New Arctic Marine Sediment Certified Reference Material for Elemental Analysis

A multi-elemental certified reference material (CRM) based on Arctic marine sediment was prepared and labeled GBW 07481. Approximately 4.5?kg of the sediment was collected during the third Chinese Arctic Expedition. The sediment was processed in procedures that included air drying, debris removal, drying, and milling. The final product contained particles that were generally smaller than 74?;m representing 99% of the total mass. The powder was poured into clean 10-mL brown glass vials and a total of 300 vials were obtained. The homogeneity and stability were preliminarily investigated to assess the suitability of the marine sediment as a candidate CRM. The candidate material was demonstrated to be suitable for this purpose; and hence the certification project was accomplished with nine reputable laboratories. More than 10 reliable analytical methods, including inductively coupled plasma-mass spectrometry (ICP-MS), inductively coupled plasma-atomic emission spectrometry (ICP-AES), and x-ray fluorescence (XRF), were used for analyzing the sediment for 68 elements. The results should be useful for assessing the analytical accuracy of major, minor, and trace elements in marine sediments. Therefore, the CRM is expected to play an important role in Arctic geochemical surveys and environmental assessment.     

Micro-heterogeneity study of trace elements in BCR CRM 680 by means of synchrotron micro-XRF

BCR CRM 680 is a newly released reference material (RM) with a polyolefinic matrix, doped with various metallic compounds in trace concentrations, to be used for calibration of multi-element trace analytical methods. The micro-heterogeneity of this new CRM was investigated to evaluate the suitability as a RM for trace-level micro analytical techniques. Synchrotron micro-XRF, a trace-level micro analytical method, allows to quantitatively measure the degree of heterogeneity of inorganic trace constituents in solid materials with a homogeneous matrix. The procedure for calculating the minimal sampling mass for homogeneous measurements was employed for BCR CRM 680. By repeating the entire procedure on several samples of the same material, the repeatability of the micro-heterogeneity characterization based on micro-XRF was investigated. Afterwards, the micro-heterogeneity results from the BCR CRM 680 material were used to evaluate the suitability of the micro-heterogeneity procedure by means of a Monte Carlo simulation model. Also the existence of nuggets in the polymer material is looked into.     

Micro-heterogeneity study of trace elements in BCR CRM 680 by means of synchrotron micro-XRF

BCR CRM 680 is a newly released reference material (RM) with a polyolefinic matrix, doped with various metallic compounds in trace concentrations, to be used for calibration of multi-element trace analytical methods. The micro-heterogeneity of this new CRM was investigated to evaluate the suitability as a RM for trace-level micro analytical techniques. Synchrotron μ-XRF, a trace-level micro analytical method, allows to quantitatively measure the degree of heterogeneity of inorganic trace constituents in solid materials with a homogeneous matrix. The procedure for calculating the minimal sampling mass for homogeneous measurements was employed for BCR CRM 680. By repeating the entire procedure on several samples of the same material, the repeatability of the micro-heterogeneity characterization based on μ-XRF was investigated. Afterwards, the micro-heterogeneity results from the BCR CRM 680 material were used to evaluate the suitability of the micro-heterogeneity procedure by means of a Monte Carlo simulation model. Also the existence of nuggets in the polymer material is looked into.     

Development of a simple desulfurization procedure for the determination of butyltins in complex sediment samples using gas chromatography-pulsed flame photometric detection

In this study a rapid solid phase extraction (SPE) procedure was developed to minimize the effect of different sulfur species for the determination of butyltin in sediments. The organosulfur species and organotins were firstly retained on C8 cartridges and then organotins were selectively eluted and analyzed by gas chromatography-pulsed flame photometric detection (GC-PFPD). Optimal conditions for the SPE procedure were obtained using an experimental design approach. The method's accuracy was established by analyzing a certified reference material (CRM), BCR-646 freshwater sediment. The experimental values were found to be in agreement with the assigned values for butyltins. Finally, complex sediment samples collected from a Chilean harbor were analyzed using this methodology to demonstrate its analytical potential for the determination of butyltin in environmental samples.     

