Four-stage Sequential Extraction Research Articles

Studies on the Contamination of Heavy Metals and Their Chemical Speciation in Sediment from Selected Locations of Pune District

The heavy metal speciation analysis in sediments helps us understand and evaluate essential and unavoidable issues in terms of both health and environmental hazards imposed by these metals in our lives. Analyzing the total content of heavy metals enables us to understand only the quantity of the contaminants. To understand the different species or the chemical forms of heavy metals available in the sediments, we must study their speciation. Speciation studies help us determine their possible sources as well as their environmental stability in terms of availability to plants and other organisms. The heavy metals in this study were specified using four-stage sequential extraction, also known as the BCR technique. This study mainly highlights the quantification of metal contamination of Cu, Zn, Pb, Ni, Cd & Cr, and chemical forms as species in sediment samples collected from different Pune District, Maharashtra sites. Heavy metal contamination from the collected samples was analyzed with the use of flame atomic absorption spectrometry. This study indicated that Zn and Ni are among the most abundant metals in the sediment samples; however, Cu and Cd belong to the least abundant category. The oxidizable and residual forms (immobile and cannot be used by the organisms readily) appeared dominant for most heavy metals. Very significant differences were observed in the speciation of heavy metals from sample to sample, which was probably due to differences in water/soil composition and the agrochemicals like pesticides, weedicides, and fertilizers used in agricultural practices; the wastewater generated from different pharmaceuticals, chemical processing and manufacturing industries as well as the improper wastewater treatment methods.

The assessment of phosphorus recovery potential in sewage sludge incineration ashes — a case study

A sewage sludge incineration ash contains large amounts of phosphorus, which are considered as a novel anthropogenic waste–based substitute for phosphorus natural resources. Phosphorus is accumulated at most in phosphate minerals of whitlockite structure, that contain Fe, Ca, and Mg and in the matrix composed of Si, Al, Fe, Ca, P, Mg, K, Na in various proportions. The goal of this study was to estimate phosphorus recovery potential. A four-stage sequential extraction, following the modified Golterman procedure, was applied. Separation of four independent fractions enabled to understand better the manner of phosphorus occurrence in the studied ash. The results of the extraction indicated the greatest release of phosphorus combined with organic matter using sulfuric acid. The release was on average at the level of 64%. The chelating Na-EDTA compound indicated lower ability to extract phosphorus (at the level of 35%), and the highest ability to extract heavy metals and potentially toxic elements (As, Zn, Mo). The sequential extraction led to the total recovery of phosphorus of around 40–60%

Heavy metals speciation and its bioavailability in sewage sludge pyrolysis residue

The presence of unstable heavy metals can influence the safe recycling of sewage sludge. Since the bioleaching effects of heavy metals from pyrolysis residue were sparely studied, heavy metals speciation and its bioavailability in sewage sludge pyrolysis residue (SSPR) were investigated in this study. Pyrolysis of sewage sludge, as well as bioleaching of SSPR, was carried out successively. Besides, a four-stage sequential extraction, Community Bureau of Reference, was adopted to analyze the heavy metals speciation in SSPR and its bioleaching residue. Results indicated that pyrolysis can enrich the concentrations of Cu, Ni, Zn, and Pb in sewage sludge except for Cd. Different physical properties of heavy metals, as well as the decrease in organics and moisture in sewage sludge, would result in the enrichment phenomena of heavy metals in SSPR. Thus, the concentrations of Cu, Zn, and Ni in SSPR were higher than those of Cu, Zn, and Ni in sludge standard for agricultural use. In addition, heavy metals in SSPR could be bioleached by Acidithiobacillus ferrooxidans which is commonly grown in nature. Most of the remained heavy metals after bioleaching were distributed in F3 (oxidizable) and F4 (residual) fractions, which meant the heavy metals in SSPR were further stabilized by Acidithiobacillus ferrooxidans. Hence, the combination of pyrolysis and bioleaching can be used to stabilize heavy metals in sewage sludge, and the concentrations of heavy metals in bioleaching residue can satisfy the sludge standard for agricultural use.

