Soil Reference Materials Research Articles

Partition of iodine ( 129I and 127I) isotopes in soils and marine sediments

Natural organic matter, such as humic and fulvic acids and humin, plays a key role in determining the fate and mobility of radioiodine in soil and sediments. The radioisotope 129I is continuously produced and released from nuclear fuel reprocessing plants, and as a biophilic element, its environmental mobility is strongly linked to organic matter. Due to its long half-life (15.7 million years), 129I builds up in the environment and can be traced since the beginning of the nuclear era in reservoirs such as soils and marine sediments. Nevertheless, partition of the isotope between the different types of organic matter in soil and sediment is rarely explored. Here we present a sequential extraction of 129I and 127I chemical forms encountered in a Danish soil, a soil reference material (IAEA-375), an anoxic marine sediment from Southern Norway and an oxic sediment from the Barents Sea. The different forms of iodine are related to water soluble, exchangeable, carbonates, oxides as well as iodine bound to humic acid, fulvic acid and to humin and minerals. This is the first study to identify 129I in humic and fulvic acid and humin. The results show that 30–56% of the total 127I and 42–60% of the total 129I are associated with organic matter in soil and sediment samples. At a soil/sediment pH below 5.0–5.5, 127I and 129I in the organic fraction associate primarily with the humic acid while at soil/sediment pH > 6 129I was mostly found to be bound to fulvic acid. Anoxic conditions seem to increase the mobility and availability of iodine compared to oxic, while subaerial conditions (soils) reduces the availability of water soluble fraction compared to subaqueous (marine) conditions.

Comparison of extraction and clean-up techniques for the determination of polycyclic aromatic hydrocarbons in contaminated soil samples

The development of a fast, efficient and quantitative technique for the extraction, clean-up, and preconcentration of the 16 United States Environmental Protection Agency (USEPA) priority polycyclic aromatic hydrocarbons (PAHs) was carried out on contaminated soils. The effect of Soxhlet, ultrasonication and mechanical shaking used in the extraction of a low-level PAH soil certified reference material (CRM131-100) was investigated. Six different extraction solvents: acetone, cyclohexane, 2- propanol, methanol, acetonitrile and dichloromethane, were tested to select the most suitable solvent for the extraction of the 16 PAHs from the certified soil reference material. The results were compared to determine the method with the highest extraction efficiency. The clean up and preconcentration procedures for the PAHs were optimised using the solid phase extraction (SPE). Acetonitrile, dichloromethane and tetrahydrofuran were tested as eluants for the optimisation of SPE clean up. Chromatographic conditions for the separation of PAHs using High Performance Liquid Chromatography (HPLC) using UV-DAD and fluorimetric detection with programmed excitation and emission wavelengths were also optimised. The optimised ultrasonic extraction procedure and SPE clean-up extracted the PAHs from the certified reference material with recoveries ranging from 63.6 % to over 100%.

Improved Analytical Extraction and Clean-up Techniques for the Determination of PAHs in Contaminated Soil Samples

Development and optimisation of fast, efficient, quantitative, economic and environmentally friendly analytical extraction techniques for the extraction clean up, and pre-concentration in the quantification of 16 USEPA priority polycyclic aromatic hydrocarbons (PAHs) in contaminated soils have been carried out. Three different extraction methods (Soxhlet, ultra sonication and mechanical shaking) were investigated on a low-level PAH soil certified reference material (CRM131-100) and the results were compared to determine the technique with the highest extraction efficiency. The clean up and pre-concentration procedures were optimized using both the conventional method (i.e. column packing with silica gel) as well as the solid phase extraction (SPE). Chromatographic conditions for the separation of PAHs using High Performance Liquid Chromatography (HPLC) using UV-DAD and fluorimetric detection with programmed excitation and emission wavelengths were also optimized. Six different extraction solvents: acetone, cyclohexane, 2- propanol, methanol, acetonitrile and dichloromethane, were tested to select the most suitable solvent for the extraction of the 16 PAHs from the certified soil reference material. Acetonitrile, dichloromethane and tetrahydrofuran were also tested as eluants for the optimisation of SPE clean up. The optimized ultrasonic extraction procedure utilizing four 15 minutes extraction cycles at 50 oC and SPE clean up with tetrahydrofuran: acetonitrile (1:1) and subsequent separation by gradient reversed phase HPLC with fluorimetric detection extracted the PAHs from the certified reference material with recoveries ranging from 63.6 % to over 100 % .

