Development of some natural matrix standards — Progress report

Substantial progress has been made in the production of environmental level, natural matrix, radioactivity standards of soil of low organic and low carbonate content, and of human lung and human liver. This is in response to the deliberations of the 1977 ICRM meeting at which the need for such standards was voiced and the criteria suggested. The soil samples have been reduced to optimum particle size and are ready for blending and standardization. A ten year supply of this standard should be ready in a year or less. Reducing the dried lung and liver to less than 74 μm has proven formidable because of the natural fat and oil content. Using cyrogenic milling techniques more than three quarters of the total mass of each has been reduced to the desired particle size; the balance will either be reduced or removed and we can then proceed to the final standardization.     

Statistical assessment of subsampling procedures

As shown by the examples in this paper, the concentrations in subsamples are not necessarily independently and normally distributed despite vigorous grinding and mixing of the original sample. Studies of the statistical properties of subsample concentrations should test for deviations from independence and normality and, if deviations are found, should model the observed distribution. The tests include an analysis of variance to check for less variation among nearby subsamples than among widely spaced subsamples, as well as the computation of the probability plot correlation coefficient to check for nonnormality. These tests are illustrated with ${}^{239}\text{Pu}\text{+}{}^{240}\text{Pu}$ measurements on subsamples prepared for use as standard reference materials. These materials are used in quality assurance for environmental radioactivity measurements. The material consisting of Human Liver (SRM 4352) exhibits dependence, which may be due to inadequate mixing or to later handling that caused segregation. The material consisting of Human Lung (SRM 4351) and the material consisting of soil from Rocky Flats (SRM 4353) exhibit nonnormality due to the particulate nature of some plutonium-bearing fractions of the material. The lung measurements are modeled with the gamma distribution. The soil measurements are modeled with a combination of the normal distribution and a distribution that models the occurrence of outliers. The use of these models to describe the subsamples involves assessment of the contribution of the measurement error.     

Optimizing the removal of carbon phases in soils and sediments for sequential chemical extractions by coulometry

We have developed a coulometric technique to optimize the removal of the carbonate and organic fractions for sequential chemical extractions of soils and sediments. The coulometric system facilitates optimizing these two fractions by direct real-time measurement of carbon dioxide (CO2) evolved during the removal of these two fractions. Further analyses by ICP-MS and alpha-spectrometry aided in interpreting the results of coulometry experiments. The effects of time, temperature, ionic strength and pH were investigated. The sensitivity of the coulometric reaction vessel/detection system was sufficient even at very low total carbon content (< 0.1 mol kg-1). The efficiency of the system is estimated to be 96% with a standard deviation of 8%. Experiments were carried out using NIST Standard Reference Materials 4357 Ocean Sediment (OS), 2704 Buffalo River Sediment (BRS), and pure calcium carbonate. Carbonate minerals were dissolved selectively using an ammonium acetate-acetic acid buffer. Organic matter was then oxidized to CO2 using hydrogen peroxide (H2O2) in nitric acid. The carbonate fraction was completely dissolved within 120 min under all conditions examined (literature suggests up to 8 h). For the OS standard, the oxidation of organic matter self-perpetuates between 45 and 50 degrees C, a factor of two less than commonly suggested, while organic carbon in the BRS standard required 80 degrees C for the reaction to proceed to completion. For complete oxidation of organic matter, we find that at least three additions of H2O2 are required (popular methods suggest one or two).     

Comparative study of non-invasive methods for assessing Daphnia magna embryo toxicity

Embryos, unlike adults, are typically sessile, which allows for an increase in the available metrics that can be used to assess chemical toxicity. We investigate Daphnia magna development rate and oxygen consumption as toxicity metrics and compare them to arrested embryo development using four different techniques with potassium cyanide (KCN) as a common toxicant. The EC₅₀ (95 % CI) for arrested development was 2,535 (1,747–3,677) μg/L KCN. Using pixel intensity changes, recorded with difference imaging, we semi-quantitatively assessed a decrease in development rate at 200 μg/L KCN, threefold lower than the arrested development lowest observed effect concentration (LOEC). Respirometry and self-referencing (SR) microsensors were two unique techniques used to assess oxygen consumption. Using respirometry, an increase in oxygen consumption was found in the 5 μg/L KCN treatment and a decrease for 148 μg/L, but no change was found for the 78 μg/L KCN treatment. Whereas, with SR microsensors, we were able to detect significant changes in oxygen consumption for all three treatments: 5, 78, and 148 μg/L KCN. While SR offered the highest sensitivity, the respirometry platform developed for this study was much easier to use to measure the same endpoint. Oxygen consumption may be subject to change during the development process, meaning consumption assessment techniques may only be useful only for short-term experiments. Development rate was a more sensitive endpoint though was only reliable four of the six embryonic developmental stages examined. Despite being the least sensitive endpoint, arrested embryo development was the only technique capable of assessing the embryos throughout all developmental stages. In conclusion, each metric has advantages and limitations, but because all are non-invasive, it is possible to use any combination of the three.     

Radioactivity standards for environmental monitoring. II

The current environmental-monitoring-standards efforts of the low-level-radioactivity laboratory in the Radioactivity Group of the National Bureau of Standards are described. The calibration efforts include traceability programs, natural-matrix Standard Reference Materials, alpha-particle-emitting standards, and international radioactivity intercomparisons. New radiometrology efforts under development include a prototype radon-222 in water standard, γ-ray emission-rate measurement techniques in the 60-keV region, and atom-counting techniques for radioactivity measurements.