Development of two fine particulate matter standard reference materials (<4 µm and <10 µm) for the determination of organic and inorganic constituents.

Two new Standard Reference Materials (SRMs), SRM 2786 Fine Particulate Matter (<4 µm) and SRM 2787 Fine Particulate Matter (<10 µm) have been developed in support of the US Environmental Protection Agency's National Ambient Air Quality Standards for particulate matter (PM). These materials have been characterized for the mass fractions of selected polycyclic aromatic hydrocarbons (PAHs), nitrated PAHs, brominated diphenyl ether (BDE) congeners, hexabromocyclododecane (HBCD) isomers, sugars, polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) congeners, and inorganic constituents, as well as particle-size characteristics. These materials are the first Certified Reference Materials available to support measurements of both organic and inorganic constituents in fine PM. In addition, values for PAHs are available for RM 8785 Air Particulate Matter on Filter Media. As such, these SRMs will be useful as quality control samples for ensuring compatibility of results among PM monitoring studies and will fill a void to assess the accuracy of analytical methods used in these studies. Graphical Abstract Removal of PM from filter for the preparation of SRM 2786 Fine Particulate Matter.

Retrospective Analysis of NIST Standard Reference Material 1450, Fibrous Glass Board, for Thermal Insulation Measurements.

Thermal conductivity data acquired previously for the establishment of Standard Reference Material (SRM) 1450, Fibrous Glass Board, as well as subsequent renewals 1450a, 1450b, 1450c, and 1450d, are re-analyzed collectively and as individual data sets. Additional data sets for proto-1450 material lots are also included in the analysis. The data cover 36 years of activity by the National Institute of Standards and Technology (NIST) in developing and providing thermal insulation SRMs, specifically high-density molded fibrous-glass board, to the public. Collectively, the data sets cover two nominal thicknesses of 13 mm and 25 mm, bulk densities from 60 kg·m(-3) to 180 kg·m(-3), and mean temperatures from 100 K to 340 K. The analysis repetitively fits six models to the individual data sets. The most general form of the nested set of multilinear models used is given in the following equation: [Formula: see text]where λ(ρ,T) is the predicted thermal conductivity (W·m(-1)·K(-1)), ρ is the bulk density (kg·m(-3)), T is the mean temperature (K) and ai (for i = 1, 2, … 6) are the regression coefficients. The least squares fit results for each model across all data sets are analyzed using both graphical and analytic techniques. The prevailing generic model for the majority of data sets is the bilinear model in ρ and T. [Formula: see text] One data set supports the inclusion of a cubic temperature term and two data sets with low-temperature data support the inclusion of an exponential term in T to improve the model predictions. Physical interpretations of the model function terms are described. Recommendations for future renewals of SRM 1450 are provided. An Addendum provides historical background on the origin of this SRM and the influence of the SRM on external measurement programs.

Development of a Standard Reference Material for metabolomics research.

The National Institute of Standards and Technology (NIST), in collaboration with the National Institutes of Health (NIH), has developed a Standard Reference Material (SRM) to support technology development in metabolomics research. SRM 1950 Metabolites in Human Plasma is intended to have metabolite concentrations that are representative of those found in adult human plasma. The plasma used in the preparation of SRM 1950 was collected from both male and female donors, and donor ethnicity targets were selected based upon the ethnic makeup of the U.S. population. Metabolomics research is diverse in terms of both instrumentation and scientific goals. This SRM was designed to apply broadly to the field, not toward specific applications. Therefore, concentrations of approximately 100 analytes, including amino acids, fatty acids, trace elements, vitamins, hormones, selenoproteins, clinical markers, and perfluorinated compounds (PFCs), were determined. Value assignment measurements were performed by NIST and the Centers for Disease Control and Prevention (CDC). SRM 1950 is the first reference material developed specifically for metabolomics research.

Breakfast cereal sampling study for nutritional elements.

