Speciation of cadmium,copper, lead,and zinc in contaminated soils

Abstract

To investigate the activity of free cadmium (Cd²⁺), copper (Cu²⁺), lead (Pb²⁺), and zinc (Zn²⁺) ions and analyze their dependence on pH and other soil properties, ten contaminated soils were sampled and analyzed for total contents of Cd, Cu, Pb, and Zn (Cd_T, Cu_T, Pb_T, and Zn_T, respectively), 0.43 MHNO₃‐extractable Cd, Cu, Pb, and Zn (Cd_N, Cu_N, Pb_N, and Zn_N, respectively), pH, dissolved organic matter (DOC), cation exchange capacity (CEC), ammonium oxalate extractable aluminum (Al) and iron (Fe), and dissolved calcium [Ca²⁺]. The activity of free Pb²⁺, Cd²⁺, Cu²⁺, and Zn²⁺ ions in soil solutions was determined using Donnan equilibrium/graphite furnace atomic absorption (DE/GFAA). The solubility of Cd in soils varied from 0.16 to 0.94 μg L^‐1, Cu from 3.43 to 7.42 μg L^‐1, Pb from 1.23 to 5.8 μg L^‐1, and Zn from 24.5 to 34.3 μg L^‐. In saturation soil extracts, the activity of free Cd²⁺ ions constituted 42 to 82% of the dissolved fraction, for Cu²⁺the range was 0.1 to 7.8%, for Pb²⁺ 0.1 to 5.1% and for Zn²⁺2 to 72%. The principal species of Cd, Cu, Pb, and Zn in the soil solution is free metal ions and hydrolyzed ions. Soil pH displayed a pronounced effect on the activity of free Cd²⁺, Cu^2t, Pb²⁺, and Zn²⁺ ions.     

Biodegradation of rhamnolipid, EDTA and citric acid in cadmium and zinc contaminated soils

Rhamnolipid, a metal sequestering agent produced by Pseudomonas Sp., has been effective in the removal of metals in soil washing technologies. Rhamnolipid has a strong affinity for cadmium (Cd) compared to some other metals (e.g. cobalt (Co), nickel (Ni)) and might also be useful in chelate-assisted phytoextraction. There have been many studies investigating the formation of metal-rhamnolipid complexes and the ability of rhamnolipid to remove metals from soil. However, to date, the longevity of rhamnolipid in soil has not been measured. Therefore, this study investigated the rate of rhamnolipid degradation in soils of varying physicochemical properties and contaminated with varying concentrations of Cd and zinc (Zn). The rate of rhamnolipid degradation was compared with ethylene diamine tetraacetic acid (EDTA) and citric acid. Our results indicate that citric acid was rapidly degraded, with 20% degradation occurring between 1 and 4 d depending on the level of soil contamination and 70% degradation within 20 d. EDTA was more persistent in the soils; only 14% of the EDTA was degraded after 20 d. Rhamnolipid had cumulative degradation between those of citric acid and EDTA. In most contaminated soils, cumulative degradation of the chelates and ligands were lower than in the uncontaminated soils. These results show that rhamnolipid may remain in the soil long enough to enhance metal phytoextraction, but not remain long enough to raise concerns regarding metal transport in the long-term.     

Characterization of mercury species in contaminated floodplain soils

The chemical form or speciation of mercury (Hg) in the floodplain soils of the East Fork Poplar Creek in Oak Ridge, Tennessee, a site contaminated from past industrial activity, was investigated. The speciation of Hg in the soils is an important factor in controlling the fate and effect of Hg at the site and in assessing human health and ecological risk. Application of three different sequential extraction speciation schemes indicated the Hg at the site was predominantly relatively insoluble mercuric sulfide or metallic Hg, though the relative proportions of each did not agree well between procedures. Application of X-ray and electron beam studies to site soils confirmed the presence of metacinnabar, a form of mercuric sulfide, the first known evidence of authigenic mercuric sulfide formation in soils.     

Resistance and resilience of zinc tolerant nitrifying communities is unaffected in long-term zinc contaminated soils

Zinc (Zn) tolerant nitrifying communities were previously identified in soil samples of a long-term Zn contaminated transect towards a galvanised pylon. We questioned whether Zn tolerance increased the vulnerability of the nitrifying communities to stressors. The influence of pesticide addition, freeze-thaw or dry-wet cycles on the soil nitrification (‘functional stability’) was assessed in a series of these soils representing a Zn contamination and Zn tolerance gradient. The immediate effect of the stressors to the nitrification (‘resistance’) and the residual effect after 3 weeks incubation (‘resilience’) were determined. Our results show that neither resistance nor resilience to these stressors was affected by adaptation of the nitrifying communities to elevated Zn concentrations in the long-term contaminated soils.     

