NH4NO3 extractable trace element contents of soil samples prepared for proficiency testing – a stability study

In view of its intended use as a sample for proficiency testing or as a reference material the stability of the extractable trace element contents of a soil from an irrigation field was tested using the extraction with 1 mol/L ammonium nitrate solution according to DIN 19730. Therefore, changes of the extractability of sterilized and non sterilized soil samples stored at different temperatures were evaluated over a period of 18 months. Sets of bottles were kept at –20?°C, +4?°C, about +20?°C and +40?°C, respectively. The NH₄NO₃ extractable contents of Cd, Cr, Cu, Ni, Pb and Zn were determined immediately after bottling and then after 3, 6, 12 and 18 months with ICP-AES or ETAAS. Appropriate storage conditions are of utmost importance to prevent deterioration of soil samples prepared for the determination of NH₄NO₃ extractable trace element contents. Temperatures above +20?°C must be avoided. The observed changes in the extractability of the metals (especially for Cr and Cu) most likely could be related to thermal degradation of the organic matter of the soil. There is no need to sterilize dry soil samples, because microbiological activity in soils with a low moisture content appears to be negligible with regard to trace element mobilization.     

A study of the direct determination of Cd, Cr, Cu, Pb and Zn in certified reference materials of soils by solid sampling electrothermal atomic absorption spectrometry

A simple and rapid method for the direct determination of Cd, Cr, Cu, Pb and Zn in soil was developed. The method was developed using three certified reference materials of soil: Eutric Cambisol, Orthic Luvisols and Rendzina, which differed in their matrix composition. Chemical modifiers were essential to achieve reproducible and interference-free signals for the analytes studied. The best results were obtained with a Pd/Mg(NO₃)₂ admixture for the determination of Cd, Pb and Zn and NH₄F for Cu. The combination of W (as a permanent modifier) and Mg(NO₃)₂ provided well-defined signal profiles for Cr. The following spectral lines were used: Cd 228.8 nm, Cr 520.6 nm, Cu 218.2 nm, Pb 205.3 nm and Zn 307.6 nm. The limit of detection was 4.2 ng g^− 1 for Cd, 1.1 μg g^− 1 for Cr, 0.5 μg g^− 1 for Cu, 1.3 μg g^− 1 for Pb and 8.6 μg g^− 1 for Zn for the maximum sample mass used. Under optimized conditions, the analyte and matrix were separated effectively in situ, and aqueous standards could be used for calibration.     

Statistical Evaluation of Bioavailability of Metals to Grapes Growing in Contaminated Vineyard Soils using Single Extractants

This article describes the statistical evaluation of concentrations of Cd, Co, Cr, Cu, Fe, Mn. Ni, Pb. Zn, Ca. and Mg metals determined in twenty-two grape and corresponding soil samples from around a zinc smelter in Kayseri. Turkey. In the analyses of soil samples. three different extraetants. 0.1 M HCl in 0.025 M H₂SO₄, 1 M NH₄OAc, and aqua regia (1HNO₃ + 3HCl), were used to extract and determine the leachable metal contents which are acid soluble, exchangeable, and total. respectively. A mixture of HNO₃ and HCIO₄ was used to dissolve grape samples. The determinations of metals were performed by flame atomic absorption spectrometry (FAAS). The analytical data were evaluated by using principal component analysis (PCA). hierarchial cluster analysis (HCA), correlation analysis (CA), and enrichment factors (EF). The relationship between the grapemetal and soil-extractable-metal concentrations was examined to evaluate the bioavailability of metals in soil to grape samples. As a consequence of statistical evaluations. Cd, Pb, Zn. Mn. and Fe labile levels in soil were related to total grape-metal contents indicating the method’s suitability for bioavailability studies in polluted soil–plant systems.     