The National Institute of Standards and Technology (NIST) has established a Dietary Supplement Laboratory Quality Assurance Program (DSQAP) in collaboration with the National Institutes of Health Office of Dietary Supplements (NIH-ODS). The DSQAP invites laboratories twice annually to participate in interlaboratory studies where participants elect to measure concentrations of nutritional and/or toxic elements as well as active and/or marker compounds. One of these studies was designed to determine the effects of material granularity and sample processing techniques on measurement variability (precision) as well as to provide participating laboratories information on their performance relative to the NIST assigned values (bias) and to the other participants (concordance). Participants were asked to determine the mass fractions of Ca, Fe, and Zn, in mg/kg, in six breakfast cereal samples. Cereal samples consisted of three ground materials (homogenized wheat, wheat, and rice), two flake materials (wheat and rice) and a partially crushed material (a wheat/rice mixture). In general, approximately 25% of the laboratories processed and analyzed the suite of six cereal materials with adequate to exemplary measurement precision. Over half of the laboratories (60%) experienced measurement issues related to only a particular type of cereal matrix or for only a single element. A small number (15%) of laboratories experienced significant sample processing or measurement problems. Future studies planned by the DSQAP may be designed to use commercial products to aid laboratories with their sampling and analytical techniques.

Milk and serum standard reference materials for monitoring organic contaminants in human samples.

Four new Standard Reference Materials (SRMs) have been developed to assist in the quality assurance of chemical contaminant measurements required for human biomonitoring studies, SRM 1953 Organic Contaminants in Non-Fortified Human Milk, SRM 1954 Organic Contaminants in Fortified Human Milk, SRM 1957 Organic Contaminants in Non-Fortified Human Serum, and SRM 1958 Organic Contaminants in Fortified Human Serum. These materials were developed as part of a collaboration between the National Institute of Standards and Technology (NIST) and the Centers for Disease Control and Prevention (CDC) with both agencies contributing data used in the certification of mass fraction values for a wide range of organic contaminants including polychlorinated biphenyl (PCB) congeners, chlorinated pesticides, polybrominated diphenyl ether (PBDE) congeners, and polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) congeners. The certified mass fractions of the organic contaminants in unfortified samples, SRM 1953 and SRM 1957, ranged from 12 ng/kg to 2200 ng/kg with the exception of 4,4'-DDE in SRM 1953 at 7400 ng/kg with expanded uncertainties generally <14 %. This agreement suggests that there were no significant biases existing among the multiple methods used for analysis.

Effects of sample preparation on bacterial colonization of polymers.

Characterization of materials developed for medical usage frequently includes studies in which the materials are inoculated with bacteria in order to assess bacterial colonization and biofilm formation. Observed differences in bacterial growth are typically considered to be due to the material or the incubation conditions. To our knowledge, the method used to prepare the materials has generally not been considered with regard to its influence on bacterial colonization. The objective of this study was to determine the effects that various preparation methods exert on bacterial colonization of polymer disks. Polymer disks of the same dimethacrylate composition were photopolymerized: (1) between untreated glass slides, (2) between polyester release film, (3) between glass slides treated with an alkyl silane, (4) between glass slides treated with a perfluorinated silane, or (5) with one free surface in an argon-purged chamber. Surface chemistry was quantified using X-ray photoelectron spectroscopy, hydrophobicity was assessed by water contact angle, and topography was characterized using atomic force microscopy. The disks were inoculated with Streptococcus mutans for 4 h, fixed, and visualized using confocal laser scanning microscopy. Differences among all groups were found with regard to surface chemistry, hydrophobicity, topography, and bacteria morphology, density, and coverage, indicating that the method of sample preparation strongly affects both the surface properties and the initial bacterial colonization. Polymerization on untreated slides was selected as the preferred method of preparation due to minimal material transfer to the polymer and consistent, reproducible bacterial colonization.

Separation of 26 toxaphene congeners and measurement in air particulate matter SRMs compared to technical toxaphene SRM 3067.

