation of metals to the plant of Brassica juncea L. Czern. (var. Vaibhav). The extraction capacity of the metals was found in the order: EDTA>DTPA>NH(4)NO(3)>CaCl(2)>NaNO(3). Cluster analysis between different extractants showed close relationship between DTPA, CaCl(2), NH(4)NO(3) except EDTA and NaNO(3), which showed dispersed relationship. Principal components analysis (PCA) applied to metals extracted with EDTA showed different grouping of metals (i) Na, Co, Pb, Ni and (ii) K, Mn, Zn, Cr, in the loading plot which showed similar availability from contaminated soil. PCA applied on metals accumulation data in the plants also exhibited different grouping of variables (i) Cu, Co, Ni, Cd and (ii) Mn, Zn, Pb, Fe showed almost similar accumulation pattern in the plants. The data displayed positive loading for Mn and negative loading for Cr with PC(2). Cd and Zn have shown high loadings in PC(1) and PC(2), respectively. The translocation of most of the tested metals (Pb, Mn, Cd, Ni, Fe) in the shoot of the plant was found better except Cr, Cu, Co and K. The correlation analysis between different extractable metals and metal accumulation in the shoot of the plant showed significant positive correlation with Pb and Cr. Overall, extraction capacity and cluster analysis augmented that EDTA was found suitable extractant for tannery wastewater contaminated soil to B. juncea.     

Distribution of extractable fractions of heavy metals in sludge during the wastewater treatment process

Sludge samples were collected from different treatment steps of Gaobeidian wastewater treatment plant (WWTP) of Beijing City, PR China, to investigate the distributions of total and chemical fractions of Fe, Mn, Ni, Cu, Zn, Cr, Pb, and Mo in different sludges. The highest total concentrations were found for Fe, Mn, Pb, and Mo in digested sludge (DS), Ni and Cr in thickened sludge (TS), Zn in dewatering sludge (DWS), and Cu in active sludge (AS). The lowest concentrations were observed in AS, except for Cu in TS. Significant differences of total metal concentration were observed between AS and TS (or DS), suggesting that sludge thickening and digesting treatments significantly influenced the total metal concentrations. Fe, Cu, Ni, Cr, Mo, and Pb distributed principally in the residual fraction in all sludges, while Zn and Mn presented in a highly available fraction. For same metal in different sludges, the portion of easily mobile fraction decreased significantly along the wastewater treatment process, and metals in AS presented in the highest available fraction. Organic matter contents, TN, and TP of sludges exhibited a significant positive correlation with the concentrations of exchangeable and reducible fraction of Pb, Mo, Cr, Cu, and Fe, while sludge pH demonstrated significant negative correlations with the concentrations of these metals.     

Contamination assessment of copper, lead, zinc, manganese and nickel in street dust of Baoji, NW China

Street dusts collected from Baoji, NW China were analyzed for Cu, Pb, Zn, Mn and Ni by using PANalytical PW-2403 wavelength dispersive X-ray fluorescence spectrometry and assessed the contamination level of heavy metals on the basis of geoaccumulation index (I(geo)), enrichment factor (EF), pollution index (PI) and integrated pollution index (IPI). The results indicate that, in comparison with Chinese soil, street dusts in Baoji have elevated metal concentrations as a whole. The concentrations of heavy metals investigated in this paper are compared with the reported data of other cities. The calculated results of I(geo) and EF of heavy metals reveal the order of I(geo) and EF are Pb>Zn>Cu>Ni>Mn. The high I(geo) and EF for Pb, Zn and Cu in street dusts indicate that there is a considerable Pb, Zn and Cu pollution, which mainly originate from traffic and industry activities. The I(geo) and EF of Mn and Ni are low and the assessment results indicate an absence of distinct Mn and Ni pollution in street dusts. The assessment results of PI also support Pb, Zn and Cu in street dusts presented serious pollution, and IPI indicates heavy metals of street dust polluted seriously.     