Assessment of mobility and bioavailability of mercury compounds in sewage sludge and composts

Content of heavy metals, including mercury, determines the method of management and disposal of sewage sludge. Excessive concentration of mercury in composts used as organic fertilizer may lead to accumulation of this element in soil and plant material. Fractionation of mercury in sewage sludge and composts provides a better understanding of the extent of mobility and bioavailability of the different mercury species and helps in more informed decision making on the application of sludge for agricultural purposes. The experimental setup comprises the composing process of the sewage sludge containing 13.1mgkg−1 of the total mercury, performed in static reactors with forced aeration. In order to evaluate the bioavailability of mercury, its fractionation was performed in sewage sludge and composts during the process. An analytical procedure based on four-stage sequential extraction was applied to determine the mercury content in the ion exchange (water soluble and exchangeable Hg), base soluble (Hg bound to humic and fulvic acid), acid soluble (Hg bound to Fe/Mn oxides and carbonates) and oxidizable (Hg bound to organic matter and sulphide) fractions. The results showed that from 50.09% to 64.55% of the total mercury was strongly bound to organo-sulphur and inorganic sulphide; that during composting, increase of concentrations of mercury compounds strongly bound with organic matter and sulphides; and that mercury content in the base soluble and oxidizable fractions was strongly correlated with concentration of dissolved organic carbon in those fractions.

Heavy metals and its chemical speciation in sewage sludge at different stages of processing

ABSTRACTThe analysis of heavy metal concentrations and forms in sewage sludge constitutes an important issue in terms of both health and environmental hazards the metals pose. The total heavy metals concentration enables only the assessment of its contamination. Hence the knowledge of chemical forms is required to determine their environmental mobility and sludge final disposal. Heavy metals speciation was studied by using four-stage sequential extraction BCR (Community Bureau of Reference). This study was aimed at determining the total concentration of selected heavy metals (Zn, Cu, Ni, Pb, Cd, Cr and Hg) and their chemical forms (except for Hg) in sludge collected at different stages of its processing at two municipal Wastewater Treatment Plants in southern Poland. Metals contents in sludge samples were determined by using flame atomic absorption spectrometry (FAAS) and electrothermal atomic absorption spectrometry (ETAAS). This study shows that Zn and Cu appeared to be the most abundant in sludge, while Cd and Hg were in the lowest concentrations. The sewage sludge revealed the domination of immobile fractions over the mobile ones. The oxidizable and residual forms were dominant for all the heavy metals. There was also a significant difference in metals speciation between sludges of different origin which was probably due to differences in wastewater composition and processes occurring in biological stage of wastewater treatment. The results indicate a negligible capability of metals to migrate from sludge into the environment. Our research revealed a significant impact of thickening, stabilization and hygienization on the distribution of heavy metals in sludge and their mobility.

Sequential and Selective Extraction of Copper in Different Soil Phases and Plant Parts from Former Industrialized Area

Copper (Cu) is an essential trace element for all living organisms; however, excess amounts in soil, plants, and food have negative impacts on the environment and human health. The aim of this study was to determine Cu levels in different chemical phases of soils and the relationship between Cu levels in soil phases and concentrations in plants. Soils and plants grown in these soils from an industrialized area in Turkey were analyzed using a selective and four-stage sequential extraction procedure. Copper levels in exchangeable fractions were found up to 658 mg kg−1 while total levels were in the range of 133–5609 mg kg−1. Copper concentrations in plant parts (roots and stem) were in the range of 2.6–240 mg kg−1. The exchangeable forms of Cu were in the range of 3–22% of total Cu concentrations. The relationships were observed between soil Cu and Rumex plant Cu, and soil Cu and root of Brassicasea plant Cu.

Arsenic and trace metals in river water and sediments from the southeast portion of the Iron Quadrangle, Brazil

The Iron Quadrangle has been one of the most important gold production regions in Brazil since the end of the seventeenth century. There, arsenic occurs in close association with sulfide-rich auriferous rocks. The most abundant sulfide minerals are pyrite and arsenopyrite, yet trace metal sulfides occur in subordinate phases as well. Historical mining activities have been responsible for the release of As and trace metals to both aquatic and terrestrial environments close to mining sites in the region. Therefore, this study was aimed to evaluate the distribution and mobility of As, Cd, Co, Cr, Cu, Ni, Pb, and Zn in streams in the southeast portion of the Iron Quadrangle between the municipalities of Ouro Preto and Mariana, the oldest Brazilian Au mining province. Total concentrations of some trace metals and arsenic in water were determined. The four-stage sequential extraction procedure proposed by the commission of the European Communities Bureau of Reference (BCR) was used to investigate the distribution of these elements in stream sediments. Arsenic concentration in water was > 10 μg L⁻¹ (maximum limit permitted by Brazilian environmental regulations for water destined for human consumption) at all sampling sites, varying between 36.7 and 68.3 μg L⁻¹. Sequential extraction in sediments showed high concentrations of As and trace metals associated with easily mobilized fractions.

