Evaluation of "labile" metal in sediments by anodic stripping voltammetry

A procedure for determining the "labile" metal content of contaminated sediments (in different chemical environments) has been critically examined. The sediments were extracted overnight with different chemical solutions and the suspensions were analysed by differential pulse anodic stripping voltammetry. The extractants used have been recommended for soil/sediment speciation schemes, and by examination of the suspensions directly in the ASV cell, errors due to re-adsorption of released metal ion were minimized. The existence of different chemical forms of metal was signified by changes in peak shape and position or by the appearance of additional peaks. With complexing agents present the peak size was pH-dependent. The limitations of the ASV/suspension analysis technique have been carefully evaluated by using ten different extractants and seventeen sediments. The "lability" results obtained have been compared with the values obtained from a cation-exchanger transfer procedure. For characterizing the lability behaviour of the metal contents of sediments, preliminary extraction into a minimum of four base solutions is advisable, e.g., 0.02M nitric acid (low-pH labile); hydroxylamine in acetic acid (reducing conditions); acetic acid/acetate buffer (weakly sorbed and carbonate-bound) and 0.05M calcium chloride (exchangeable fraction at natural system pH), where the terms in parentheses describe the character of the fraction. The results are critically compared with those obtained by atomic-absorption analysis of the extracts and with those obtained by an earlier ion-exchange fractionation scheme. The advantages and limitations of the ASY systems are discussed.     

Measuring bioavailable trace metals from freshwater sediments by diffusive gradients in thin films (DGT) in monitoring procedures for quality assessment

An experimental design using passive samplers was set up in our laboratories with the aim of preparing a procedure for the assessment of trace metals bioavailability in freshwater sediments. Trace metal (Cd, Cu, Pb, Ni, and Zn) bioavailability in sediment samples were measured by diffusive gradients in thin films (DGT) devices and compared to those simultaneously extracted (SEM) in 1N HCl with acid-volatile sulfide (AVS). During experiments DGT devices were exposed at various times (from 4 to 336 h) in sediments with different physical and chemical properties and metal content, after equilibration with ambient water (1:2) for 24 h. Trace metal were progressively accumulated in DGT units and after at least 24-48 h metal fluxes became constant. No relation was found between metal available fractions measured by DGTs and total concentrations in sediments or pore waters. On the contrary good relations were found between available metals measured by DGT and metals simultaneously extracted (SEM) in HCl 1N with acid volatile sulfide (AVS).     

Extraction of mercury(II) from aqueous thiocyanate solutions with 5-(4-pyridyl)nonane in benzene, and its subsequent atomic-absorption spectrometric determination

Tracer ( approximately 10(-8)M) mercury(II) can be quantitatively extracted with 5-(4-pyridyl)nonane in benzene from aqueous thiocyanate solutions that are up to 6M in HCl, 1M in H(2)SO(4) or 0.25M in HNO(3), in a single extraction. Optimal conditions for the extraction are given, based on a critical study of the relevant factors such as the effects of the acids, thiocyanate, salting-out and complexing agents and the reagent concentration. The mechanism underlying these extractions is discussed on the basis of the results obtained from partition and slope-analysis data. The extraction of the metal as Hg(PyN)(2)(SCN)(2) is indicated. The extracted mercury can be stripped from the non-aqueous layer with various aqueous solutions, including nitric acid (2M), sodium citrate ( 1M) and sodium thiosulphate (0.1 M). Common salts do not depress the extraction. Distribution coefficients and separation factors of several elements relative to mercury(II) are reported for media that contain the optimal concentrations of the mineral acids and are in 0.2M in potassium thiocyanate. The data have been applied for the determination of mercury in soil and water samples by atomic-absorption spectrometry.     

