Analysis of urban particulate standard reference materials for the determination of chlorinated organic contaminants and additional chemical and physical properties

A previously issued National Institute of Standards and Technology (NIST) Standard Reference Material (SRM), SRM 1649, Urban Dust/Organics has been analyzed for chlorinated organic contaminants (polychlorinated biphenyls and chlorinated pesticides) to provide certified values for a new class of compounds relative to the former certification. The material will be reissued as SRM 1649a. Four different analytical techniques were used. Specifically, two different methods of extraction (Soxhlet and pressurized fluid extraction) were used in conjunction with sample analysis by gas chromatography with two different columns (5% phenyl-methyl polysiloxane and 50% methyl C-18 dimethyl polysiloxane) that exhibit distinct selectivity, and with two different modes of detection (electron capture detection and mass spectrometry). The results from these techniques were combined to generate certified concentrations for 35 PCB congeners (some in combination) and 8 chlorinated pesticides. Ancillary assessments of additional chemical and physical properties of SRM 1649a include homogeneity, moisture, total organic carbon, extractable mass, and the particle-size distribution. The approach and the results for the certification of the PCB congeners and chlorinated pesticides in SRM 1649a, and the determination of the additional chemical and physical properties are described. In addition, the determination of PCBs and chlorinated pesticides in SRM 1648, Urban Particulate Matter (a particulate material certified for inorganic constituents), is also discussed although certified values are not presented. Received: 8 June 1998 / Revised: 4 September 1998 / Accepted: 26 September 1998     

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].     

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.Electronic Supplementary Material Supplementary material is available in the online version of this article at . A link in the frame on the left on that page takes you directly to the supplementary material.     

Certification of standard reference material (SRM) 1941a, organics in marine sediment

SRM 1941a, Organics in Marine Sediment, has been recently issued with certified concentrations for 23 polycyclic aromatic hydrocarbons, 21 polychlorinated biphenyl congeners, 6 chlorinated pesticides, and sulfur. Noncertified concentrations have been also reported for additional PAHs, PCB congeners, and chlorinated pesticides and for percent total organic carbon (TOC), aliphatic hydrocarbons, and trace elements. SRM 1941a is the most extensively characterized natural matrix SRM issued by the National Institute of Standards and Technology (NIST).     

Certification of SRM 1589a PCBs,pesticides, PBDEs,and dioxins/furans in human serum

The Certificate of Analysis for SRM 1589a PCBs, Pesticides, PBDEs, and Dioxins/Furans in Human Serum has been updated to include certified concentration values for 27 polychlorinated biphenyl (PCB) congeners, three chlorinated pesticides, and four polybrominated diphenyl ether (PBDE) congeners as well as reference concentration values for 27 additional PCB congeners, six additional chlorinated pesticides, three additional PBDE congeners, and selected polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). This represents an addition of concentration values for 29 PCB congeners and for PBDE congeners that were not quantified in the previous issue of SRM 1589a. With the increased number of certified and reference concentration values for PCBs and the inclusion of certified and reference concentration values for PBDEs, this serum material will be more useful as a reference material for contaminant monitoring in human tissues and fluids. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Preparation and analysis of a marine sediment reference material for the determination of trace organic constituents

Summary A new marine sediment Standard Reference Material (SRM) has been prepared and analyzed for the determination of trace organic constituents. SRM 1941, Organics in Marine Sediment, has been certified for concentrations of 11 PAHs using results obtained from gas chromatography (GC) with flame ionization detection, gas chromatography-mass spectrometry, and liquid chromatography with fluorescence detection. Non-certified values for 24 additional PAHs are also reported. GC with electron capture detection was used to provide non-certified concentrations for 15 PCB congeners and 7 chlorinated pesticides. In addition to the organic contaminants, concentrations of 32 major and trace elements were determined using neutron activation analysis, and the sulfur content was also determined using isotope dilution thermal ionization mass spectrometry.     