Speciation of butyltin compounds in marine sediments with headspace solid phase microextraction and gas chromatography mass spectrometry

A method for the determination of organotin compounds (monobutyl = MBT, dibutyl = DBT, and tributyltin = TBT) in marine sediments by headspace Solid Phase Microextraction (SPME) has been developed. The analytical procedure involved 1) extraction of TBT, DBT and MBT from sediments with HCl and methanol mixture, 2) in situ derivatization with sodium tetraethylborate and 3) headspace SPME extraction using a fiber coated with poly(dimethylsiloxane). The derivatized organotin compounds were desorbed into the splitless injector and simultaneously analyzed by gas chromatography - mass spectrometry. The analytical method was optimized with respect to derivatization reaction and extraction conditions. The detection limits obtained for MBT, DBT and TBT ranged from 730 to 969 pg/g as Sn dry weight. Linear calibration curves were obtained for all analytes in the range of 30-1000 ng/L as Sn. Analysis of a standard reference sediment (CRM 462) demonstrates the suitability of this method for the determination of butyltin compounds in marine sediments. The application to the determination of TBT, DBT and MBT in a coastal marine sediment is shown.     

Speciation of butyltin compounds in marine sediments with headspace solid phase microextraction and gas chromatography – mass spectrometry

A method for the determination of organotin compounds (monobutyl = MBT, dibutyl = DBT, and tributyltin = TBT) in marine sediments by headspace Solid Phase Microextraction (SPME) has been developed. The analytical procedure involved 1) extraction of TBT, DBT and MBT from sediments with HCl and methanol mixture, 2) in situ derivatization with sodium tetraethylborate and 3) headspace SPME extraction using a fiber coated with poly(dimethylsiloxane). The derivatized organotin compounds were desorbed into the splitless injector and simultaneously analyzed by gas chromatography – mass spectrometry. The analytical method was optimized with respect to derivatization reaction and extraction conditions. The detection limits obtained for MBT, DBT and TBT ranged from 730 to 969 pg/g as Sn dry weight. Linear calibration curves were obtained for all analytes in the range of 30–1000 ng/L as Sn. Analysis of a standard reference sediment (CRM 462) demonstrates the suitability of this method for the determination of butyltin compounds in marine sediments. The application to the determination of TBT, DBT and MBT in a coastal marine sediment is shown.     

Validation of an isotope dilution, ICP-MS method based on internal mass bias correction for the determination of trace concentrations of Hg in sediment cores

The development and validation of a method for the determination of mercury in sediments using a sector field inductively coupled plasma mass spectrometer (SF-ICP-MS) for detection is described. The utilization of isotope dilution (ID) calibration is shown to solve analytical problems related to matrix composition. Mass bias is corrected using an internal mass bias correction technique, validated against the traditional standard bracketing method. The overall analytical protocol is validated against NRCC PACS-2 marine sediment CRM. The estimated limit of detection is 12ng/g. The proposed procedure was applied to the analysis of a real sediment core sampled to a depth of 160m in Lake Como, where Hg concentrations ranged from 66 to 750ng/g.     

Comparison of action of mixed permanent chemical modifiers for cadmium and lead determination in sediments and soils by slurry sampling graphite furnace atomic absorption spectrometry

Slurry sampling atomic absorption spectrometry with electrothermal atomization was used to the determination of cadmium (Cd) and lead (Pb) in soils and sediments using permanent modifiers. Comparison of action of mixed permanent modifiers niobium (Nb)/iridium (Ir) and tungsten (W)/iridium (Ir) were studied in detail. The effect of amount of Ir, W and Nb on analytical signals of Cd and Pb was examined. The optimal amounts of modifiers for Cd and Pb determination were stated. Niobium carbide formation on graphite surface was studied for different pyrolysis temperatures. Finally for Cd determination in sediments and soils 200 μg of Nb mixed with 5 μg of Ir was used as permanent modifiers and 15 μg of Nb mixed with 200 μg of Ir for Pb determination. Suspensions were prepared in 5% HNO₃. The analytical procedure was optimized carefully basing on data from pyrolysis and atomization curves studies. Ammonium dihydrogen phosphate was used additionally as matrix modifier during Cd determination in samples in order to prevent interferences coming from matrix components. The analysis of CRMs confirmed the reliability of the proposed approach. The precision and accuracy of Cd and Pb determination by the described method for soils and sediments were acceptable.     

Evaluation and comparison of two selective extraction procedures for heavy metal speciation in sediments.

Two sequential extraction procedures (the former proposed by the Standard, Measurements and Testing-SM&T-program of European Union and the latter derived from those of Tessier and Forstner with various modifications) have been compared, by analyzing a reference material (CRM 601) certified for the content of heavy metals in the three solutions resulting from the SM&T procedure. Scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX) was used to evaluate the composition of the residues after various extractions. Reliable results, both in terms of precision and accuracy, were obtained for the first two steps of the SM&T scheme. As regards the third step, because it was modified during this work, a direct comparison of our results with those certified is not possible. SEM analysis confirmed that the scheme previously used in the laboratory was more aggressive compared to the SM&T procedure, which has also the advantage that the only CRM available for metal partitioning in sediments is certified using this method.     

