An appraisal of microwave-assisted Tessier and BCR sequential extraction methods for the analysis of metals in sediments and soils

Purpose  

The purpose of this research was to assess the precision and accuracy of a BCR and Tessier microwave-assisted sequential extraction procedure, in comparison to the conventional versions for a range of metals using a soil, lake and estuarine certified reference material (CRM).     

Effects of trace elements on urease activity in soils

Disposal of sewage sludges and effluents on agricultural land is becoming a widespread practice. Most sludge samples disposed on soils contain large quantities of various trace elements. Studies of 20 trace elements commonly found in sludge samples showed that they inhibit the activity of urease in soils and that their order of effectiveness as inhibitors of urease depends on the soil. When the trace elements were compared by using 5 μmiol·g^?1 soil, however, some of them showed the same order of effectiveness as urease inhibitors in the six soils studied i.e., for the monovalent and divalent ions, Ag⁺ ≥ Hg²⁺ >Cu²⁺ >Cd²⁺ >Zn²⁺ >Sn²⁺ >Mn²⁺, and generally, Fe²⁺ >Fe²⁺andCu²⁺ >Cu⁺. Other trace element ions that inhibited urease were Ni²⁺, Co²⁺, Pb²⁺, Ba²⁺, As³⁺ B³⁺, Cr³⁺, Al³⁺. V⁴⁺ Se⁴⁺ and Mo⁶⁺. Of the trace element ions studied, only As⁵⁺ and W⁶⁺ did not inhibit urease activity in soils.Studies on the distribution of urease activity showed that it is concentrated in surface soils and decreases with depth. Urease activity was proportional to organic C distribution in each soil profile and was significantly correlated with organic C in the surface soils studied.     

Extractability of major and trace elements from agricultural soils using chemical extraction methods: Application for phytoavailability assessment

Abstract

To assess soil-to-plant transfer of various elements more precisely, the concentrations of the elements extracted from soil samples using eight chemical solutions were compared with the results of a pot cultivation experiment of komatsuna (Brassica rapa L. var. perviridis) or buckwheat (Fagopyrum esculentum M.) using the soils. From agricultural fields in Aomori, Japan, 16 soil samples were collected. Elements in the samples were extracted using acids (1 mol L^?1 HNO₃, 0.1 mol L^?1 HNO₃, 0.01 mol L^?1 HNO₃), chelating agents (0.05 mol L^?1 EDTA), neutral salt solutions (1 mol L^?1 NH₄OAc, 1 mol L^?1 NH₄NO₃, 0.01 mol L^?1 CaCl₂) and pure water. The 28 elements in the extracted solutions and plant samples were determined. The extractability of many metals was higher in 1 mol L^?1 HNO₃, 0.1 mol L^?1 HNO₃ and the 0.05 mol L^?1 EDTA solutions than in the other extractants. Higher extractability using the NH₄OAc solution than the NH₄NO₃ solution was observed for some elements, in particular U. Extractability by pure water was not always lowest among these methods, probably because of dispersion of colloidal substances in the extracted solution. The pot cultivation experiment showed that the concentrations in soil and in the extracted fraction using 1 mol L^?1 HNO₃, 0.1 mol L^?1 HNO₃ or the EDTA solution did not correlate with the concentration in plant samples for most elements. Plant uptake of Zn, Y and La by komatsuna correlated well with their concentrations in extracts with neutral salt solutions or 0.01 mol L^?1 HNO₃. Concentrations of Al, Cu and Cd in buckwheat were also correlated with the concentrations in the extracts.     

