Use of water activity characteristics enables a simplified approach for defining the reference moisture condition for FDA cocoa powder in-house reference material.

The Food and Drug Administration uses water activity behavior characteristics when adjusting test portion mass to correct for the moisture condition of its cocoa powder in-house reference material. The cocoa powder's moisture condition, and therefore weight, equilibrates according to the relative humidity (RH) of its surroundings. This process is predictable and defined by an isotherm. The reference values in the certificate of analysis are relative to the material's condition at 30% RH, which is assumed to be mid-range for typical laboratory settings. Since mass variations are relatively small within a 15-50% RH range, the mass may be measured immediately after removing a test portion from a storage bottle and used without correction if a standard uncertainty of 0.7% is acceptable for the mass. If greater accuracy is needed and the laboratory RH is known, a very simple and quick procedure can be used whereby the test portion is left open and exposed to the laboratory air overnight before weighing. After applying a correction, the standard uncertainty for mass measurement drops to 0.3%.

Revalidation and long-term stability of National Institute of Standards and Technology Standard Reference Materials 1566, 1567, 1568, and 1570.

Multiple units of Standard Reference Materials (SRMs) 1566 Oyster Tissue, 1567 Wheat Flour, 1568 Rice Flour, and 1570 Trace Elements in Spinach, produced by the National Institute of Standards and Technology (NIST, then the National Bureau of Standards), were analyzed 17-20 years after the original certification dates and 12-15 years after the certificates became invalid. Instrumental neutron activation analysis and thermal neutron prompt gamma-ray activation analysis were used to measure mass fractions for 27 elements in these SRMs to revalidate them for use in quality assurance (QA) programs required for food analysis programs within the U.S. Food and Drug Administration. With the exception of Se in SRM 1567, all element mass fractions were in agreement with certified values and literature data. Some evidence of B loss from SRM 1568 was observed. These materials were judged to be suitable for continued use in QA programs. Findings showed that these matrixes exhibited stability of moisture, mass fraction, and weight basis for far longer (> or =15 years) than was indicated by the 5-year validity statement on the NIST Certificates of Analysis.

Br concentration as an indication of pre-baking bromation of bread products.

Br concentration in bread for baked bread products was shown to be linearly proportional to the amount of Br added per kg of flour used to make the product. Br concentration in bread can be used to help identify those bread products with the greatest likelihood of containing bromate residues. Instrumental neutron activation analysis was used to determine Br in test portions of bread products from commercial bakeries, homemade bread, flour, and unbaked dough. High performance liquid chromatography was used to determine the bromate residue in selected test portions.

Element and radionuclide concentrations in food: FDA Total Diet Study 1991-1996.

Food purchased throughout the United States during 1991-1997 under the U.S. Food and Drug Administration's Total Diet Study (TDS) program were analyzed for elements and radionuclides. The program is described with emphasis on food analysis and quality control, including independent interlaboratory exercises. Analytical results are summarized for Cd, Pb, Ni, As, Hg, Se, Cu, Zn, Mn, Fe, Mg, Ca, P, K, and Na and for 137Cs, 131I, 106Ru, and 90Sr. Concentration data are provided to expand the information base used to support assessments of the safety and nutritive value of the U.S. food supply and for their potential use in food composition databases. For selected foods, comparisons were made with past TDS results and with those reported in the literature. An extensive listing of the analytical data is available on the FDA CFSAN Website.

Determination of sodium in biological materials by instrumental neutron activation analysis.

A formalized method for determining sodium in biological materials by instrumental neutron activation analysis is presented. The method includes common procedures from the numerous options available to this historically nonformalized analytical technique. The number of procedural options is restricted to minimize the method's complexity, yet the method is still applicable to a variety of neutron activation facilities. High accuracy and precision are achieved by placing bounds on allowed uncertainty at critical stages of the analysis. Analytical results from the U.S. Food and Drug Administration laboratory and 4 other laboratories demonstrate the method's performance.

Nondestructive determination of lead, cadmium, tin, antimony, and barium in ceramic glazes by radioisotope X-ray fluorescence spectrometry.

Quantitation capabilities of radioisotope X-ray fluorescence spectrometry (RXRFS) for determining lead, cadmium, tin, antimony, and barium in ceramic glazes were investigated. Twenty-one air-dried glazes and 85 fired glazes on test tiles were analyzed by using 109Cd and 57Co excitation sources. Accurate Pb determinations, with limits of detection (LODs) of about 0.3 mg/cm2 for 5 min counting times, were achieved by using the 75 keV K alpha 1 X-ray photopeak and a Pb foil calibration procedure. Cd, Sn, Sb, and Ba concentrations were determined with LODs from about 0.5 to 1.5 mg/cm2. For Pb and Ba, results obtained by using absorption corrections based only on element concentrations determined by RXRFS and an iterative approach led to analytical biases of < or = 4% relative to results obtained by using corrections based on known total element compositions. Biases were more severe for Cd, Sn, and Sb because lower X-ray energies were involved and sensitivities varied as a function of matrix Pb content. Pb concentrations were above LODs (1.3-40 mg/cm2) in 39 of 47 fired "food-safe" glazes and in 33 of the other 38 fired glazes (0.4-39 mg/cm2).

Identification of lead and other elements in ceramic glazes and housewares by 109Cd-induced X-ray fluorescence emission spectrometry.