Labile rhizosphere soil solution fraction for prediction of bioavailability of heavy metals and rare earth elements to plants

A labile rhizosphere soil solution fraction has been recommended to predict the bioavailability of heavy metals and rare earth elements to plants. This method used moist rhizosphere soil in combination with a mixture of 0.01 mol L(-1) of low-molecular-weight organic acids (LMWOAs) as extractant. The extracted soil solutions were fractionated into two colloidal fractions of <0.45 microm (F(3)) and <0.2 microm (F(2)), and one truly dissolved fraction including free metal ions and inorganic and organic complexes (fractionr(0.2 microm, LMWOAs) approximately r(0.45 microm, LMWOAs). In the case of rare earth elements the good correlation was obtained for both the wheat roots and shoots. Generally, the correlation coefficients obtained by LMWAOs were better than that obtained by the first step of BCR method. Therefore, LMWAOs and F(lrss) were strongly recommended to predict the bioavailability of metals in soil pools to plants.     

Heavy metal in sediments and bioaccumulation in the bivalve Corbula gibba in a drilling discharge area

The longterm bioavailability of heavy metals in sediments of a Northern Adriatic Sea shelf area affected by drilling mud and cutting discharges was discussed. Levels of Mn, Cu, Cr, Zn and Pb in different geochemical phases of the sediment and in soft tissues of the bivalve Corbula gibba were recorded and the relationships between biological and geochemical metal investigated. Total metal content, acetic acid extractable-, exchangeable-, carbonate-, easily reducible-, moderately reducible-, oxidable- and residual-fractions were determined on sediment samples. Corbula gibba was collected from wet sediments at the same times and sites, and the soft-tissue metal contents were determined. Correlations show that the fractions with greatest bioavailability are the exchangeable and carbonate for Cr and the exchangeable, carbonate, easily and moderately reducible fractions for Zn. Data also show a possible bioavailability of Pb only from the residual fraction, consisting of very resistant matter of more recent anthropogenic origin. Near the platform, total Mn content in sediments and in C. gibba tissues show a strong correlation suggesting that this organism is sensitive to variations of the Mn-oxi-hydroxides superficial film. No relationships were found between biological and sediment-bound Cu, however the discharged muds did not cause Cu enrichment. The metal fraction determined by weak acetic acid extraction at no point seems related to metal levels in Corbula gibba.     

Determination of mercury ions on a diphenylcarbazone bulk modified graphite electrode

A bulk modified electrode prepared by pressing a mixture of carbon powder and diphenylcarbazone at 15.2 MPa was used for the determination of mercury in aqueous solutions. Mercury(II) ions are concentrated by complexation with the modifier in acidic (HNO₃) solution. After exchange of the medium for 1 M HCl and 1 M CaCl₂, mercury is reduced at ?0.8 V vs. SCE. The signal is generated by anodic stripping in the differential-pulse mode. The calibration graph is linear in the range 5×10^?8?5× 10^?6 M with a relative standard deviation of 7%. After enrichment for 10 min the detection limit is 5×10^?8 M. Silver, chromate and strong complexing agents interfere. The use of the electrode to determine the labile fraction in mercury speciation is discussed.     

Comparison of Two Sequential Extraction Procedures for Trace Metal Partitioning in Sediments

Abstract

Two sequential extraction schemes (a modified Tessier procedure with five steps and a three steps protocol designed by BCR) are applied to four sediment samples with different heavy metal contents. The results obtained for Cd, Cr, Cu, Ni, Pb and Zn partitioning show that the metal distribution obtained with both procedures are significantly different. With the second procedure amounts of all the heavy metals are extracted with the oxidizing reagent (third fraction) whereas with the first one the non residual metals are distributed among the second, third and fourth fractions (acetic acid-acetate buffer (pH=5), reducing and oxidizing reagents respectively). The residual fraction obtained applying the three steps procedure is in general higher than that obtained using the five steps procedure, except for cadmium.     

Comparison of single and sequential extraction procedures for the study of rare earth elements remobilisation in different types of soils