Background levels of trace and ultra-trace elements in soils of Japan

Five hundred and fourteen soil samples collected from 78 sites in Japan were analyzed for their contents of trace and ultra-trace elements. We estimated the background levels (natural abundance) of 57 elements in soils. The concentration ranges were so wide that the ratios of the highest values to the lowest values were more than 100 for all the elements, with the exception of Be, Ga, Mo, Ag, In, Sn, and Ba. While the concentrations of the first transition elements (₂₁Sc to ₃₀Zn in atomic numbers) were higher than the concentration of the other elements, those of lighter (₃Li and ₄Be) and heavier elements tended to decrease, with an increase or decrease of atomic numbers, with the apparent exception of Pb, Th, and U. Concentrations of elements with even atomic numbers were, in most of the cases, higher than the concentrations of both adjacent elements with odd atomic numbers. Frequency distribution of most of the elements was strongly positively skewed. Markedly positive correlation coefficients (r>0.9) were observed among the elements within the same group in the Periodic Table in many combinations. The dendrogram obtained by cluster analysis showed that the occurrence and distribution of the elements in soils were mostly controlled by the chemical properties of each element, rather than by the nature and properties of individual soil samples. The total contents of the elements in soils were strongly dependent on the chemical composition of the parent rocks from which respective soils were derived.     

Assessment of a sequential extraction procedure for fractionation of soil arsenic in contaminated soils

A sequential fractionation scheme, based on a soil phosphorous fractionation, was developed to assess the chemical nature, and thus the potential bioavailability and mobility of As, at the sites. Soil As was separated into five fractions with (i) anion exchange resin, (ii) NaHCO₃, (iii) NaOH, (iv) HCl, (v) residual. Most sites contained relatively low concentrations of As in the two most labile fractions. The bulk of the contaminant As at the sites seemed to be associated with soil amorphous Fe and Al minerals and the dominant clay minerals which help in As sorption are montmorillonite and mica. Resin-extractable As in particular might provide a good index of potential As bioavailability and mobility.     

评估土壤微量元素生物有效性测定方法

Trace element-contaminated soils (TECSs) are one of the consequences of the past industrial development worldwide.Excessive exposure to trace elements (TEs) represents a permanent threat to ecosystems and humans worldwide owing to the capacity of metal(loid)s to cross the cell membranes of living organisms and of human epithelia,and their interference with cell metabolism.Quantification of TE bioavailability in soils is complicated due to the polyphasic and reactive nature of soil constituents.To unravel critical factors controlling soil TE bioavailability and to quantify the ecological toxicity of TECSs,TEs are pivotal for evaluating excessive exposure or deficiencies and controlling the ecological risks.While current knowledge on TE bioavailability and related cumulative consequences is growing,the lack of an integrated use of this concept still hinders its utilization for a more holistic view of ecosystem vulnerability and risks for human health.Bioavailability is not generally included in models for decision making in the appraisal of TECS remediation options.In this review we describe the methods for determining the TE bioavailability and technological developments,gaps in current knowledge,and research needed to better understand how TE bioavailability can be controlled by sustainable TECS management altering key chemical properties,which would allow policy decisions for environmental protection and risk management.     

Evaluation of a sequential extraction procedure for the fractionation of thallium in soils and determination of the content by flame atomic absorption spectrometry

Abstract

The release of carbonyl sulfide (COS) from 7 unamended paddy soils was estimated under aerobic and waterlogged conditions. The addition of organic materials to the soils increased the amount of COS evolved under waterlogged conditions. To assess the sources of the COS released from the soils, the soils were incubated under aerobic and waterlogged conditions after treatment with 17 inorganic or organic S-containing compounds. It was concluded that the following compounds represented sources of the COS released from the paddy soils: cystine, cysteine, thiocyanate, lanthionine and djenkolic acid.     

