A test of sequential extractions for determining metal speciation in sewage sludge-amended soils

Sequential extraction procedures are widely used to estimate the quantity of trace metals bound to different solid fractions in contaminated soils. However, reliability of speciation of trace metals by these procedures remains largely unexamined. In the present study, the selectivity of each extraction step was tested by observing the effect of reversing the extraction order in the procedure. Two different sequential extraction methods and their reversed modes were used for metal fractionation in sewage sludge-amended soils. Significantly increased amounts of extractable metals (Cd, Cu, Pb and Zn) were evident in the sludge-amended soils compared to control soil by all extraction schemes; however, the amounts of metals extracted by each step were strongly dependent on the order of extraction, the type of reagents and the nature of the individual metals. Caution is advised in deducing the forms of soil metals from sequential extraction results from metal-contaminated soils.     

Speciation of heavy metals in estuarine sediments in the northeast of Brazil

An analytical procedure involving a three-step sequential extraction was used to determine the chemical association of heavy metals (Zn, Cr, Mn and Fe) with the major phases (exchangable, reducible and oxidizable) in samples from a fishpond of estuarine sediments. The pond is located in the Capibaribe River estuary, within the boundaries of the city of Recife, in the State of Pernambuco in the northeast of Brazil. The total metal content was determined as well. All metals were extracted from the residual fraction at a percentage greater than 50%.     

An ultrasonic assisted extraction method to release heavy metals from untreated sewage sludge samples

A rapid ultrasound accelerated sequential extraction procedure has been used to develop sequential extraction proposed by BCR protocol (the community Bureau of Reference now the European Union "Measurement and Testing Programme"). The effects of the ultrasonic treatment on the extraction of Cu, Cd, Cr, Pb, Ni and Zn from untreated sewage sludge collected from industrial site of Hyderabad city (Pakistan) were compared with those obtained from conventional sequentional extraction procedure of modified BCR protocol. In BCR method, each extraction steps takes 10h, where as with the use of compromise sonication conditions in ultrasonic bath, steps 1-3 of the sequential extraction (excluding the hydrogen peroxide digestion in step 3, which was not performed with sonication) could be completed in 30, 30 and 30 min, respectively. Extractable Cd, Cr, Pb and Ni contents were obtained by both comparable methodologies were measured by electrothermal atomic absorption spectrometry (ETAAS), while for Cu and Zn Flame atomic absorption spectrometry (FAAS) was used. The validations of both methods were compared by the analysis of certified reference material of soil amended with sewage sludge (BCR 483). According to statistical evaluation of the results, the proposed accelerated extraction method is valid alternative to conventional shaking with much shorter extraction time with p value <0.05. The overall metal recoveries in steps 1-3 (excluding residual step) were 95-100% of those obtained with the conventional BCR protocol, except for Cu extracted (91.6%) as related to indicative values of Cu in BCR 483 obtained in 1-3 steps. The results of the partitioning study of untreated industrial waste water sewage sludge, indicate that more easily mobilized forms (acid exchangeable) were predominant for Cd and Zn, in contrast, the largest amount of Pb and Cr was associated with the iron/manganese oxide and organic matter/sulphide fractions.     

Complexes of fulvic acid on the surface of hematite, goethite, and akaganeite: FTIR observation

The present work extended our knowledge on the binding and complexation of a fulvic acid (FA) derived from leonardite and the iron oxides (hematite, goethite and akaganeite) by Fourier transform infrared spectroscopy (FTIR). As a prerequisite, the iron oxides were firstly prepared and characterized by transmission electron micrograph (TEM). All iron phases were single and well-described crystalloid. The FTIR data obtained by two different sampling preparation methods gave the consisting evidences that under our experimental conditions the interaction mechanism was to the ligand-exchange involving carboxylic functional groups of the FA and the surfaces sites of both hematite and goethite, while no complexation can be evidenced in the case of akaganeite, only surface adsorption. In general, the binding affinities of the iron oxides with the FA was in the order of hematite>goethite>akaganeite. The present method, although associated with some uncertainties, provided an opportunity to increase the knowledge in the field of the humic chemistry.     

