Development and certification of the new SRM 695 trace elements in multi-nutrient fertilizer.

During the past seven years, several states within the US have enacted regulations that limit the amounts of selected non-nutritive elements in fertilizers. Internationally, several countries, including Japan, China, and Australia, and the European Union also limit the amount of selected elements in fertilizers. The elements of interest include As, Cd, Co, Cr, Cu, Hg, Mo, Ni, Pb, Se, and Zn. Fertilizer manufacturers and state regulatory authorities, faced with meeting and verifying these limits, need to develop analytical methods for determination of the elements of concern and to validate results obtained using these methods. Until now, there were no certified reference materials available with certified mass fraction values for all elements of interest in a blended, multi-nutrient fertilizer matrix. A new standard reference material (SRM) 695 trace elements in multi-nutrient fertilizer, has been developed to help meet these needs. SRM 695 has recently been issued with certified mass fraction values for seventeen elements, reference values for an additional five elements, and information values for two elements. The certificate of analysis includes an addendum listing percentage recovery for eight of these elements, determined using an acid-extraction inductively-coupled plasma optical-emission spectrometry (ICP-OES) method recently developed and tested by members of the Association of American Plant Food Control Officials.

Recent developments in food-matrix Reference Materials at NIST.

Since 1996, the National Institute of Standards and Technology (NIST) has developed several food-matrix Standard Reference Materials (SRMs) characterized for nutrient concentrations. These include SRM 1544 Fatty Acids and Cholesterol in a Frozen Diet Composite, SRM 1546 Meat Homogenate, SRM 1548a Typical Diet, SRM 1566b Oyster Tissue, SRM 1846 Infant Formula, and SRM 2383 Baby Food Composite. Three additional materials--SRM 1946 Lake Superior Fish Tissue, SRM 2384 Baking Chocolate, and SRM 2385 Spinach--are in preparation. NIST also recently assigned values for proximate (fat, protein, etc.), individual fatty acid, and total dietary fiber concentrations in a number of existing SRMs and reference materials (RMs) that previously had values assigned for their elemental composition. NIST has used several modes for assignment of analyte concentrations in the food-matrix RMs, including the use of data provided by collaborating laboratories, alone and in combination with NIST data. The use of data provided by collaborating food industry and contract laboratories for the analysis of food-matrix RMs has enabled NIST to provide assigned values for many analytes that NIST does not have the resources or analytical expertise to measure.

Quality assurance in analysis of cryogenically stored liver tissue specimens from the NIST National Biomonitoring Specimen Bank (NBSB).

Portions of liver tissue specimens originally stored in the National Biomonitoring Specimen Bank (NBSB) and analyzed between 1980 and 1987 were re-analyzed in 1997 using instrumental neutron activation analysis (INAA) for the determination of 17 trace elements. Duplicate portions of each specimen had been stored at two different temperatures. The first was stored in a liquid nitrogen vapor-cooled freezer at -150 degrees C, standard NBSB storage conditions, and the other in an electric freezer maintained at -80 degrees C. Two portions of seven livers from each storage temperature were re-analyzed for this work. Results showed no changes in trace element content as a function of storage temperature, within the uncertainty of the method used. Results from these analyses agreed with results of initial analyses for most analytes in most sub-samples. Of the exceptions, five were due, in part, to an incorrect basis mass for the initial sub-specimen of one tissue, five with variable Zn results were attributed to difficulties in peak fitting for this element during INAA data processing, and the remaining were isolated differences discussed in this paper. Results of this work indicate that specimen storage and processing protocols are adequate to prevent noticeable contamination of specimens with trace elements, with the exception of Cr. Variability in Cr content was observed for the liver tissues which may have been caused by Cr contamination of the samples by the Teflon mill. Analyses of portions of Standard Reference Material (SRM) 1566a Oyster Tissue (certified in 1989) and SRM 1577a Bovine Liver (certified in 1982) were also included in this study for the purpose of quality control and to assess the stability of these freeze-dried powders that were stored at room temperature. No changes were observed in these materials.

