Chemical Speciation Of Zn Research Articles

Identification and Quantification of Chemical Forms of Cu and Zn in MSWI Ashes Using XANES

Incineration is in many countries a common treatment method for municipal solid waste, and utilization of the ash residues has attracted significant interest. The bottom ash is best suited as a secondary construction material, whereas the fly ash is being investigated as a secondary raw material for recovery of, for example, Zn, Cu, and salts. For both types of application, knowledge about the chemical speciation of Zn and Cu in the ashes is valuable. The present work focuses on identifying and quantifying the chemical species of Zn and Cu in 12 samples of fly ash and bottom ash from three waste-to-energy plants using X-ray absorption near edge structure (XANES). The XANES spectra of the ash samples showed similar distinctive features, and both in the bottom and fly ash samples, the same chemical forms were identified but in various ratios. Cu and Zn occurred in several chemical forms, with typically 5-7 forms present in the same sample. For Cu, the XANES spectra of the fly ash samples were nearly identical, indicating very similar chemical speciation (same chemical forms and similar ratios). Cu was found to exist in various oxide, hydroxide, chloride, silicate, and metallic forms. The most commonly occurring Zn compounds were the aluminate, ferrite, silicate, and oxide along with chloride, basic carbonate (hydrozincite), and occasionally metallic forms, probably alloyed with Cu in brass. Cu occurred in different oxidation states from zero to +II, with a higher prevalence of the lower oxidation states in bottom ash than in fly ash. Zn occurred mainly in oxidation state +II in all ashes analyzed. Finally, we showed that during outdoor storage of bottom ash, levels of Cu and Zn hydroxycarbonates were increased compared to fresh bottom ash. This carbonate formation aims to make Cu and Zn less leachable.

Effect of ageing of bare and coated nanoparticles of zinc oxide applied to soil on the Zn behaviour and toxicity to fish cells due to transfer from soil to water bodies

This study evaluated the influence of ageing of ZnO nanoparticles (NPs) applied to soil on the potential availability and chemical speciation of Zn, and also of their toxicity to aquatic organisms due to transfer of contaminants from soil to water. To this end, soil samples were spiked with two types of bare nanoparticles: b1ZnO NPs (rod- and elongated-shaped) and b2ZnO NPs (near-spherical shaped) and ZnO NPs coated with (3-aminopropyl)triethoxysilane (cZnO NPs) within the 0–800 mg Zn kg−1 soil dose range, and were left to age for 0, 30, 60 and 90 days. The available concentration and speciation of Zn in soil were determined by the DGT (diffusive gradients in thin films) technique and sequential extraction procedures, respectively. The toxicity of the aqueous extracts from the ZnO NP-treated soils was assessed in vitro in established fish cell lines (RTG-2). The highest distribution percentages of the applied Zn occurred in the organically complexed (OC), followed by the exchangeable (EXC) fraction, for all NP types, applied doses and incubation times. The toxicity of NPs depended on their intrinsic properties: b1ZnO NPs affected the membrane function, reductase enzyme activity and, to a lesser extent, reactive oxygen species (ROS) levels of fish cells, whereas b2ZnO NPs and cZnO NPs affected mainly ROS generation. Ageing increased Zn soil availability, but toxicity to fish cells showed no trend over time. The particle dissolution of ZnO NPs did not explain the observed toxicity, hence a nanoparticles-specific effect should be assumed. The findings of this study seem to indicate that the transfer of ZnO NP from contaminated soils to aquatic ecosystems should be addressed.

Effect of carbonation on leachability, strength and microstructural characteristics of KMP binder stabilized Zn and Pb contaminated soils

This study presents a systematic investigation of effects of carbonation on the contaminant leachability and unconfined compressive strength of KMP stabilized contaminated soils. A field soil spiked with Zn and Pb individually and together is stabilized using a new KMP additive under standard curing conditions and also with carbonation. The KMP additive is composed of oxalic acid-activated phosphate rock, monopotassium phosphate and reactive magnesia. The stabilized soils are tested for acid neutralization capacity, toxic characteristics leaching characteristics, contaminant speciation and unconfined compression strength. X-ray diffraction, scanning electron microscope and energy dispersive spectroscopy analyses are performed to assess reaction products. The results demonstrate that carbonation increases both acid buffer capacity index and unconfined compressive strength, but decreases leachability of KMP stabilized soils. These results are interpreted based on the changes in chemical speciation of Zn and Pb and also stability and solubility of the reaction products (metal phosphates and carbonates) formed in the soils. Overall, this study demonstrates that carbonation has positive effects on leachability and strength of the KMP stabilized soils.