Comparison of In Vitro PBET and Phosphoric Acid Extraction as an Approach to Estimate Selenite and Selenate Bioaccessibility from Soil

Several approaches have been used to estimate the bioaccessibility of trace metals from soils. Here, we applied phosphoric acid extraction and the in vitro test physiologically based extraction (PBET) to soils containing selenium (Se) and compared their performance in estimating the bioaccessibility of Se. For this purpose, we used two soil samples and two Certified Reference Material soil samples with a range of Se concentrations. The total Se contents were measured in the samples and in the extracts by hydride generation–atomic fluorescence spectroscopy. Moreover, we also measured selenite and selenate in the soil extracts (from phosphoric acid and from the PBET) using the coupled techniques liquid chromatography–UV photooxidation–atomic fluorescence spectroscopy and liquid chromatography–mass spectrometry with inductively coupled plasma. From the results obtained in the present study, the PBET showed that the selenium bioaccessible fraction was mainly attributed to the gastrointestinal step. When comparing the results from PBET with those of the phosphoric acid extraction, similar values of Se (IV) and Se (VI) were obtained for both extraction systems. An estimation of the bioaccessibility percentage of Se is also reported.

K0-INAA quality assessment by analysis of soil reference material GBW07401 using the comparator and neutron flux monitor approaches

It is possible to apply the k(0)-method using a simplified equation for concentration calculations using Excel spreadsheet, using comparators without making corrections. The objective of this study was to confirm that the k(0)-standardization method is more efficient and accurate than this "k(0)-comparator" procedure, applying suitable software that takes into account several corrections. The reference material GBW07401 soil was analyzed in this study. Relative Bias and u-score tests were used in order to evaluate the overall results.

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(NO 3) 2 admixture for the determination of Cd, Pb and Zn and NH 4F for Cu. The combination of W (as a permanent modifier) and Mg(NO 3) 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.

Estimation of mercury speciation in soil standard reference materials with different extraction methods by ion chromatography coupled with ICP-MS

Analytical methods for the speciation of mercury, based on microwave extraction and sonication extraction, have been tested to determine the inorganic mercury and methyl mercury contents in two standard soil reference materials: SRM 2710 Montana Soil and BCR 580 estuarine sediment. Prior to applying the speciation extraction methods, the mineral compositions were analyzed via XRD analysis, with SRM 2710 shown to be composed mostly of aluminum silicate minerals, while carbonate minerals were the major constituent in BCR 580. Two extraction methods, microwave and sonication, were tested for the analysis and recovery efficiency of total mercury. The accuracy and efficiency of each extraction method was also compared. In the analysis of total mercury, the microwave extraction method, with using methanol and HCl as extractants, was better for SRM2710, while the application of the sonication extraction method was more efficient for the calcite-based BCR 580. The results showed good separation and recovery efficiencies, with values reaching 100% of those estimated. The sonication method was selected for the speciation of mercury, especially in BCR 580. An extraction solution comprising of a 1:1 mixture of methanol and HCl was used for the sonication extraction of BCR 580, with the resulting extractants analyzed by IC-HG-ICP-MS for methyl mercury and inorganic mercury. As a simple, rapid, sensitive, and accurate method, sonication extraction was found to be satisfactory.

Preparation of soil candidate reference materials for the analysis of organochlorine pesticides in soils

The preparation method of new soil candidate certified reference materials (CRM) for the analysis of organochlorine pesticides in soils has been developed. The soil sample was dried, ground, homogenized and packed. After Soxhlet extraction and Florisil purification, the organochlorine pesticides in soil candidate were further determined using gas chromatography-mass spectrometry. The results showed that the soil collected from Shenyang was an ideal soil candidate material for organochlorine pesticide analysis. This method established a foundation for the development of soil reference materials for the analysis of organochlorine pesticides.

The benzene polycarboxylic acid (BPCA) pattern of wood pyrolyzed between 200 °C and 1000 °C

Environmental charcoals represent a poorly defined part of the black carbon (BC) combustion continuum and may differ widely in their chemical and physical properties, depending on combustion conditions and source material. The benzene polycarboxylic acid (BPCA) molecular marker method is well established to quantify the BC component in charcoal, soil and sediment, although observed variations between labs could stem from subtle differences in methods. The objectives of this study were to identify and improve potential sources of analytical uncertainty. The improved method was then used to qualitatively characterize wood charred at 200–1000 °C. One significant improvement of the BPCA method was to replace citric acid with phthalic acid as an internal standard, which is more stable in acidic solution and more similar to the target compounds. Also, including a soil reference material as a quality control in each analysis proved to be a robust tool to detect for variations in reproducibility. For the thermosequence, elemental O/C and H/C ratios typically decreased with temperature to ⩽0.03 at 1000 °C, whereas BPCA concentrations peaked at 700 °C. With temperature B6CA proportions increased consistently (6–98%), except for a plateau at 250–500 °C. Thus, relative contributions of B6CA reflected the pyrolysis temperature and probably also the degree of condensation of the charcoals we investigated. Future work will show if our results can be directly related to charcoal produced under oxygen limited conditions, including charcoal formed at wildfires or so called biochar for agricultural use.