Determinations of subnanomole elemental levels by NAA and their possible impact on human health related issues.

Neutron activation analysis (NAA) is an appropriate tool for the determination of trace elements in biological systems. The virtually blank-free NAA procedures fittingly complement precautions employed in sampling and sample preparation of biological matrices. Results from instrumental NAA procedures used to establish baseline values and time trends for elements in human tissues demonstrate the advantages as well as the limits of these procedures for nanomole and, in a considerable number of instances, subnanomole elemental levels. In addition, subnanomole mass fractions have been determined with extremely low limits of detection by employing NAA with radiochemical separations isolating very low levels of radioactivity from the matrix background. The elements reviewed in this article include Cr, Se, Pt, and others that have been determined by NAA at subnanomole levels in human tissues and body fluids and in biological macromolecules.

Bioaccumulation of vanadium and other trace metals in livers of Alaskan cetaceans and pinnipeds.

Concentrations for 38 elements are routinely measured in the marine mammal liver tissues archived in the National Biomonitoring Specimen Bank (NBSB). Results show that hepatic concentrations of vanadium, selenium, silver, cadmium, and mercury are positively correlated with age for beluga whales (Delphinapterus leucas) and of vanadium, selenium, cadmium, and mercury with length for ringed seals (Phoca hispada). Many researchers have reported linear correlations of hepatic selenium, cadmium, and mercury with marine mammal age; however, there is only one other report of a linear correlation of hepatic vanadium with marine mammal age. Vanadium levels are at or below detection limits (< or = 0.01 micrograms/g) in liver tissues of U.S. east coast marine mammals from the NBSB but are present at levels ranging from 0.02 to 1.2 micrograms/g of wet weight in the tissues of Alaskan marine mammals. Although only three bearded seal (Eriganthus barbatus) and three bow-head whale (Balaena mysticetus) liver samples have been analyzed, hepatic vanadium levels also increased with animal size for these species. The presence of relatively high levels of vanadium in the livers of these Alaskan animals may reflect a unique dietary source of vanadium, a unique geochemical source of vanadium, or anthropogenic input to the Alaskan marine environment.

Trace element concentrations in cetacean liver tissues archived in the National Marine Mammal Tissue Bank.

The National Biomonitoring Specimen Bank (NBSB), a collaborative project of several U.S. government agencies, includes marine mammal tissues collected for the Alaska Marine Mammal Tissue Archival Project (AMMTAP) and the National Marine Mammal Tissue Bank (NMMTB). Tissues were collected from 139 animals representing 13 species of marine mammals from around the U.S. Recently, concentrations for up to 30 elements in liver tissues of nine long-finned pilot whales (Globicephala melas), six harbor porpoises (Phocoena phocoena), and four white-sided dolphins (Lagenorhynchus acutus) from the NMMTB were measured using instrumental neutron activation analysis. Results from analyses of these tissues are presented, compared with results for liver tissues from other marine mammals from the AMMTAP, and compared with published values.

Determination of tin in biological materials by atomic absorption spectrophotometry and neutron activation analysis.