Certified reference materials—Hay Powder (CRM 129) and Rye Grass (CRM 281)—for the quality control of analysis of animal feed

Analyses of nutritive elements are routinely performed in grass or hay for animal feed in order to improve the state of health and growth of domestic animals. To control the quality of such determinations, the Community Bureau of Reference (BCR) so far has produced two certified reference materials: Hay Powder (CRM 129) and Rye Grass (CRM 281). After a careful preparation procedure of the materials, a homogeneity study and a long-term stability study, the contents of the elements Ca, K, Mg, P, S, Zn, I, N and Kjeldahl-N were certified in CRM 129, whereas CRM 281 was certified for As, B, Cd, Cu, Hg, Mn, Mo, Ni, Pb, Sb, Se and Zn. This paper presents the certification exercise and especially concentrates on the elements I, B and Mo as examples of analytical work. Indicative values for Co, Cr, Fe, Cl and Na were also obtained.     

Certification of a New Naringenin Reference Material by Coulometric Titrimetry Combined HPLC‐MS

Certified reference material (CRM) is a kind of measuring tool with high accuracy and traceability. CRMs are the important guarantee of accurate and reliable results of analysis methods. They are the medium of international communication of experimental data. CRMs are widely used in various fields and play a pivotal role in analytical science. However, in the characterization of CRMs, available absolute analysis methods are very limited. In this situation, accurate and reliable relative analysis methods should be applied. In this work, coulometric titrimetry (CT) was applied to the characterization of flavone naringenin CRM according to its structure. For further illustration of the principle of CT, high‐performance liquid chromatography tandem mass spectrometry (HPLC‐MS) was utilized to analyze the titration products in detail. As the conclusion of this paper, the advantages and the influence factors of CT were given. Mass balance (MB) method was employed to verify the result of CT, and consistent result was obtained.     

Radiochemical neutron-activation analysis of uncertified ultra-trace rare earth elements in two biological certified reference materials

Radiochemical neutron activation analysis (RNAA) has been used for the determination of eight rare earth elements (La, Ce, Nd, Sm, Eu, Tb, Yb, and Lu) in two Chinese certified reference materials (CRM), GBW 08503 (wheat powder) and GBW 09101 (human hair). These determinations are important for possible certification of the above mentioned ultra-trace elements, so far not certified. A simple one-step (REE)F3 precipitation was used. Chemical yields were determined for all relevant elements by means of tracer experiments. The two CRM were also analyzed by inductively coupled plasma-mass spectrometry (ICP-MS) to compare the merits and draw-backs of these two major trace analytical techniques for these particular elements. RNAA was proven to be a reliable technique for ultra-trace analysis, especially in the certification of some ultra-trace elements.     

Simultaneous determination of mono-, di- and tributyltin in environmental samples using isotope dilution gas chromatography mass spectrometry

The development of a rapid, precise and accurate speciation method for the simultaneous determination of mono-, di- and tributyltin in environmental samples is described. The method is based on using isotope dilution gas chromatography/mass spectrometry (GC/MS) with electron ionization, a widely used technique in routine testing laboratories. A mixed spike containing (119)Sn-enriched monobutyltin (MBT), dibutyltin (DBT) and tributyltin (TBT) was used for the isotope dilution of the samples. Five molecular ions were monitored for each analyte, corresponding to the (116)Sn, (117)Sn, (118)Sn, (119)Sn and (120)Sn isotopes. The detection at masses corresponding to (116)Sn and (117)Sn were used to correct for m + 1 and m + 2 contributions of (13)C from the organic groups attached to the tin atom on the (118)Sn, (119)Sn and (120)Sn masses with simple mathematical equations and the concentrations of the butyltin compounds were calculated based on the corrected (118)Sn/(119)Sn and (120)Sn/(119)Sn isotope ratios. The (119)Sn-enriched multispecies spike was applied with satisfactory results to the simultaneous determination of MBT, DBT and TBT in three certified reference materials: two sediments, PACS-2 and BCR 646, and the mussel tissue CRM 477. The method was compared with a previously published GC/inductively coupled plasma MS isotope dilution procedure, developed in our laboratory, by injecting the same samples into both instruments. Comparable analytical results in terms of precision and accuracy are demonstrated for both atomic and molecular mass spectrometric detectors. Thus, reliable quantitative organotin speciation analysis can be achieved using the more widespread and inexpensive GC/MS instrument.     