Aqueous free radical chemistry of mercury in the presence of iron oxides and ambient aerosol

The effect of goethite (α-FeOOH), hematite (α-Fe₂0₃) and maghemite (γ-Fe₂0₃) on the aqueous photoreduction of divalent mercury with organic acids (oxalate, formate and acetate) is investigated. Laboratory photochemistry experiments with synthetic iron oxides and simulated sunlight were performed to assess the role of the oxides on the photoreduction. Ambient aerosol was also collected and introduced as the solid phase to compare its effect with that of synthetic oxides. It is observed that the presence of various iron oxides or aerosol particles enhances the photoreduction. It is also found that the hydroxyl radicals produced in the hematite-oxalate systems can re-oxidize the reduced mercury back to Hg(II). Based on the experimental observations, mechanisms responsible for the Hg(II) reduction are proposed. The kinetics of Hg⁰ oxidation by hydroxyl radicals was also studied by a steady-state kinetic technique using nitrate photolysis as the * OH radical source. The second-order rate constant is determined to be 2.0 × 10⁹ M⁻ s⁻¹. The implications of the studied reactions on the atmospheric chemistry of mercury are discussed.     

Simple and sequential extractions of heavy metals from different sewage sludges

The presence of heavy metals in the sludges produced in waste-water treatment plants restricts their use for agricultural purposes. This study looks at different types of sludges (aerobic, anaerobic, unstabilised and sludge from a waste stabilisation pond) and compares the distribution of the heavy metals they contain according to the treatment that they have undergone. Some agronomic parameters necessary for characterising a sludge as suitable for use as amendment were determined. The aim of this study is to compare the availability and the localisation of heavy metals in different sewage sludges using simple (water and DTPA) extraction and the BCR (Community Bureau of Reference) sequential extraction procedure. It was confirmed that the total concentration of heavy metals did not exceed the limits set out by European legislation and that the stabilisation treatment undergone by the sludges strongly influenced the heavy metal distribution and the phases to which they were associated and their bioavailability level. The DTPA extraction procedure is cheap and easy to perform and the obtained results are similar to those obtained with the sequential procedure.     

Heavy metal sequential extraction methods--a modification for tropical soils

Sequential extractions of metals can be useful to study metal distributions in various soil fractions. Although several sequential extraction procedures have been suggested in the literature, most were developed for temperate soils and may not be suitable for tropical soils with high contents of Mn and Fe oxides. The objective of this study was to develop a sequential fractionation procedure for Cu and Zn in tropical soils. Extractions were performed on surface (0–20 cm) samples of ten representative soils of Sao Paulo State, Brazil. Chemically reactive Mn forms were satisfactorily assessed by the new modified procedure. Amorphous and crystalline Fe oxides were more selectively extracted in a new two-step extraction. Soil-born Zn and Cu were primarily associated with recalcitrant soil fractions. The proposed procedure provided more detailed information on metal distribution in tropical soils and better characterization of the various components of the soil matrix. The new procedure is expected to be an important tool for predicting the potential effects of environmental changes and land application of metals on the redistribution of chemical forms of metals in tropical soils.     

Evaluation of new surfactant expanded zirconium and titanium phosphates for polycyclic aromatic hydrocarbons extraction from waters

A newly synthesized family of materials prepared with surfactant as organic template were tested for the extraction of polycyclic aromatic hydrocarbons (PAHs) from water, using pyrene (Pyr) and benzo[a]pyrene (B[a]P) as PAHs representatives. Particular attention was paid to the evaluation of the recovery factors with dichloromethane as eluent in order to estimate their potential as adsorbing solid phases for PAH remediation or analysis. Eleven lamellar MCM-50 type materials incorporating n-alkyl- (n = 12, 16, 18) trimethylammonium bromide molecules with different concentrations and chain lengths and two hexagonal MCM-41 type materials incorporating octadecyl-trimethyl ammonium bromide were tested. Best results were obtained by preparing lamellar MCM-50 zirconium and titanium phosphates in the presence of n-dodecyl-trimethylammonium at a relative molar concentration (surfactant/phosphate) of 1.     