Assessment of single extractions for the determination of mobile forms of metals in highly polluted soils and sediments--analytical and thermodynamic approaches

Highly polluted forest/tilled soils and stream sediments from a mining and smelting area were subjected to single-extraction procedures to determine the extractable contents of Cd, Cu, Pb, and Zn. The results obtained from four widely used operationally defined single extraction tests were compared: deionised water, 0.01 mol L⁻¹ CaCl₂, 1 mol L⁻¹ NH₄NO₃ and 0.005 mol L⁻¹ DTPA. The analytical data were coupled with measurement of the pH and Eh in extracts, mineralogical investigations and thermodynamic modelling using the PHREEQC-2 code. The changes in the pH of the equilibrated suspensions significantly influenced the metal extractabilities, with higher values in the lower pH regions. Although the DTPA procedure generally extracted the highest amounts of metals, it was found to be unsuitable for highly organic acidic forest soils, where anionic metal-DTPA complexes are assumed to be re-adsorbed on the positively charged surfaces of soil organic matter and oxides. The NH₄NO₃ extraction was also unsuitable due to the high ionic strength (1 mol L⁻¹), limiting the use of the thermodynamic speciation model and the formation of the Cu(NH₃)²⁺ complex, leading to acidification of the suspension. 0.01 mol L⁻¹ CaCl₂ can be proposed as the most appropriate extraction medium, suitable for speciation modelling and analytical determinations using ICP-techniques and having an ionic strength similar to that of the soil solution. The metals are present in free ionic forms or chlorocomplexes in the CaCl₂ extracts, preventing their re-adsorption on the positively charged surfaces of soil solids (organic matter, Fe- and Mn-oxides) in acidic and circum-neutral conditions.     

Determination of cadmium, copper and lead in soils, sediments and sea water samples by ETAAS using a Sc + Pd + NH(4)NO(3) chemical modifier

Cadmium, copper and lead in soils, sediments and spiked sea water samples have been determined by electrothermal atomic absorption spectrometry (ETAAS) with Zeeman effect background corrector using NH₄NO₃, Sc, Pd, Sc + NH₄NO₃, Pd + NH₄NO₃, Sc + Pd and Sc + Pd + NH₄NO₃ as chemical modifiers. A comprehensive comparison was made among the modifiers and without modifier in terms of pyrolysis and atomization temperatures, atomization and background absorption profiles, characteristic masses, detection limits and accuracy of the determinations. Sc + Pd + NH₄NO₃ modifier mixture was found to be preferable for the determination of analytes in soil and sediment certified and standard reference materials, and sea water samples because it increased the pyrolysis temperature up to 900 °C for Cd, 1350 °C for Cu and 1300 °C for Pb. Optimum masses of mixed modifier components found are 20 μg Sc + 4 μg Pd + 8 μg NH₄NO₃. Characteristic masses of Cd, Cu and Pb obtained are 0.6, 5.3 and 15.8 pg, respectively. The detection limits of Cd, Cu and Pb were found to be 0.08, 0.57 and 0.83 μg l⁻¹, respectively. Depending on the solid sample type, the percent recoveries were increased up to 103% for Cd, Cu and Pb by using the proposed modifier mixture. The accuracy of the determination of analytes in the sea water samples was also increased.     

Source apportionment of trace elements in the Eastern Mediterranean atmosphere

Concentrations of elements and ions, measured in aerosol samples collected during 1993 were investigated to identify sources and source composition of aerosols in the Eastern Mediterranean atmosphere. The factor analysis have shown that Eastern Mediterranean aerosol is a four-component system, including a crustal component, long-range transported pollution component, a marine component and a local pollution component. Main anthropogenic component, which reaches to the region by long-range transport accounts for 70%-90% of the concentrations of Zn, Se, NO_3-, nss-SO₄ ^2-, NH₄ ⁺ and smaller fractions of V, Sb, Cr and Mn concentrations. According to the quantitative analysis of local and Saharan dust components, the most promising marker elements to distinguish Saharan dust from local soil were found to be Cr, Nd, Mg and Cs as they have significantly different compositions in the local soil and Saharan dust.     