Radioisotope x-ray fluorescence spectrometry was investigated as a potential screening method for Pb and other elements in housewares. Thirty-six commercial houseware items and 87 ceramic test tiles (85 fired with hobby glazes and 2 blank bisques) were examined qualitatively for the presence of Pb by using 109Cd-induced L x-ray fluorescence emission spectrometry. For the housewares, the technique provided fast, nondestructive analysis of areas with about 10 cm diameters (general regions) to about 4 mm diameters (isolated design regions). Pb was found in 25 of 28 ceramicware items, in all 8 other housewares, and in all the test-tile glazes above the limit of detection of 1 count per second (cps) for Pb L beta x-rays. For housewares, Pb identification did not always correspond to Pb leachability. For 68 test-tile glazes labeled as containing Pb (39 of which were also labeled 'dinnerware safe' or 'safe for food containers'), count rates ranged from 290 to 730 cps, whereas for the other 17 glazes labeled (with one exception) 'non-toxic,' much lower count rates (5-61 cps) were obtained. Other elements found in the housewares or test glazes were As, Au, Ca, Co, Cr, Cu, Fe, Mn, Nb, Ni, Rb, Sr, Y, Zn, and Zr.

Radionuclides in domestic and imported foods in the United States, 1987-1992.

Findings from the U.S. Food and Drug Administration's Radionuclides in Foods program are summarized for foods collected between October 1, 1986, and September 30, 1992. Concentrations of radionuclide activity in the Total Diet Study and reactor-survey foods were in Range 1 or low in Range II of the surveillance and control recommendations of the Federal Radiation Council; no control actions were suggested. Dietary intake of 90Sr continued the general decline observed since 1961. Approximately 2600 test portions of imported foods were analyzed for contamination associated with the Chernobyl nuclear accident. Concentrations of radionuclide activity were below limits of detection for the vast majority of the imported food test portions but were above the levels of concern for 23 portions. Since 1986, the fraction of imported food test portions having measurable amounts of contamination has steadily declined, as have the average concentrations of radionuclide activity; however, contamination is still occasionally found. Continued monitoring of both domestic and imported foods is planned.

Neutron capture prompt-gamma activation analysis of foods.

The suitability of neutron capture prompt-gamma activation analysis (PGAA) for multielement analysis of foods was investigated. A total of 22 elements was observed in 40 food and mineral supplements. Hydrogen, B, C, N, Na, S, Cl, and K concentrations were determined in NIST RM 8431a Mixed Diet and in a wet diet composite made from FDA Total Diet Study collections. Because the neutron flux is so low for PGAA, the method is nondestructive and reanalysis of analytical portions is possible. Both diet materials were analyzed before and after freeze-drying to check for element losses during this process. No losses were found for RM 8431a, but significant losses of B and Na were observed for the wet composite. The measured loss of hydrogen for the wet composite was not consistent with the assumption that the lost mass was water only.

Radionuclides in domestic and imported foods in the United States, 1983-1986.

Findings in the Food and Drug Administration's Radionuclides in Foods program are summarized for samples collected between October 1, 1982, and September 30, 1986. All radionuclide findings for Total Diet and reactor samples were either in Action Range I or low in Range II of the surveillance and control recommendations given by the Federal Radiation Council. The only long-range trend noted was a continuation of the general decline in dietary intake of 90Sr since 1961. Imported food samples were analyzed for contamination after the Chernobyl nuclear accident. The findings for imported foods indicate that the surveillance efforts successfully targeted contaminated foods, and that contamination levels were below levels of concern for all but one oregano and 3 cheese samples.

Application of an instrumental neutron activation analysis procedure to analysis of food.

The capabilities of a relatively simple instrumental neutron activation analysis procedure were demonstrated by performing multielement analyses of 240 Food and Drug Administration Total Diet Studies food composites. The analytical results provide a comprehensive database for a wide range of food types. The procedure incorporates only two irradiations and counts, polyethylene packaging and no sample transfer after irradiation. Concentrations were determined for 19 elements, 16 of which were found in most composites. Detection limits were calculated for all food groups and are given for the 22 elements included in the quantitative analysis scheme. In a qualitative search for 18 additional elements for which no standards were run, none were detected in any of the composites. Specific factors such as interferences from the blank are discussed in regard to their effects on the uncertainties associated with the experimental data and the detection limits. Modifications to the procedure are also suggested for lowering the detection limits for specific elements.

Coenzyme--substrate adducts as inhibitors of mouse liver 3,4-dihydroxyphenylalanine decarboxylase.

N-(5'-Phosphopyridoxyl) derivatives of several aromatic amino acids have been prepared by conventional methods and tested as inhibitors of mouse liver L-3,4-dihydroxyphenylalanine (Dopa) decarboxylase (EC 4.1.1.26; L-aromatic-amino-acid decarboxylase). The L-tyrosine, L-phenylalanine, and DL-2-hydroxyphenylalanine derivatives were effective inhibitors at concentrations of 10(-5) M. Because of the spontaneous formation of a tetrahydroisoquinoline cyclic condensation product with pyridoxal phosphate (Pictet--Spengler reaction), the Dopa derivative could not be prepared by the usual procedures. The synthesis of the desired N-(5'-phosphopyridoxyl)-Dopa was accomplished using selective blocking--deblocking methods; its properties are described. This proved to be the most effective inhibitor of those tested. Neither the tetrahydroisoquinoline of L-Dopa and pyridoxal phosphate nor the N-(5'-deoxypyridoxyl)-Dopa was an effective inhibitor of Dopa decarboxylase. These coenzyme amino acid adducts are suggested to act as stage inhibitors of the enzyme.