Toxaphene is a complex technical mixture that has been found ubiquitously in the environment but has caused issues for analysis, especially of individual congeners. This paper reports the elution order of 26 major toxaphene congeners on three gas chromatographic columns. The three different stationary phases generally had similar elution orders for the toxaphene congeners, but fewer co-elutions occurred on a low-bleed, low-polarity column. These congeners (except for two that co-eluted and were not added to the calibration mixture) were examined in air particulate matter standard reference materials (SRMs), 1648a, 1649a, and 1649b as well as SRM 3067 toxaphene in methanol for assignment of reference values. SRM 3067 had mass fractions an order of magnitude greater than the air particulate SRMs, which ranged from 0.568 +/- 0.018 ng g(-1) dry mass (B9-2006 in SRM 1648a) to 12.9 +/- 0.20 ng g(-1) dry mass (B9-715 (P 58) in SRM 1649a). The three air particulate SRMs all had different mass fractions and proportions of congeners relative to the sum of the toxaphene congeners. SRM 3067 may be useful as a technical mixture toxaphene congener calibrant. SRMs 1648a and 1649b will serve as reference materials for the analysis of 21 (three congeners were not included due to values below the detection limit or a potential polychlorinated biphenyl co-elution) toxaphene congeners in atmospheric particulate samples.

Polycyclic aromatic hydrocarbons (PAHs) in a coal tar standard reference material--SRM 1597a updated.

SRM 1597 Complex Mixture of Polycyclic Aromatic Hydrocarbons from Coal Tar, originally issued in 1987, was recently reanalyzed and reissued as SRM 1597a with 34 certified, 46 reference, and 12 information concentrations (as mass fractions) for polycyclic aromatic hydrocarbons (PAHs) and polycyclic aromatic sulfur heterocycles (PASHs) including methyl-substituted PAHs and PASHs. The certified and reference concentrations (as mass fractions) were based on results of analyses of the coal tar material using multiple analytical techniques including gas chromatography/mass spectrometry on four different stationary phases and reversed-phase liquid chromatography. SRM 1597a is currently the most extensively characterized SRM for PAHs and PASHs.

Determination of perfluorinated alkyl acid concentrations in human serum and milk standard reference materials.

Standard Reference Materials (SRMs) are certified reference materials produced by the National Institute of Standards and Technology that are homogeneous materials well characterized with values for specified properties, such as environmental contaminant concentrations. They can be used to validate measurement methods and are critical in improving data quality. Disagreements in perfluorinated alkyl acid (PFAA) concentrations measured in environmental matrices during past interlaboratory comparisons emphasized the need for SRMs with values assigned for PFAAs. We performed a new interlaboratory comparison among six laboratories and provided, for the first time, value assignment of PFAAs in SRMs. Concentrations for perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), and other PFAAs in two human serum and two human milk SRMs are reported. PFAA concentration measurements agreed for serum SRM 1957 using different analytical methods in six laboratories and for milk SRM 1954 in three laboratories. The interlaboratory relative standard deviation for PFOS in SRM 1957 was 7%, which is an improvement over past interlaboratory studies. Matrix interferences are discussed, as well as temporal trends and the percentage of branched vs. linear isomers. The concentrations in these SRMs are similar to the present-day average concentrations measured in human serum and milk, resulting in representative and useful control materials for PFAA human monitoring studies.

Characterization of SiGe films for use as a National Institute of Standards and Technology Microanalysis Reference Material (RM 8905).

Bulk silicon-germanium (SiGe) alloys and two SiGe thick films (4 and 5 microm) on Si wafers were tested with the electron probe microanalyzer (EPMA) using wavelength dispersive spectrometers (WDS) for heterogeneity and composition for use as reference materials needed by the microelectronics industry. One alloy with a nominal composition of Si0.86Ge0.14 and the two thick films with nominal compositions of Si0.90Ge0.10 and Si0.75Ge0.25 on Si, evaluated for micro- and macroheterogeneity, will make good microanalysis reference materials with an overall expanded heterogeneity uncertainty of 1.1% relative or less for Ge. The bulk Ge composition in the Si0.86Ge0.14 alloy was determined to be 30.228% mass fraction Ge with an expanded uncertainty of the mean of 0.195% mass fraction. The thick films were quantified with WDS-EPMA using both the Si0.86Ge0.14 alloy and element wafers as reference materials. The Ge concentration was determined to be 22.80% mass fraction with an expanded uncertainty of the mean of 0.12% mass fraction for the Si0.90Ge0.10 wafer and 43.66% mass fraction for the Si0.75Ge0.25 wafer with an expanded uncertainty of the mean of 0.25% mass fraction. The two thick SiGe films will be issued as National Institute of Standards and Technology Reference Materials (RM 8905).