With the continual increase in the utilisation of rare earth elements (REE) for industrial and agricultural purposes, research into the environmental and biogeochemical behaviour of REE had attracted much interest in recent times. This study principally describes the distribution of REE in four different types of soils like lateritic soil (S-1), in situ natural soil (S-2), soil contaminated by mining activity (S-3) and accidentally polluted soil (S-4) utilizing the optimised BCR sequential extraction procedure and partial extractions with various types of single extractants such as unbuffered salt solutions 0.1 M NaNO₃, 0.01 M CaCl₂, 1 M NH₄NO₃; complexing agents 0.005 M DTPA and 0.05 M EDTA; acid solutions 0.43 M CH₃COOH and 1 M HCl. Comparison of the sum of the four BCR fractions, which included an aqua regia attack on the residue, with the pseudo-total aqua regia digest values to assess the accuracy of the BCR partioning approach has been undertaken. Partial extraction results with several single extractants have also been reported for all the REE elements including yttrium which have been analysed by the optimised BCR procedure. Results obtained after 24 h extraction with each of the single extractant have also been discussed. The extraction with 1 M HCl during 24 h yielded similar quantities of REE as those released under the combined steps of 1, 2 and 3 of the BCR sequential extraction for all the four different type of soil samples indicating that this reagent can be used successfully to estimate the total extractable contents of REE in various types of soil samples.     

Extractability of HgS (cinnabar and metacinnabar) by hydrochloric acid

In this work we investigated the behaviour of pure HgS during extraction with dilute HCl to establish its extractability in 1 and 6 M HCl at the concentration level close to those occurring in natural sediments and soils. We found that neither cinnabar nor metacinnabar were soluble in 1 M HCl, whereas both were partially extracted by 6 M HCl. Metacinnabar precipitated in the laboratory was most prone to dissolution in 6 M HCl (up to 90%), followed by crystalline (commercial) metacinnabar (up to 70%) and cinnabar (up to 15%). Solubility of HgS in 6 M HCl was found to be dependent on its concentration, and an exponential relationship between quantity of HgS added to 20 mL of 6 M HCl (the range of 0.1-10 mg was used) and the solubility in 6 M HCl was established. For higher concentrations of HgS (10 mg in 20 mL of acid), a similarly low solubility of cinnabar was obtained as found in the literature. A study of dissolution kinetics of HgS in 6 M HCl indicated that it was a fairly slow process. Unexpected oxidation of HgS in water or 1 M HCl was found for extractions performed in Teflon vials previously used for the digestion of residual undissolved HgS by aqua regia. We presumed that the Teflon material could preserve some oxidising gases (presumably Cl(2)) developed during digestion with aqua regia which can then oxidise HgS during extraction with water or 1 M HCl. Regarding the extraction of Hg from natural sediments, we concluded that 6 M HCl could not be used to extract reactive Hg and predict bioavailability of mercury in sediments containing HgS and that experiments with model compounds should not be done at a concentration level several orders of magnitude higher than in natural samples.     

Sediment analysis--lability of selectively extracted fractions

Contaminated sediment samples and wastes were extracted with a series of chemical solutions widely used in soil and sediment analyses. The Cu, Pb and Cd contents of the extracts were then determined by both AAS and ASV, and it was found that not all of the metal ion retrieved was "labile". Differences between selected extraction values were compared with the bonding-mode category values obtained by using a well-known sequential extraction procedure, and it was found that the series and sequential approaches yielded different results for Pb and Cu. The advantages and limitations of ASV monitoring in sediment studies are considered and the inappropriateness of some operationally defined fraction categories is indicated.     

Preconcentration and separation of copper (II) with solvent extraction using N,N′-bis(2-hydroxy-5-bromo-benzyl)1,2 diaminopropane

Preconcentration and separation with solvent extraction of Cu(II) from aqueous solution using N,N′-bis(2-hydroxy-5-bromo-benzyl)1,2 diaminopropane (H₂L) as the new extractant has been studied. Separation of Cu(II) from other metal ions such as Cd(II), Ni(II), Zn(II), Pb(II), Cr(III), Co(II) and Mn(II) at aqueous solutions of various pH values and complexing agent H₂L, has been described. The possible extraction mechanism and the compositions of the extracted species have been determined. The separation factors for these metals using this reagent are reported while efficient methods for the separation of Cu(II) from other metal ions are proposed. From the loaded organic phase, Cu(II) stripping was carried out in one stage with different mineral acid solutions. The stripping efficiency was found to be quantitative in case of HNO₃ and HCl. From quantitative evaluation of the extraction equilibrium data, it has been deduced that the complex extracted is the simple 1:1 chelate, CuL. The extraction constant has a value of logK_ex=−4.05±0.04.     