Solid phase speciation of arsenic by sequential extraction in standard reference materials and industrially contaminated soil samples

Availability, mobility, (phyto)toxicity and potential risk of contaminants is strongly affected by the manner of appearance of elements, the so-called speciation. Operational fractionation methods like sequential extractions have been applied for a long time to determine the solid phase speciation of heavy metals since direct determination of specific chemical compounds can not always be easily achieved. The three-step sequential extraction scheme recommended by the BCR and two extraction schemes based on the phosphorus-like protocol proposed by Manful (1992, Occurrence and Ecochemical Behaviours of Arsenic in a Goldsmelter Impacted Area in Ghana, PhD dissertation, at the RUG) were applied to four standard reference materials (SRM) and to a batch of samples from industrially contaminated sites, heavily contaminated with arsenic and heavy metals. The SRM 2710 (Montana soil) was found to be the most useful reference material for metal (Mn, Cu, Zn, As, Cd and Pb) fractionation using the BCR sequential extraction procedure. Two sequential extraction schemes were developed and compared for arsenic with the aim to establish a better fractionation and recovery rate than the BCR-scheme for this element in the SRM samples. The major part of arsenic was released from the heavily contaminated samples after NaOH-extraction. Inferior extraction variability and recovery in the heavily contaminated samples compared to SRMs could be mainly contributed to subsample heterogeneity.     

Potentially toxic element fractionation in technosoils using two sequential extraction schemes

This study reports the chemical fractionation of several potentially toxic elements (Zn, Pb, Cd, As, and Sb) in contaminated technosoils of two former smelting and mining areas using two sequential extraction schemes. The extraction schemes used in this study were the Tessier’s scheme and a modified BCR scheme. The fractions were rearranged into four equivalent fractions defined as acid soluble, reducible, oxidizable, and residual to compare the results obtained from two sequential extraction schemes. Surface soils were samples from a waste landfill contaminated with Zn, Pb, and Cd located at Mortagne-du-Nord (MDN; North France) and from a settling basin contaminated with PTE such as As, Pb, and Sb located at La Petite Faye (LPF; Limoges, France). The study of the Zn, Pb, Cd, As, and Sb partitioning in the acid soluble, reducible, oxidizable, and residual fractions of the technosoils revealed that Zn, Cd, and Pb were mainly associated with the acid soluble and reducible fractions for MDN site, while As, Sb, and Pb were associated with residual fraction for LPF site. Fractionation results indicate that the percentages of Zn, Pb, Cd, As, and Sb extracted in Fe–Mn oxide bound fraction of Tessier’s scheme were always higher than those extracted by modified BCR scheme. This may be attributed to the stronger Tessier’s scheme conditions used to extract this fraction. In contrast the percentages of Zn, Pb, Cd, As, and Sb extracted in the organic fraction of the modified BCR scheme were always higher than those of the Tessier’s scheme. The order of mobility of PTE was as follows: Cd?>?Zn?>?Pb in MDN site and As?>?Sb?>?Pb in LPF site. PTE were distributed in all soil fractions, with the most relevant enrichments in extractable and residual fractions. A significant amount of Cd, Pb, and Zn were rather mobile, which suggests that these elements can be readily available to plants and soil organisms.     

Sequential Extraction Versus Comprehensive Characterization of Heavy Metal Species in Brownfield Soils

The applicability of sequential extraction as a means to determine species of heavy-metals was examined by a study on soil samples from two Superfund sites: the National Lead Company site in Pedricktown, NJ, and the Roebling Steel, Inc., site in Florence, NJ. Data from a standard sequential extraction procedure were compared to those from a comprehensive study that combined optical- and scanning-electron microscopy, X-ray diffraction, and chemical analyses. The study shows that larger particles of contaminants, encapsulated contaminants, and/or man-made materials such as slags, coke, metals, and plastics are subject to incasement, non-selectivity, and redistribution in the sequential extraction process. The results indicate that standard sequential extraction procedures that were developed for characterizing species of contaminants in river sediments may be unsuitable for stand-alone determinative evaluations of contaminant species in industrial-site materials. However, if employed as part of a comprehensive, site-specific characterization study, sequential extraction could be a very useful tool.     

