Marine Sediment Certified Reference Materials Research Articles

Tessier sequential extraction on 17 elements from three marine sediment certified reference materials (HISS-1, MESS-4, and PACS-3).

The four-step Tessier sequential extraction procedure is a well-known approach used for environmental and geochemical studies in soil and sediments. However, a lack of reference materials limits its use making implementation and quality control cumbersome. This study applied Tessier sequential extraction to three globally used marine sediment certified reference materials (CRMs) including HISS-1, MESS-4, and PACS-3 with varying levels of contamination. The study analyzed the distribution of 17 elements throughout the extraction phases. Overall, the percent recovery (sum of steps vs total metal concentration) of all analyzed elements in Tessier extraction was 92%+40% in HISS-1, 101%+12% in MESS-4, and 102%+10% in PACS-3. The observed uncertainty of the individual elemental concentrations averaged at 13%, which compares favorably with the 16% target uncertainty derived from the Horwitz equation. The reference data set produced here using the Tessier sequential extraction procedure will serve as a quality control and method development tool for laboratories. Graphical abstract.

Determination of 27 metals in HISS-1, MESS-4 and PACS-3 marine sediment certified reference materials by the BCR sequential extraction

The BCR sequential extraction procedure developed by the European Community Bureau of Reference was applied to the three marine sediment certified reference materials (CRMs). These CRMs are designated as HISS-1, MESS-4, and PACS-3 and comprise respectively pristine, moderately-contaminated, and highly-contaminated sediments, respectively. The study aimed to provide values of extractable elements in reference materials of varied geological origin to support method development and quality control efforts. Concentrations of 27 elements extracted in the three sequential extraction steps and in the residue were determined. The extraction steps consisted of: Step 1 – acetic acid extraction (targeting the exchangeable, water- and acid-soluble fraction); Step 2 – hydroxylammonium chloride extraction (targeting the reducible fraction); and Step 3 – hydrogen peroxide extraction (targeting the oxidizable fraction). The results from two independent laboratories using the sequential extraction procedure for the 27 elements were combined using the DerSimonian-Laird method of analysis implemented in the NIST Consensus Builder software.The percent recovery (sum steps vs total metal content) of 27 elements ranged from 68% to 125% in HISS-1, 76%–119% in MESS-4, and 70%–125% in PACS-3, based on the certified values. The combined uncertainty (k = 2) was from 1% to 39% for HISS-1, 3%–45% for MESS-4, and 3%–21% for PACS-3. Comparing the three extraction steps, the uncertainty of Step 3 was the highest for all the three CRMs. The agglomerate sediments in MESS-4 resulted in high uncertainty when compared to HISS-1 and PACS-3. The method validation showed the BCR sequential extraction procedure can apply to other elements including As, Co, Li, Mn, and V.

A new marine sediment certified reference material (CRM) for the determination of persistent organic contaminants: IAEA-459.

A new marine sediment certified reference material (IAEA 459) with very low concentrations (μgkg-1) for a variety of persistent organic contaminants (POPs) listed by the Stockholm Convention, as well as other POPs and priority substances (PSs) listed in many environmental monitoring programs was developed by the IAEA. The sediment material was collected from the Ham River estuary in South Korea, and the assigned final values were derived from robust statistics on the results provided by selected laboratories which demonstrated technical and quality competence, following the guidance given in ISO Guide 35. The robust mean of the laboratory means was assigned as certified values, for those compounds where the assigned value was derived from at least five datasets and its relative expanded uncertainty was less than 40% of the assigned value (most of the values ranging from 8 to 20%). All the datasets were derived from at least two different analytical techniques which have allowed the assignment of certified concentrations for 22 polychlorinated biphenyl (PCB) congeners, 6 organochlorinated (OC) pesticides, 5 polybrominated diphenyl ethers (PBDEs), and 18 polycyclic aromatic hydrocarbon (PAHs). Mass fractions of compounds that did not fulfill the criteria of certification are considered information values, which include 29 PAHs, 11 PCBs, 16 OC pesticides, and 5 PBDEs. The extensive characterization and associated uncertainties at concentration levels close to the marine sediment quality guidelines will make CRM 459 a valuable matrix reference material for use in marine environmental monitoring programs.