Extractive separation of trace amounts of mercury, cadmium and zinc

A simple solvent extraction procedure is reported for the sequential separation of mercury(II), cadmium(II) and zinc(II). Mercury is separated first using 1,3-diphenyl-2-thiourea in chloroform at an overall acidity of 0.3M HCl. Then cadmium separated using the same reagent at pH 10 into dichloromethane. The zinc which is remaining in the aqueous phase is then quantitatively extracted into toluene-cyclohexanol mixture using 2-mercaptobenzoxazole. Suitable stripping solutions have been proposed for the re-extraction of these metal ions for their subsequent estimations. The method has been made highly selective by the use of appropriate masking agents and has been applied in conjunction with estimation procedures for the determination of these metal ions in city waste incineration ash (CRM 176), mercuric chloride (A. R. grade) and in magnesium alloy samples.     

Liquid-liquid extraction of zinc from aqueous thiocyanate solutions with 5-(-4-pyridyl)nonane in benzene

5-(4-Pyridyl)nonane dissolved in benzene has been applied to the extraction of zinc, down to very low concentration (< 10(-6)M), from aqueous thiocyanate solutions. The metal can be quantitatively extracted from neutral and acidic thiocyanate solutions (up to 5M HCl, 0.25M HNO(3) or 0.25M H(2)SO(4)) in a single extraction. Equilibration times of 5 min are sufficient for almost complete extraction. The optimum thiocyanate concentration range is 0.05-0.5M. Among the common anions chloride exerts a slight depressing effect on extraction from neutral solution when present in high concentration. The extraction mechanism and the composition of the extracted complexes of zinc are discussed. The metal is predominantly extracted by means of a solvate mechanism. The effect of chloride, nitrate, sulphate, acetate, citrate, oxalate and ascorbate ions on the extraction of zinc is described. Several elements, including those of interest in separation of zinc, have been tested for extraction from O.1M KSCN at the optimal concentrations of the mineral acids, and the separation factors estimated.     

Extraction and speciation of arsenic in lacustrine sediments

Arsenic was partially extracted with 4.OM hydrochloric acid, from samples collected at 25-cm intervals in a 350-cm column of sediment at Milltown Reservoir, Montana and from a 60-cm core of sediment collected at the Cheyenne River Embayment of Lake Oahe, South Dakota. The sediment in both reservoirs is highly contaminated with arsenic. The extracted arsenic was separated into As(III) and As(V) on acetate form Dowex 1-X8 ion-exchange resin with 0.12M HCl eluent. Residual arsenic was sequentially extracted with KClO(3) and HCl. Arsenic was determined by graphite-furnace atomic-absorption spectrometry. The analytical results define oxidized and reduced zones in the sediment columns.     

Extraction of gallium(III) by 1-{[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]methyl}-1H-1,2,4-triazole from hydrochloric acid solutions

The extraction of gallium(III) with 1-{[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2- yl]methyl}-1H-1,2,4-triazole from hydrochloric acid solutions into toluene was studied. It was found that gallium( III) was efficiently extracted from 5–10 M solutions of HCl by the anion-exchange mechanism. The following metal extraction order was determined in the above aqueous phase acidity range: Ga(III) > In(III) > Al(III). The concentration constants and the thermodynamic parameters of the reaction of gallium(III) extraction from 6 M solutions of HCl at 25 °C were calculated.     

The Analysis of Inorganic and Organic Pollutants in Soil with Special Regard to Their Bioavailability

Abstract

The most important inorganic pollutants in soil are the heavy metals. Problems related to the determination of the total and soluble content are discussed. Soluble contents are of interest in connection with studies about bioavailability. Because some of the heavy metals are essential for plant growth, most of the work about bioavailability has been done in the field of plant nutrition. Much less is known about the situation in polluted soils.

It was shown that neutral salt solutions which do not really change the pH of soil during the extraction procedure are best suited to define thresholds of excess. This is in contrast to much stronger extractants like EDTA or DTPA often proposed for the analysis of soils which are deficient in trace elements.