Sequential Extraction Versus Comprehensive Characterization of Heavy Metal Species in Brownfield Soils

The applicability of sequential extraction as a means to determine species of heavy-metals was examined by a study on soil samples from two Superfund sites: the National Lead Company site in Pedricktown, NJ, and the Roebling Steel, Inc., site in Florence, NJ. Data from a standard sequential extraction procedure were compared to those from a comprehensive study that combined optical- and scanning-electron microscopy, X-ray diffraction, and chemical analyses. The study shows that larger particles of contaminants, encapsulated contaminants, and/or man-made materials such as slags, coke, metals, and plastics are subject to incasement, non-selectivity, and redistribution in the sequential extraction process. The results indicate that standard sequential extraction procedures that were developed for characterizing species of contaminants in river sediments may be unsuitable for stand-alone determinative evaluations of contaminant species in industrial-site materials. However, if employed as part of a comprehensive, site-specific characterization study, sequential extraction could be a very useful tool.     

Multicriteria optimisation of a simultaneous supercritical fluid extraction and clean-up procedure for the determination of persistent organohalogenated pollutants in aquaculture samples

A useful tool based on a single-step extraction and clean-up procedure for the determination of 15 organohalogenated pollutants (including brominated flame retardants) in aquaculture samples, using aluminium oxide basic and acidic silica gel in the supercritical extraction cell followed by gas chromatography with electron capture detection or mass spectrometry has been developed. This effective clean-up step ensures a minimum of chromatographic difficulties related to complex matrix components such as aquaculture feed. The extraction procedure has been screened by a fractional factorial design for the preliminary statistically significant parameters. The factors selected were extraction temperature, pressure, static extraction time, dynamic extraction time and carbon dioxide flow rate. The Doehlert design, followed by a multicriteria decision-making strategy, was then performed in order to determine the optimum conditions for the two most significant factors: pressure (165 bar) and dynamic extraction time (27 min). Under optimal conditions, the procedure developed with GC-MS/MS provides an excellent linearity, detection (0.01-0.2 ng g(-1)) and quantification limits (0.05-0.8 ng g(-1)) for most of the analytes investigated. The feasibility of the proposed supercritical fluid extraction method was validated by analysing two reference materials and fish feed and shellfish samples with satisfactory results.     

Photocatalytic degradation of atrazine by porphyrin and phthalocyanine complexes

This study principally focused on a new kind of photochemical reaction catalyst: porphyrin and phthalocyanine complexes. In a first step, the preparation of the catalysts was optimized. A resin has been chosen to be the support of the complexes. Efficiency of catalytic activity is performed on the degradation of a pesticide: atrazine. The best atrazine degradation occurs with 4.6% of complexes versus substrate. The role of the surface has also been shown to be important. Then, their performances were demonstrated in terms of kinetics and degradation routes, compared to a classical catalyst: titanium dioxide. This study seeks to assess the efficiency of these systems both in a mercury lamp reactor and under solar irradiation which reduces energy costs. The best atrazine degradation half-life found for the complexes is about 200 min with the iron phthalocyanine. These catalysts exhibit particular oxidation activities. Indeed, the degradation routes have been found different between the semi-conductor and the metallic complexes. These complexes are able to cleave the triazinic ring more efficiently than the titanium dioxide.     