Preparation and analysis of a river sediment Standard Reference Material for the determination of trace organic constituents

Summary A river sediment Standard Reference Material (SRM) has been prepared and analyzed for determination of the concentrations of trace organic constituents. SRM 1939, Polychlorinated Biphenyls (PCBs) in River Sediment A, has been certified for the concentrations of three PCB congeners using the results obtained from capillary column gas chromatography with electron capture detection (GC-ECD) and from multidimensional (dual column) capillary gas chromatography with mass spectrometric detection (MCGC-MSD). For SRM certification, two independent analytical procedures are usually required. If only one analytical technique is used or if the procedures are not independent, then the concentrations are reported as noncertified or informational values rather than certified values. Noncertified values for 14 additional PCB congeners and five chlorinated pesticides, determined by GC-ECD, are also reported as well as noncertified concentrations for five polycyclic aromatic hydrocarbons (PAHs), determined using gas chromatography with mass spectrometric detection (GC-MSD). SRM 1939 complements SRM 1941, Organics in Marine Sediment, since both materials have 12 PCB congeners, five PAHs and five chlorinated pesticides in common. However, the concentrations differ by an order of magnitude for PAHs, and from one to over two orders of magnitude for the PCB congeners and chlorinated pesticides.     

Pressurized liquid extraction of organochlorine pesticides from certified solid materials

In order to propose a versatile method to use in laboratories devoted to environmental analysis, a scheme for the determination of organochlorine pesticides from different solid matrices is evaluated. Pressurized liquid extraction is chosen as the sample preparation technique, followed by the purification of the extract by means of solid-phase extraction with Envi-carb cartridge (100 m(2)/g). Finally, the extracts are analyzed by programmed temperature vaporization (PTV)-gas chromatography (GC)-electron-capture detection and PTV-GC-mass spectrometry. The suitability of the method for the analysis of different matrices is determined by the extraction and analysis of four certified reference materials of solid matrices: CRM 804-050 (soil), SRM 1941b (organics in marine sediment), SRM 1944 (New York/New Jersey waterway sediment) and SRM 1649a (Urban Dust). Good statistical concordance between the results obtained and the certified or reference concentration are observed for most of the analyzed pesticides.     

Comparison of methods for the gas-chromatographic determination of PCB congeners and chlorinated pesticides in marine reference materials

Summary Three gas-chromatographic (GC) columns with different selectivity (DB-5, DB-1701, and C-18) and two different GC detectors (electron-capture and mass-spectrometric) were used to analyze three Standard Reference Materials (SRMs), which are available from the National Institute of Standards and Technology (NIST), and two Certified Reference Materials (CRMs), which are available from the Community Bureau of Reference (BCR), for polychlorinated biphenyl (PCB) congeners and chlorinated pesticides. The materials analyzed were: SRM 1588, Organics in Cod Liver Oil; SRM 1941, Organics in Marine Sediment; SRM 1974, Organics in Mussel Tissue (Mytilus edulis); CRM 349, Chlorobiphenyls in Cod Liver Oil; and CRM 350, Chlorobiphenyls in Mackerel Oil. Results from these different methods are compared, and concentrations for additional PCB congeners and chlorinated pesticides in these reference materials, which have not been measured previously, are reported.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

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.

Three new mussel tissue standard reference materials (SRMs) for the determination of organic contaminants