3557 POSTER Phase I study of docetaxel, oxaliplatin and S-1 (DOS) for patients with advanced gastric cancer

Content of heavy metals, including mercury, determines the method of management and disposal of sewage sludge. Excessive concentration of mercury in composts used as organic fertilizer may lead to accumulation of this element in soil and plant material. Fractionation of mercury in sewage sludge and composts provides a better understanding of the extent of mobility and bioavailability of the different mercury species and helps in more informed decision making on the application of sludge for agricultural purposes. The experimental setup comprises the composing process of the sewage sludge containing 13.1 mg kg−1 of the total mercury, performed in static reactors with forced aeration. In order to evaluate the bioavailability of mercury, its fractionation was performed in sewage sludge and composts during the process. An analytical procedure based on four-stage sequential extraction was applied to determine the mercury content in the ion exchange (water soluble and exchangeable Hg), base soluble (Hg bound to humic and fulvic acid), acid soluble (Hg bound to Fe/Mn oxides and carbonates) and oxidizable (Hg bound to organic matter and sulphide) fractions. The results showed that from 50.09% to 64.55% of the total mercury was strongly bound to organo-sulphur and inorganic sulphide; that during composting, increase of concentrations of mercury compounds strongly bound with organic matter and sulphides; and that mercury content in the base soluble and oxidizable fractions was strongly correlated with concentration of dissolved organic carbon in those fractions.

Leachability and metal-binding capacity in ageing landfill material

In order to study the stability of landfilled heavy metals, landfill material from a combined household and industrial waste landfill was aerated for 14 months to simulate the natural ageing processes as air slowly begins to penetrate the landfill mass. During aeration, the pH of the landfill material decreased from around 8.6 to 8.1 and the carbon content also decreased. In order to investigate the possible fate of metals in ageing landfills, a four-stage sequential extraction technique was applied. The ability of the materials to bind metal ions by electrostatic attractions and to form stronger complexes was studied separately. The amount of exchangeable cations, the capacity to bind metal ions by electrostatic attraction and the capacity of the landfill material to complex copper ions were increased by the aeration process. However, results from the sequential analysis showed an increased solubility of sulphur and some metals (Cd, Co, Cu, Ni and Zn). Equilibrium speciation models (Medusa) indicated that the organic matter deposit had a significant capacity to bind metal ions provided that pH was sufficiently high. However, as carbonates are consumed over time, the risk for metal mobility increases. Therefore, the landfills can become an environmental risk, depending on variations in the solubility of metal ions due to changes in pH, redox status and the availability of organic material.

Soil and groundwater pollution of an urban catchment by trace metals: case study of the Addis Ababa region, central Ethiopia

Analysis of the total heavy metal (Cr, Cd, Pb, As, Cu, Ni, Zn, Co) concentration was performed on 33 soil samples taken from different profiles and soil types in a highly urbanized and industrial sector of Addis Ababa, central Ethiopia. They were analyzed using aqua regia extraction coupled with a four-stage sequential extraction (SE) procedure. The objectives of the analysis were to investigate the degree of soil heavy metal contamination, its binding forms, mobility and the implications for the groundwater resource. The results show a relatively high content of the analyzed trace metals in the soil attributed to anthropogenic and geogenic sources. Although most of the trace metals are found in the upper few centimeters of the residual soils, because of churning processes within the black cotton soils, vertical distribution of the trace metals is complex. According to the heavy metal SE analysis, the major heavy metal contribution is from the residual followed by the hydroxide phases. Groundwater heavy metal contamination is present with more than 90 and 50% of the analyzed groundwater samples exceeding WHO guidelines for Cr and Cd, respectively. Since the degree of soil heavy metal contamination has apparently not surpassed the soil’s buffering capacity, it appears that the transport path of these toxic metals to the groundwater is through fractures, joints, and related preferential flow paths.

Resolution of uncertainty of a four-stage sequential extraction procedure using analysis of variance.

Sequential extraction procedures are mostly applied to soils and sediments. Investigations were made for testing the applicability of a selected extraction scheme on spoil pile material. Therefore, different spoil pile samples from uranium mining were extracted into four steps (exchangeable, reducible, oxidizable, and aqua regia soluble phase) and the contents of the elements Cr, Cu, Fe, K, Ni, and Zn were analyzed. To substitute the sequential extraction by a sequence of single extractions and thus keep uncertainties of extraction on a low level, both procedures were compared regarding conformity of their results. The effects of sample handling as well as those of analysis on the measured metal contents were determined by means of analysis of variance and sources of uncertainties were discussed.