Determination of Al, Cu, Fe, Mn, Pb and Zn in certified reference materials using the optimized BCR sequential extraction procedure

Sequential extraction procedures are widely used to characterize the fractionation of metal species in solid media. With the variety of different sequential procedures used in environmental and geochemical exploration studies, it is difficult to compare results between studies. Thus, harmonization and standardization are required to provide greater inter-study comparability for fraction-specific metals. In this study, the optimized BCR three-step sequential extraction procedure is applied to five certified reference materials (SRM 2710, SRM 2711, CRM 483, CRM 601 and CW 7). Four fractions are reported, acid extractable, reducible, oxidizable, and residual for Al, Cu, Fe, Mn, Pb and Zn. The objectives of this study were to characterize experimental precision and/or accuracy and to establish baseline data of fraction-specific element concentrations for future studies applying the optimized BCR three-step extraction procedure. The optimized procedure was found to be precise (typically <5%) for all metals in all fractions. Accuracy was acceptable (typically ±15% relative to published indicative values for Cu, Pb and Zn for CRM 483 and CRM 601) for all individual fractions. Detailed fraction-specific concentration data are presented, based on five replicates, for the first time using the optimized procedure for Al, Fe and Mn in CRM 483 and CRM 601, and for Al, Cu, Fe, Mn, Pb and Zn in SRM 2710, SRM 2711 and CW 7.     

Mercury determination in solid phases from application of the modified BCR-sequential extraction procedure: a valuable tool for assessing its mobility in sediments

The present paper presents a feasibility study for the evaluation of mercury mobility in sediments by application of the modified BCR three-step sequential extraction procedure (BCR-SEP). The aim of the study was to evaluate the effect of acidification, reduction and oxidation processes on mercury mobility from sediments, once the SEP was validated with other trace metals.As extractable mercury amounts were mostly found below detection limits of the advanced mercury analyser (AMA-254) used for measuring the extracts (L.D.<0.5 ng), the use of a solid sampling atomic absorption spectrometer with a specially designed furnace for Hg atomisation was found to be an optimal technique to quantify Hg in the solid residues coming from the SEP.With this approach, mercury was found to be hardly mobile and only for one of the moderately polluted sediments (BCR CRM 320), extractable mercury (exchangeable fraction, BCR procedure step 1) has been found. An oxidation step with H(2)O(2) was required to obtain extractability up to 64% of the total content in a highly polluted lagoon sediment.     

Development of melamine certified reference material in milk using two different isotope dilution mass spectrometry techniques

A new certified reference material (CRM) of melamine in milk GLHK-11-02 was developed aiming to address the great demand from the testing community after the melamine crises. The material was prepared by adding an appropriate quantity of melamine into the skimmed milk samples and the final product was in the form of fine lyophilized powder. Characterization of the material relied on two newly developed gravimetric isotope dilution mass spectrometry (IDMS) methods, one using liquid chromatography-tandem mass spectrometry (LC-MS/MS) and another gas chromatography-mass spectrometry (GC-MS). Experimental parameters with crucial effects on the performance of the two IDMS methods were thoroughly investigated. These included purity of standard used, equilibration time of isotopes, efficiency of extraction methods as well as possible interferences from the matrix and melamine analogues. Precision was found to be excellent with a coefficient of variation of 2.5% for the LC-IDMS/MS (n=46) and 1.9% for the GC-IDMS (n=30) respectively. Using one-tail Student's t-test at 95% confidence interval, analytical data sets generated from the two methods were found to exhibit no significant difference. Measurement accuracy of the methods was further verified through an Asia Pacific Metrology Program (APMP) pilot study. Analytical results of the present LC-IDMS/MS for the two milk test samples at the concentration level of about 0.45 and 3.5 mg kg(-1) were proven to be very good. There were excellent overlaps between our results and the assigned reference values, and the absolute deviation was less than 3.2%. Both the LC-IDMS/MS and GC-IDMS methods were shown to be sufficiently reliable and accurate for certification of the melamine CRM. Certified value of melamine in dry mass fraction in GLHK-11-02 was 1.14 mg kg(-1). Expanded uncertainty due to sample inhomogeneity, long term and short term stability and variability in the characterization procedure was at 7.1% or 0.08 mg kg(-1). The CRM is primarily used to provide a complete method validation for and to improve the technical competence of melamine analysis to food and chemical testing laboratories.     