Effects of freeze-thaw on characteristics of new KMP binder stabilized Zn- and Pb-contaminated soils

For viable and sustainable reuse of solidified/stabilized heavy metal-contaminated soils as roadway subgrade materials, long-term durability of these soils should be ensured. A new binder, KMP, has been developed for solidifying/stabilizing soils contaminated with high concentrations of heavy metals. However, the effects of long-term extreme weather conditions including freeze and thaw on the leachability and strength of the KMP stabilized contaminated soils have not been investigated. This study presents a systematic investigation on the impacts of freeze-thaw cycle on leachability, strength, and microstructural characteristics of the KMP stabilized soils spiked with Zn and Pb individually and together. For comparison purpose, Portland cement is also tested as a conventional binder. Several series of tests are conducted including the toxicity characteristic leaching procedure (TCLP), modified European Community Bureau of Reference (BCR) sequential extraction procedure, unconfined compression test (UCT), and mercury intrusion porosimetry (MIP). The results demonstrate that the freeze-thaw cycles have much less impact on the leachability and strength of the KMP stabilized soils as compared to the PC stabilized soils. After the freeze-thaw cycle tests, the KMP stabilized soils display much lower leachability, mass loss, and strength loss. These results are assessed based on the chemical speciation of Zn and Pb, and pore size distribution of the soils. Overall, this study demonstrates that the KMP stabilized heavy metal-contaminated soils perform well under the freeze-thaw conditions.

Influence of population density on the concentration and speciation of metals in the soil and street dust from urban areas

Street dust and soil from high, medium and low populated cities and natural area were analysed for selected physical–chemical properties, total and chemical speciation of Zn, Pb, Cu, Cr, Cd, Co, Ni to understand the influence of human activities on metal accumulation and mobility in the environment. The pH, salinity, carbonates and organic carbon contents were similar between soil and dust from the same city. Population density increases dust/soil salinity but has no influence on metals concentrations in soils. Increases in metal concentrations with population density were observed in dusts. Cu, Zn, Pb, Cr can be mobilized more easily from dust compared to the soil. In addition, population density increase the percentage of Pb and Zn associated to reducible and carbonate phase in the dust. The behaviour of metals except Cd in soil is mainly affected by physico-chemical properties, while total metal influenced the speciation except Cr and Ni in dusts.

Speciation and Mobility of Heavy Metals in Tailings from Dachang Mine, China

Two carbonate tailing samples were collected from Dachang mine tailing reservoirs, Guangxi Province, China. The chemical speciation of Zn, As, Cd and Sb contained in tailing samples were determined by Dold seven-stage sequential extraction procedure, as well as mineralogical and chemical analysis. Then the potential migration abilities of these heavy metals were evaluated. The tailing analysis results showed that the main minerals were calcite, quartz, sphalerite and pyrite, the major elements were Si, S, Ca, Fe and Al, and the trace heavy metals included Zn, As, Cd and Sb. Zn mainly existed in secondary sulfide, primary sulfides and residual fraction, and As was in primary sulfide and residue, but Sb and Cd was residual fraction. The mobility of heavy metals followed the order: Zn > Sb > Cd > As.

Chemical speciation of Zn in acidic soils: suitable soil extractant for assessing Zn availability to maize (Zea mays L.)