Concentrations of Tin (Sn) were determined in botanical, dietary and biological reference materials (RMs), and in human livers from Japanese and American subjects using atomic absorption spectrophotometry (AAS) and neutron activation analysis (NAA), either in the instrumental mode (INAA) or in the radiochemical mode (RNAA). The mean Sn concentrations (+/- 1 S.D.) found in various RMs are: total diet (NIST SRM-1548) 3.57 +/- 0.52 and 3.61 +/- 0.52 microgram/g by AAS and INAA, respectively; non-fat milk powder (NIST SRM-1549) 2.5 +/- 1.4 ng/g and 1.9 +/- 0.3 ng/g; bovine liver (NBS SRM-1577) 18 +/- 2 and 20 +/- 0.3 ng/g; and citrus leaves (NIST SRM-1542) 0.25 +/- 0.02 and 0.243 +/- 0.006 microgram/g by AAS and RNAA, respectively. These comparisons demonstrate good agreement between the two methods. In apple leaves (NIST SRM-1515) and peach leaves (NIST SRM-1547), the measured concentrations by AAS were 77.1 +/- 20 and 85 +/- 15 ng/g; interferences by 160Tb did not permit an accurate assessment by INAA at this concentration. The Sn results obtained for the American human liver specimens by RNAA ranged from 0.135-0.712 microgram/g wet weight, and the Sn concentrations in Japanese human liver specimens determined by AAS ranged from 0.078-1.122 microgram/g wet weight in 23 individuals. The results from this study show that it is feasible to use INAA/RNAA and AAS in combination to establish recommended values in RMs.

External gamma-ray counting of selected tissues from a Thorotrast patient.

Results of gamma-ray measurements of selected tissues from a patient who was injected with Thorotrast almost 36 y ago are reported. The purposes of this study were: 1) to determine the relative tissue distribution and activities of specific radionuclides in the 232Th decay chain, specifically 228Ra (as measured by 228Ac), 212Pb, and 224Ra (measured directly and as measured by 212Pb), and 2) to evaluate the level of radioactive disequilibrium among the daughter products. The spleen and liver had the highest concentrations of radioactivity. Bone also appears to be a long-term sink for 232Th daughter products based on estimates from a small portion of one rib. Larynx and esophagus contained measurable activity, which may have been due to their proximity to the "Thorotrastoma." Radioactivity in the remaining measured tissues were low, as expected. Secular equilibrium could be demonstrated in bone, pancreas, larynx, esophagus, and breast. Significant disequilibrium was observed for spleen, liver, kidney, and red blood cells. Radioactivity measurements reported here will be useful in estimating radiation doses to selected tissues. Such dose estimates are valuable in refining current risk estimates (e.g., liver) and in identifying tissues at risk for further epidemiologic studies. These results, while consistent with other published studies, should be interpreted with caution since measurements were made on only one patient.

Neutron activation analysis of biological samples with a preirradiation chemical separation.

A preirradiation separation procedure has been developed to separate Al, Cu, Mn, and V from biological materials. Chelex-100 resin is used as the separation medium, and the resin is irradiated directly. Three NIST biological Standard Reference Materials and five samples of human blood serum, obtained under carefully controlled conditions, have been analyzed by NAA following this separation.

"A bintel brief" the editor as compleat therapist.

Emigration took the people out of traditional, accustomed environments and replanted them in strange ground among strangers, where modes of behavior were no longer adequate, for the problems of life were new and different. With old ties snapped, men faced the enormous compulsion of working out new relationships, new meaning to their lives, often under harsh and hostile circumstances...

Cadmium analysis by radiochemical neutron activation analysis.

Radiochemical neutron activation analysis (RNAA) has been routinely used at the National Bureau of Standards to analyze Cd in a variety of environmentally important matrices. The method used to separate Cd from other neutron-activated products is solvent extraction. Zinc diethyldithiocarbamate [Zn(DDC)2] in chloroform will quantitatively extract Cd from an aqueous solution over a pH range from 1 to 12. In addition to the extraction of Cd, Zn(DDC)2 will also extract Cu, which can interfere with the Cd analysis by producing a high background level of radiation. This can be avoided by first extracting with Bi(DDC)3 in chloroform which removes Cu, but not Cd. Copper concentrations can, therefore, be determined in addition to Cd. This two extraction radiochemical separation procedure is very versatile and is often used as part of a larger multi-element analysis scheme. One such scheme involves the use of an inorganic-ion exchanger, Hydrated Manganese Dioxide (HMD), to retain As, Sb, Se, and Cr prior to extraction. The eluted fraction is then extracted with Bi(DDC)3 to remove Cu, and then with Zn(DDC)2 to remove Cd.