Improvement of the capabilities of inductively coupled plasma optical emission spectrometry by replacing the desolvation system of an ultrasonic nebulization system with a pre-evaporation tube

The effect of replacing the desolvation system (i.e., heater/condenser (HC) and membrane desolvator (MD)) of an ultrasonic nebulizer (USN) system with a pre-evaporation tube (PET) that is heated to about 400 °C on the analytical capabilities of inductively coupled plasma optical emission spectrometry (ICP–OES) was investigated. A multivariate optimisation was conducted in each case to find operating conditions maximizing plasma robustness. Under optimum conditions, the analytical performance of ICP–OES was significantly improved (i.e., better sensitivity, detection limit and plasma robustness) with USN–PET compared to that achieved with both the commercially-available USN–HC–MD and a conventional pneumatic nebulizer/spray chamber sample introduction system. However, only the USN–PET approach allows the determination of Hg, which appears to otherwise be lost in the heater/condenser system. Using a simple external calibration, without any matrix matching, and using an argon emission line for internal standardization, the results obtained for the determination of trace elements in certified soil reference materials (SRM 2710 and 2711) by USN–PET were in good agreement with certified values. This is unlike with conventional sample introduction systems where internal standardization using an Ar line is unusual, as it does not compensate for physical interferences, and either internal standardization (with internal standards added to the sample and standard solutions) or matrix-matched calibration is required.

Utilization of W/Mg(NO 3) 2 modifiers for the direct determination of As and Sb in soils, sewage sludge and sediments by solid sampling electrothermal atomic absorption spectrometry

A simple method has been developed for the determination of arsenic and antimony in environmental samples by solid sampling electrothermal atomic absorption spectrometry, which was validated using certified reference materials of soils (S-VM — Soil Eutric Cambisol; S-MS — Soil Orthic Luvisols; S-SP — Soil Rendzina), sewage sludge (WT-L; WT-M) and sediments (NIES2; GBW07906). The analytical procedure combines solid sampling with utilization of a matrix modifier admixture containing 5 µg of W and 5 µg of Mg. The tungsten in the admixture serves to stabilize the solid matrix during atomisation, which results in dramatically reduced non-specific absorption compared with the conventional palladium modifier. Magnesium was efficient in reducing the accumulation of the matrix residue on the platform. An alternative resonance line of 197.2 nm for arsenic and 206.8 nm for Sb was used in order to eliminate the spectral interferences caused by aluminum compounds, and silicon and iron compounds, respectively. Under optimized experimental conditions, the effective in situ analyte/matrix separation was achieved so that the use of aqueous standards for calibration became possible. With the modifier, a 3 SD detection limit of 0.5 µg g − 1 As and 0.1 µg g − 1 Sb and 10 SD quantification limit of 1.7 µg g − 1As and 0.3 µg g − 1 Sb and a characteristic mass of 65 pg As and 53 pg Sb were obtained. For all the matrices under scrutiny, a good agreement with certified values was achieved with RSD values less than 10%.

Analysis of soil reference materials for vanadium(+5) species by electrothermal atomic absorption spectrometry

Solid Certified Reference Materials (CRMs) with known vanadium(+5) content are currently not commercially available. Because of this, vanadium species have been determined in solid CRMs of soil, viz. CRM023-50, CRM024-50, CRM049-50, SQC001 and SQC0012. These CRMs are certified with only total vanadium content. Vanadium(+5) was extracted from soil reference materials with 0.1M Na(2)CO(3). The quantification of V(+5) was carried out by electrothermal atomic absorption spectrometry (ET-AAS). The concentration of V(+5) in the analyzed CRMs was found to be ranging between 3.60 and 86.0 microg g(-1). It was also found that SQC001 contains approximately 88% of vanadium as V(+5) species. Statistical evaluation of the results of the two methods by paired t-test was in good agreement at 95% level of confidence.

