Total and “Selective” Extraction Methods for Trace Metals in Marine Sediment Reference Samples (Mess-1, NBS 1646)

Trace metals (Cd, Cr, Cu, Mn, Pb and Zn) and Fe were analyzed in two sediment reference samples (NBS 1646, MESS-1) with AAS fitted with graphite furnace, using five different (three total and two selective) extraction procedures.

The comparison of the total digestion methods (hot strong acids) with reference materials gave good results for almost all of them, and the “teflon bomb” was preferred for its rapidity and ease of operation. Some non-referenced data on total and organic carbon, total nitrogen and minerals are given. The two selective leaching extractions (nitric and cold hydrochloric) were also compared with reference values.

The use of certified reference materials (CRM) for environmental chemistry is recommended, together with the determination of organic matter and fundamental mineralogical composition.     

Heavy metals in soils and crops in Southeast Asia 2. Thailand

A reconnaissance soil geochemical and concomitant plant survey based on 318 soil (0-15 cm) and 122 plant samples was used for the assessment of heavy metal pollution of agricultural soils and crops of Thailand. Arsenic (As), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), mercury (Hg), nickel (Ni), lead (Pb) and zinc (Zn) were determined in soils using aqua regia digestion, and in plants using nitric acid digestion. Organic carbon (C), pH, electrical conductivity (EC) and available phosphorus (P) were determined on the soil samples using appropriate procedures. Results indicated that concentrations of heavy metals varied widely among the different regions of Thailand. Regression analysis between the concentrations of metals in soil (aqua regia extractable) and edible plant parts indicated a small but positive relationship for Cd in all the plants sampled in the survey (R2 = 0.081, p < 0.001). There was also a positive relationship between soil and plant Cd concentrations in rice (R2 = 0.242, p < 0.010), and negative relationships for Zn in rice (R2 = 0.385, p < 0.001), and Cu (R2 = 0.355, p < 0.001) and Zn (R2 = 0.122, p < 0.026) in glutinous rice. Principal component analysis of the soil data suggested that concentrations of As, Co, Cr, Cu, Hg, Ni and Pb were strongly correlated with concentrations of Al and Fe, which is suggestive of evidence of background variations due to changes in soil mineralogy. Thus, the evidence for widespread contamination of soils by these elements through agricultural activities is not strong. On the other hand, Cd and Zn were strongly correlated with organic matter and concentrations of available and aqua regia extractable P. This is attributed to input of contaminants in agricultural fertilisers and soil amendments (e.g. manures, composts).     

Evaluation of dilute hydrochloric acid and acid ammonium oxalate as extractants for some heavy metals from Nile River sediments

The suitability of a 0.5 M HCl solution for extraction of Fe, Mn, Cd, Co, Cu, Pb, and Zn from Nile River sediments was evaluated by comparing its effectiveness with that of conventional acid ammonium oxalate (Tamm's solution) and aqua regia extraction solutions. The present study has shown that although the extraction data indicate that both 0.5 M HCl and acid ammonium oxalate solutions are able to extract heavy metals simultaneously from the adsorbed, organic, and precipitated phases of Nile sediments, the 0.5 M HCl solution is preferred. It provides a rapid, reliable, and inexpensive method of measuring environmentally mobile metal concentrations in the aquatic sediments. From an analytical chemistry point of view, the 0.5 M HCl extracts do not clog the atomizer of the spectrophotometer. Extraction with dilute HCl solution obviates the need to use chemicals, some of which are toxic or not available readily as a high-purity grade. A standard extraction method should be relatively simple, to conduct a routine analysis of large numbers of sediment samples, yet at the same time it should provide sufficient information for assessment of the environmental impact of particulate metals. Therefore, extraction with 0.5 M HCl solution is very suitable for heavy-metal pollution monitoring in the Nile River     

Heavy Metals in Superficial Sediments from the Ligurian Sea, Italy

In this paper we are presenting the concentrations and the distributions of trace metals (Fe, Ni, Cr, Cu, Pb and Zn) in the coastal area of the Ligurian Sea between Capo Noli and Capo Mele. Fifty-six samples were subjected to textural, organic carbon and chemical analyses. Three different extraction methods were used: 1N NH₂OH.HCl plus 25% CH₃COOH, nitric acid solution, and total attack with HClO₄-HF mixture. The solutions were analysed by atomic absorption spectrophotometry. The results obtained confirm that the extraction methods which are most informative for environmental purposes are the cold or the easily extractable metal techniques. The results also show that for the study area the concentrations of Fe, Ni, Cr, Cu, Pb, and Zn do not indicate traces of anthropogenic inputs.     

