2002 Analytical Chemistry Division Archive News
New and Renewal SRMS Released
New SRMs - SRMs 2721 and 2722 Crude Oil SRMs for Sulfur, Mercury, and Water Analysis
W.Robert Kelly, Analytical Chemistry Division
NIST announces the release of two Standard Reference Materials (SRMs) - 2721 Crude Oil (Light-Sour) and 2722 Crude Oil (Heavy-Sweet) which are certified for sulfur, mercury, and water. These two SRMs are commercial crude oils from two different Texas fields. They will be useful for evaluating current and new analytical techniques and calibrating instruments for total sulfur, mercury, and water in crude oil and materials of a similar matrix.
Each crude oil used was passed through a 10µm filter and blended before being ampouled. A unit of each crude oil consists of five amber ampoules, each containing approximately 10 mL of crude oil.
With recent increased global interest in sulfur and mercury contaminants in fuels, these SRMs are expected to be valuable additions to petroleum laboratories worldwide.
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New SRMs - SRM 2241 Relative Intensity Correction Standard for Raman Spectroscopy
Steven Choquette, Analytical Chemistry Division
SRM 2241 Relative Intensity Correction Standard for Raman Spectroscopy is a certified spectroscopic standard for the correction of the relative intensity of Raman spectra obtained with instruments employing 785 nm laser excitation. SRM 2241 consists of an optical glass that emits a broadband luminescence spectrum when excited with 785 nm laser radiation. The relative spectral intensity of the glass luminescence has been determined through the use of a white-light, uniform-source, integrating sphere that has been calibrated for its irradiance at NIST.
The shape of the luminescence spectrum of this glass is described by a polynomial expression that relates the relative spectral intensity to the wavenumber (cm-1) expressed as the Raman shift from the excitation wavelength of 785 nm. This polynomial, together with a measurement of the luminescence spectrum of the standard, can be used to determine the spectral intensity response corrction that is unique to each Raman system. The resulting instrument-intensity response correction may then be used to obtain Raman spectra that are instrument independent.
This SRM is intened for use in measurements over the range of 20 °C to 25 °C and with Raman systems that employ laser excitation at 785 nm. It may also be used for Raman excitation with lasers that range from 784nm to 786 nm in excitation wavelength.
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New SRMs - SRM 2298 Sulfur in Gasoline (High Octance)
W.Robert Kelly, Analytical Chemistry Division
Federal, state, and foreign nations' guidelines and standards for the release of sulfur from high-octane gasoline to the atmosphere are constantly being tightened. Certain high-performance automobile engines, as well as aircraft engines require high octane gasoline, but these engines also must reduce their sulfur emissions to the atmosphere, to comply with ever more stringent guidelines. To ensure that engine emissions meet these guidelines, the manufacture of high octane gasoline with sharply reduced sulfur content is required. Manufacturers must show that the use of their products will ensure that engines meet emission guidelines.
NIST announces the release of reference values for its SRM 2298 Sulfur in Gasoline (High Octane), which will be applied to evaluating methods and calibrating instruments used to determine total sulfur in gasoline or materials of similar matrix. A unit of SRM 2298 consists of five amber ampoules, each one of which contains about 20 mL of gasoline, which was donated by ExxonMobil Company (Fairfax, VA).
The certified value is based on analyses by isotope dilution thermal ionization mass spectrometry (ID-TIMS). Homogeneity testing was done by X-ray fluorescence spectrometry. The uncertainty in the certified value, expressed as an expanded uncertainty, is calculated according to the method in the ISO Guide, and is based on a 95 % prediction interval. The certification is valid until 31 December 2008 and is considered to be stable during the period of certification, but it is nullified if the SRM is damaged, contaminated, or otherwise modified.
Certified Value (mass fraction) Sulfur: 4.7 µg/g ± 1.3 µg/g.
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New SRMs - SRM 2299 Sulfur in Gasoline (Reformulated)
W.Robert Kelly, Analytical Chemistry Division
Federal, state, and foreign nations' guidelines and standards for the release of sulfur from reformulated gasoline to the atmosphere are constantly being tightened. Gasoline had to be reformulated with certain oxygen-containing compounds because of the ban on tetraethyl lead as an anti-knock compound and also because of requirements for reformulation that would reduce automotive emissions of ozone/smog precursors. In addition, automotive emissions of sulfur to the atmosphere must be curtailed, to comply with ever more stringent guidelines. To ensure that engine emissions meet these guidelines, the manufacture of reformulated gasoline with sharply reduced sulfur content is required. Manufacturers must show that the use of their products will ensure that engines meet emission guidelines.
NIST announces the release of reference values for its SRM 2299 Sulfur in Gasoline (Reformulated), which will be applied to evaluating methods and calibrating instruments used to determine total sulfur in gasoline or materials of similar matrix. A unit of SRM 2299 consists of five amber ampoules, each one of which contains about 20 mL of gasoline, which was donated by ExxonMobil Company (Fairfax, VA).
The certified value is based on analyses by isotope dilution thermal ionization mass spectrometry (ID-TIMS). Homogeneity testing was done by X-ray fluorescence spectrometry. The uncertainty in the certified value, expressed as an expanded uncertainty, is calculated according to the method in the ISO Guide, and is based on a 95 % prediction interval. The certification is valid until 31 December 2008 and is considered to be stable during the period of certification, but it is nullified if the SRM is damaged, contaminated, or otherwise modified.
Certified Value (mass fraction) Sulfur: 13.6 µg/g ± 1.3 µg/g
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New SRMs - SRMs 3143 Rhenium. and 3144 Rhodium
Gregory Turk, Analytical Chemistry Division 
NIST announces the availability of SRM 3143 Rhenium, and SRM 3144 Rhodium Standard Solutions. These standards are much anticipated renewals and part of the 3100 series of high purity, single element in solution standards. The rhenium and rhodium standards have been a particular challenge to produce. Because of newly developed certification measurement methods at NIST, the standards should be in good supply for some time. The method of certification is based on high performance inductively coupled plasma optical emission spectrometry. (HP-ICP-OES). Rhodium metal is very difficult to dissolve and NIST had to prepare a set of primary standards from rhodium metal using a Carius tube digestion in order to certify the SRM. Commercial standards laboratories also experience the same problems in preparing rhodium standards from the metal. With the release of the SRM 3144, these labs can use more soluble rhodium salts and rely on the SRM 3144 to assure the accuracy of their standards.
Rhenium and rhodium are both very expensive metals. Rhodium is most often associated with use as an industrial catalyst and in automobile catalytic converters.It can sell for over $500 per gram, and imprecise measurements can cost commercial users tens of millions of dollars annually. Rhenium is used for filaments for mass spectrographs and ion gauges and as a catalyst in chemical manufacturing and refining.
Both SRMs have a five-year shelf life.
Each unit of SRM 3143 and SRM 3144 is packaged as a set of five, 10 mL sealed borosilicate ampoules of an acidified aqueous solution.
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Renewal SRMS - SRM 956a Electrolytes in Frozen Human Serum
Michael Welch, Analytical Chemistry Division