On‐Line Selective Solid‐Phase Extraction of Copper with a Surface Ion Imprinted Silica Gel Sorbent

AbstractCopper(II)‐ion imprinted silica gel (Cu‐IISG) sorbent was synthesized by surface imprinting technique and was employed as a selective solid‐phase extraction material for on‐line preconcentration and separation, then coupled with atomic absorption spectrometry (AAS) determination of Cu(II). The higher selectivity coefficient of Cu‐IISG for Cu(II) in the presence of competitive ions such as Fe(III), Ni(II) and Zn(II) was above 411, which was 35 times of NISG. The static adsorption capacity and dynamic adsorption capacity were 41.11 mg g−1 and 16.20 mg g−1, respectively. The Cu‐IISG offered a fast kinetics for the adsorption and desorption of Cu(II), which can be used for on‐line preconcentration and detection. Two certified reference materials of GBW07301a sediment and GBW07401 soil were analyzed and the determined values were in a good agreement with the certified values. The developed method was also successfully applied to the determination of trace copper in tea leaf with satisfactory results (recovery between 96.3% and 102.3%).

Measurement of PAHs in environmental matrices: results from an interlaboratory comparison on the different steps of the measurement procedure

Proficiency testing (PT) is becoming a feature of laboratory accreditation and the PT results are used to assess the technical competence of the participating laboratories. ISPRA (former APAT) plays an important role in supporting the Italian laboratories belonging to the network of the Regional Environmental Agencies to improve the quality of their analytical measurements. As a consequence, ISPRA organized an interlaboratory comparison to assess the performance of the laboratories on PAH measurement procedure. The interlaboratory comparison was drawn separating the different steps of the measurement (from the extraction to the instrumental measurement). Two matrix reference materials: (1) a polluted soil and (2) an extract reference material of the same polluted soil and a “blind” PAH mixture standard stock solution were distributed to 59 Italian laboratories. The results of interlaboratory comparison showed a significant dispersion of the PAH measurements that masks the effects of the different extraction and cleanup procedures used, but it is consistent with the results of other European interlaboratory comparisons.

Comparison of Two Extraction Methods for the Determination of Polycyclic Aromatic Hydrocarbons in Surface Soils Using Headspace SPME with GC-FID

Two simple methods using headspace solid-phase microextraction (HS-SPME) coupled to a gas chromatograph with a flame ionization detector were compared for the determination of polycyclic aromatic hydrocarbons (PAH) in soils. These compounds were included in the US Environmental Protection Agency's Priority Pollutants list. Direct hot water HS-SPME extraction and sonication organic extraction followed by HS-SPME were optimized using experimental designs. The first method was chosen for PAH determination. The validation of the proposed method was carried out by analyzing PAHs in the certified soil reference material RTC-CRM 123. The accuracy obtained for the PAHs was shown to be inside the prediction interval with the certified material. The optimized method was applied to the analysis of several superficial soils from Gipuzkoa (Basque Country, North Spain).

Simultaneous determination of Cr, Ga, In and V in soil and water samples by tungsten coil atomic emission spectrometry

Tungsten coil atomic emission spectrometry is employed for the simultaneous determination of Cr, Ga, In, and V. Both V and In are detected by this technique for the first time. The atomizer is a simple, inexpensive tungsten filament extracted from a mass-produced, commercially-available 150 W, 15 V microscope bulb. A 25 µl sample aliquot is placed directly on the coil and a small constant-current power source is used to carefully dry, ash and atomize the sample. Analytical signals are detected with a Czerny-Turner spectrograph and a charge coupled device detector. Multiple emission lines from all 4 elements are monitored simultaneously in a 54 nm spectral window. Concentration limits of detection are in the µg l − 1 range for all elements, and the absolute limits of detection are 0.2, 2, 0.5, and 10 ng for Cr, Ga, In, and V, respectively. Even lower values may be obtained by combining the signals for the multiple emission lines of a single element. The method precision is typically better than 5.0% relative standard deviation, and sometimes as good as 0.95% (Ga). Standard reference materials of soil and water are used to check the method accuracy. After a simple acid extraction, the values determined by the method presented no significant difference from the reported values at the 95% confidence level.

スルホキシドカラムクリーンアップを用いた底質及び魚肉試料中ポリ臭素化ジフェニルエーテル類の分析

An analytical method for the determination of polybrominated diphenyl ethers (PBDEs) in sediment and fish samples has been developed by using a sulfoxide cartridge column as an effective clean-up procedure. After saponification of samples, PBDEs were extracted with hexane. Then the extract was treated with sulfuric acid and frorisil column chromatography. The eluate from the florisil column was loaded on a sulfoxide cartridge column, and then PBDEs were eluted with 20 mL of 10 % acetone/hexane. The measurement of PBDEs was carried out by HRGC-HRMS. By cleaning with a sulfoxide cartridge column, the number of peaks on SIM chromatograms that cause the drop of lock mass signal during GC-MS measurement and interfere with the quantification of PBDEs was dramatically reduced. The developed method was applied to the analysis of certificated reference materials of fish tissue and soil. The results obtained were within the range of certificated values except for 2,2′,3,4,4′,5′,6-heptabromodiphenyl ether (#183).