Heavy Metals in Superficial Sediments from the Ligurian Sea,Italy

In this paper we are presenting the concentrations and the distributions of trace metals (Fe, Ni, Cr, Cu, Pb and Zn) in the coastal area of the Ligurian Sea between Capo Noli and Capo Mele. Fifty-six samples were subjected to textural, organic carbon and chemical analyses. Three different extraction methods were used: 1N NH₂OH.HCl plus 25% CH₃COOH, nitric acid solution, and total attack with HClO₄-HF mixture. The solutions were analysed by atomic absorption spectrophotometry. The results obtained confirm that the extraction methods which are most informative for environmental purposes are the cold or the easily extractable metal techniques. The results also show that for the study area the concentrations of Fe, Ni, Cr, Cu, Pb, and Zn do not indicate traces of anthropogenic inputs.     

Comparison of extraction methods for polycyclic aromatic hydrocarbon determination in sediments

Different sample preparation methods for the determination of polycyclic aromatic hydrocarbons (PAHs) in lake and river sediments were compared and evaluated. Freeze‐dried sediment materials were extracted using Soxhlet extraction, ultrasonic agitation and digestion with various solvents and solvent mixtures. Similarly, clean‐up methods using various types of sorbents for separation of PAHs tested.

The following method gives the best results for the determination of PAHs: freeze‐dried sediment samples were extracted using Soxhlet extractor with dichloromethane (6 hr, dark), extracts were cleanup using Silica gel and a mixture of n‐hexa‐ne‐dichloromethane was used for the elution of PAHs.

This method was used for the determination of 7 selected PAHs in sediment samples from Finnish lakes and Czech streams.     

Soil remediation using in situ immobilisation techniques

The main objective of this study was to investigate the efficiency of different substrates to reduce the extraction of heavy metals concentration in a heavily contaminated soil. Two contaminated soils by Cu and Zn were used to evaluate the effectiveness of eight substrates (calcium carbonate, bentonite, kaolinite, charcoal, manganese oxide, iron oxide, zeolite, phosphate) to reduce metal availability and to study the change of metals speciation in different forms using sequential extraction technique (single step). Sequential extraction technique (single step, 0.11 M acetic acid, HONH₃Cl, H₂O₂+NH₄OAc, Aqua regia) was applied on contaminated soils after and before treatment to evaluate metals speciation. Results indicate that the most effective treatments in decreasing available metal concentrations were calcium carbonate, zeolite and manganese or iron oxide. Metal sequential fractionations indicate that the exchangeable fraction of Cu and Zn in contaminated soils can be transformed into unavailable forms after chemical remediation.     

Modelling the concentrations of dissolved contaminants (Cd,Cu, Ni,Pb, Zn) in floodplain soils

Central European floodplain soils are often contaminated with potentially toxic metals. The prediction of their aqueous concentrations is a prerequisite for an assessment of environmental concerns. We tested the aqueous concentrations of cadmium (Cd), copper (Cu), nickel (Ni), lead (Pb) and zinc (Zn) derived from multi-surface adsorption modelling (on hydrous iron, aluminum and manganese oxides, clay and soil organic matter) against those analyzed in situ in the soil solution of four horizons of floodplain soils at the Elbe River, Germany. The input data for the reactive metals were derived from a seven-step sequential extraction scheme or from extraction with 0.43 M nitric acid (HNO₃) and evaluated in four modelling scenarios. In all scenarios, measured and modelled concentrations were positively related, except partially for Pb. Close reproduction of the measured data was obtained using measured data of accompanying cations and anions together with amounts of reactive metals from both the sequential extraction or from 0.43 M HNO₃ extraction, except for Cu, which was often strongly overestimated, and partially Cd. We recommend extraction with 0.43 M HNO₃ to quantify reactive metals in soil because the modelling results were metal-specific with better or equal results using the single extractant, the application of which is also less laborious. Approximations of ion concentrations and water contents yielded similar results. Modelled solid-phase speciation of metals varied with pH and differed from that from sequential extraction. Multi-surface modelling may be an effective tool to predict both aqueous concentrations and solid-phase speciation of metals in soil.     