Certification for trace elements and methyl mercury mass fractions in IAEA-456 marine sediment sample

Marine sediment certified reference material (CRM), IAEA-456 was recently produced by the Environment Laboratories of the International Atomic Energy Agency (IAEA) and certified for trace elements and methyl mercury (CH3Hg). This paper presents the sample preparation methodology, material homogeneity and stability studies, evaluation of results from the characterisation campaign, the assignment of property values and their associated uncertainty. The reference values and associated expanded uncertainty for nine trace elements (Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn) and CH3Hg in marine sediment sample are established. The new CRM can be used for the development and validation of analytical methods, for the determination of trace elements and methyl mercury in sediments and also for quality assurance/quality control purposes.

Preconcentration of Nickel(II) by a Mini-Flow System with a Novel Ternary Oxide Solid Phase and Flame Atomic Absorption Spectrometry

ABSTRACTA SiO2/Al2O3/Sb2O5 mixed oxide was synthesized via a sol-gel method and applied to the on-line preconcentration of Ni(II) with determination by flame atomic absorption spectrometry. The mixed oxide was characterized by infrared spectroscopy, scanning electron microscopy, energy dispersive X-ray fluorescence, thermogravimetric analysis, and the specific surface area. Analysis was performed by percolating 20.0 mL of sample at pH 7.1 through 100 mg of SiO2/Al2O3/Sb2O5 packed into a mini-column at 9.5 mL min−1. Under the optimum conditions, a preconcentration factor of 77.5-fold, linear dynamic range from 5.0 to 270.0 µg L−1, and limits of detection and quantification of 0.48 and 1.61 µg L−1 were obtained. The effects of several concomitant ions were evaluated and no interferences were observed. The method was employed for the analysis of water with good recoveries (92.9–100.6%) and the accuracy was verified by using a marine sediment certified reference material (MESS-3).

3-mercaptopropyltrimethoxysilane-Modified Multi-walled Carbon Nanotubes as a New Functional Adsorbent for Flow Injection Extraction of Pb(II) from Water and Sediment Samples

In the present study, a novel synthesized adsorbent material based on 3-mercaptopropyltrimethoxysilane-functionalized multi-walled carbon nanotubes was used to increase the Pb2+ adsorption from aqueous solutions in a flow injection solid-phase extraction system coupled to flame atomic absorption spectrometry. Spectroscopic and microscopic techniques (Fourier transform infrared spectroscopy, energy dispersive spectroscopy, and scanning electron microscopy) were employed to confirm the chemical modification of the adsorbent surface. Preconcentration conditions (sample pH, flow rate, buffer solution, and eluent concentrations) were optimized using factorial and Doehlert matrix designs that made it possible to construct a linear graph in the 5.0- to 130.0-μg L−1 range (r = 0.9999) and estimate detection and quantification limits (1.7 and 5.7 μg L−1, respectively). The method precision was found to be 4.20 and 1.97 % for 5.0 and 100.0 μg L−1 Pb2+ solutions, respectively. When using the 3-mercaptopropyltrimethoxysilane-functionalized multi-walled carbon nanotubes, the sensitivity for the Pb2+ trace determination was improved to 95 % compared with the oxidized multi-walled carbon nanotubes, thus evidencing the significant enhancement of the adsorption capacity. The developed method was successfully applied to the analysis of Pb2+ species in different water samples and the PACS-2 marine sediment-certified reference material.

Determination of Total Chromium in the Marine Sediment Certified Reference Material by Inductively Coupled Plasma Optical Emission Spectrometry after Pressurized Acid Decomposition

(1) The marine sediment (NMIJ CRM 7302a) was directly decomposed with a mixture of 1 mL of hydrofluoric acid, 1 mL of nitric acid and 8 mL of (1 + 1)sulfuric acid in a Teflon sealed vessel at 230°C for 16 h. The total chromium was determined. (2) An indirect acid method after the decomposition of organic materials by H2SO4-HNO3 was compared to a direct acid decomposition method (1). The analytical results of the total-chromium (t-Cr) by methods (1) and (2) coincided with the certified value of the NMIJ CRM 7302a. The direct method of (1) was recommended for a pre-treatment of a marine sediment sample. On the other hand, an electron probe micro-analyzer (EPMA) was applied to an element analysis of the trace precipitation in a direct acid decomposition process in a Teflon-sealed vessel. The white trace precipitation was a crystal of AlF, and the black trace precipitation was carbon. Trace chromium was not detected by the precipitations. How to obtain accurate data from the pre-treatments was discussed regarding the data of this method and other data : that is EPA 3050B, ISO 11466, EPA 3052B, or NAA found from the Union Internationale des Laboratories Indepentants, Inter-Laboratoriy Practice report. The importance of deciding the assigned value was discussed for a statistical evaluation of the data of participants in a proficiency testing. The certified reference materials (CRM) should be furnished by both the sheet decomposition methods of CRM in addition to methods (sheet) for accurate quantitative analyses of the analytes in the CRM.