Relative intensity correction of Raman spectrometers: NIST SRMs 2241 through 2243 for 785 nm, 532 nm, and 488 nm/514.5 nm excitation.

Standard Reference Materials SRMs 2241 through 2243 are certified spectroscopic standards intended for the correction of the relative intensity of Raman spectra obtained with instruments employing laser excitation wavelengths of 785 nm, 532 nm, or 488 nm/514.5 nm. These SRMs each consist of an optical glass that emits a broadband luminescence spectrum when illuminated with the Raman excitation laser. The shape of the luminescence spectrum is described by a polynomial expression that relates the relative spectral intensity to the Raman shift with units in wavenumber (cm(-1)). This polynomial, together with a measurement of the luminescence spectrum of the standard, can be used to determine the spectral intensity-response correction, which is unique to each Raman system. The resulting instrument intensity-response correction may then be used to obtain Raman spectra that are corrected for a number of, but not all, instrument-dependent artifacts. Peak area ratios of the intensity-corrected Raman spectrum of cyclohexane are presented as an example of a methodology to validate the spectral intensity calibration process and to illustrate variations that can occur in this measurement.

Excitation-emission matrix fluorescence spectroscopy for natural organic matter characterization: a quantitative evaluation of calibration and spectral correction procedures.

The influence of different data collection procedures and of wavelength-dependent instrumental biases on fluorescence excitation-emission matrix (EEM) spectral analysis of aqueous organic matter samples was investigated. Particular attention was given to fluorescence contours (spectral shape) and peak fluorescence intensities. Instrumental bias was evaluated by independently applying excitation and emission correction factors to the raw excitation and emission data, respectively. The peak fluorescence intensities of representative natural organic matter and tryptophan were significantly influenced by the application of excitation and emission spectral correction factors and by the manner in which the raw data was collected. Humification and fluorescence indices were also influenced by emission correction factors but were independent of reference (excitation) intensity normalization or correction. EEM surface contours were dependent on normalization of the fluorescence intensity to the reference intensity but were not influenced by either excitation or emission spectral correction factors. Authors should be explicit in how excitation and emission spectral correction procedures are implemented in their investigations, which will help to facilitate intra-laboratory comparisons and data sharing.

Potassium Bromate Assay by Redox Titrimetry Using Arsenic Trioxide.

Bromate, a disinfectant, is one of the analytes of interest in wastewater analysis. Environmental laboratories have a regulatory need for their measurements to be traceable to NIST standards. Bromate is not currently certified as a NIST Standard Reference Material (SRM). Therefore, a traceable assay of potassium bromate (KBrO3) is needed. KBrO3 was dissolved in water and assayed by redox titrimetry using arsenic trioxide (As2O3). A nominal (0.1 g) sample of As2O3 was dissolved in 10 mL of 5 mol/L sodium hydroxide. The solution was acidified with hydrochloric acid and about 95 % of the KBrO3 titrant was added gravimetrically. The end point was determined by addition of dilute (1:3) titrant using an automated titrator. The KBrO3 assay was determined to be 99.76 % ± 0.20 %. The expanded uncertainty considered the titrations of three independently prepared KBrO3 solutions.

Standard Reference Materials (SRMs) for the Calibration and Validation of Analytical Methods for PCBs (as Aroclor Mixtures).