Arsenic, lead, and zinc compounds in contaminated soils according to EXAFS spectroscopic data: A review

The application of the synchrotron technique of the third generation in soil science has permitted researchers to perform a quantitative mineralogical microanalysis in undisturbed samples and to reveal the relationship between the microelements and the solid phase of soils. Three principal methods are used in this technique: microfluorescence (μXRF), microdiffraction (μXRD), and the expanded analysis of the fine structure of the adsorption spectra. By the data of EXAFS spectroscopy, secondary arsenic was found to occur in three forms in soils, i.e., As adsorbed on iron hydroxides, scorodite (FeAsO₄ · 2H₂O, and As⁵⁺ containing jarosite. Despite the high share of carboxyl groups in the organic substance of soils, lead is more readily chelated by the functional groups of aromatic rings to form bidentant complexes. Lead phosphates are the most stable form of Pb in soils. One of the phosphates, i.e., pyromorphite Pb₅(PO₄)₃Cl has been found in ore tailings, lawn soils, soils near some chemical plants, and in soils within geochemical anomalies. The secondary Zn compounds are represented by Zn-containing silicate (kerolith) Si₄Zn₃O₁₀(OH)₂ and, to a lesser extent, by zinc fixed by manganese oxides (birnessite) and iron hydroxides (feroxyhyte).     

Arbuscular mycorrhizal abundance in contaminated soils around a zinc and lead deposit

In order to study the variations in spore abundance and root colonization parameters of arbuscular mycorrhizal (AM) fungi in a naturally heavy metals polluted site and their relationships with soil properties, 35 plots in the Anguran Zn and Pb mining region were selected along a transect from the mine to 4500 m away. Within each plot, a composite sample of root and rhizospheric soil from a dominant indigenous plant was collected. The soil samples were analyzed for their physico-chemical characteristics. Spores were extracted, counted and identified at genus level. The roots were examined for colonization, arbuscular abundance, mycorrhizal frequency and intensity. Along the transect, the total and available (DTPA-extractable) concentration of Zn decreased from 6472 to 45 mg kg⁻¹ and 75 to 5 mg kg⁻¹, respectively. For Pb the values varied from 5203 to 0 mg kg⁻¹ and 32 to 0 mg kg⁻¹, respectively. In parallel, root colonization rate in the dominant native plants (except Alyssum sp.) varied from 35% to 85% and the spore numbers from 80 to 1306 per 200 g dry soil along the transect. Spores of Glomus were abundantly found in all plots as dominant, while Acaulospora spores were observed only in some moderately polluted and in control plots. AM fungal propagules never disappeared completely even in soils with the highest rates of both heavy metals. Spore numbers were more affected by Zn and Pb concentrations than root colonization. The variations of AM fungi propagules were better related to available than to total concentration of both metals. Spore numbers were positively correlated with mycorrhizal colonization parameters, particularly with arbuscular abundance.     

Characterization of zinc adsorption sites in two mineral soils

The adsorption of Zn, as compared with Mg, on two mineral soils, which differed in their major cation-exchange materials and with and without Ca-saturation, was measured in the presence of free CaCl₂.

The adsorption of Zn as well as Mg occurred on cation-exchange sites. The Zn adsorption data conformed to a two-term Langmuir equation. The presence of two kinds of adsorption sites and their numbers and bonding energies were deduced. However, the Langmuir approach was not adopted on the basis of comparison between the total number of the adsorption sites for Zn deduced and the CEC of the soils.

As an alternative approach, the selectivity coefficient as defined by the equation:

was calculated for each adsorption equilibrium and plotted against the amount of Zn adsorbed. This [Zn]_soil plot was used to estimate the capacities of the soil to adsorb Zn with specified affinities. The value varied between 1 and 1,000, whereas the corresponding value varied only between 0.5 and 1. The value was dependent upon the amount of Zn adsorbed, the status of exchangeable cations, and the major cation-exchange materials (montmorillonite VS. allophane-imogolite) in the soils. The importance of surface OH groups in allophane-imogolite as specific adsorption sites for Zn was suggested.     