With three sets of experiments the correlation between the contents of cadmium, copper, nickel and zinc extracted by 0.1 M NaNO₃ (as an example of a neutral salt solution) and the plant response (phyto- or zootoxicity) are shown:

—pot experiments using soils which were contaminated by metal salt solutions

—pot experiments using soils from contaminated areas

—field studies in polluted areas. In these studies the aspect of heavy metal leaching was also considered.

The results were converted to indicative values in the Swiss Ordinance of Pollutants in the Soil. These indicative values derived from plant reactions were checked by the carbon mineralisation as an example of a soil microbiological process.

As it was found that organic pollutants are not easily taken up by plant roots the problem of bioavailability is much less important. However, the biodegradation and formation of metabolites has to be considered.     

Antimony Film Microelectrode for Anodic Stripping Measurement of Cadmium(II), Lead(II) and Copper(II)

The antimony film microelectrode (SbFME) is presented for measuring trace heavy metal ions in combination with anodic stripping voltammetry. The SbFME was tested in model solutions of 0.01 M HCl containing Cd(II) and Pb(II) in the presence of dissolved oxygen. The microsensor exhibited good linear behavior in the examined concentration range 20 μg L⁻¹ to 100 μg L⁻¹ and LoD of 1.9 and 3.1 μg L⁻¹ for Cd(II) and Pb(II), respectively. The suitability of SbFME for measuring trace levels of Cu(II) was demonstrated using the standard reference material of natural water exploiting the sensor's specific characteristic of low re‐oxidation signal for antimony.     

Precipitation of metal ions by organic acids as a mean for metal recovery and decontamination of wastewater

The dicarboxylic and oxycarboxylic acids known as complexing agents for metal ions under the conditions when the amount of metal ions exceeds that in metal complexes, act as precipitants for metal ions. The completeness of precipitation, depends on the kind of metal and organic acid, pH and the concentrations of substances. The abundance of metals in metal finishing industry enables to use such precipitation for regeneration and decontamination of the complexing agents containing solutions.     

Metal ion distribution between water and river sediment: speciation model and spectroscopic validation

Natural sediments show sequestering properties that can lead to a process of self-purification of aquatic environment from metal pollution. The study of the interaction between metal ions and sediment particles enhances what is known about the distribution and bioavailability of heavy metals in natural systems. Our contribution concerns the characterisation of the sequestering ability of a River Po sediment with regard to calcium(II), magnesium(II), cadmium(II), nickel(II) and copper(II), in fixed experimental conditions, through pH-metric and spectrometric measurements. A batch titration procedure was adopted and, in each solution, after equilibration, both pH and pM (M = Ca(II), Mg(II), Cd(II), Ni(II), Cu(II)) (via Inductively Coupled Plasma - Optical Emission Spectroscopy, ICP-OES) values were measured. The experimental data were first processed with a specific software to evaluate the concentration and protonation constants of the sediment ligand site(s). The speciation model was then assessed, together with the values of complexation constants, for the different sediment/metal cation systems. In order to better characterise the copper(II)-sediment interaction and to obtain more information about the nature of ligand site(s) involved, EPR (Electronic Paramagnetic Resonance) measurements were also made on the dry sediment before and after reaction with copper(II) ions.     

Solvent extraction of chromium(VI) from base metal ions with diphenyl-2-pyridylmethane as a liquid anion exchanger

The extraction of chromium(VI) from aqueous hydrochloric, nitric and sulfuric acid solutions by diphenyl-2-pyridylmethane(DPPM) dissolved in chloroform has been studied. Chromium(VI) is quantitatively extracted from hydrochloric acid solutions in the range 0.1–1M. With increasing acid concentration, the extraction of chromium diminishes and in concentrated acid solutions practically all the chromium remains in the aqueous phase. The quantitative back-extraction of chromium from the organic phase is possible with HCl or HNO₃ at concentrations higher than 5M through the use of reducing agents. The composition of the extracted chromium(VI) species was studied in solution. The complexes (DPPMH)⁺HCrO ₄ ⁻ and (DPPMH)₂Cr₂O ₇ ⁻ are extracted for tracer and macro amounts of chromium(VI) respectively. The data have been utilized for the separation of chromium(VI) from base metal ions.