M. M. Mason

The study of human nails as an intake monitor for arsenic using neutron activation analysis

Arsenic is toxic to humans with the lethal dose being approximately 1 mg/kg/day. At much lower long-term exposures, arsenic is hypothesized to increase the risk of certain cancers. We have developed an irradiation position for the neutron activation analysis (NAA) of nail specimens for arsenic, in support of a case-control study involving New Hampshire residents consuming well water above the EPA Safe Drinking Water Standard of 0.050 ppm. Arsenic is bound to nail keratin through sulfhydryl groups proportional to intake providing a convenient means of integrating arsenic intake in population-based studies. Our objective was to develop the necessary facilities and procedures by which relatively small samples (i.e. 20 to 100 mg) could be accurately analyzed for arsenic, so that affordable nutritional epidemiology investigations, requiring large numbers of samples (>1000 in this case), could be undertaken. A high-flux reflector position, with minimal axial variation throughout the fuel cycle, suitable for pneumatic-tube irradiations, was characterized by measurement of the neutron flux distribution (thermal and epithermal) within the irradiation capsule over time. Results from application of the method to a case-control study of basal and squamous cell skin cancer will be presented.

Determination of iodine in urine, using epithermal instrumental neutron activation analysis (EINAA), at the University of Missouri Research Reactor (MURR)

There is currently great interest in iodine as a micro nutrient. Both high and low intakes have been associated with thyroid cancer incidence. Development of dietary iodine monitors is needed to supplement the use of dietary recall methods which have not been well validated for iodine. In this study, 30 pooled urine samples, from ethnic groups on various islands in the South Pacific, were analyzed for iodine using epithermal instrumental neutron activation analysis (EINAA).

Determination of fluoride in human nails via cyclic instrumental neutron activation analysis

The role of fluorine in human health has become somewhat controversial. It is widely accepted as protective against dental caries, may be protective against osteoporosis, and has been very conservatively implicated with osteosarcoma in male rats. In this study, we repot on the development of a neutron activation analysis method and its application to the analysis of human nails. We have found that toenails collected in population-based epidemiology studies apparently reflect fluoride intake.

Longitudinal study of iodine in toenails following IV administration of an iodine-containing contrast agent

The literature on the relationship between diet and thyroid cancer (TC) risk and the higher incidence of TC among Asian immigrants to the US compared to second and third generation subgroups has prompted epidemiologists to hypothesize that increased levels of iodine consumption may be associated with TC risk, particularly among persons with a history of clinical or subclinical thyroid dysfunction. At the University of Missouri Research Reactor (MURR), we have applied epiboron neutron activation analysis to investigate human nails as a dietary monitor for iodine. Preliminary studies have indicated a positive correlation between dietary iodine intake and the concentration of iodine in toenails. However, these studies are confounded by high iodine levels (up to 30 ppm) in approximately 5% of the nails studied. We hypothesize that, in the subjects we have studied, the high iodine levels may be due to iodine-containing medications, in particular contrast-agents containing iopamidol. This paper will report on longitudinal studies using contrast agent subjects who were followed-up for almost two years compared to a longitudinal control and a population mean. Based on this study, we suggest that iodine-containing contrast agents contaminate nail samples via non-specific binding in the short term followed by incorporation in the nail as a result of absorption.

Comparison of whole blood, plasma and nails as monitors for the dietary intake of selenium

The measurement of dietary selenium intake in a free-living population using dietary recall techniques has been shown to be spurious. Consequently, in our laboratory, we have focused on the development of biologic monitors such as blood, nails, hair and urine. In this paper, we report on the neutron activation analysis of whole blood, plasma and nail specimens collected from 285 Caucasian subjects, all permanent residents of Hawaii, participating in a malignant melanoma trial. Correlations between monitors are presented and discussed in the context of selenium determinants and integration of selenium intake.