The forms of cobalt in some Scottish soils as determined by extraction and isotopic exchange

The results of fractionation and correlation studies provided evidence that cobalt in soils is associated predominantly with the soil oxide fraction, particularly the manganese oxides. Only a small proportion of the total cobalt present in soils was extracted by acetic acid, EDTA, pyrophosphate or hydroxylamine. Cobalt extracted with these reagents was considered to be derived principally from easily reducible manganese oxides, although the origin of the cobalt extracted by acetic acid in particular was not well defined. The bulk of the cobalt present in soils appeared to be occluded by more highly crystalline oxide materials or was present in the structures of primary and secondary minerals. Labile cobalt in soil was assessed by extraction with acetic acid and EDTA and by determination of isotopically exchangeable cobalt. The amounts of cobalt extracted by both EDTA and acetic acid were highly dependent on the length of extraction period and on the temperature of extraction. Neither of these reagents appeared likely to give good estimates of the quantity or intensity factors of soil cobalt supply to plants as defined by the isotopic exchange determinations.     

Characterizing the availability of metals in contaminated soils. I. The solid phase: sequential extraction and isotopic dilution

Abstract. The two approaches most commonly applied to characterizing the chemical form and 'reactivity' of metals in the soil solid phase are sequential extraction procedures (SEPs) and isotopic dilution (ID). The development and limitations of both approaches are described and their application to contaminated soils discussed. It may be argued that ID offers a better means of discriminating between 'reactive' and 'inert' forms of metal. However, the literature on SEPs is considerably larger, providing greater scope for comparative analysis of new data. Although ID methods are subject to operational constraints, the procedural dependency of SEPs is probably much greater. Thus greater effort has been expended to standardize and verify methodologies for SEPs. However, despite achieving a level of 'political ratification' at the procedural level, the use of SEPs within risk assessments for planning or development purposes is currently almost absent. The future for ID methods in this context may lie in site-specific risk assessments that include improved methods for the prediction of metal solubility and bioavailability.     

Sequential extractions and 31P-NMR spectroscopy of phosphorus forms in animal manures, whole soils and particle-size separates from a densely populated livestock area in northwest Germany

The solubility and forms of phosphorus (P) were investigated in manures from chicken and pigs, eight whole soil samples and clay-, silt-, and sand-size separates from an arable and a grassland soil. Total P (P_t) in liquid pig manure (16.2 g kg^–1) and dry chicken manure (26.2 g kg^–1) was distributed between residual P (39–41% P_t), H₂SO₄–P (17–27% P_t), labile resin- and NaHCO₃–P (24–39% P_t), and NaOH-P (3–10% P_t). Most soils had larger proportions of NaOH-P and residual P, indicating reactions of manure-derived P compounds with pedogenic oxides and humic substances. Clay-size separates had the highest P-concentrations in all fractions and were particularly enriched in exchangeable and labile P forms. Solution ³¹P-nuclear magnetic resonance (NMR) spectra of 0.5 M NaOH extracts from manures and some soil samples showed greater signal intensities for orthophosphate and monoester P than 0.1 M NaOH extracts. This can be explained by alkaline hydrolysis phosphate diesters at higher NaOH concentrations and/or by preferential extraction of diesters at lower concentrations. The ³¹P-NMR spectra showed differences between the two manures and confirmed that increasing proportions of ester-P can be expected if they are spread to soils. The NaOH extracts of soil samples were characterized by large proportions of orthophosphate-P (mean 77% of assigned P compounds), which seemed to be slightly enriched in clay fractions whereas the extracts from silt contained more ester-P. Sequential extractions and ³¹P-NMR spectroscopy both showed that these excessively manured soils are likely to lose large amounts of P. Received: 15 July 1996     

Rates of leaching of radium from contaminated soils: An experimental investigation of radium bearing soils from Port Hope,Ontario

Water, Air, & Soil Pollution - The leachability of Ra-226 from soil at Port Hope, Ontario contaminated by waste from a long established U refinery is described here. A small-scale static leach...     

Characterization of phosphorus engineered biochar and its impact on immobilization of Cd and Pb from smelting contaminated soils

Journal of Soils and Sediments - Biochar has been used as an amendment to immobilize toxic metals (TMs) and increase nutrient content in the contaminated soil. In this study, Ca(H2PO4)2-engineered...     

Inter-relationships between soil properties and the uptake of cadmium,copper, lead and zinc from contaminated soils by radish (Raphanus sativus L.)

Radish was grown in 46 garden plots in England and Wales. Some of the gardens had been contaminated by heavy metals from lead mining. The soils were analysed for pH, organic content and cation exchange capacity; also for Cd, Cu, Pb, and Zn (total, organic bound, exchangeable and specifically sorbed). Acetic acid-soluble P and exchangeable K, Mg and Zn were also determined. Radish bulbs and leaves were analysed for heavy metals. The results were interpreted using linear and multiple linear correlation and regression analysis. Acetic acid satisfactorily predicted Cd uptake and Pb uptake was best predicted by total soil Pb. These regressions were not improved by including other soil properties. Zinc uptake was best modeled using exchangeable Zn and the predictive power of the regression was improved by including pH. However, the pH term was positive suggesting that raising soil pH would increase uptake. A poor relationship between total and exchangeable Zn was changed to a highly significant relationship by including cation exchange capacity and pH. The latter term was strongly negative. Uptake of Cu was not satisfactorily predicted.     