Standards are essential for promoting accuracy in measurements pertaining to human health and nutrition.Electrolyte concentrations in the body affect most intra- and inter-cellular processes. Abnormal levels of electrolytes may cause or result from a variety of conditions. Thus, measurement of serum levels of electrolytes is a vital part of health status assessment
NIST announces the addition of reference values for ionized calcium and chloride in its SRM 956a Electrolytes in Human Serum with the revision of its certification of 13 November 1996.The values for these new analytes complement the previously certified values for total calcium, lithium, magnesium, potassium, and sodium in the material, all of which were determined by primary clinical methods. The new chloride values were determined by microcoulometry. The new, ionized calcium values were determined by ion selective electrode potentiometry, the candidate designated comparison method of the NCCLS. The usefulness of SRM 956a as an ionized calcium reference material was established by an interlaboratory study involving 19 industrial and clinical laboratories using various types of commercial instrumentation.
This SRM can be used for standardizing direct-reading ion-selective electrode analyzers and for validating working or secondary reference materials for electrolytes in either diluted or undiluted human serum or plasma.
A unit of SRM 956a consists of six flame-sealed ampoules of frozen human serum: two ampoules each of three different concentration levels. Each ampoule contains approximately 2.00 mL of human serum. The development of this SRM is the result of a cooperative effort between NIST and the NCCLS Subcommittee on Electrolytes.