Determination of iodine in human nails via epithermal neutron activation analysis

An epithermal instrumental neutron activation analysis (EINAA) method, using a boron nitride irradiation capsule compatible with use in the University of Missouri Research Reactor pneumatic-tube irradiation facility, has been developed for the analysis of iodine in human nails. The principal objective was to determine if the nail could be used as a means of monitoring dietary intake of iodine. The EINAA method was used to analyze nails from subjects having iodine intakes that could be qualitatively differentiated. Iodine concentrations in nails from these subjects were positively correlated with apparent iodine intake.

Longitudinal study of iodine in market milk and infant formula via epiboron neutron activation analysis

Iodine is an essential nutrient in the human diet. Its primary role is expressed as a component of thyroxine (T4) and the corresponding deiodinated triiodothyronine (T3) hormones produced by the thyroid as part of the system that regulates growth, mental development and metabolism. The recommended daily allowance (RDA) for iodine ranges from 50 μg/day for infants to 150 μg/day for adults. Reports over the last 15 years have indicated that the U.S. diet provides 2 to 7 times the iodine RDA and that dairy products typically provide 20 to 60 percent of the dietary iodine intake. Measurements of iodine in dietary components and composites reported in FDA studies have been done calorimetrically. These studies have, according to the authors, both under reports (by up to −50%) and over reports (by up to +80%) the iodine, depending on food type, compared to a radiochemical NAA reference method. Milk is typically under reported by −20%. The objective of this study was to utilize epiboron neutron activation analysis (EBNAA) to study the iodine concentrations, and seasonal variations of iodine, and market milk and infant formula, collected 15 years apart, in comparison with the Food and Drug Administration (FDA) market-basket reports.

Investigation of the appearance of supplemental enriched Se-76 using the human nail as a dietary monitor

The principal objective of this study was to determine if the use of a stable enriched tracer of Se-76 could be used to determine the delay time between a dietary intake of selenium and its appearance in fingernails and toenails. Selenium is an essential trace element in human nutrition. It has been studied at the Missouri University Research Reactor (MURR) for the past 15 years using an Instrumental Neutron Activation Analysis (INAA) technique. The principal route of human exposure to selenium is through the diet. Selenium concentrations of nails, blood, hair, and urine have been used as indicators of dietary selenium intake. In this study, a cohort consisting of seven men and five women ingested three selenium supplements of 150 μg each over a three day period. The selenium was enriched in Se-76 (96.48%) and ingested as selenite in orange juice following an overnight fast. Fingernails and toenails were collected prior to the selenium supplementation and for several months afterward to be used as biochemical indicators. The peak76Se concentration in the fingernails and toenails occurred at 19–23 and 16–32 weeks after supplementation, respectively.

Determination of total, and bound Se in sera by INAA

In this study we report on the comparison between the total selenium in serum (“total Se”) with that which is apparently bound to high molecular weight (>12,000 D) species, presumably proteins (“bound Se”). Nine hundred seventy seven (977) serum samples arising out of a population-based epidemiological study were prepared in duplicate for the determination of “total Se” by pipeting directly into irradiation vials; and separate duplicate aliquots were dialyzed against DI water for the determination of “bound Se”. All samples were analyzed by neutron activation analysis via77mSe (17.4 s). A small dialyzable Se component (∼6%) (“free Se”), defined as the difference between the “total Se” minus the “bound Se”, was identified.

The determination of selenium in urine

The selenium excreted in urine can be measured to assess the dietary status of selenium, an essential trace element in human nutrition. The objectives of this work were: 1) to develop a procedure, capable of high sample throughout, by which the major interferences can be reduced such that selenium concentrations can be measured in urine by Neutron Activation Analysis (NAA) using77mSe (17.4 s; and 2) to apply the method to a human dietary selenium study in which several selenium monitors were compared. The method involves a pre-irradiation arsenic-coprecipitation separation of the selenium from urine in the presence of a high specific-activity75Se tracer. The processed urine samples are analyzed using NAA. The procedure was applied to 58 urine specimens longitudinally collected from 12 subjects consuming three different levels of selenium. A dose-response relationship was observed in urine as well as a high correlations with both serum and whole blood selenium concentrations.