Removal and recovery of heavy metals from electroplating wastewater by using Kyanite as an adsorbent

Kyanite, a commercial mineral has been utilized as an adsorbent for the removal of heavy metals, such as Ni(II), Zn(II), Cr(VI) and Cu(II) from electroplating wastewater. The effect of contact time, pH, concentration, adsorbent doses, particle size of the adsorbent, salinity and hardness, both in natural and wastewater on the adsorption of Cu(II) have been studied in detail. The adsorption of metal ions seems to be an ion exchange process. The adsorbed metals ions from electroplating wastewater were recovered by batch as well as column operation using dilute HCl solution. The column operation was found to be more effective compared to batch process.     

Preconcentration and determination of trace metal ions from aqueous samples by newly developed gallic acid modified Amberlite XAD-16 chelating resin

Gallic acid was immobilized on Amberlite XAD-16 by coupling it through -N=N group. The resulting chelating resin Amberlite XAD-16 gallic acid, characterized by thermogravimetric analysis (TGA), infrared (IR) spectra and BET analysis, was used to preconcentrate Cr(III), Mn(II),Fe(III),Co(II), Ni(II) and Cu(II)ions. The resin was employed for the preconcentration of the metal ions present in river water and industrial area aqueous samples. Several parameters like effect of pH, effect of time, effect of sample volume and flow rate of sample were investigated. The sorption capacities for the resin were 216 micromol g(-1), 180 micromol g(-1), 403 micromol g(-1), 281 micromol g(-1), 250 micromol g(-1) and 344 micromol g(-1) for Cr(III), Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) respectively. The preconcentration factors for Cr(III), Mn(II), Fe(III), Ni(II), Co(II) and Cu(II) were found out to be 300, 200, 400, 285.7, 300 and 400 respectively. The effect of various interfering ions was also studied. Results were validated by using standard addition method for river water sample.     

β-Galactosidase-based colorimetric paper sensor for determination of heavy metals

We demonstrate a novel approach for rapid, selective, and sensitive detection of heavy metals using a solid-phase bioactive lab-on-paper sensor that is inkjet printed with sol-gel entrapped reagents to allow colorimetric visualization of the enzymatic activity of β-galactosidase (B-GAL). The bioactive paper assay is able to detect a range of heavy metals, either alone or as mixtures, in as little as 10 min, with detection limits as follows: Hg(II) = 0.001 ppm; Ag(I) = 0.002 ppm, Cu(II) = 0.020 ppm; Cd(II) = 0.020 ppm; Pb(II) = 0.140 ppm; Cr(VI) = 0.150 ppm; Ni(II) = 0.230 ppm. The paper-based assay was immune to interferences from nontoxic metal ions such as Na(+) or K(+), could be used to detect heavy metals that were spiked into tap water or lake water, and provided quantitative data that was in agreement with values obtained by atomic absorption. With the incorporation of standard chromogenic metal sensing reagents into a multiplexed bioactive paper sensor, it was possible to identify specific metals in mixtures, albeit with much lower detection limits than were obtained with the enzymatic assay. The paper-based sensor should be valuable for rapid, on-site screening of trace levels of heavy metals in resource limited areas and developing countries.     

Removal of Cr(VI) and Ni(II) from aqueous solution by fused yeast: study of cations release and biosorption mechanism

Biosorption of Cr(VI) and Ni(II) by a fused yeast from Candida tropicalis and Candida lipolytica under varying range of pH, initial metal concentration and reaction time was investigated. Net cation release and Cr removal reached 2.000mmol/l and 81.37% when treating 20mg/l Cr(VI) at pH 2 with 25mg/l biomass for 30min, while for Ni were 0.351mmol/l and 64.60%, respectively. Trace metal elements such as Co, Cu, Mn, Mo, Se and Zn played active role in biosorption as important ingredients of functional enzymes. Cr(VI) was reduced to less toxic Cr(III) and chelated with extracellular secretions, and further accumulated inside the cells. For Ni biosorption, however, largely a passive uptake process influenced by ion gradient led to lower adsorption capacity and cations release. Fourier transform infrared (FTIR) spectrum analysis indicated that amide and pyridine on cells were involved in binding with Cr, but for Ni, bound-OH and nitro-compounds were the main related functional groups. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) analysis confirmed that considerable amounts of metals precipitated on cell surface when dealing with high concentration metals.     