A pilot study on iodine in soils of Greater Kabul and Nangarhar provinces of Afghanistan

A robust and rapid methodology for the determination of iodine by inductively coupled plasma mass spectrometry in environmental samples is presented. Data were initially obtained for the validation of the analytical measurements, using 17 commercially available soil reference materials. The methodology was then tested on soil and water samples collected in Afghanistan where iodine deficiency and its effects are reportedly prevalent. Sample collections were conducted in Greater Kabul; the iodine in agricultural soils was determined to be in the range of 1.6-4.2 mg/kg and that in water drawn for drinking and irrigation was found to range from 9.9 to 22.7 microg/L. Samples were also collected in a second region, Nangarhar province, which is located to the east of Kabul, where goitres in the local population had been reported. The iodine content in soils and water at this location was 0.5-1.9 mg/kg and 5.4-9.4 microg/L, respectively. The organic content of soils in Kabul was found to be in the range of 1.9-4.2%; in Nangarhar, organic content ranged from 1.7 to 4.5%. All of the Afghan soils were slightly alkaline at pH 7.6-8.2.

Evaluation of alternate lines of Fe for sequential multi-element determination of Cu, Fe, Mn and Zn in soil extracts by high-resolution continuum source flame atomic absorption spectrometry

The usefulness of the secondary line at 252.744 nm and the approach of side pixel registration were evaluated for the development of a method for sequential multi-element determination of Cu, Fe, Mn and Zn in soil extracts by high-resolution continuum source flame atomic absorption spectrometry (HR-CS FAAS). The influence of side pixel registration on the sensitivity and linearity was investigated by measuring at wings (248.325, 248.323, 248.321, 248.329, and 248.332 nm) of the main line for Fe at 248.327 nm. For the secondary line at 252.744 nm or side pixel registration at 248.325 nm, main lines for Cu (324.754 nm), Mn (279.482 nm) and Zn (213.875 nm), sample flow-rate of 5.0 mL min −1 and calibration by matrix matching, analytical curves in the 0.2–1.0 mg L −1 Cu, 1.0–20.0 mg L −1 Fe, 0.2–2.0 mg L −1 Mn, 0.1–1.0 mg L −1 Zn ranges were obtained with linear correlations better than 0.998. The proposed method was applied to seven soil samples and two soil reference materials (IAC 277; IAC 280). Results were in agreement at a 95% confidence level (paired t-test) with reference values. Recoveries of analytes added to soil extracts containing 0.15 and 0.30 mg L −1 Cu, 7.0 and 14 mg L −1 Fe, 0.60 and 1.20 mg L −1 Mn, 0.07 and 0.15 mg L −1 Zn, varied within the 94–99, 92–98, 93–101, and 93–103% intervals, respectively. The relative standard deviations ( n = 12) were 2.7% (Cu), 1.4% (Fe – 252.744 nm), 5.7% (Fe – 248.325 nm), 3.2% (Mn) and 2.8% (Zn) for an extract containing 0.35 mg L −1 Cu, 14 mg L −1 Fe, 1.1 mg L −1 Mn and 0.12 mg L −1 Zn. Detection limits were 5.4 μg L −1 Cu, 55 μg L −1 Fe (252.744 nm), 147 μg L −1 Fe (248.325 nm), 3.0 μg L −1 Mn and 4.2 μg L −1 Zn.

Quantification of measurement uncertainty in the sequential determination of 210Pb and 210Po by liquid scintillation counting and alpha-particle spectrometry

Methodologies for the quantification of measurement uncertainties associated with the determination of 210Pb- and 210Po-specific activities by liquid scintillation counting (LSC) and alpha-particle spectrometry are presented, and are demonstrated using the soil reference material IAEA-326. Major contributors to the combined uncertainty associated with the measurement result of 210Pb were the uncertainties of net count rates in the 210Pb energy region of the sample spectrum and in the 210Bi energy region of the blank spectrum. The predominant sources of uncertainty in the measurement of 210Po were the uncertainties of net count rates in the regions of interest of 209Po and 210Po. The relative standard uncertainty of 210Po exponentially increases with the time interval between the sampling date and the separation date of Po, and this effect is strongly dependent on the 210Po/210Pb activity ratio. When the specific activity of 210Pb is much higher than that of 210Po in the sample, the relative standard uncertainty of the 210Po determination increases significantly within a short time interval between the sampling date (or reference date) and the separation date of Po in samples.