Exchangeable fraction of elements in alluvial sediments under waste disposal site (Zagreb, Croatia)

Concentrations of Ag, Ba, Cd, Ce, Cs, Co, Cr, Eu, Fe, Rb, Sc, Sr, Th, and Zn exchangeable fractions were determined in alluvial sediments at waste disposal site area in the vicinity of water-well field. Samples have been leached with 0.5M NH₄Cl at a sample/solution ratio of 120 during 24 hours without shaking. INAA of dry NH₄Cl residues show that the concentrations of exchangeable elements determined in the most of the sediments below the wastes have natural levels. Ag, Ba and Sr are readily exchangeable; Rb, Cs and Zn have lower exchangeability, while Cd, Ce, Th, Sc, Eu, Cr, Fe and Co are rather immobile. Extremely high total and exchangeable silver concentration was found at 6.5–6.8 meters below waste in the aerated layer occasionally under the water table. Exchangeable concentrations in deeper water-bearing sediment layers are not elevated. Due to this, one can presume that the upper sediment layers act as chemical filter generally preventing the infiltration from overlying wastes into water-bearing layers.     

Study of partitioning and dynamics of metals in contaminated soil using modified four-step BCR sequential extraction procedure

The modified four-step BCR sequential extraction procedure (exchangeable and weak acid available species, reducible, oxidisable and residual fractions) was used to examine the distribution of As, Cd, Cr, Cu, Pb, and Zn with soil depth in an area (Baia Mare — Bozanta, Romania) with both high natural level of elements considered as toxic and historical pollution resulting from nonferrous metallurgy. The BCR approach proved a high metal input of anthropogenic origin down to 40 cm, while at lower depths the naturally elevated metal content must be considered. Results of the partitioning study and XRD analysis of solid matrix showed the greatest potential for chemical remobilisation of Cd, Zn, and Cu in weak acidic medium as well as their affinity for the oxidisable fraction (organic matter/sulphide). The tendency of Cr, Pb, and As to be immobilised as residual or reducible species on Fe-Mn oxides was evident. Although the partitioning of As in chemically inactive forms such as scorodite (FeAsO₄ · 2H₂O) soluble under reducible conditions and beudantite (PbFe₃(AsO₄)(SO₄)(OH)₂)), a residual species soluble in acid media, chemical mobilisation from soil in groundwater was confirmed. Dynamic processes of metal retention in soil under different conditions, namely acidic, reducing or oxidisable, were predicted from the Pearsonșs correlation analysis of element species with soil characteristics and components such as Fe, Mn, organic matter content, pH, and total element content, respectively. At the moment of the study, soil and groundwater in the area were found to be polluted with As, Cd, Cu, Pb and Zn. Presented at the 35th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 26–30 May 2008.     

Synthesis and crystal structure of New Amminecopper(II) Nitrates: [Cu(NH3)2](NO3)2 and [Cu(NH3)](NO3)2

[Cu(NH₃)₂](NO₃)₂ ( I ) and [Cu(NH₃](NO₃)₂ ( II ) were synthesized by interaction of molten NH₄NO₃ with [Cu(NH₃)₄](NO₃)₂ and Cu(NO₃)₂ · 3 H₂O, respectively, at 180 to 195°C for 24 hr. According to X-Ray single crystal analysis, I is orthorhombic (sp. gr. Pbca) with a = 5.678(1), b = 9.765(2), c = 11.596(2) Å, Z = 4, R = 0.060; II is monoclinic (sp. gr. P2₁/c) with a = 6.670(1), b = 8.658(2), c = 9.661(2) Å, β = 101.78(2)°, Z = 4, R = 0.027. In both structures, the nearest coordination environment of Cu is a slightly distorted square formed by N (from NH₃) and O atoms (from NO₃ groups). The structure of I consists of centrosymmetrical [Cu(NH₃)₂](NO₃)₂ molecules linked by hydrogen bonds. The Cu? N and Cu? O distances are 1.98 and 2.01 Å, respectively. In II , the Cu? N distance is 1.95 Å, the Cu? O distances are 1.96, 2.02, and 2.03 Å. The [CuO₃NH₃] squares are connected by NO₃ bridges into zigzag chains, which are linked into layers by longer Cu? O interactions (2.31 Å). Obviously, the layers are additionally strengthened and held together by hydrogen bonds.     