Relative extraction ratio (RER) for arsenic and heavy metals in soils and tailings from various metal mines, Korea

This study focused on the evaluation of leaching behaviours for arsenic and heavy metals (Cd, Cu, Ni, Pb and Zn) in soils and tailings contaminated by mining activities. Ten representative mine soils were taken at four representative metal mines in Korea. To evaluate the leaching characteristics of the samples, eight extraction methods were adapted namely 0.1?M HCl, 0.5?M HCl, 1.0?M HCl, 3.0?M HCl, Korean Standard Leaching Procedure for waste materials (KSLP), Synthetic Precipitation Leaching Procedure (SPLP), Toxicity Characteristic Leaching Procedure (TCLP) and aqua regia extraction (AR) methods. In order to compare element concentrations as extraction methods, relative extraction ratios (RERs, %), defined as element concentration extracted by the individual leaching method divided by that extracted by aqua regia based on USEPA method 3050B, were calculated. Although the RER values can vary upon sample types and elements, they increase with increasing ionic strength of each extracting solution. Thus, the RER for arsenic and heavy metals in the samples increased in the order of KSLP?相似文献   

Der Mikrowellenaufschluss als richtungsweisendes Totalaufschlussverfahren in der geochemischen Analytik

Wet-chemical total digestion sample preparation is one of the most important geochemical analytical methods. This method is commonly used to dissolve rock, soil and mineral samples in order to determine element composition in a wide concentration range, ranging from minute traces to ten fold percentages. In the past common practices using hydrofluoric acid, hydrochloric acid, nitric acid and perchloric acid at high temperatures and pressure have been applied. These methods are however somewhat disadvantageous with the potential danger incurred in using acids and the associated time factor. At the Bavarian Geological Survey, a microwave digestion procedure has been developed thereby yielding similar results comparable with classical methodologies. Having optimised measurement conditions and adjusting the methodology (ICP-AES and ICP-MS), the results derived from the pressure digestion method in accordance with Ruppert [1] were compared with those from the aforementioned microwave digestion method. A common water analytical statistical analysis and evaluation was applied. The outcome shows that under such analytical conditions (e.g. detection limits) comparable results have been derived.     

Preconcentration of cadmium and copper ions on magnetic core–shell nanoparticles for determination by flame atomic absorption

Magnetic core–shell nanoparticles modified by (3-aminopropyl) trimethoxy silane were prepared and used as adsorbent for the extraction and preconcentration of cadmium and copper ions. The ions were desorbed with nitric acid followed by determination with flame atomic absorption spectrometry. The extraction conditions were investigated systematically. The method was applied for the determination of Cd(II) and Cu(II) ions in different water samples. The accuracy was also evaluated through analysis of certified reference material.     

Trace elemental characterization of fly ash

The purpose of this study was to determine heavy metal concentrations in ash samples taken from the filter of the gas cleaning system of biomass incinerators in Austria. Knowing the concentrations of heavy metals is important for the decision of further treatment or utilization of the ashes. The heavy metals contained in the ashes remain in the bottom ash of the incinerator or leave the incinerator with the off-gas and are collected in the off-gas filter. The amount of the metals in the collected fly ash depends on the composition of the input material. The aim of this study was to examine this influence and compare the results with literature data. For measurement, the fly ash samples were at first dissolved in a microwave digestion unit using nitric acid and hydrochloric acid. Afterwards, 20 metals were analyzed by inductively coupled plasma optical emission spectrometry. Al, Fe, Mg, Mn, and Zn were found in higher concentrations in the fly ash samples. The enrichment factor between the concentrations in the fly ash and the concentrations in the input material was on average in the range of 18.     

Biosorbents for solid-phase extraction of toxic elements in waters

Some trace metals are highly toxic for the environment. There is therefore a need for reliable methods for the determination of metals at trace levels. To this end, new sample pretreatment methods such as separation, preconcentration and speciation prior to the determination of metal ions have developed rapidly. Biosorption has become a major tool for solid-phase extraction methods. This review covers selected biosorbents such as algae, bacteria, filamentous fungi and yeasts, as new sorbents used in the solid-phase extraction of metal ions from various water sample matrices. A survey of the literature over 2004-2014 shows possible applications of selected new sorbents available for use in trace metal analysis in waters using solidphase extraction. We highlight the preconcentration of the toxic elements prior to their determination by atomic spectrometry.     