Chemical fractions of soil Zn namely: water soluble (WS), exchangeable (EX), Pb displaceable (Pb-disp.), acid soluble (AS), Mn oxide occluded (MnOX), organically bound (OB), amorphous Fe oxide occluded (AFeOX), crystalline Fe oxide occluded (CFeOX), residual (RES) were determined in 20 surface (0–15 cm) samples of acidic soils from the provinces of Uttarakhand and Uttar Pradesh, India. The chemical fractions of soil Zn in acidic soils were found to be in the following descending order of Zn concentration: RES > CFeOX > Pb-Disp. > AFeOX > MnOX > AS > OB > EX > WS. These soil samples were also extracted by: DTPA (pH 7.3), DTPA (pH 5.3), AB-DTPA (pH 7.6), Mehlich 3 (pH 2.0), Modified Olsen, 0.01 N CaCl2, 1 M MgCl 2 and ion exchange resins. Chemical fractions and the soil extractable content of Zn estimated by different soil extractants were significantly correlated with some general soil properties. Maize (cv. Pragati) plants were grown in these soils for 35 days after emergence and Zn uptake by plants was compared with the amount of Zn extracted by different soil extractants and chemical fractions of Zn. Among chemical fractions of soil Zn, Pb-displaceable and acid soluble chemical fractions of soil Zn showed a significant and positive correlation with Zn uptake by maize. Path coefficient analysis also revealed that the acid soluble Zn fraction showed the highest positive and direct effect on Zn uptake (P=0.960). Among different multinutrient soil extractants evaluated for their suitability to assess Zn availability in acidic soils, DTPA (pH=5.3) was most suitable soil extractant, as the quantity of soil Zn extracted by this extractant showed a significant and positive correlation with the dry matter yield, Zn concentration and uptake by maize plants.

Speciation of heavy metals in River Rhine

Chemical speciation of Zn, Cu, Ni, Cd and Pb in River Rhine was studied by measuring free ion concentration and distribution in nanoparticles, and by comparing the measurement with speciation modeling. Concentrations of free metal ions were determined in situ using Donnan Membrane Technique (DMT). The percentage of free over total (filtered) metal concentration is 52%, 33%, 2.6%, 0.48% and 0.12% for respectively Zn, Cd, Ni, Pb and Cu, i.e. the degree of metal complexation in the river is the lowest for Zn and the highest for Cu. Metals in 1–300 nm particles were analyzed using Asymmetric Flow Field Flow Fractionation (AsF-FFF), but the overall recovery is quite low. The nano-sized Cu detected is mainly associated with DOM of 1–5 nm, whereas Pb and Zn are dominantly associated with particles of iron hydroxides and clay of larger size (30–100 nm). Free ion concentrations calculated with the speciation modeling are in good agreement with the measurements, except for Pb. Based on the model, DOM-bound is the most important complexed form for Cu and Cd, whereas formation of (bi)carbonate and EDTA complexes are more important for Ni and Zn. Adsorption of Pb to DOM is probably overestimated by the model, whereas Pb adsorption to iron hydroxides is underestimated.

Speciation Distributions and Availability of Zn, Pb, Cu and Ni in a Mine Drainage Contaminated Paddy Soils

Various depths paddy soils, which collected from nearby one of the abandoned Pb-Zn mines in Lanping County of China, were analyzed, determining the total metal concentration by acid digestion and the chemical speciation of Zn, Pb, Cu and Ni by a somewhat modified Tessier’s sequential extraction method. High concentrations of Zn and Pb were found in surface soils indicating that the paddy soils seriously suffered from Zn and Pb contamination. The extraction percentage of Zn, Pb, Cu and Ni with modified Tessier’s sequential extraction procedures were at the ranges of 93.15-96.41%, 93.26-96.25%, 91.51-94.75% and 91.28-94.25%, respectively. Extraction efficiencies demonstrated that this sequential extraction approach is suitable to evaluate these metals potential risk among this contaminated site. Extraction results showed that the residual fraction was the predominant fraction for Zn, Pb, Cu and Ni among all tested soils. However, the exchangeable fraction was the lowest among all fractions. Meanwhile, the metals mobility and bioavailability in tested soils were compared and predicted using mobility coefficients and bioavailability coefficients. The mobility coefficients of metals decreased in the order of Cu> Ni> Zn> Pb, and the bioavailability coefficients of metals decreased in the order of Pb>Cu>Zn/Ni.

Comparative study of a Zn-enriched post-methanation bio-sludge and Zn sulfate as Zn sources for a rice–wheat crop rotation