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Renewal SRMs - SRM 1575 Pine Needle
Robert Greenberg, Analytical Chemistry Division
NIST announces a new release of SRM 1575a Pine Needles, which is intended primarily for use in the evaluation of inorganic analytical techniques used to determine element content of botantical and agricultural materials. The needles were collected in North Carolina from freshly felled loblolly pine (Pinus taeda) trees of about the same age and origin. One unit of SRM 1575a consists of approximately 50 g of dried, jet-milled, and sterilized pine needles. Certified and reference concentrations are provided for 23 elements. This material replaces the original SRM 1575 Pine Needles.
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Renewal SRMs - SRM 1941b Organics in Marine Sediment
Stephen Wise, Analytical Chemistry Division
This SRM is widely used by marine pollution monitoring programs for assessing the condition of the marine environment. Most contaminants in aquatic systems, including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), pesticides, and organo-tin compounds, are associated with particulate matter and tend to accumulate in sediments. Resuspension of sediment by dredging, storms, and currents often result in desorption of the contaminants into the water column.
This is the third issue of SRM 1941b since 1989. The sediment used for SRM 1941b was collected from the Chesapeake Bay at the mouth of the Baltimore, MD harbor, very near the sites where SRM 1941 and SRM 1941a were collected. The sediment contains natural levels of contaminants in this area (not spiked). SRM 1941b is intended for use in evaluating analytical methods for the determination of PAHs, PCB congeners, and chlorinated pesticides in sediment. The material is certified for the concentrations of 24 PAHs, 29 PCB congeners, and 7 chlorinated pesticides. There are also reference values for 43 additional PAHs; 13 additional PCB congeners; 2 additional pesticides; mono-, di-, and tributyltin; total tin; and total organic carbon. SRM 1941b has certified and reference values for approximately 50 more organic constituents than in the previous issue for SRM 1941 and is the first SRM with values assigned for the organotins. In addition, there are information values for carbon, hydrogen, and nitrogen contents. SRM 1941b complements SRM 1944 (New York/New Jersey Waterway Sediment) with concentrations of the PAHs and PCB congeners approximately an order of magnitude lower in SRM 1941b as compared to SRM 1944. The concentrations in these two materials span the range found in most urban waterways around the world.
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Renewal SRMS -  SRM 3190, 3198, & 3199 Aqueous Electrolytic Conductivity Standard
Franklin Guenther, Analytical Chemistry Division

Date: September 2002


Specimens Collected from Pilot Whale Stranding for NIST Specimen Bank
Rebecca Pugh, Analytical Chemistry Division, Hollings Marine Laboratory, Charleston, SC
Barbara J. Porter, Analytical Chemistry Division, Gaithersburg, MD

On Monday, July 29, 2002 a mass stranding of 57 long-finned pilot whales (Globicephala melas) occurred in Dennis, MA on Cape Cod. Strandings of marine mammals occur regularly at Cape Cod; however, a stranding of this magnitude creates considerable activity among the scientific and volunteer personnel of the local stranding networks and aquariums, as well as tourists and the press. Barbara Porter and Rebecca Pugh of the Analytical Chemistry Division of CSTL participated at the stranding site in the collection of tissue specimens from the whales for archival in the NIST National Biomonitoring Specimen Bank (NBSB).

Since 1987, the NIST NBSB has participated in collecting and banking of tissues from marine mammals from U.S. waters of the Atlantic, Gulf of Mexico, and Pacific, including Alaska. The NBSB is designed to cryogenically preserve environmental and biological specimens over long periods of time (decades) for future retrospective analyses. A major activity of the NBSB is the National Marine Mammal Tissue Bank (NMMTB), established by Federal Legislation in 1992, and maintained at the NBSB through partial support from the National Oceanic and Atmospheric Administration (NOAA), National Marine Fisheries Service (NMFS) and the U.S. Geological Survey, Biological Resources Division.