Six Standard Reference Materials (SRMs®) have been prepared by the National Institute of Standards and Technology (NIST) for the determination of PCBs as different Aroclor mixtures in methanol. Six additional SRMs of the same Aroclors in transformer oil have also been prepared. Specifically, solutions of Aroclors 1016, 1232, 1242, 1254, and 1260 have been gravimetrically prepared (individually) in methanol and transformer oil, mixed, and transferred to amber glass ampoules in approximately 1.2 mL aliquots. Gas chromatography with electron capture detection (GC-ECD) has been used to verify the gravimetric data for each solution and transformer oil SRM. Liquid chromatography was used for the isolation of the Aroclors from the transformer oil SRMs prior to GC-ECD analysis. Separate calibration solutions and oils were prepared with Aroclor levels similar to those in each methanol solution and transformer oil SRM and were processed alongside the samples. The GC-ECD response of each Aroclor was monitored relative to internal standards that were added to the complex mixtures for quantification. The gravimetric concentrations of Aroclors 1242 and 1254 in methanol were also examined by the same method of analysis (GC-ECD) using several different sources of Aroclors and two different capillary GC columns: a 5 % phenyl methylpolysiloxane phase and a relatively non-polar phase. The preparation of the materials, the gas chromatographic results, and the certified concentration values for each Aroclor SRM are described in this paper.

Determination of polybrominated diphenyl ethers in environmental standard reference materials.

Standard reference materials (SRMs) are valuable tools in developing and validating analytical methods to improve quality assurance standards. The National Institute of Standards and Technology (NIST) has a long history of providing environmental SRMs with certified concentrations of organic and inorganic contaminants. Here we report on new certified and reference concentrations for 27 polybrominated diphenyl ether (PBDE) congeners in seven different SRMs: cod-liver oil, whale blubber, fish tissue (two materials), mussel tissue and sediment (two materials). PBDEs were measured in these SRMs, with the lowest concentrations measured in mussel tissue (SRM 1974b) and the highest in sediment collected from the New York/New Jersey Waterway (SRM 1944). Comparing the relative PBDE congener concentrations within the samples, we found the biota SRMs contained primarily tetrabrominated and pentabrominated diphenyl ethers, whereas the sediment SRMs contained primarily decabromodiphenyl ether (BDE 209). The cod-liver oil (SRM 1588b) and whale blubber (SRM 1945) materials were also found to contain measurable concentrations of two methoxylated PBDEs (MeO-BDEs). Certified and reference concentrations are reported for 12 PBDE congeners measured in the biota SRMs and reference values are available for two MeO-BDEs. Results from a sediment interlaboratory comparison PBDE exercise are available for the two sediment SRMs (1941b and 1944).

Development of a house dust standard reference material for the determination of organic contaminants.

National-level health survey studies, such as the National Human Exposure Assessment Survey field program, have targeted the determination of organic contaminants in house dust in an effort to characterize human exposure in the domestic environment. As the effort to further understand human health effects in relation to organic contaminants associated with indoor dust accelerates, the need for an indoor dust Standard Reference Material (SRM) that is characterized for organic contaminants has become critical. To meet this need, a new organic contaminant house dust SRM has been developed. SRM 2585 Organic Contaminants in House Dust is intended for use in evaluating analytical methods for the determination of selected polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyl (PCB) congeners, chlorinated pesticides, and polybrominated diphenyl ether (PBDE) congeners in house dust and similar matrices. The material may also be useful for evaluation and comparison of methods or instruments used for sampling in the indoor environment. Moreover, because of the material's extensive characterization (140 organic contaminant concentrations), the material may be useful in toxicity studies related to indoor air (in vitro or in vivo). The determination of the concentrations of PAHs (including alkyl-PAHs and PAHs with molecular mass 300 and 302), PCBs, and chlorinated pesticides is reported here, and these results are compared to values reported in the literature for house dust.

Development of a murre (Uria spp.) egg control material.

The Seabird Tissue Archival and Monitoring Project (STAMP) is a collaborative Alaska-wide effort by the US Fish and Wildlife Service's Alaska Maritime National Wildlife Refuge (USFWS/AMNWR), the US Geological Survey's Biological Resources Division (USGS/BRD), the Bureau of Indian Affairs Alaska Region Subsistence Branch (BIA/ARSB), and the National Institute of Standards and Technology (NIST) to monitor long-term (decadal) trends in environmental contaminants using seabird eggs. To support this effort, a matrix- (seabird egg) and concentration-specific control material was needed to ensure quality during analytical work. Although a herring gull egg quality assurance (HGQA) material is available from Environment Canada (EC), contaminant concentrations in this material tended to be higher than those observed in Alaskan murre (Uria spp.) eggs. Therefore, to prepare a more appropriate control material, a total of 12 common murre (U. aalge) and thick-billed murre (U. lomvia) eggs from four Bering Sea and Gulf of Alaska nesting locations were cryohomogenized to create 190 aliquots each containing approximately 6 g. This new control material was analyzed by different methods at NIST and EC facilities for the determination of concentrations and value assignment of 63 polychlorinated biphenyl (PCB) congeners, 20 organochlorine pesticides, and 11 polybrominated diphenyl ether (PBDE) congeners. The total PCB concentration is approximately 58 ng g(-1) wet mass. Results obtained for analytes not listed on the certificates of analysis of the previously used control materials, HGQA and NIST's Standard Reference Material (SRM) 1946 Lake Superior Fish Tissue, are also presented.