A field experiment was carried out during 2005–2007 to compare the efficacy of Zn-enriched post-methanation bio-sludge (ZEMB, 4.4% Zn) and ZnSO4 (ZSH, 22% Zn) as Zn source to rice (Oryza sativa L.)—wheat (Triticum aestivum L.) rotation. A new Zn source (ZEMB) contained most of the Zn (98.4% of total Zn) in citrate-soluble form as compared to ZSH which had all Zn in water-soluble form. Chemical speciation of Zn in the aqueous solution of both fertilizers revealed that 85.8% of water-soluble Zn present in ZEMB existed as complexes of dissolved organic matter. In the field experiment, application of ZEMB at 5 kg Zn ha−1 to I-year rice increased the grain yields of rice and wheat in both years significantly over the control while application of ZSH at 5 kg Zn ha−1 to I-year rice increased only grain yields of I- and II-year rice (first year and second year, respectively). The magnitude of increase in grain yields was also higher with ZEMB than with ZSH. Application of ZEMB at 5 kg Zn ha−1 to I-year rice maintained significantly higher concentrations of Zn in the flag leaves of rice and wheat in both years, in the grains of I- and II-year rice, and also in the straw of I-year rice than ZSH applied at an equivalent dose. Total Zn uptake values for I-year rice and wheat and II-year rice, apparent recovery of applied Zn and also DTPA-extractable Zn in soil were significantly higher with ZEMB at 5 kg Zn ha−1 than with ZSH at an equivalent dose.

Elevated sulfate reduction in metal‐contaminated freshwater lake sediments

Although sulfate‐reducing prokaryotes have long been studied as agents of metals bioremediation, impacts of long‐term metals exposure on biologically mediated sulfur cycling in natural systems remains poorly understood. The effects of long‐term exposure to metal stress on the freshwater sulfur cycle were studied, with a focus on biologic sulfate reduction using a combination of microbial and chemical methods. To examine the effects after decades of adaptation time, a field‐based experiment was conducted using multiple study sites in a natural system historically impacted by a nearby zinc smelter (Lake DePue, Illinois). Rates were highest at the most metals‐contaminated sites (∼35 μmol/cm3/day) and decreased with decreased pore water zinc and arsenic contamination levels, while other environmental characteristics (i.e., pH, nutrient concentrations and physical properties) showed little between‐site variation. Correlations were established using an artificial neural network to evaluate potentially non‐linear relationships between sulfate reduction rates (SRR) and measured environmental variables. SRR in Lake DePue were up to 50 times higher than rates previously reported for lake sediments and the chemical speciation of Zn was dominated by the presence of ZnS as shown by X‐ray Absorption Spectroscopy (XAS). These results suggest that long‐term metal stress of natural systems might alter the biogeochemical cycling of sulfur by contributing to higher rates of sulfate reduction.

Trace metal cycling in the Whau Estuary, Auckland, New Zealand

Environmental context. The accumulation of trace metals from urban runoff is a serious environmental concern. In the present paper we show that, in the case of the Whau Estuary, Auckland, New Zealand, there is a significant particulate Zn input, of which a significant amount of Zn is lost from the particulate phase into the dissolved phase within the water column, and via molecular diffusion across the water–sediment interface. The present study shows that changes in the chemical speciation of Zn, associated with changes in salinity, play a major role in regulating the recycling of this metal between the particulate and dissolved phases. Abstract. Dissolved Zn, Cd, Cu, Fe, and Pb concentrations were measured along a salinity gradient in the Whau Estuary, Auckland, New Zealand. We found a mid-salinity maximum in dissolved Zn and Cd concentrations, consistent with significant loss of these metals from the particulate phase into the dissolved phase. Changes in the chemical speciation of these two metals were coupled to changes in salinity and this was the major driver for Zn and Cd loss from particulate material. Contrastingly, Cu concentrations were conservative with salinity, whereas there was significant scavenging of Fe and Pb from the dissolved phase into the particulate phase. Analysis of sediment pore-water metal concentrations indicated a peak in Zn concentration within the suboxic layer. The peak occurred at a shallower depth than those for Mn and Fe. The concentration gradient across the sediment–water interface suggests that diffusional loss of Zn from the sediment pore water into the overlying water column was occurring. Conversely, the diffusion of Cu from the water column into the sediment pore water was likely to occur because pore-water Cu concentrations were lower than the overlying water column concentrations. The results from the present study show the importance of chemical speciation and the lability of metals attached to particulate material as potentially being a critical determinant on sediment metal concentrations.