Heavy metals in soils and crops in Southeast Asia

In a reconnaisance soil geochemical and plant survey undertaken to study the heavy metal uptake by major food crops in Malaysia, 241 soils were analysed for cation exchange capacity (CEC), organic carbon (C), pH, electrical conductivity (EC) and available phosphorus (P) using appropriate procedures. These soils were also analysed for arsenic (As), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), mercury (Hg), nickel (Ni), lead (Pb) and zinc (Zn) using aqua regia digestion, together with 180 plant samples using nitric acid digestion. Regression analysis between the edible plant part and aqua regia soluble soil As, Cd, Cr, Cu, Hg, Ni, Pb and Zn concentrations sampled throughout Peninsular Malaysia, indicated a positive relationship for Pb in all the plants sampled in the survey (R2 = 0.195, p < 0.001), for Ni in corn (R2 = 0.649, p < 0.005), for Cu in chili (R2 = 0.344, p < 0.010) and for Zn in chili (R2 = 0.501, p < 0.001). Principal component analysis of the soil data suggested that concentrations of Co, Ni, Pb and Zn were strongly correlated with concentrations of Al and Fe, which is suggestive of evidence of background variations due to changes in soil mineralogy. Thus the evidence for widespread contamination of soils by these elements through agricultural activities is not strong. Chromium was correlated with soil pH and EC, Na, S, and Ca while Hg was not correlated with any of these components, suggesting diffuse pollution by aerial deposition. However As, Cd, Cu were strongly associated with organic matter and available and aqua regia soluble soil P, which we attribute to inputs in agricultural fertilisers and soil organic amendments (e.g. manures, composts).     

Relative extraction ratio (RER) for arsenic and heavy metals in soils and tailings from various metal mines,Korea

This study focused on the evaluation of leaching behaviours for arsenic and heavy metals (Cd, Cu, Ni, Pb and Zn) in soils and tailings contaminated by mining activities. Ten representative mine soils were taken at four representative metal mines in Korea. To evaluate the leaching characteristics of the samples, eight extraction methods were adapted namely 0.1 M HCl, 0.5 M HCl, 1.0 M HCl, 3.0 M HCl, Korean Standard Leaching Procedure for waste materials (KSLP), Synthetic Precipitation Leaching Procedure (SPLP), Toxicity Characteristic Leaching Procedure (TCLP) and aqua regia extraction (AR) methods. In order to compare element concentrations as extraction methods, relative extraction ratios (RERs, %), defined as element concentration extracted by the individual leaching method divided by that extracted by aqua regia based on USEPA method 3050B, were calculated. Although the RER values can vary upon sample types and elements, they increase with increasing ionic strength of each extracting solution. Thus, the RER for arsenic and heavy metals in the samples increased in the order of KSLP < SPLP < TCLP < 0.1 M HCl < 0.5 M HCl < 1.0 M HCl < 3.0 M HCl. In the same extraction method, the RER values for Cd and Zn were relatively higher than those for As, Cu, Ni and Pb. This may be due to differences in geochemical behaviour of each element, namely high solubility of Cd and Zn and low solubility of As, Cu, Ni and Pb in surface environment. Thus, the extraction results can give important information on the degree and extent of arsenic and heavy metal dispersion in the surface environment.     

Fractionation of heavy metals in surface sediments of Taihu Lake, East China

The BCR (European Communities Bureau of Reference) three-step sequential extraction procedure was applied to fractionate heavy metals in the sediment of Taihu Lake. For the determination of total metal concentration of the sediments, sample digestion was achieved by using HF/H2O2/HNO3 (2/1/1) acid mixture in a microwave-irradiated closed vessel system. The concentrations of Cd, Ni, Cr, Zn, Cu and Pb in various extracts solutions were analyzed by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES). The results obtained from the BCR three-step sequential extraction indicated relatively high mobility of Zn, Cu, Pb and Ni in the sediments while Cd and Cr were poorly mobile. Enrichment of heavy metals was found in the sediments collected in the northern parts of Taihu Lake. In the sediments collected in the southern and western sides of the Lake, heavy metal concentrations were relatively low. The relationship between total organic carbon (TOC) and heavy metals concentrations in the sediments is discussed.     

