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.

Elemental composition of liver and kidney tissues of rough-toothed dolphins (Steno bredanensis).

On December 14, 1997, 62 rough-toothed dolphins (Steno bredanensis) stranded on Cape San Blas, on the Florida coast of the Gulf of Mexico. Approximately 30 animals died either on the beach or in rehabilitation facilities. Two were successfully rehabilitated and released. Liver, kidney, blubber, and muscle tissues were collected from 15 animals that died on the beach. Portions of the liver and kidney from each dolphin were analyzed using instrumental neutron activation analysis and inductively coupled plasma mass spectrometry to determine mass fractions of 37 elements. Levels of several electrolytes (Na, Cl, K, Br, Rb, I, Cs) and of the essential trace elements Fe, Cu, and Zn in both tissues were similar to those found in other Odontoceti. Mass fractions of Ca ranged from 60 mg/kg to 1,200 mg/kg (wet mass basis), indicating significant inhomogeneity in the kidney tissues of several animals. Necropsy reports noted that the kidneys of many of these animals contained fibrous nodules. The measured Ca inhomogeneity may be due to mineralization of the fibrous kidney tissue. Hepatic levels of Hg and Se were at the high end of the ranges generally found in livers of other Odontoceti and were slightly higher in animals with fibrous kidneys than in the others. Mass fractions of Se, Ag, and Hg in liver tissues increased with the size and age of the animals indicating accumulation of these elements in the liver with age. Results also indicate that Se and Hg accumulate in rough-toothed dolphin kidney. Accumulation of these elements with age has been reported commonly for marine mammals and other species.

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.

Concentrations of chlorinated hydrocarbons and trace elements in marine mammal tissues archived in the U.S. National Biomonitoring Specimen Bank.

The U.S. National Biomonitoring Specimen Bank (NBSB) provides for the long term storage of well documented and preserved specimens representing several types of environmental matrices. A major part of this inventory consists of marine mammal tissues (e.g., blubber, liver, kidney, and muscle). Within the NBSB selected specimens are periodically analyzed for chlorinated hydrocarbons and trace elements. Although only 20% of the 560 marine mammal specimens in the NBSB have been analyzed, the database is of value in evaluating the stability of analytes and sample degradation during storage, for comparing with results from samples collected in the future for long-term monitoring, and for comparing with analytical results from other laboratories on samples collected at the same time for monitoring purposes. The NBSB analytical database contains results for 37 elements, many of which are not analyzed routinely by conventional analytical techniques used in monitoring programs, and the following organic compounds: selected PCB congeners. DDT compounds, alpha- and gamma-HCH, HCB, heptachlor epoxide, oxychlordane, cis-chlordane, trans-chlordane, cis-nonachlor, trans-nonachlor, and dieldrin in 9 marine mammal species: northern fur seal (Callorhinus ursinus), ringed seal (Phoca hispida), spotted seal (P. largha), bearded seal (Erignathus barbatus), pilot whale (Globicephala melas), harbor porpoise (Phocoena phocoena), white-sided dolphin (Lagenorhynchus acutus), beluga whale (Delphinapterus leucas), and bowhead whale (Balaena mysticetus). Analyses of beluga whale blubber for toxaphene and additional chlorinated hydrocarbons are obtained through collaboration with the Department of Fisheries and Oceans Canada.

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.

Effects of target temperature on analytical sensitivities of cold-neutron capture prompt gamma-ray activation analysis.

Cold-neutron prompt gamma-ray activation analysis sensitivities are often decreased because of an increase in the average neutron energy on scattering within room temperature targets. Experiments were performed to determine whether target cooling would alleviate these effects. Cooling the targets to 77 K increased hydrogen sensitivity by as much as 25%. Target cooling decreases those effects of neutron scattering on CNPGAA sensitivities that are the result of an increased average neutron energy. However, cold-neutron scattering may also change the average path length traveled, and this effect on sensitivity is not alleviated by controlling temperature.

Analytical applications of guided neutron beams.

Guided beams of thermal and cold neutrons have become available to analysts at several reactors during the past decade. The very pure beams from these guides have led to lower backgrounds and higher sensitivities for prompt-gamma activation analysis (PGAA), and thus to new applications for this technique. For analytical accuracy, the details of neutron scattering within the sample need to be taken into account; this consideration is especially important for most materials of biological origin.

Use of spherical targets to minimize effects of neutron scattering by hydrogen in neutron capture prompt gamma-ray activation analysis.

For hydrogenous targets that are thinner than they are wide, element sensitivities (counts.s-1.mg-1) for determining concentrations of elements by neutron capture prompt gamma-ray activation analysis (PGAA) are enhanced relative to sensitivities obtained from measurements on nonhydrogenous materials. These enhancements are caused mainly by elastic neutron scattering by H, which changes the average neutron fluence rate within the matrix. The magnitude of the effect depends on the macroscopic scattering and absorption cross sections and on the size, shape, and orientation of the target with respect to the neutron beam. Sensitivities increase linearly with H density for thin targets of constant size and shape and also vary with target shape. Theoretical work was shown that element sensitivities for hydrogenous targets in the form of spheres are least affected by neutron scattering. Methods were devised for creating solid spheres and for containing liquids in spherical shapes. Element sensitivities were determined for spheres and disks of several hydrogenous materials. For H, B, Cl, K, Br, and Cd, sensitivities for spheres were found to be less affected by neutron scattering. Exceptions were Sm and Gd sensitivities measured in liquids contained in quartz globes.

Effects of target shape and neutron scattering on element sensitivities for neutron-capture prompt gamma-ray activation analysis.

Results are presented for a study of the effects of neutron scattering by hydrogen on element sensitivities for in-beam neutron capture prompt gamma-ray activation analysis. In a scattering matrix, sensitivities vary as a function of both the scattering density, i.e., the number of scatters per unit volume and the magnitude of scattering cross sections, and the target geometry, i.e., the target shape and orientation with respect to the neutron beam. Element sensitivities (counts.s-1.mg-1) increased linearly with H density (g.mL-1) for H, B, Na, Cl, K, Mn, Br, Ag, Cd, I, Sm, and Gd, measured for liquids packaged in Teflon bags. Nine of the 12 elements studied had 1.69 +/- 0.18% sensitivity enhancement per percent increase in H density. Samarium sensitivity was enhanced by only 0.54 +/- 0.07%/% H, which may indicate that neutron scattering by H causes a shift in the energy distribution of the neutrons. Manganese sensitivity was enhanced by 2.44 +/- 0.26%/% H. The enhancement of the sensitivity for H itself varied with matrix composition. For several series of disk-shaped, solid, hydrogenous targets, element sensitivities increased with decreasing target thickness until, at some limiting thickness, this trend was reversed. Consistent with theory, sensitivities measured for spherical hydrogenous targets showed no enhancement.

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.