Zinc distribution in soils amended with different kinds of sewage sludge

Sewage sludge (SS) can be applied to cropland to supply and recycle nutrients and organic carbon. Potentially toxic elements in the sludge, however, are of environmental concern. This study evaluates the changes in chemical speciation of Zn in three representative pristine soils of the Pampas Region, Argentina, measured with sequential extraction over a one-year period. Pure SS or SS containing 30% (DM) of its own incineration ash (AS) was applied to the soils at an application rate of 150 Mg ha −1. Zn was sequentially fractionated into exchangeable, organically bound, inorganic and residual fractions. The application of the SS and AS amendments significantly increased Zn concentration in all soil fractions at each sampling date. At day 1, Zn was mainly found in the residual fraction. A year after the application of the amendments, redistribution towards the inorganic fraction was observed (41–76% of total Zn content). Zn found in exchangeable and inorganic fractions depended on soil pH rather than on the type of soil used. A negative and significant correlation was found between exchangeable Zn concentrations and soil pH ( r=0.94), and a positive and significant correlation between inorganic Zn concentrations and soil pH ( r=0.92). For each amended soil and sampling date, no significant differences were observed between SS or AS treatments for the exchangeable fraction. Moreover, the use of AS did not cause significant differences in Zn concentration in the other soil fractions compared to SS. Based on these results, land spreading of AS may be similar to SS diaposal in terms of Zn mobility.

Extractability and bioavailability of zinc over time in three tropical soils incubated with biosolids

Phytotoxicity of heavy metal is the primary concern in applying biosolids (sewage sludge) to agricultural land. This study evaluates the changes in chemical speciation of Zn in three tropical soils of Taiwan measured with sequential extraction over a one-year period. Biosolids were applied to the soils at application rates of 10, 50 and 100 Mg ha −1, and correlated diethylene triamine pentaacetic acid (DTPA) and sequential extraction as extract for prediction of Zn bioavailability to Chinese cabbage ( Brassica chinensis L.). Experimental results indicated that the exchangeable (F1) and Fe–Mn oxide (F3) fractions in the sequential extractions increased with application rate of biosolids in the soils over time. Large amounts of Zn in the soils following the cessation of biosolids application were identified as soluble and were adsorbed by Fe–Mn oxides. The organically bound Zn, which is associated with readily decomposable carbon, is in limited amounts in the biosolid-treated soils. The DTPA-extractable concentrations of Zn in all biosolid-treated soils decreased over the time. A positive and significant correlation ( r 2 = 0.96) was found between the Zn concentrations extracted with DTPA and sum of F1 and carbonate-bound (F2) fractions in the sequential extractions. Additionally, the concentrations of Zn extracted with DTPA were strongly correlated with the concentrations of Zn in the shoots of Chinese cabbages, indicating that F1 + F2 in the sequential extractions was reliable for predicting Zn bioavailability to Chinese cabbage in the biosolid-treated soils.

Chemical speciation of Zn, Cd, Cu, and Pb in pore waters of agricultural and contaminated soils using Donnan dialysis.

Knowledge of trace metal speciation in soil pore waters is important in addressing metal bioavailability and risk assessment of contaminated soils. Numerous analytical methods have been utilized for determining trace metal speciation in aqueous environmental matrixes; however, most of these methods suffer from significant interferences. The Donnan dialysis membrane technique minimizes these interferences and has been used in this study to determine free Zn2+, Cd2+, Cu2+, and Pb2+ activities in pore waters from 15 agricultural and 12 long-term contaminated soils. The soils vary widely in their origin, pH, organic carbon content, and total metal concentrations. Pore water pM2+ activities also covered a wide range and were controlled by soil pH and total metal concentrations. For the agricultural soils, most of the free metal activities were below detection limit, apart from Zn2+ for which the fraction of free Zn2+ in soluble Zn ranged from 2.3 to 87% (mean 43%). Five of the agricultural soils had detectable free Cd2+ with fractions of free metal ranging from 59 to 102% (mean 75%). For the contaminated soils with detectable free metal concentrations, the fraction of free metal as a percentage of soluble metal varied from 9.9 to 97% (mean 50%) for Zn2+, from 22 to 86% (mean 49%) for Cd2+, from 0.4 to 32.1% (mean 5%) for Cu2+, and from 2.9 to 48.8% (mean 20.1%) for Pb2+. For the contaminated soils, the equilibrium speciation programs GEOCHEM and WHAM Model VI provided reasonable estimates of free Zn2+ fractions in comparison to the measured fractions (R2 approximately 0.7), while estimates of free Cd2+ fractions were less agreeable (R2 approximately 0.5). The models generally predicted stronger binding of Cu2+ to DOC and hence lower fractions of free Cu2+ as compared with the observed fractions. The binding of Cu2+ and Pb2+ to DOC predicted by WHAM Model VI was much strongerthan that predicted by GEOCHEM.