Application of countercurrent chromatography to the purification of chemical reagents

Countercurrent chromatography has been employed for the purification of solid chemical reagents, such as (NH₄)₂SO₄, NH₄HSO₄, NH₄F and NH₄Cl from a number of most common metal impurities (Fe, Al, Zn, Cu, Co, Cd, Ni, Cr, Ca, Mg, K) in order to gain high-purity reagents. After evaporation these can be used for fusion decomposition purposes in trace analysis of various refractory materials (e.g. high tech ceramics). N,N-hexamethylenedithiocarbamic acid, 8-hydroxyquinoline, dibenzo-18-crown-6 and dicyclohexano-18-crown-6 were used as extracting reagents.     

NO2对Cu/SAPO-34分子筛催化剂上NH3选择性催化还原NO性能的影响

主要考察了NO₂对Cu/SAPO-34 分子筛催化剂在整个温度范围内（100-500 ℃）NH₃选择性催化还原（SCR）NO性能的影响. 研究所使用样品为新鲜Cu/SAPO-34 催化剂在750 ℃下水热处理4 h 的稳定期样品.通过X射线衍射（XRD）和扫描电子显微镜（SEM）对样品的结构以及形貌进行表征,采用SCR活性评价、动力学实验以及原位漫反射傅里叶变换红外光谱（in situ-DRIFTS）表征催化剂的性能以及催化剂表面物种的变化. 活性评价实验结果表明,NO₂会抑制催化剂的低温（100-280 ℃）活性,但其存在会提高催化剂的高温（280 ℃以上）活性. 与此同时,随着反应物中NO/NO₂的摩尔比例减少,由于NH₄NO₃物种的分解,副产物（N₂2O）的浓度增大. 动力学结果表明,Cu/SAPO-34 催化剂上快速SCR反应的表观活化能（E_a=64.02 kJ·mol^-1）比标准SCR反应的表观活化能（E_a=48.00 kJ·mol^-1）更大. In situ-DRIFTS实验结果表明NO比NO₂更容易在催化剂表面形成硝酸盐,并且NO₂更容易与吸附在Brønsted 酸性位上的NH₃物种反应生成NH₄NO₃. 低温下,催化剂表面的NH₄NO₃物种会覆盖SCR反应的活性位,造成活性降低,但在高温时,形成的NH₄NO₃物种一部分会被NO还原为N2,而另一部分会直接热分解为N₂O,造成催化剂的选择性降低.     

Organic Ion Exchangers. Synthesis and Their Behaviour in the Retention of Some Metal Ions

Summary: Three pyridine strong base anion exchangers as beads were obtained by quaternization reactions of a 4-vinylpyridine : 8% divinylbenzene copolymer of gel type. These resins possess methyl / ethyl / butyl radicals as substituents on N⁺ atoms and have exchange capacities of 4.80 mEq/g and 2.10 mEq/mL. For pyridine strong base anion exchangers, the behaviours in the retention processes of Cr(VI) as oxyanions and Ga(III) as [GaCl₄]⁻ complex anion were evaluated with the bath method. All the resins exhibited retention properties, but the retained amounts of the metal cations are different as a function of the alkyl length as substituent on N⁺ atoms and the complex anion nature. Thus, Cr(VI) oxyanions are best retained by the resin with  CH₃ as substituent on N⁺ atoms while [GaCl₄]⁻ complex anion by the resin with  C₄H₉ as substituent on N⁺ atoms. By aminolysis reaction of an ethylacrylate : acrylonitrile : divinylbenzene copolymer as beads of macroporous type with NH₂OH · HCl in the presence of C₂H₅OH a new chelating ion exchanger was performed which contains both amidoxime and hydroxamic acid functional groups. This ion exchanger has the retention property for different metal cations but its retention capacities values are strongly dependent of the nature of metal cation and the counterion as well as pH of the solution. Thus, in the static conditions Zn(II) cation with NOequation/tex2gif-stack-1.gif anion as counterion is retained with the best result at pH = 5. As an example, for the aqueous metal cation solution of 10⁻² M concentration for Zn(NO₃)₂ the resin possess at equilibrium a retention capacity of 6.70 mmol Zn/g dry resin and for Cu(II) from Cu(NO₃)₂ solution of same concentration, the retention capacity is 0.22 mmol Cu/g dry resin and Fe(III) from Fe(NO₃)₃ solution is not retained.     