基于红外衰减全反射光谱的温室土壤盐分特征研究

与传统的露地耕作土壤不同,温室土壤在耕作过程中受较多的人为调控,但在调控的过程中产生了多种问题,如大量施肥导致的土壤盐渍化[1]。因此,研究如何表征温室土壤的离子特征并预测温室土壤的发展是当前设施农业发展所面临的重要问题。常规农化分析只从不同的角度分析温室土壤的特征,很难实现整体上的综合表征。红外光谱能够综合反应土壤的理化性质,在温室土壤研究中有具有明显的特点。常规的透射光谱在研究土壤时存在制样时间长和难以定量的缺点,而衰减全反射红外光谱(ATR-FTIR)则可克服这一缺点,结合化学计量学的方法,能够实现土壤的定性与定量分析[2,3]。红外光谱包含大量化学键信息,在分析时需进行合理的降维,抽取     

Volatilisation of aromatic hydrocarbons from soil: Part I,fluxes from coal tar contaminated surface soils

The non-steady-state fluxes of aromatic hydrocarbons were measured in the laboratory from the surface of soils contaminated with coal tar. Four soil samples from a former gasworks site were used for the experiments. The fluxes were quantified for 11 selected compounds, 4 mono- and 7 polycyclic aromatic hydrocarbons, for a period of up to 8 or 16 days. The concentrations of the selected compounds in the soils were between 0.2 and 3,100 µg/g. The study included the experimental determination of the distribution coefficient of the aromatic hydrocarbons between the sorbed phase and the water under saturated conditions. The determined distribution coefficients showed that the aromatic hydrocarbons were more strongly sorbed to the total organic carbon including the coal tar pitch — by a factor of 8 to 25 — than expected for natural organic matter. The fluxes were also estimated using an analytical solution of the Fick's diffusion equation and assuming that the compounds diffused independently of each other and that instant equilibrium existed between the air, water and sorbed phases. A relatively good agreement was found between the predicted and the measured flux. The predicted fluxes were between 0.11 and 7.5 time the measured fluxes. The fluxes were overestimated for the monocyclic aromatic hydrocarbons and underestimated for 3-rings-PAHs.     

Nitrogen fixation by white clover (Trifolium repens) in grasslands on soils contaminated with cadmium, lead and zinc

The nitrogenase activity (potential nitrogen fixation) of a mixed white clover-grass sward growing on a range of soils containing up to 216 μg g^?1 Cd, 30 000μg g^?1 Pb and 20 000 μg g^?1 Zn was determined using the acetylene-reduction assay. The plants were incubated in situ using an intact soil-core technique. Little change in the rate of C₂H₂ reduction was observed during the daylight hours although a marked seasonal fluctuation was found, the maximum activity during the spring and declining to 20% of this by the autumn. Some reductions of nodule and plant size, and in nitrogenase activity, was observed in the most heavily contaminated sites. These effects were small; the plants and nodules otherwise appeared healthy. The potential for nitrogen fixation was equally high in all the sites at up to 80 g N ha^?1 h^?1 in the spring.     

Seasonal fluctuations in nitrogen fixation (acetylene reduction) by free-living bacteria in soils contaminated with cadmium, lead and zinc

Acetylene reduction by non-symbiotic, heterotrophic micro-organisms in a range of soils containing different concentrations of heavy metals was determined using intact soil cores. The suitability of this method for the soils used in this investigation was established. Samples were collected seasonally, and were incubated under standard conditions (darkness: 15°). Mean values of metal concentrations in the soil (μg g^?1) were: Cd: 1–200; Pb: 60–8000; Zn: 70–26000, Cu: 20–40. Rates of acetylene reduction were generally low, from 2800 to 50000 nmol C₂H₄, m^?2 day^?1. Assuming a 3:1 ratio of C₂H₂ reduction to N₂ fixation, this represents a rate of 0.3 to 5.0 g N fixed ha^?1 day^?1 in the surface 150 mm of soil. No consistent effect of heavy metal concentration was found. The most important factors determining activity were soil moisture content and possibly inorganic nitrogen concentration. It thus appears that the bacteria in polluted soils are capable of adapting to potentially toxic concentrations of heavy metals, or that these metals are present in the soils tested in unavailable or non-toxic forms.