Comprehensive study of the parameters influencing the detection of organotin compounds by a pulsed flame photometric detector in sewage sludge

An investigation of the operating conditions of a pulsed flame photometric detection (PFPD) system for the determination of organotin compounds (OTCs) in sewage sludge is reported. During the analyses, some spectral interferences were observed. For their elimination detector parameters such as gate delay and gate width were investigated. In addition, the applicability of three different internal standards was evaluated. Under optimised analytical conditions (gate delay 3 ms, gate width 2 ms, tripropyltin as internal standard) limits of detection (LOD) were determined. The LOD for butyltins ranged between 8 and 16 ng Sn g(-1), for phenyltins around 8 ng Sn g(-1) and for octyltins between 5 and 10 ng Sn g(-1). Since there is no certified reference material (CRM) available for sewage sludge, the accuracy of the analytical procedure was checked by the analysis of CRM PACS-2 (marine sediment) and a spiked sludge sample. Good agreement between determined and certified values was obtained. Sewage sludge from a local wastewater treatment plant was analysed and the results compared with data from the literature.     

Optimal strategies for determination of free/extractable and total microcystins in lake sediment

The optimization of analytical procedures for the quantification of free and total microcystins (MCs) in natural sediments was systematically examined based on solvent extraction and Lemieux oxidation. In this optimized analytical procedure, a sequential solvent extraction using 50% (v/v) methanol and EDTA-sodium pyrophosphate was selected as the optimal extraction solvent for free MCs analysis, after which the purified extracts and sediment residuals were applied to the optimized Lemieux oxidation for determination of total MCs in lake sediments. The optimized procedures were shown to be efficient and reliable for the routine analysis of both free and total MCs in lake sediment samples, as indicated by the minimal adverse impact of sediment organic matter on the recovery of free MCs and yield of MMPB (2-methyl-3-methoxy-4-phenylbutyric acid). Finally, the developed procedures were applied to field sediment samples collected from Lake Dianchi during a bloom season and seven of thirty samples showed positive results.     

New Sediment and Soil CRMs for Extractable Trace Metal Content

Abstract

The lack of uniformity in leaching procedures used to measure broadly defined forms of heavy metals does not allow the results to be compared world-wide nor the methods to be validated since the results obtained are “operationally defined”. An attempt was made to certify several mineral soils CRMs for single extraction by using acetic acid, EDTA and DTPA for Cd, Cr, Cu, Ni, Pb and Zn. Recently, to complete the series of soil CRMs, an organically enriched soil was prepared SO25. For sediments a CRM 601 was produced and certified for metals extractable by using the BCR three step sequential extraction. Not all the trace elements were certified and only indicative values were given for some of them due to poor reproducibility. We performed a systematic study of the effect of the variables identified as potential sources of uncertainty in the use of this scheme. With this study the sources of uncertainty were revealed and an optimised version of the protocol was proposed. With this new version it was possible to certify all the trace elements studied. New sediment material S33 is now proposed for certification and additional data are given for the sediment CRM 601. This modified procedure was also applied to a soil CRM 483 and good results were obtained. This procedure may thus be applied to polluted soils.     

Optimized procedure for the determination of antimony in lipid-rich environmental matrices by flow injection hydride generation atomic absorption spectrometry

An analytical procedure for the reliable determination of Sb in digests of lipid-rich environmental matrices in the low ng l-1-range based on flow injection hydride generation atomic absorption spectrometry (FI-HG-AAS) has been developed. Prior to HG-AAS, aliquots (250 to 320 mg) of dry samples were mineralized with 3 ml nitric acid and 0.5 ml of each sulfuric and perchloric acids in open digestion vessels made of glassy carbon in a heating block. Procedure detection and quantification limits of a previously developed procedure for the determination of Sb in plant materials by FI-HG-AAS were decreased with respect to the lower Sb concentrations in animal tissues, the sensitivity of the instrumental response was increased, and the composition of the acid digestion mixture was re-optimized for lipid-rich samples. The accuracy and precision of the developed procedure was evaluated by the analysis of the two reference materials Bovine Liver 1577a and Pig Kidney CRM 186. These reference materials have been additionally spiked with appropriate amounts of Sb to obtain recovery data. The solution detection limit (3 sigma) in digested samples was 0.021 microgram l-1, the detection limit for the whole procedure based on the dry powders was 7 pg g-1, the method quantification limit for a reliable determination of Sb was 23 pg g-1. The reproducibility of repetitive measurements was 6.0% at 0.1 microgram Sb l-1 and 2.2% at 0.5 microgram Sb l-1. Calibration curves were linear from 0.05 to 3 micrograms Sb l-1. To demonstrate the suitability of the developed method, concentrations of Sb have been determined in pigeon eggs (approximately 2 ng Sb g-1), as well as in bream livers (approximately 4 ng g-1) and in deer livers (approximately 5 to 8 ng g-1) from animals living in remote and urban-industrialized areas of Germany, respectively.