Determination of polybrominated diphenyl ethers in indoor dust standard reference materials.

Polybrominated diphenyl ethers (PBDEs) have been measured for the first time in three different indoor dust Standard Reference Materials (SRMs) prepared by the National Institute of Standards and Technology (NIST). Two of these, SRM 2583 (Trace Elements in Indoor Dust) and SRM 2584 (Trace Elements in Indoor Dust), have been certified previously for lead and other inorganic constituents. A third, SRM 2585 (Organics in Indoor Dust), is a new indoor dust reference material prepared by NIST which will be certified for various organic compounds (polycyclic aromatic hydrocarbons, pesticides and polychlorinated biphenyls) in 2005 including certified concentrations for 16 individual PBDE congeners and reference values for an additional three PBDE congeners. Dust SRMs were analyzed for 30 PBDE congeners using high-resolution gas chromatography combined with low-resolution mass spectrometry operated in both negative chemical ionization (GC/ECNI-MS) and electron impact ionization (GC/EI-MS) modes. Sensitivity was an order of magnitude higher using GC/ECNI-MS relative to GC/EI-MS. These SRMs have been characterized and compared to the three PBDE commercial products (pentaBDE, octaBDE and decaBDE). PentaBDE and DecaBDE were present in all three SRMs and were the dominant commercial products, making up approximately 33% and 58%, respectively. Recent studies suggest that house dust may be a leading source of human exposure to PBDEs. These SRMs are the first reference materials with certified concentrations for PBDEs, which will aid in validating future measurements of PBDEs in house dust and other similar matrices.

Determination of polychlorinated biphenyl congeners and chlorinated pesticides in a fish tissue standard reference material.

The concentrations of a wide range of polychlorinated biphenyl congeners (PCBs) and chlorinated pesticides in a fish tissue Standard Reference Material (SRM) have been determined using multiple methods of analysis. This material, SRM 1946, Lake Superior Fish Tissue, was recently issued by the National Institute of Standards and Technology (NIST) and complements a suite of marine environmental natural-matrix SRMs that are currently available from NIST for the determination of organic contaminants such as aliphatic hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), PCBs, and chlorinated pesticides. SRM 1946 is a fresh tissue homogenate (frozen) prepared from filleted adult lake trout (Salvelinus namaycush namaycush) collected from the Apostle Islands region of Lake Superior. SRM 1946 has certified and reference concentrations for PCB congeners, including the three non- ortho PCB congeners, and chlorinated pesticides. Certified concentrations are available for 30 PCB congeners and 15 chlorinated pesticides. Reference concentrations are available for 12 PCB congeners and 2 chlorinated pesticides. In addition, SRM 1946 is characterized for additional chemical constituents and properties: fatty acids, extractable fat, methylmercury, total mercury, selected trace elements, proximates, and caloric content. The characterization of chlorinated compounds is described in this paper with an emphasis on the approach used for the certification of the concentrations of PCB congeners and chlorinated pesticides. The PCB congener and chlorinated pesticide data are also compared to concentrations in other marine natural-matrix reference materials available from NIST (fish oil, mussel tissue, whale blubber, and a second fresh frozen fish tissue homogenate prepared from filleted adult lake trout collected from Lake Michigan) and from other organizations such as the National Research Council Canada (ground whole carp), the International Atomic Energy Agency (fish homogenate), and the European Commission Joint Research Centre [fish oils (cod and mackerel) and mussel tissue].