Geochemical analysis of marine sediments using fused glass disc by X-ray fluorescence spectrometry

A method was developed for content determination of Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Nb, Zr, Y, Sr, Rb, Ba, La and Ce etc. covering 26 major, minor, and trace elements in marine sediment samples using fused glass disc by X-ray Fluorescence spectrometry. Calibration was made using marine sediment certified reference materials and the synthetic standard samples prepared by mixing several marine sediments with stream sediment and carbonate standard samples in different proportions. The matrix effect was corrected using theoretical alpha coefficients, experience coefficients and the scattered radiation as the internal standard (for the trace elements). The accuracy of the method was evaluated by analysis of certified reference materials GBW07314, GBW07334 and GSMS6. The results are in good agreement with the certified values of the standards with RSD less than 2.60%, except for Y, Cr, Ga, Ce, La, Nb, Rb, and V with RSD less than 9.0% (n=12).

Matrix certified reference materials for environmental monitoring from the National Metrology Institute of Japan (NMIJ)

Matrix certified reference materials (CRMs) are playing an increasingly important role in environmental monitoring in Japan. The National Metrology Institute of Japan (NMIJ)/National Institute of Advanced Industrial Science and Technology (AIST) has been developing matrix CRMs for environmental monitoring since 2001, and has issued nine kinds of CRMs as NMIJ CRMs. The development of the CRMs was conducted in NMIJ in cooperation with candidate material producers. The isotope dilution mass spectrometry (IDMS) was principally adopted to give reliable certified values. Meanwhile, two or more analytical methods, whose levels of accuracy were well evaluated, were applied to avoid any possible analytical bias. Two typical certification processes, the certification of river water CRMs for trace element analysis and that of marine sediment CRMs for PCB and organochlorine pesticide analysis, are outlined as examples.

Sediment certified reference materials for the determination of polychlorinated biphenyls and organochlorine pesticides from the National Metrology Institute of Japan (NMIJ)

Two marine sediment certified reference materials, NMIJ CRM 7304-a and 7305-a, have been issued by the National Metrology Institute of Japan in the National Institute of Advanced Industrial Science and Technology (NMIJ/AIST) for the determination of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs). The raw materials of the CRMs were collected from a bay near industrial activity in Japan. Characterization of these CRMs was conducted by NMIJ, where the sediments were analyzed using multiple analytical methods such as pressurized liquid extraction (PLE), microwave-assisted extraction (MAE), saponification, Soxhlet extraction, supercritical fluid extraction (SFE), and ultrasonic extraction; the target compounds were determined by one of the primary methods of measurements, isotope dilution-mass spectrometry (ID-MS). Certified values have been provided for 14 PCB congeners (PCB numbers 3, 15, 28, 31, 70, 101, 105, 138, 153, 170, 180, 194, 206, 209) and 4 OCPs (gamma-HCH, 4,4'-DDT, 4,4'-DDE, 4,4'-DDD) in both CRMs. NMIJ CRM 7304-a has concentrations of the contaminants that are a factor of 2-15 greater than in CRM 7305-a. Both CRMs have information values for PCB homolog concentrations determined by collaborative analysis using a Japanese official method for determination of PCBs. The total PCB concentrations in the CRMs are approximately 920 and 86 microg kg(-1) dry mass respectively.