Speciation of nickel in airborne particulate matter by means of sequential extraction in a micro flow system and determination by graphite furnace atomic absorption spectrometry and inductively coupled plasma mass spectrometry.

A four-stage sequential extraction procedure for the speciation of nickel has been applied to ambient aerosol samples. The determination of the soluble, sulfidic, metallic and oxidic Ni fractions in particulate matter was carried out by graphite furnace (electrothermal) atomic absorption spectrometry (ETAAS) and inductively coupled plasma mass spectrometry (ICP-MS). An EDTA solution, a mixture of diammonium citrate and hydrogen peroxide, and a KCuCl3 solution were used as leaching agents for the determination of the soluble, sulfidic and metallic species, respectively, and nitric acid was used for the determination of oxidic compounds after microwave digestion of particulate matter sampled on filters. A new micro scale filter holder placed in a closed flow injection analysis (FIA) system for use in nickel speciation by means of sequential extraction, and the results of the optimisation of the extraction conditions are described. The temperature program for ETAAS was optimised for all extraction solutions with the aid of temperature curves. Pyrolysis temperatures of 900. 600 and 1,000 degrees C were found to be optimum for EDTA, hydrogen peroxide plus ammonium citrate and KCuCl3-containing solutions, respectively. Airborne dust was sampled on lilters at two locations near to a metallurgical plant in Dortmund, Germany. Concentrations in the low ng m(-3) range down to the detections limits (0.1-0.3 ng m(-3)) and various nickel species were found to be present in the collected dust. The mean fractions of total nickel (sampling period of one month) were found to contain 36+20% of soluble, 6 +/- 4% of sulfidic, 11 +/- 15% of metallic and 48 +/- 18% of oxidic nickel.

Metal phase associations in soils from an urban watershed, Honolulu, Hawaii

Soils of Manoa watershed, Hawaii, have received varying inputs of anthropogenic trace metals, with roadside soils primarily influenced by automobile contributions. A four-stage sequential extraction procedure was used to fractionate 13 topsoil (0–2.5 cm) and 13 subsoil (7.5–10.0 cm) samples into: (i) an adsorbed, exchangeable and carbonate (AEC) phase; (ii) a reducible phase; (iii) an oxidizable phase; and (iv) a residual phase. Phases (i)–(iii) were considered ‘labile’, with the residual fraction ‘non-labile’ under normal circumstances. An examination of eight elements (Al, Co, Cu, Fe, Mn, Ni, Pb and Zn) indicated that Pb was the trace metal most impacted by anthropogenic inputs. Roadside soil Pb enrichment was apparent with data from a 0.5 M HCl leach exhibiting a maximum concentration of 1000 mg/kg compared with a median background value of 12 mg/kg. Sequential extraction results indicated the following order with respect to phase dominance for Pb: reducible>residual>oxidizable>AEC. The identification of the reducible phase as the primary pool of available Pb supports previous work from temperate roadside soil environments. The reducible phase is characterized by hydrous Fe and Mn oxides and mobilization of fixed elements can occur with decreases in pH and redox potential. Iron was the least labile of the elements examined with only 5–6% of total Fe removed by the first three steps of the extraction procedure. Lead had the highest labile percentage with average values between 74 and 81%. Therefore, results from this study support earlier research in this watershed which identified Pb as the primary trace metal of concern from a contamination perspective.

Determination of heavy metals and their speciation in lake sediments by flame atomic absorption spectrometry after a four-stage sequential extraction procedure

A four-stage sequential extraction procedure for determination of the speciation of extractable heavy metals, proposed by the Commission of the European Communities Bureau of Reference (BCR) as a mean of comparison of data of extractable heavy metals, has been applied to lake sediments collected from the lakes of a water-laden area of Sultansazliǧi, Kayseri, Turkey. The determination of extractable heavy metals such as chromium, cobalt, nickel, copper, zinc, cadmium (below the detection limit), lead, manganese and iron in the sediment samples was carried out by flame atomic absorption spectrometry (FAAS) using an injection method. Acetic acid, hydroxyl ammonium chloride, hydrogen peroxide plus ammonium acetate, and aqua regia stages of the sequential extraction procedure were applied to the sediment samples, respectively. Recoveries were quantitative (≥ 95%). The accuracy, obtained by comparing the pseudo-total metal concentrations with the sum of the four extraction stages, was found to be satisfactory. The limit of detection for different elements was found to be between 0.04 and 0.69 μg ml −1 for the various extraction stages.