Horizontal and vertical variabilities of mercury concentration and speciation in sediments of the Gdansk Basin,Southern Baltic Sea

The mercury compounds introduced to the environment because of anthropogenic activity are accumulated, mainly, in marine sediments. Both distribution of mercury in the Baltic Sea and factors affecting it are remain largely unknown. Due to its complex chemistry and variable conditions in the Baltic Sea bottom sediments, mercury may be reemitted to the overlaying water, and thus to the environment.The aim of this study was twofold. Total mercury contents were measured in sediments of the Gdansk Basin along a Vistula mouth (main source)--Gdansk Deep (deposition area) transect in order to assess spatial distribution of the element. Soft and sandy bottom sediment cores were collected and cut into slices. The mercury measurements consisted of acid digestion followed by CV-AAS determination. A five-step sequential extraction procedure involving measurements of mercury species water soluble, bound to humic substances and insoluble, was employed in order to investigate mercury speciation. On the basis of speciation results stability and remobilisation potential was assessed. The second aim was demonstrating that mercury gradients in vertical profiles of the investigated sediment cores exist.Total mercury contents varied in range from 28 ng/g x dw to 844 ng/g. Mercury associated with organic matter and sulphides, (respectively 39% and 49%) were the dominant species of the element. The results indicated that the river run-off is a source of mercury in the area. Vertical gradients of both total content and speciation of mercury in the soft sediments were attributed to both remobilisation from sediments, and decreasing trend in the anthropogenic load of the element deposited to sediments.     

Sorption of cobalt and nickel on anaerobic granular sludges: isotherms and sequential extraction

The objective of this study was to investigate the sorption capacity and the fractionation of sorbed nickel and cobalt onto anaerobic granular sludges. Two different anaerobic granular sludges (non-fed, pH=7) were loaded with nickel and cobalt in adsorption experiments (monometal and competitive conditions). The combination of sequential extraction with the sorption isotherm analysis allowed the assessment of the sorption capacity of individual fractions present in the anaerobic granular sludges. The operational fractionation of the sorbed heavy metals was determined using a modified Tessier sequential extraction procedure. The sorption characteristics of each extracted fraction (exchangeable, carbonates, organic matter/sulfides and residual fractions) fitted well to the Langmuir model. The organic matter/sulfides fraction showed the highest affinity for cobalt and nickel in both sludges investigated compared to the other operationally defined fractions. The presence of iron negatively affected cobalt and nickel accumulation in this organic matter/sulfides fraction. The trace metals-iron sulfide interactions are likely to be the key process in controlling the distribution of cobalt and nickel during sorption onto non-fed methanogenic granules due to the high affinity of iron sulfides towards the metals studied.     

Heavy metal levels and solid phase speciation in street dusts of Delhi,India

Street dust samples were collected from three different localities (industrial, heavy traffic and rural) situated in the greater Delhi area of India. The samples analyzed for Cd, Zn, Pb, Ni, Cu, and Cr indicated remarkably high levels of Cr, Ni, and Cu in the industrial area, whilst Pb and Cd did not show any discernible variations between the three localities. A multivariate statistical approach (Principal Component Analysis) was used to define the possible origin of metals in dusts. The street dusts were sequentially extracted so that the solid pools of Cd, Zn, Pb, Ni, Cu, Cr could be partitioned into five operationally defined fractions viz. exchangeable, bound to carbonates, bound to Fe-Mn oxides, bound to organic matter and residual. Metal recoveries in sequential extractions were +/- 10% of the independently measured total metal concentrations. Cd was the only metal present appreciably (27.16%) in the exchangeable fraction and Cu was the only metal predominantly associated (44.26%) with organic fraction. Zn (45.64%) and Pb (28.26%) were present mainly in the Fe-Mn oxide fraction and the residual fraction was the most dominant solid phase pool of Cr (88.12%) and Ni (70.94%). Assuming that the mobility and bioavailability are related to the solubility of geochemical forms of the metals and decrease in order of extraction, the apparent mobility and potential metal bioavailability for these highly contaminated street dust samples is: Cd>Zn approximately equal Pb>Ni>Cu>Cr.     