Certification of butyltins and phenyltins in marine sediment certified reference material by species-specific isotope-dilution mass spectrometric analysis using synthesized 118Sn-enriched organotin compounds

A new marine sediment certified reference material, NMIJ CRM 7306-a, for butyltin and phenyltin analysis has been prepared and certified by the National Metrological Institute of Japan at the National Institute of Advanced Industrial Science and Technology (NMIJ/AIST). Candidate sediment material was collected at a bay near industrial activity in Japan. After air-drying, sieving, and mixing the material was sterilized with γ-ray irradiation. The material was re-mixed and packaged into 250 glass bottles (15 g each) and these were stored in a freezer at −30 °C. Certification was performed by use of three different types of species-specific isotope-dilution mass spectrometry (SSID–MS)—SSID–GC–ICP–MS, SSID–GC–MS, and SSID–LC–ICP–MS, with 118Sn-enriched organotin compounds synthesized from 118Sn-enriched metal used as a spike. The 118Sn-enriched mono-butyltin (MBT), dibutyltin (DBT), and tributyltin (TBT) were synthesized as a mixture whereas the 118Sn-enriched di-phenyltin (DPhT) and triphenyltin (TPhT) were synthesized individually. Four different extraction methods, mechanical shaking, ultrasonic, microwave-assisted, and pressurized liquid extraction, were adopted to avoid possible analytical bias caused by non-quantitative extraction and degradation or inter-conversion of analytes in sample preparations. Tropolone was used as chelating agent in all the extraction methods. Certified values are given for TBT 44±3 μg kg−1 as Sn, DBT 51 ± 2 μg kg−1 as Sn, MBT 67 ± 3 μg kg−1 as Sn, TPhT 6.9 ± 1.2 μg kg−1 as Sn, and DPhT 3.4 ± 1.2 μg kg−1 as Sn. These levels are lower than in other sediment CRMs currently available for analysis of organotin compounds.

Two new marine sediment standard reference materials (SRMs) for the determination of organic contaminants

Two new marine sediment standard reference materials (SRMs), SRM 1941b Organics in Marine Sediment and SRM 1944 New York/New Jersey Waterway Sediment, have been recently issued by the National Institute of Standards and Technology (NIST) for the determination of organic contaminants including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyl (PCB) congeners, and chlorinated pesticides. Both sediment SRMs were analyzed using multiple analytical methods including gas chromatography/mass spectrometry (GC/MS) on columns with different selectivity, reversed-phase liquid chromatography with fluorescence detection (for PAHs only), and GC with electron capture detection (for PCBs and pesticides only). SRM 1941b has certified concentrations for 24 PAHs, 29 PCB congeners, and 7 pesticides, and SRM 1944 has certified concentrations for 24 PAHs, 29 PCB congeners, and 4 pesticides. Reference concentrations are also provided for an additional 58 (SRM 1941b) and 39 (SRM 1944) PAHs, PCB congeners, and pesticides. SRM 1944, which was collected from multiple sites within New York/New Jersey coastal waterways, has contaminant concentrations that are generally a factor of 10-20 greater than SRM 1941b, which was collected in the Baltimore (Maryland) harbor. These two SRMs represent the most extensively characterized marine sediment certified reference materials available for the determination of organic contaminants.

Solid phase extractive preconcentration of uranium(VI) onto diarylazobisphenol modified activated carbon

Diarylazobisphenol (DAB) 1 and diarylazobisphenol modified carbon 2 were synthesized and characterised. The latter has been used for solid phase extractive preconcentration and separation of trace amounts of uranium(VI) from other inorganics. In this, a column mode preconcentration of uranium(VI) was carried out in the pH range 4.0–5.0, eluted with 1.0moll−1 HCl and determined by an Arsenazo III spectrophotometric procedure. Calibration graphs were rectilinear over the uranium(VI) concentrations in the range 5–200μgl−1. Five replicate determinations of 25μg of uranium(VI) present in 1l solution gave a mean absorbance of 0.032 with a relative standard deviation of 2.52%. The detection limit corresponding to three times the standard deviation of the blank was found to be 5μgl−1. The accuracy of the developed preconcentration method in conjunction with the Arsenazo III procedure was tested by analysing MESS-3, a marine sediment certified reference material. Further, the above procedure has been successfully employed for analysis of uranium(VI) in soil and sediment samples.

Certification of mono-, di-, and tributyltin compounds in marine sediment certified reference material by species-specific isotope dilution mass spectrometric analysis using synthesized 118Sn-labeled butyltins.