The investigation of metal concentrations in street dust samples in Aqaba city,Jordan

The concentrations of metals (Fe, Zn, Cu, Cr, Pb, Cd, Ni, Mn and Co) in 140 street dust samples were collected from Aqaba city, Jordan. These samples were determined using flame atomic absorption spectrophotometry after digestion with aqua regia. The highest levels of metal concentrations were found in the samples from heavy traffic. While the lowest levels of metal ions were noted in the street dust samples from hospital and health centers and school gardens. The results of this study were compared with several cities around the world. The levels of the metal concentrations found were generally below the mean world-wide values of street dust samples. Metal values in urban street dust samples were several times higher than the control levels. The statistical analyses were applied to the data matrix to determine the analytical results and to identify the possible source of pollution in the studied area. Correlations between the metal concentrations of the street dust samples were obtained. Factor analysis showed that the area was mainly influenced by three sources, namely lithogenic, traffic, and industrial.     

Modified pretreatment method for total microbial DNA extraction from contaminated river sediment

Extraction of high-quality microbial DNA from contaminated environmental samples is an essential step in microbial ecological study. Based on previously published methods for soil and sediment samples, a modified pretreatment method was developed for extracting microbial DNA from heavily contaminated river sediment samples via selection of optimal pretreatment parameters (i.e., reagent solution, reaction duration, and temperature). The pretreatment procedure involves washing the river sediment sample for three times with a solution containing 0.1 mol·L^-1 ethylene diamine tetraacetic acid (EDTA), 0.1 mol·L^-1 Tris (pH 8.0), 1.5 mol·L^-1 NaCl, 0.1 mol·L^-1 NaH₂PO₄, and Na₂HPO₄ at 65°C with 180 r·min^-1 for 15 min to remove humic materials and heavy metals prior to the employment of standard DNA extraction procedures. We compared the results of standard procedure DNA extraction following pretreatment, without pretreatment, and with using a commercial PowerSoil^TM DNA Isolation Kit. The results indicated that the pretreatment significantly improved the DNA quality based on DNA yield, DNA fragment length, and determination of prokaryotic diversity. Prokaryotic diversity exhibited in the DNA with the pretreatment was also considerably higher than that extracted with the PowerSoil^TM DNA Isolation Kit only. The pretreatment method worked well even with a small amount of sediment sample (0.25 g or even lower). The method provides a novel, simple, cost-effective tool for DNA extraction for microbial community analysis in environmental monitoring and remediation processes.     

Fractionation of Heavy Metals in Surface Sediments of Taihu Lake, East China

The BCR (European Communities Bureau of Reference) three-step sequential extraction procedure was applied to fractionate heavy metals in the sediment of Taihu Lake. For the determination of total metal concentration of the sediments, sample digestion was achieved by using HF/H₂O₂/HNO₃(2/1/1) acid mixture in a microwave-irradiated closed vessel system. The concentrations of Cd, Ni, Cr, Zn, Cu and Pb in various extracts solutions were analyzed by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES). The results obtained from the BCR three-step sequential extraction indicated relatively high mobility of Zn, Cu, Pb and Ni in the sediments while Cd and Cr were poorly mobile. Enrichment of heavy metals was found in the sediments collected in the northern parts of Taihu Lake. In the sediments collected in the southern and western sides of the Lake, heavy metal concentrations were relatively low. The relationship between total organic carbon (TOC) and heavy metals concentrations in the sediments is discussed.     

Stabilization of the As-contaminated soil from the metal mining areas in Korea

The stabilization efficiencies of arsenic (As) in contaminated soil were evaluated using various additives such as limestone, steel mill slag, granular ferric hydroxide (GFH), and mine sludge collected from an acid mine drainage treatment system. The soil samples were collected from the Chungyang area, where abandoned Au-Ag mines are located. Toxicity characteristic leaching procedure, synthetic precipitation leaching procedure, sequential extraction analysis, aqua regia digestion, cation exchange capacity, loss on ignition, and particle size distribution were conducted to assess the physical and chemical characteristics of highly arsenic-contaminated soils. The total concentrations of arsenic in the Chungyang area soil ranged up to 145 mg/kg. After the stabilization tests, the removal percentages of dissolved As(III) and As(V) were found to differ from the additives employed. Approximately 80 and 40% of the As(V) and As(III), respectively, were removed with the use of steel mill slag. The addition of limestone had a lesser effect on the removal of arsenic from solution. However, more than 99% of arsenic was removed from solution within 24 h when using GFH and mine sludge, with similar results observed when the contaminated soils were stabilized using GFH and mine sludge. These results suggested that GFH and mine sludge may play a significant role on the arsenic stabilization. Moreover, this result showed that mine sludge can be used as a suitable additive for the stabilization of arsenic.