The CSTL scientists worked with scientists and volunteers from the New England Aquarium, the Northeast Stranding Network, the NMFS, and the Woods Hole Oceanographic Institute to obtain samples for inclusion in the NMMTB. Tissue specimens were collected from 11 animals that died on the first day of the stranding. Three late stage pregnancies were found among the 11 whales, and tissue specimens were also removed from the 3 fetuses for a total of 14 animals sampled. Tissue specimens for the NMMTB are collected and processed following rigid standard operating procedures designed to reduce any contamination to the tissue. After processing, the tissue samples were immediately frozen and eventually stored in liquid nitrogen vapor freezers at the NIST NBSB satellite facility located at the Hollings Marine Laboratory in Charleston, SC. These specimens, along with over 2,000 tissue specimens from over 715 other marine mammals already archived in the NBSB, will be used to determine the levels of contaminants not only in marine mammals, but the health of the marine environment as well, and they will be available to scientists for evaluation for many years to come.

Covering Whales with Water
Cooling Whales Stranded on Beach
Cape Cod Bay Map
One Whale Stranded
Figure1. Volunteers use buckets to keep the skin of the dying whales moist. Figure 2. Whales stranded on the beach with onlookers watching. Figure 3. Map of Cape Cod Bay; location of this stranding. Figure 4. Whale being helped off shore.
Photos courtesy of the Cape Cod Times.

Date: July 2002

NIST Reaffirms Commitment to Cement Industry with Updated SRMs
John R. Sieber, Analytical Chemistry Division, CSTL

The entire suite of NIST cement and clinker Standard Reference Materials (SRMs) have been updated. These SRMs have been essential to laboratories which certify concrete products for performance and evaluate mechanisms for concrete corrosion and failure.

For more information on Cement SRMs, see the Standard Reference Material website: http://ts.nist.gov/ts/htdocs/230/232/232.htm

Date: September 2002

Photo is Courtesy of Ash Grove Cement Company.


NIST Chemists Define and Refine Properties of Plastic Microsystems
Laurie Locascio, Analytical Chemistry Division, CSTL
David Ross, Process Measurements Division, CSTL
Tim Johnson

There may well be a plastic biochip in your future, thanks in part to the National Institute of Standards and Technology (NIST).
Microfluidics devices, also known as “lab-on-a-chip” systems, are miniaturized chemical and biochemical analyzers that one day may be used for quick, inexpensive tests in physicians’ offices. Most microfluidics devices today are made of glass materials. Cheaper, disposable devices could be made of plastics, but their properties are not yet well understood.
NIST is contributing to the development of these plastic microfluidics. One study looked at how fluids flowed in plastic microchannels by tracking fluorescent dye in the fluids. NIST researchers also developed an easy technique for accurately
measuring fluid temperatures—an important parameter for chemical reactions.
A third project spawned a method for concentrating and separating an ionic (charged) substance in solution within microchannels. The technique concentrates the substance as much as 10,000-fold or more, making it easier to detect in ultrasmall quantities (nanoliters—a billionth of a liter—or less).
Finally, NIST staff designed a novel system to overcome the difficult problem of slow mixing in microfluidics devices. The mixer consists of a T-shaped microchannel imprinted in plastic that is modified with a laser to create a series of slanted wells.
The wells speed the mixing of two streams entering the passage.

Date: August 2002

Temperature Gradient Focusing Microfluidic Mixers
1. Temperature Gradient Focusing. Concentration and separation of a wide variety of analytes using temperature gradient focusing in a microfluidic channel. 2. Microfluidic Mixers. White-light and fluorescence microscopy images of passive mixing for various ablated patterns under low and high EO flowrates. Note that mixing is only achieved at low flowrates for the middle column, but is achieved at high flowrates for the pattern shown in the right column. At high flowrates (middle column) stream splitting is seen.