Fractionation of heavy metals in liquefied chromated copper arsenate 9-treated wood sludge using a modified BCR-sequential extraction procedure

Chromated copper arsenate (CCA)-treated wood was liquefied with polyethylene glycol/glycerin and sulfuric acid. After liquefaction, most CCA metals (98% As, 92% Cr, and 83% Cu) were removed from liquefied CCA-treated wood by precipitation with calcium hydroxide. The original CCA-treated wood and liquefied CCA-treated wood sludge were fractionated by a modified Community Bureau of Reference (BCR) sequential extraction procedure. The purpose of the BCR-sequential extraction used in this study was to examine the availability of CCA metals in treated wood for reuse. Both As and Cr had a slightly higher concentration in the sludge sample than in original CCA-treated wood. The sequential extraction showed that As and Cr were principally existed in an oxidizable fraction (As, 67%; Cr, 88%) in original CCA-treated wood. Only 1% of both As and Cr were extracted by hot nitric acid with the last extraction step. The distribution of As and Cr changed markedly in liquefied CCA-treated wood sludge.The amount of As in the exchangeable/acid extractable fraction increased from 16% to 85% while the amount of Cr increased from 3% to 54%. Only about 3% of As was present in the oxidizable fraction. However, there was still about 34% of Cr in the same fraction. Based on these results from sequential extraction procedures, it can be concluded that the accessibilities of CCA metals increase markedly by the liquefaction–precipitation process.     

Migration behavior of naturally occurring radionuclides at the Nopal I uranium deposit, Chihuahua, Mexico

Oxidation of pyrite at the Nopal I uranium deposit, Peña Blanca district, Chihuahua, Mexico has resulted in the formation of Fe-oxides/hydroxides. Anomalous U concentrations (i.e. several hundred to several thousand ppm) measured in goethite, hematite, and amorphous Fe-oxyhydroxides in a major fracture that crosscuts the deposit and the absence of U minerals in the fracture suggest that U was retained during secondary mineral growth or sorbed on mineral surfaces. Mobilization and transport of U away from the deposit is suggested by decreasing U concentrations in fracture-infilling materials and in goethite and hematite with distance from the deposit. Greater than unity ²³⁴U/²³⁸U activity ratios measured in fracture-infilling materials indicate relatively recent ( < 1 Ma) U uptake from fluids that carried excess ²³⁴U. Systematic decreases in ²³⁴U/²³⁸U activity ratios of fracture materials with distance from the deposit suggest a multistage mobilization process, such as remobilization of U from ²³⁴U-enriched infill minerals or differential or diminished transport of U-bearing solutions containing excess ²³⁴U.     

Fate of Lu(III) sorbed on 2-line ferrihydrite at pH 5.7 and aged for 12 years at room temperature. I: insights from ICP-OES,XRD, ESEM,AsFlFFF/ICP-MS,and EXAFS spectroscopy

Two-line ferrihydrite (2LFh) was aged for 12 years under ambient conditions and sheltered from light in the presence of Lu(III) used as surrogate for trivalent actinides. 2LFh aging produced hematite rhombohedra with overgrown acicular goethite particles. Analysis of the homogeneous suspension by asymmetrical flow field-flow fractionation (AsFlFFF) coupled to ICP-MS indicated that particles have a mean hydrodynamic diameter of about 140 nm and the strong correlation of the Fe and Lu fractograms hinted at a structural association of the lanthanide with the solid phase(s). Unfortunately, recoveries were low and thus results cannot be considered representative of the whole sample. The suspension was centrifuged and X-ray absorption spectroscopy (XAS) at the Lu L₃-edge on the settled particles indicated that Lu(III) is sixfold coordinated by oxygen atoms, pointing to a retention by structural incorporation within particles. This result is consistent with AsFlFFF results on the same suspension without centrifugation. The detection of next nearest Fe and O atoms were consistent with the structure of goethite, ruling out incorporation within hematite. After centrifugation of the suspension, only nanoparticulate needle-like particles, very likely goethite, could be detected in the supernatant by ESEM. AsFlFFF data of the supernatant were comparable to that obtained for the homogeneous suspension, whereas XAS indicated that Lu(III) is predominantly present as dissolved species in the supernatant. Results from both techniques can be interpreted as a major fraction of Lu present as aqueous ions and a minor fraction as structurally incorporated. Findings from this study are corroborated by STEM-HAADF data and results from DFT calculations in a companion paper.