Three new mussel tissue standard reference materials (SRMs) have been developed by the National Institute of Standards and Technology (NIST) for the determination of the concentrations of organic contaminants. The most recently prepared material, SRM 1974b, is a fresh frozen tissue homogenate prepared from mussels (Mytilus edulis) collected in Boston Harbor, Massachusetts. The other two materials, SRMs 2977 and 2978, are freeze-dried tissue homogenates prepared from mussels collected in Guanabara Bay, Brazil and Raritan Bay, New Jersey, respectively. All three new mussel tissue SRMs complement the current suite of marine natural-matrix SRMs available from NIST that are characterized for a wide range of contaminants (organic and inorganic). SRM 1974b has been developed to replace its predecessor SRM 1974a, Organics in Mussel Tissue, for which the supply is depleted. Similarly, SRMs 2977 and 2978 were developed to replace a previously available (supply depleted) freeze-dried version of SRM 1974a, SRM 2974, Organics in Freeze-Dried Mussel Tissue. SRM 1974b is the third in a series of fresh frozen mussel tissue homogenate SRMs prepared from mussels collected in Boston Harbor starting in 1988. SRM 1974b has certified concentration values for 22 polycyclic aromatic hydrocarbons (PAHs), 31 polychlorinated biphenyl congeners (PCBs), and 7 chlorinated pesticides. Reference values are provided for additional constituents: 16 PAHs, 8 PCBs plus total PCBs, 6 pesticides, total extractable organics, methylmercury, and 11 trace elements. PAH concentrations range from about 2 ng g^–1 dry mass (cyclopenta[cd]pyrene) to 180 ng g^–1 dry mass (pyrene). PCB concentrations range from about 2 ng g^–1 dry mass (PCB 157) to 120 ng g^–1 dry mass (PCB 153). The reference value for total PCBs in SRM 1974b is (2020 ± 420) ng g^–1 dry mass. Pesticide concentrations range from about 4 ng g^–1 dry mass (4,4-DDT) to 40 ng g^–1 dry mass (4,4-DDE). SRM 2977 has certified values for 14 PAHs, 25 PCB congeners, 7 pesticides, 6 trace elements, and methylmercury. Reference values for 16 additional PAHs and 9 inorganic constituents are provided, and information values are given for 23 additional trace elements. SRM 2978 has certified and reference concentrations for 41 and 22 organic compounds, respectively, and contains contaminant levels similar to those of SRM 1974b. Organic contaminant levels in SRM 2977 (mussels from Guanabara Bay, Brazil) are typically a factor of 2 to 4 lower than those in SRM 1974b and SRM 2978. The organic contaminant concentrations in each new mussel tissue SRM are presented and compared in this paper. In addition, a chronological review of contaminant concentrations associated with mussels collected in Boston Harbor is discussed as well as a stability assessment of SRM 1974a.Electronic Supplementary Material Supplementary material is available in the online version of this article at . A link in the frame on the left on that page takes you directly to the supplementary material.     

Determination of polychlorinated dibenzo-p-dioxin and dibenzofuran congeners in air particulate and marine sediment standard reference materials (SRMs)

Due to the limited number of environmental matrix certified reference materials (CRMs) with assigned values for natural levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), an interlaboratory study was undertaken by the National Institute of Standards and Technology (NIST) and Environment Canada to establish reference concentration values for selected PCDD/Fs in two well-characterized NIST Standard Reference Materials (SRMs): SRM 1649a (Urban Dust) and SRM 1944 (New York/New Jersey Waterway Sediment). Results from 14 laboratories were used to provide reference values for the seventeen 2, 3, 7, 8-substituted PCDD/F congeners, the totals for individual tetra- through hepta-substituted PCDD/F homologues, and the total amount of tetra- through hepta-substituted PCDD/Fs. The mass fractions for the individual 2, 3, 7, 8-substituted congeners range from approximately 0.01 microg/kg to 7 microg/kg dry mass.     

Determination of polychlorinated dibenzo-p-dioxin and dibenzofuran congeners in air particulate and marine sediment standard reference materials (SRMs)

Due to the limited number of environmental matrix certified reference materials (CRMs) with assigned values for natural levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), an interlaboratory study was undertaken by the National Institute of Standards and Technology (NIST) and Environment Canada to establish reference concentration values for selected PCDD/Fs in two well-characterized NIST Standard Reference Materials (SRMs): SRM 1649a (Urban Dust) and SRM 1944 (New York/New Jersey Waterway Sediment). Results from 14 laboratories were used to provide reference values for the seventeen 2, 3, 7, 8-substituted PCDD/F congeners, the totals for individual tetra- through hepta-substituted PCDD/F homologues, and the total amount of tetra-through hepta-substituted PCDD/Fs. The mass fractions for the individual 2, 3, 7, 8-substituted congeners range from approximately 0.01 μg/kg to 7 μg/kg dry mass.     

用于气相色谱和气相色谱-质谱测定植物样品中含氯有机污染物残留的样品前处理方法

根据植物样品中的主要干扰物质,建立了用于气相色谱(GC)和气相色谱-质谱联用(GC-MS)测定植物样品中含氯有机污染物残留的样品前处理方法,有效提高了对植物样品中有机氯农药及多氯联苯检测的灵敏度。采用均质提取法对样品进行提取,考察了凝胶渗透色谱(GPC)和固相萃取(SPE)对提取液的净化效果。结果发现,采用GC测定目标物时,提取液需经GPC和SPE两次净化;而采用GC-MS测定目标物时,仅用SPE一次净化即可。该方法快速、经济、灵敏,适合多种植物样品中有机污染物残留分析的样品前处理要求。     

Quantitative determination of polycyclic aromatic hydrocarbons, polychlorinated biphenyls and organochlorine pesticides in sewage sludges using supercritical fluid extraction and mass spectrometric detection.