Determination of Heavy Metals in Soil Extracts and Plant Tissues at Around of a Zinc Smelter

Abstract

Extractable contents of heavy metals such as Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb and Bi in soil and plant tissue samples (fruit, leaf, twig and root) collected, along a distance of 1100 m to the West, from the surroundings of a metallurgical factory producing mainly zinc, cadmium and lead were determined by flame atomic absorption spectrometry (FAAS). In addition, the determinations of Ca and Mg, macro nutrient elements for plants, were also performed. Three extractant solutions were used for dissolution of soil samples, namely aqua regia (1 HNO₃₊ 3 HCl) for total metal analysis, 1 mol L^?1 ammonium acetate for exchangeable metal contents, and a dilute acid mixture (0.1 M HCl in 0.025 M H₂SO₄) for acid soluble metal contents. A mixture of HNO₃ and HClO₄ was used to analyze the fruit samples. The analyses of the leaf, the twig, and the root tissue samples were made by dry ashing method. The detection limits of the metals were in the range of 0.04 to 0.45 μg/mL for all soil extracts and 0.01 to 1.50 μg/mL for the fruit samples. The recovery values for all the determinations were higher than 95%. The results obtained from the analyses of plant tissue and soil samples were evaluated using linear correlation analysis and concentration factors to identify the effect of the factory near the grape-vine area.     

Etude de l’isotherme 25°C du système quasi quaternaire H2O-Zn(NO3)2·6H2O-Cu(NO3)2·3H2O-NH4NO3;I- Isoplèthes 4 masse% NH4NO3, 8 ma

The solid-liquid equilibria of the quasi-quaternary system H₂O-Zn(NO₃)₂·6H₂O-Cu(NO₃)₂·3H₂O-NH₄NO₃ were studied at 25°C by using a synthetic method based on conductivity measurements. Three isoplethic sections has been established at 25°C and the stable solid phases which appear are: NH₄NO₃(IV), Zn(NO₃)₂·6H₂O, anhydrous Cu(NO₃)₂, Cu(NO₃)₂·3H₂O and metastable Cu(NO₃)·2.5H₂O. Neither double salts, nor mixed crystals are observed at these temperatures and composition range.     

The use of stable isotopes for Cr(VI) determination in silty-clay soil solution

In assessing the environmental hazard of Cr(VI) present in soil, exchangeable Cr(VI) is important, since it can be easily washed out from the upper part of the soil into subsurface soil, surface and ground water, and taken up by plants. The aim of this study was to evaluate the degree of species interconversion that may occur during the extraction of exchangeable Cr(VI) from silty-clay soil with phosphate buffer in order to establish an extraction method that would be effective, accurate and with minimal or no species interconversions. The Cr(VI) concentration in soil extracts was determined by speciated isotope dilution inductively coupled plasma mass spectrometry (SID-ICP-MS). The study was performed on soil samples from a field treated with tannery waste for 17 years. Samples were spiked by enriched stable isotopic solutions of ⁵⁰Cr(VI) and ⁵³Cr(III) that were added to phosphate buffers (0.1 M KH₂PO₄-K₂HPO₄ (pH 7.2) and/or 0.1 M K₂HPO₄ (pH 8)). To optimize extraction, mechanical shaking and/or ultrasound-assisted extraction were compared. The separation and detection of Cr species was performed by high-performance liquid chromatography (HPLC) ICP-MS. When mechanical shaking was applied, 90 % reduction of Cr(VI) was induced by extraction with 0.1 M KH₂PO₄-K₂HPO₄, while with 0.1 M K₂HPO₄ reduction was around 40 %. To shorten the extraction time and the possibility of species interconversions, ultrasound-assisted extraction was further applied only with 0.1 M K₂HPO₄. For total extraction of exchangeable Cr(VI) with a maximum 10 % reduction of Cr(VI), five consecutive ultrasound-assisted extractions were needed.