Evaluation of gas diffusivity models for no-tilled and tilled volcanic ash soils

Accurate quantification of soil gas diffusion is essential to understand the gas transport mechanism in soils, especially for soil greenhouse gas emissions. To date, the performance of soil gas diffusivity (D_p/D₀, where D_p is the soil gas diffusion coefficient and D₀ is the diffusion coefficient in free air) models has seldom been evaluated for no-tilled and tilled volcanic ash soils. In the present study, six commonly used models were evaluated for volcanic ash soils under two treatments by comparing the predicted and measured soil gas diffusivities at water potentials of pF 1.3–3. The Buckingham-Burdine-Campbell (BBC), soil-water-characteristic-dependent (SWC-dependent), and two-region extended Archie’s Law (2EAL) models showed better performance for both no-tilled and tilled volcanic ash soils, which is likely because porosity and pore size parameters of bimodal soils were taken into consideration in these models. Since the BBC model showed better accuracy than the SWC-dependent and 2EAL models and required fewer, more easily measurable parameters, this study recommends the BBC model for predicting soil gas diffusivity of volcanic ash soil under different tillage managements. In future studies, the BBC model should be further tested at water potentials of pF > 3, and may be improved by including the parameters of pore continuity and saturation.     

Level of trace elements in Pteridophytes growing on serpentine and metalliferous soils

A screening of Pteridophytes growing on serpentine and metalliferous soils in Northern Italy was carried out to assess the ability of these plants to tolerate or accumulate trace elements of toxicological interest. Few data are available on metal tolerance/accumulation of terrestrial ferns growing in the Mediterranean region, and several species presented here have never been investigated for this purpose. The trace‐element composition (As, Cd, Cr, Cu, Fe, Ni, Pb, Zn) and P content of aerial parts of plants (12 fern and 2 horsetail species) and of their associated soils were measured. An analysis of the relationship between element concentrations in soil and in shoot revealed a significant correlation only for Zn (p < 0.05). Hierarchical cluster analysis based on element concentrations in plant aerial parts showed two outliers, viz. Equisetum ramosissimum Desf., showing the highest levels of Cr, Fe, Cu, Ni, and As, and Nephrolepis cordifolia C. Presl., showing the highest Pb value. The bioaccumulation factor exceeded 1 only for Cd in two species, Athyrium filix‐femina and Dryopteris filix‐mas. However, also in these cases the corresponding values of the metal in the shoots were below the thresholds for hyperaccumulators. The examined Pteridophytes seem to have developed their adaptation prevalently through mechanisms of tolerance based on metal exclusion. None of these plant species seem suitable for phytoextraction, but N. cordifolia, Pteridium aquilinum ssp. aquilinum, and E. ramosissimum have potential to be used for stabilization and restoration of soils rich in heavy metals.     

Regional clarkes of chemical elements in soils of southern European Russia

Distribution patterns of 19 elements in soils of the southern part of European Russian were estimated on the basis of the analysis of more than 9000 soil samples; regional clarkes of the elements were compared with their global clarkes, The obtained data attest to the fact that southern Russia is characterized by increased concentrations of most of the microelements with a tendency for their rise in the recent decades. The great role of the aerial migration and deposition of elements results in the enrichment of the soils with technophilic elements, so that the geochemical convergence of the soils is observed. It can be concluded that natural element abundances in soils are subjected to the technogenic transformation reflecting the high rate of contamination of the biosphere.     

Proposal for advanced classification of brown forest soils in Japan with reference to the degree of volcanic ash additions

Abstract

The advanced classification of brown forest soils (BFS) is based on the specific properties of these soils, including the acid ammonium oxalate extractable aluminum (Al_ox) and lithic fragment contents, as well as their vertical distributions in the soil profile. In the present study, these properties were used to classify BFS, resulting in four types: (1) H-Al_ox-NGv BFS, (2) H-Al_ox-Gv BFS, (3) M-Al_ox BFS, (4) L-Al_ox BFS. H-Al_ox-NGv BFS is derived from volcanic ash characterized by a high Al_ox content and no lithic fragment, whereas L-Al_ox BFS is derived from weathered bedrock and has a low Al_ox content. H-Al_ox-Gv BFS and M-Al_ox BFS are derived from mixtures of volcanic ash and weathered bedrock. H-Al_ox-Gv BFS is characterized by high Al_ox content and many lithic fragments, whereas M-Al_ox BFS has moderate Al_ox content. H-Al_ox-NGv BFS and black soils (BLS) develop from accumulated volcanic ash, as indicated by declining Al_ox and clay content with decreasing depth in the surface horizons, as a result of successive additions of less-weathered volcanic ash to the soil surface.     