Electrokinetic recovery of Cd, Cr, As, Ni, Zn and Mn from waste printed circuit boards: Effect of assisting agents

The printed circuit boards (PCBs) contains large number of heavy metal such as Cd, Cr, As, Ni, Zn and Mn. In this study, the use of electrokinetic (EK) treatment with different assisting agents has been investigated to recover the heavy metals from waste PCBs, and the effectiveness of different assisting agents (HNO₃, HCl, citric acid) was evaluated. The PCBs were first pre-treated by supercritical water oxidation (SCWO) process, then subjected to EK process. The heavy metal speciation, migration and recovery efficiency in the presence of different assisting agents during EK process were discussed. The mass loss of Cd, Cr, As and Zn during the SCWO process was negligible, but approximately 52% of Ni and 56% of Mn were lost in such a process. Experimental results showed that different assisting agents have significant effect on the behavior and recovery efficiency of different heavy metals. HCl was highly efficient for the recovery of Cd in waste PCBs due to the low pH and the stable complexation of Cl⁻. Citric acid was highly efficient for the recovery of Cr, Zn and Mn. HNO₃ was low efficient for recovery of most heavy metals except for Ni.     

Adsorption of copper from aqueous solution on Brassica cumpestris (mustard oil cake)

The adsorption behavior of various heavy metals on mustard oil cake (MOC) was studied. The maximum adsorption of Cu(II) was observed followed by Zn(II), Cr(VI), Mn(II), Cd(II), Ni(II) and Pb(II). The adsorption of Cu(II) was found to be dependent on initial concentration of solution, pH, adsorbent dose, temperature and contact time. The adsorption followed pseudo-first-order and second-order kinetics but pseudo-second-order kinetic model was better obeyed since experimental data agreed well with theoretical data. Thermodynamic parameters were also evaluated. The adsorption process was found to be endothermic and spontaneous in nature. Attempts were also made to desorb Cu(II) from the adsorbent and regeneration of the spent adsorbent. The breakthrough and exhaustive capacities were found to be 5 and 10 mg g(-1), respectively.     

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.     

Statistical analysis of trace metals in the plasma of cancer patients versus controls

The plasma of cancer patients (n=112) and controls (n=118) were analysed for selected trace metals (Al, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Sb, Sr and Zn) by flame atomic absorption spectroscopy. In the plasma of cancer patients, mean concentrations of macronutrients/essential metals, Na, K, Ca, Mg, Fe and Zn were 3971, 178, 44.1, 7.59, 4.38 and 3.90 ppm, respectively, while the mean metal levels in the plasma of controls were 3844, 151, 74.2, 18.0, 6.60 and 2.50 ppm, respectively. Average concentrations of Cd, Cr, Cu, Mn, Mo, Ni, Pb, Sb, Sr and Zn were noted to be significantly higher in the plasma of cancer patients compared with controls. Very strong mutual correlations (r>0.70) in the plasma of cancer patients were observed between Fe-Mn, Ca-Mn, Ca-Ni, Ca-Co, Cd-Pb, Co-Ni, Mn-Ni, Mn-Zn, Cr-Li, Ca-Zn and Fe-Ni, whereas, Ca-Mn, Ca-Mg, Fe-Zn, Ca-Zn, Mg-Mn, Mg-Zn, Cd-Sb, Cd-Co, Cd-Zn, Co-Sb and Sb-Zn exhibited strong relationships (r>0.50) in the plasma of controls, all were significant at p<0.01. Principal component analysis (PCA) of the data extracted five PCs, both for cancer patients and controls, but with considerably different loadings. The average metals levels in male and female donors of the two groups were also evaluated and in addition, the general role of trace metals in the carcinogenesis was discussed. The study indicated appreciably different pattern of metal distribution and mutual relationships in the plasma of cancer patients in comparison with controls.