Boosting Electrocatalytic Nitrate-to-Ammonia via Tuning of N-Intermediate Adsorption on a Zn−Cu Catalyst

The renewable-energy-powered electroreduction of nitrate (NO₃⁻) to ammonia (NH₃) has garnered significant interest as an eco-friendly and promising substitute for the Haber–Bosch process. However, the sluggish kinetics hinders its application at a large scale. Herein, we first calculated the N-containing species (*NO₃ and *NO₂) binding energy and the free energy of the hydrogen evolution reaction over Cu with different metal dopants, and it was shown that Zn was a promising candidate. Based on the theoretical study, we designed and synthesized Zn-doped Cu nanosheets, and the as-prepared catalysts demonstrated excellent performance in NO₃⁻-to-NH₃. The maximum Faradaic efficiency (FE) of NH₃ could reach 98.4 % with an outstanding yield rate of 5.8 mol g⁻¹ h⁻¹, which is among the best results up to date. The catalyst also had excellent cycling stability. Meanwhile, it also presented a FE exceeding 90 % across a wide potential range and NO₃⁻ concentration range. Detailed experimental and theoretical studies revealed that the Zn doping could modulate intermediates adsorption strength, enhance NO₂⁻ conversion, change the *NO adsorption configuration to a bridge adsorption, and decrease the energy barrier, leading to the excellent catalytic performance for NO₃⁻-to-NH₃.     

Co-doping a metal (Cr,Mn, Fe,Co, Ni,Cu, and Zn) on Mn/ZSM-5 catalyst and its effect on the catalytic reduction of nitrogen oxides with ammonia

Selective catalytic reduction (SCR) of NO_x by NH₃ over a series of Mn–M/Z catalysts (M = Cr, Mn, Fe, Co, Ni, Cu, Zn, and Z = the ZSM-5 Zeolite) synthesized by wet impregnation method was investigated. Mn–Fe/Z, Mn–Co/Z, and Mn–Cu/Z catalysts exhibited approximately 100 % NO_x conversion over a wide temperature range (200–360 °C) in a defined atmospheric condition, which was noticeably greater than that of Mn–Cr/Z (340–360 °C). Furthermore, the effect of addition of second metal oxide species to the initial Mn/Z catalyst on the structure of catalysts was studied by several characterization techniques. BET measurements revealed high surface area and pore volume of the Mn–Cu/Z catalyst. In addition, the XRD and UV–Vis DR results showed that addition of co-doped metal oxide species improved the dispersion of metal ions and inhibited crystallization of metal oxides. UV–Vis studies also were in good accordance with DTA/TG results confirming the formation of cobalt oxide and copper oxide clusters in Mn–Co/Z and Mn–Cu/Z catalysts, respectively. The FTIR spectra of pyridine adsorption, in addition, suggested the Mn–Cu/Z catalyst contained the most Lewis acid sites leading to more NO_x adsorption capacity.     

Study on the simultaneous determination of some essential and toxic trace elements in honey by multi-element graphite furnace atomic absorption spectrometry