Use of the BCR three-step sequential extraction procedure for the study of the partitioning of Cd, Pb and Zn in various soil samples

A slightly modified three-step sequential extraction procedure proposed by the Community Bureau of Reference (BCR) for analysis of sediments was successfully applied to soil samples. Contaminated soil samples from the lead and zinc mining area in the Mezica valley (Slovenia) and natural soils from a non-industrial area were analysed. The total concentrations of Cd, Pb and Zn and their concentrations in fractions after extraction were determined by flame or electrothermal atomic absorption spectrometry (FAAS, ETAAS). Total metal concentrations in natural soils ranged from 0.3 to 2.6 mg kg^-1 for Cd, from 20 to 45 mg kg^-1 for Pb and from 70 to 140 mg kg^-1 for Zn, while these concentrations ranged from 0.5 to 35 mg kg^-1 for Cd, from 200 to 10000 mg kg^-1 for Pb and from 140 to 1500 mg kg^-1 for Zn in soils from contaminated areas. The results of the partitioning study applying the slightly modified BCR three-step extraction procedure indicate that Cd, Pb and Zn in natural soils prevails mostly in sparingly soluble fractions. Cd in natural soils is bound mainly to Fe and Mn oxides and hydroxides, Pb to organic matter, sulphides and silicates, while Zn is predominantly bound to silicates. In contaminated soils, Cd, Pb and Zn are distributed between the easily and sparingly soluble fractions. Due to the high total Cd, Pb and Zn concentrations in contaminated soil close to the smelter, ! and their high proportions in the easily soluble fraction (80% of Cd, 50% of Pb and 70% of Zn), the soil around smelters represents an environmental hazard.     

Selective sequential dissolution techniques for trace metals in arid‐zone soils: The carbonate dissolution step

Abstract

Dissolution capacity and kinetics of carbonates by sodium acetate (NaOAc)‐acetic acid (HOAc) at various pHs were studied. A comparative study of the selectivity, specificity, and effectivity of NaOAc‐HOAc solution on carbonate bound fraction during the sequential selective dissolution procedure was conducted by comparing the dissolution of major and trace elements from arid zone soils by this buffer solution at various pHs. The effect of the pH of NaOAc‐HOAc solution on the following fractions in the sequential selective dissolution procedure was also studied. NaOAc‐HOAc solution at pH 5.5 at a soil to solution ratio of 1:25, can dissolve all the carbonate from calcareous soils with 10–20% of carbonate; at pH 5.0 it can dissolve all the carbonate in soils with about 30–50% calcium carbonate (CaCO₃). A second extraction with fresh buffer solution at pH 5.0 is required for soils with more than 50% of carbonate. Six hours of extraction time is generally sufficient for complete carbonate dissolution. For most of agricultural soils in arid and semi‐arid zones, the attack of the buffer solution at pH 5.0 on other solid‐phases seems to be limited. But the buffer solution at pH 5.5 would be better for some forest soils with low carbonate content and high organic matter content. The part of carbonate fraction not be dissolved in this step is released in the following steps: easily reducible oxides fraction (ERO), organic matter fraction (OM), and reducible oxides fraction (RO), leading to gross misinterpretation of the elemental partitioning in arid zone soils.     