NIST Chocolate Standard Raises the 'Bar' on Accuracy
Katherine S. Sharpless, Analytical Chemistry Division, CSTL

Chocoholics, rejoice. Now there’s a way to know more precisely than ever how much fat (and other constituents) are in chocolate and similar foods. The National Institute of Standards and Technology (NIST) has issued Standard Reference Material (SRM) 2384, Baking Chocolate, which has been characterized with state-of-the-art measurement methods to show how much fat, protein, carbohydrates, individual fatty acids, elements, vitamins and other components it contains. It is part of a series of food-matrix SRMs that can be used by food processors to validate analytical methods and for quality assurance when assigning values to products with similar compositions. The baking chocolate SRM is the first standard to contain a high proportion of fat—more than 50 percent. A high-fat food standard has been identified as a priority by manufacturers. Because of this high fat content, the new SRM can be analyzed by manufacturers of chocolate and by quality assurance labs of companies that produce other types of fatty products, such as black olives and potato chips. This SRM also is the first to have values assigned for catechins (which, as antioxidants, may help protect the body against damage associated with age-related diseases) and caffeine. NIST’s food-matrix SRMs will help manufacturers comply with the Food and Drug Administration labeling requirements.

Date: August 2002


Temperature Gradient Focusing in Microfluidic Channels
David Ross, Process Measurements Division, CSTL
Laurie Locascio, Analytical Chemistry Division, CSTL

Scientists in the Process Measurements and Analytical Chemistry Divisions of CSTL have developed a new method to concentrate and separate chemical species in microfluidic channels. Microfluidic, or "lab-on-a-chip," devices are miniaturized chemical and biochemical analysis systems that one day may replace conventional bench top instruments.
The new technique, temperature gradient focusing, balances the electrophoretic motion of analytes in a microchannel against the bulk flow of buffer solution through the microchannel while applying both an electric field and a temperature gradient along the length of the channel. For buffer solutions having temperature-dependent ionic strength, the applied temperature gradient results in a corresponding gradient in the electrophoretic velocity of a charged analytes in the channel. The bulk flow velocity can then be adjusted so that the total analyte velocity (the sum of the bulk and electrophoretic velocities) is zero at some point along the channel length, and all of the analyte in the channel will be focused, or concentrated, at that point.
The technique gives simultaneous focusing and separation of differently charged analytes in a manner analogous to isoelectric focusing of proteins, but is much simpler to implement than isoelectric focusing and has the additional advantage of working with any charged analyte, rather than just proteins. Temperature gradient focusing has been demonstrated for a variety of different analytes including fluorescent dyes, amino acids, proteins, DNA, and colloidal particles. In addition, it has been shown to be capable of greater than 10,000-fold concentration of a dilute analyte. A description of the technique has been submitted for publication in the journal Analytical Chemistry.

Date: May 2002


High Accuracy Technique Revolutionizes Platinum Group Metals Assay
Marc Salit, Analytical Chemistry Division, CSTL

CSTL researchers Marc Salit and Greg Turk have developed a high performance approach to the measurement of elemental composition using inductively coupled plasma optical emission spectroscopy. This technique uses an innovative experiment design coupled with a novel drift correction approach to minimize and quantify the major sources of uncertainty in this chemical analysis. A recent publication documents the performance of the method, high performance inductively coupled plasma optical emission spectrometry, for 64 elements where the typical relative expanded uncertainty observed is 0.1 percent (Analytical Chemistry 2001, 73, 4821-4829). This technique utilizes unmodified, commercially available equipment, is well suited to automation, and yields results comparable to the best attainable by classical methods.

After we presented this technique and our results at an ASTM E01 committee meeting in May 2001, we established a collaboration to implement it with Metalor Technologies USA, North Attleboro, Mass., a precious metals and advanced materials supplier. Together, we developed methods for the determination of palladium and platinum in metallic samples. NIST provided software tools to perform the calculations. Less than one year later, this technique was in routine use at Metalor, complementing the gravimetric wet chemical technique used in their labs. According to Arnold Savolainen of Metalor, “This technique has revolutionized our Platinum Group Metals assay lab. Assay completion times which ran 20 to 30 days, now average four to six days. Assay precisions have improved by more than an order of magnitude. Accuracy, as measured by the number of assays sent for umpire laboratory analysis, has improved to the point that we have not had to go to umpire in over three months. I am now setting up the procedure for the determination of gold at major levels.”

Date: May 2002

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Date created: May 13, 2002
Last updated: January 15, 2003
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