A multi-element graphite furnace atomic absorption spectrometry (GFAAS) method was elaborated and applied for the simultaneous determination of As, Cd, Cr, Cu, and Pb in various kinds of honey samples (acacia, floral, linden, rape, and milkweed) using the transversally heated graphite atomiser (THGA) with end-capped tubes and integrated graphite platforms (IGPs). For comparative GFAAS analysis, direct (without digestion) and indirect (with digestion in a microwave oven) sample preparation procedures were tested. The effects of several chemical modifiers, such as NH₄H₂PO₄, NH₄H₂PO₄-Mg(NO₃)₂, and Pd(NO₃)₂-Mg(NO₃)₂, were studied to obtain optimal pyrolysis and atomization conditions for the set of analytes studied. The most efficient modifier was proved to be the mixture of 5 μg Pd (applied as nitrate) plus 3 μg Mg(NO₃)₂, allowing the optimal 600 °C pyrolysis and 2300 °C atomization temperatures. To prevent the sputtering and foaming of the matrix during the drying and pyrolysis steps of the furnace heating program, the sample and modifier solutions (20 + 5 μl, respectively) were dispensed together onto the IGP of the THGA pre-heated at 80 °C.The effect of increasing concentration of honey matrix was studied on the integrated absorbance (A_int) signals of analytes. The A_int signals of Cr and Pb were not altered up to 10% (m/v) matrix content in the sample solutions. The matrix effect was slightly suppressive on the A_int signals of As, Cd, and Cu above 2% (m/v) honey concentration. The recovery was found to be ranged between 85 and 115% for Cd, Cr, Cu, and Pb, whereas it was a lower, compromise value of 70-99% for As. The limit of detection (LOD) data were 1, 0.04, 0.09, 0.3, and 0.6 μg l⁻¹ for As, Cd, Cr, Cu, and Pb, respectively, which values correspond to 20, 0.8, 1.8, 5.3, and 12 ng g⁻¹, respectively, in the solid samples. The characteristic masses were found to be 21 pg As, 1.3 pg Cd, 4 pg Cr, 12 pg Cu, and 33 pg Pb. The As, Cd, Cr, Cu, and Pb contents of the studied 42 honey samples varied significantly, i.e. from below the LOD up to 13, 3.3, 109, 445, and 163 ng g⁻¹, respectively.     

An Interlaboratory Comparison of a Standardised EDTA Extraction Procedure for the Analysis of Available Trace Elements in Two Quality Control Soils

Abstract

A standardised EDTA extraction procedure was tested collaboratively by six laboratories using two in-house reference soils identified as soil A and soil B. The extracts were analysed for Zn, Cu, Pb and Mn by Inductively Coupled Plasma Spectrometry. Concentrations of extractable elements in soil A were generally much lower than those found in soil B. All laboratories produced some extreme outlying results, most of these were produced in soil B. Results for Mn were the most variable, with a range of 63.4–100.3 μg g^?1 in soil A and 226.4–415.3 μg g^?1 in soil B. In both soils, one laboratory reported high values for Zn and Mn and, one laboratory, for soil B, produced values for all four elements which were consistently low.

If outlying results are ignored, the results from most laboratories were in reasonable agreement for all elements except Mn.     

Assessment of CaCl2, NaNO3 and NH4NO3 extraction procedures for the study of Cd, Cu, Pb and Zn extractability in contaminated soils

The variety of extraction procedures used in environmental studies makes it very difficult to compare the results obtained; therefore, harmonisation and standardisation is required. The extraction of heavy metals from soil by un-buffered salt solutions is a method used to estimate soil contamination and trace metal availability to plants. The present study assesses three of these methods. All the three methods are standardised or is undergoing standardisation in Europe: 0.01 mol l⁻¹ CaCl₂ (The Netherlands), 0.1 mol l⁻¹ NaNO₃ (Switzerland) and 1 mol l⁻¹ NH₄NO₃ (Germany). The soil-reference material BCR CRM 483, with indicative values for CaCl₂, NaNO₃, NH₄NO₃ extractable metals, was analysed for quality control purposes. The three methods were also applied to 10 contaminated soils and the extracted metals (Cd, Cu, Pb, and Zn) were determined. The procedures were found to be precise (typically <10%) for all metals, taking into account the low metal concentrations extracted. The metal extraction efficiency obtained with each procedure was slightly different, and the three methods provided equivalent information while predicting the relative trace-metal mobility (Cd>Zn>Cu>Pb) in the soils studied. From the experience obtained, the 0.01 mol l⁻¹ CaCl₂ extraction procedure seems to be the most suitable method for performing a harmonisation process, since this procedure combines an appropriate extraction capacity for this type of studies with the lowest salt concentration in the extracts and, consequently, with a more simple matrix for metal determination.