Supercritical CO2 extraction (SFE) proved to be a valuable, fast, quantitative and partly selective extraction technique for determining polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and chlorinated pesticides (OCPs) in sewage sludges of different catchment areas based on a comparison study with certified reference materials (CRMs) and on recovery data. Most PCB extracts could be measured directly after SFE whereas for PAHs a short clean-up improved the final separation by high-resolution capillary gas chromatography. Due to the amount of coextracted compounds and the low levels of OCPs, extracts obtained by SFE had to be submitted to a multistep clean-up for final measurement. Average concentrations of 6.9 mg/kg dry mass (dm) for the sum of the 16 Environmental Protection Agency PAHs, 0.1 mg/kg dm for the sum of the seven PCB congeners and 0.002-0.072 mg/kg dm for the OCPs were found in the sewage sludges. Compared to studies performed earlier in our laboratory PAHs are still present in similar concentrations whereas PCB levels have decreased significantly. OCPs could be detected in only low amounts. A correlation between sludge type and degree of contamination could only be found for PAHs.     

Supercritical Fluid Extraction of Bivalve Samples for Simultaneous GC-MS Determination of Polychlorobiphenyls and Polycyclic Aromatic Hydrocarbons

Abstract

A method is presented for the simultaneous determination of polychlorobiphenyls and polycyclic aromatic hydrocarbons in bivalve samples. The method implies the fortification of the freeze-dried sample with isotopically labeled internal standards; followed by extraction with supercritical carbon dioxide modified with 3% methanol, then a simple clean-up step on a silicagel packed Pasteur pipette and, finally, determination by gaschomatography-mass spectrometry. The method requires little time and labor compared to traditional methods, uses negligible amounts of solvents and produces little wastes. Sixty different PCB congeners and seven selected PAHs are analyzed. Six replicate analyses were performed on the SRM 2974 certified material and the results are discussed.     

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. Electronic Supplementary Material Supplementary material is available for this article at http://dx.doi.org/ 10.1007/s00216-005-0227-y     

Optimization of supercritical fluid extraction by carbon dioxide with organic modifiers of polycyclic aromatic hydrocarbons from urban particulate matter

The main advantages of using supercritical fluids for the extractions of organic pollutants from environmental matrix is that they are inexpensive, contaminant free, and less costly to dispose safely than organic solvents. In this work, a series of extraction experiments were carried out using CO2 as supercritical fluid on a certified sample of "Urban dust" (NIST S.R.M. 1649a) to optimize the analytical parameters with the aim of investigating the extraction limit of organic pollutant by using an almost "organic solvent-free" technique. The certified sample contains small concentrations of several organic pollutants, as PAH and PCB. The initial tests of extraction were carried out with only CO2 in supercritical phase, by maintaining the temperature at 50 degrees C and 80 degrees C and by making the pressure vary between 230 bar and 600 bar. The effect of three organic modifiers (methanol, n-hexane and toluene), added at 5% in volume, has been considered. The yield of recovery has been estimated for anthracene, fluoranthene, chrysene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene by GC-MS according to the increasing molecular weight.     

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.     

Marine mammal blubber reference and control materials for use in the determination of halogenated organic compounds and fatty acids

The National Institute of Standards and Technology (NIST) has a diverse collection of control materials derived from marine mammal blubber, fat, and serum. Standard Reference Material (SRM) 1945 Organics in Whale Blubber was recertified for polychlorinated biphenyl (PCB) congeners, organochlorine pesticides, and polybrominated diphenyl ether (PBDE) congeners. SRM 1945 has also been assigned mass fraction values for compounds not frequently determined in marine samples including toxaphene congeners, coplanar PCBs, and methoxylated PBDE congeners which are natural products. NIST also has assigned mass fraction values, as a result of interlaboratory comparison exercises, for PCB congeners, organochlorine pesticides, PBDE congeners, and fatty acids in six homogenate materials produced from marine mammal blubber or serum. The materials are available from NIST upon request; however, the supply is very limited for some of the materials. The materials include those obtained from pilot whale blubber (Homogenates III and IV), Blainville’s beaked whale blubber (Homogenate VII), polar bear fat (Homogenate VI), and California sea lion serum (Marine Mammal Control Material-1 Serum) and blubber (Homogenate V).