A new marine sediment reference material (NMIJ CRM 7301-a) for butyltins analysis was prepared and certified by the National Metrological Institute of Japan, National Institute of Advanced Industrial Science and Technology (NMIJ/AIST). The original material of the sediment was collected at a bay near industrial activities in Japan. The sediment material was air-dried, sieved, homogenized, and packaged into 1,000 glass bottles (60 g each). Certification of NMIJ CRM 7301-a was carried out at NMIJ using two different types of species-specific isotope dilution mass spectrometry: isotope dilution-ethylation-gas chromatography/inductively coupled plasma mass spectrometry (GC/ICPMS) and isotope dilution-ethylation-gas chromatography/mass spectrometry (GC/MS). A mixture of (118)Sn-enriched monobutyltin, dibutyltin, and tributyltin was synthesized in our laboratory and was used as a spike for both techniques. Certified values are given for tributyltin (0.044+/-0.004 mg kg(-1) as Sn), dibutyltin (0.056+/-0.006 mg kg(-1) as Sn, and monobutyltin (0.058+/-0.013 mg kg(-1) as Sn), being at lower levels than currently available sediment CRMs for the analysis of organotins.

Synthesis and Analytical Applications of Uranyl Ion Imprinted Polymer Particles

Uranyl ion imprinted polymer particles were prepared by the copolymerization of styrene monomer and a crosslinking agent divinyl benzene in the presence of -5,7-dichloroquinoline-8-ol-4-vinyl pyridine ternary complex as template where in is the imprint ion in presence of 2,2′-azo-bis-isobutyronitrile as initiator. The Uranyl ion was removed from the polymer particles by leaching with 1:1 HCl, which leaves cavities in the polymer particles. The leached polymer particles preconcentrate ion from dilute aqueous and synthetic seawater solutions. Further, these particles find use in the separation of ion from various bivalent, trivalent, and tetravalent, inorganic ions. The accuracy of the developed enrichment procedure was tested by analyzing marine sediment certified reference material supplied by National Research Council (NRC), Canada. Further, the developed procedure has been successfully employed to analyze real soil and sediment samples.

Hydride generation-electrostatic deposition-graphite furnace atomic absorption spectrometric determination of arsenic, selenium and antimony

A system is described and evaluated for the in situ collection of generated hydrides of As, Se and Sb in a graphite furnace using a high voltage electrostatic field. Analytical figures of merit are derived using graphite furnace atomic absorption detection and a characterization of the electrostatic deposition (ED) process is presented based on optimization studies. Absolute detection limits (LOD) of 30, 16 and 33 pg were obtained for As, Se and Sb, respectively, reflecting overall generation/collection efficiencies of 80±5, 71±3 and 62±6%, respectively. Precision of replicate determination was typically 4% R.S.D. at a concentration 40-fold above the LOD for a 1 ml sample volume. The accuracy of the approach was demonstrated through the analysis of coastal seawater and marine sediment certified reference materials.

Marine Sediment Certified Reference Material for Tin Speciation

A certified reference material for organotin analysis (NIES CRM No. 12 Marine Sediment) was prepared at National Institute for Environmental Studies. The starting material was a surface sediment sampled at the center of Tokyo Bay in 1989. The chemical and physical properties of the material indicated homogeneity of this CRM at practical level. Certified values are given for tributhyltin (0.19±0.03 mg TBT/kg dry wt.) and total tin (10.7±1.4 mg/kg dry wt.) contents and a reference value for triphenyltin (0.008 mg TPT/kg dry wt.) based on the analytical results from collaborative analysis. The organotin levels in this CRM are higher than the current average level of, but within the range of, TBT and TPT found in marine sediment along the Japanese coast. This CRM will be of practical value in the quality assurance of organotin analysis in marine environmental monitoring programs.

Flame sample introduction system for inductively coupled plasma atomic emission spectrometry

An oxygen–hydrogen flame sample introduction system for inductively coupled plasma (ICP) atomic emission spectrometry is discussed. Linking two dissimilar sources was found to be a non-trivial exercise. A total consumption burner oxyhydrogen flame–ICP tandem source was used for the analysis of slurries of marine sediment Certified Reference Materials with particle diameters of less than 2 µm. Significant memory effects were observed. Detection limits were 0.3 ppm for Cu, 1 ppm for Mn and 1 ppm for Zn and the precision ranged between 1% and 3%(both determined using aqueous standards).