从高山火山灰中提取铝, 铁和有机碳的可供选择的方法

Montane volcanic ash soils contain disproportionate amounts of soil organic carbon and thereby play an often underestimated role in the global carbon cycle.Given the central role of Al and Fe in stabilizing organic matter in volcanic ash soils,we assessed various extraction methods of Al,Fe,and C fractions from montane volcanic ash soils in northern Ecuador,aiming at elucidating the role of Al and Fe in stabilizing soil organic matter(SOM).We found extractions with cold sodium hydroxide,ammonium oxalate/oxalic acid,sodium pyrophosphate,and sodium tetraborate to be particularly useful.Combination of these methods yielded information about the role of the mineral phase in stabilizing organic matter and the differences in type and degree of complexation of organic matter with Al and Fe in the various horizons and soil profiles.Sodium tetraborate extraction proved the only soft extraction method that yielded simultaneous information about the Al,Fe,and C fractions extracted.It also appeared to differentiate between SOM fractions of different stability.The fractions of copper chloride-and potassium chloride-extractable Al were useful in assessing the total reactive and toxic Al fractions,respectively.The classical subdivision of organic matter into humic acids,fulvic acids,and humin added little useful information.The use of fulvic acids as a proxy for mobile organic matter as done in several model-based approaches seems invalid in the soils studied.     

Field and chemical Evaluation of volcanic ash deposition in some soils of Malaysia

A study was conducted to determine the extend of volcanic ash deposition and distribution in some soils of Malaysia. A total of 12 soil types of different geology and locations from Peninsular Malaysia and West Sarawak were collected and analysed for their physico‐chemical and dissolution analysis. All soils under study belonged to either the order of Inceptisols, Ultisols or Oxisol. They were acidic and had relatively low CEC and exchangeable bases. The Al saturation percent were higher in the Ultisols as compared to the Oxisols. Field and laboratory investigations, and the dissolution analysis comprising of the binary ratio, ferrihydrite percent and allophane content, suggested that the soils under study were highly weathered and non‐allophanic. The soils of West Sarawak, however, may contain a reasonable deposits of the volcanic ash materials, as shown by the higher pH_NaF values of near 9.4, but other laboratory analysis were still not conclusive of the result.     

Evaluation of p as a limiting macronutrient in volcanic ash soils of guatemala

Abstract

P status of soils derived from volcanic ash in Guatemala was investigated. Growth chamber and greenhouse studies were conducted with H‐3 hybrid corn (Zea mays). All plants exhibited P deficiency symptoms and yielded less dry matter when they were grown on soils that received only lime at a rate equivalent to 2,240 and 4,480 kg/ha. The P content of plants was low and correlated with P deficiency symptoms. Application of P (336 and 672 kg/ha) under constant liming corrected the P deficiencies and increased dry matter. In comparative studies, plants grown on a highly fertile, non‐volcanic soil showed vigorous growth and yielded high dry matter. Apparently, P was limiting productivity in volcanic ash soils of Guatemala, and due to low exchangeable Al, addition of only lime did not produce beneficial results. The soils responded to P fertilization and they should be supplied large quantities of this macronutrient.     

Enrichment of trace elements from long-range aerosol transport in sandy podzolic soils of southwest France

Total content of trace elements (Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn), was determined to a depth of about 1 m in the horizons of three representative podzolic soils (i.e., wet moor, dry moor, and dune soil) developed on the coarse sands of the Atlantic face of southwest France. In the aged soils (wet moor and dry moor), Cr, Cu, Ni, Pb and Zn, were highly concentrated in the B horizons whereas Cd accumulated in the litter. An estimate of metal balance was made in the soil profiles, comparing the total amount of metal recovered in the A-B horizons to the amount of indigenous metal determined in a rock matter (C) layer of a similar depth as the A-B horizons. Substantial long-term enrichment of the whole upper part of the profile (A-B horizons) of three representative sites was found for Cd (0.1–0.6 kg ha^?1), Cu (3–12 kg ha^?1), Ni (1–7 kg ha^?1), Pb (20–26 kg ha^?1), and, to a lesser extent, for Co, Mn, and Zn. Since the experimental site was remote from industrial, urban and agricultural activities, the increase in soil metal content was apparently caused by the deposition of metallic aerosols via long-range transport. Total long-term inputs are estimated for average values of Cd (0.6 kg ha^?1), Cr (5 kg ha^?1), Cu (12 kg ha^?1), Ni (7 kg ha^?1), Pb (25 kg ha^?1) and Zn (6 kg ha^?1) for the 1 m depth. Several Atlantic areas of Europe are probably affected by a similar metal input.