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Updated atomic weights: Time to review our table

Despite common belief, atomic weights are not necessarily constants of nature. Scientists’ ability to measure these values is regularly improving, so one would expect that the accuracy of these values should be improving with time. It is the task of the IUPAC (International Union of Pure and Applied Chemistry) Commission on Isotopic Abundances and Atomic Weights (CIAAW) to regularly review atomic-weight determinations and release updated values. According to an evaluation published in Pure and Applied Chemistry [1], even the most simplified table abridged to four significant digits needs to be updated for the elements selenium and molybdenum. According to the most recent 2015 release of "Atomic Weights of the Elements" [2], another update is needed for ytterbium.

ChemistryViews Magazine

Isotopic compositions of the elements 2013 (IUPAC Technical Report)

The Commission on Isotopic Abundances and Atomic Weights (ciaaw.org) of the International Union of Pure and Applied Chemistry (iupac.org) has revised the Table of Isotopic Compositions of the Elements (TICE). The update involved a critical evaluation of the recent published literature. The new TICE 2013 includes evaluated data from the “best measurement” of the isotopic abundances in a single sample, along with a set of representative isotopic abundances and uncertainties that accommodate known variations in normal terrestrial materials.

Pure and Applied Chemistry

Minimum requirements for publishing hydrogen, carbon, nitrogen, oxygen and sulfur stable-isotope delta results (IUPAC Technical Report)

Stable hydrogen, carbon, nitrogen, oxygen and sulfur (HCNOS) isotope compositions expressed as isotope-delta values are typically reported relative to international standards such as Vienna Standard Mean Ocean Water (VSMOW), Vienna Peedee belemnite (VPDB) or Vienna Cañon Diablo Troilite (VCDT). These international standards are chosen by convention and the calibration methods used to realise them in practice undergo occasional changes. To ensure longevity and reusability of published data, a comprehensive description of (1) analytical procedure, (2) traceability, (3) data processing, and (4) uncertainty evaluation is required. Following earlier International Union of Pure and Applied Chemistry documents on terminology and notations, this paper proposes minimum requirements for publishing HCNOS stable-isotope delta results. Each of the requirements are presented with illustrative examples.

Pure and Applied Chemistry

Standard atomic weights of the elements 2021 (IUPAC Technical Report)

Following the reviews of atomic-weight determinations and other cognate data in 2015, 2017, 2019 and 2021, the IUPAC (International Union of Pure and Applied Chemistry) Commission on Isotopic Abundances and Atomic Weights (CIAAW) reports changes of standard atomic weights. The symbol A r °(E) was selected for standard atomic weight of an element to distinguish it from the atomic weight of an element E in a specific substance P, designated A r (E, P). The CIAAW has changed the values of the standard atomic weights of five elements based on recent determinations of terrestrial isotopic abundances: Ar (argon): from 39.948 ± 0.001 to [39.792, 39.963] Hf (hafnium): from 178.49 ± 0.02 to 178.486 ± 0.006 Ir (iridium): from 192.217 ± 0.003 to 192.217 ± 0.002 Pb (lead): from 207.2 ± 0.1 to [206.14, 207.94] Yb (ytterbium): from 173.054 ± 0.005 to 173.045 ± 0.010 The standard atomic weight of argon and lead have changed to an interval to reflect that the natural variation in isotopic composition exceeds the measurement uncertainty of A r (Ar) and A r (Pb) in a specific substance. The standard atomic weights and/or the uncertainties of fourteen elements have been changed based on the Atomic Mass Evaluations 2016 and 2020 accomplished under the auspices of the International Union of Pure and Applied Physics (IUPAP). A r ° of Ho, Tb, Tm and Y were changed in 2017 and again updated in 2021: Al (aluminium), 2017: from 26.981 5385 ± 0.000 0007 to 26.981 5384 ± 0.000 0003 Au (gold), 2017: from 196.966 569 ± 0.000 005 to 196.966 570 ± 0.000 004 Co (cobalt), 2017: from 58.933 194 ± 0.000 004 to 58.933 194 ± 0.000 003 F (fluorine), 2021: from 18.998 403 163 ± 0.000 000 006 to 18.998 403 162 ± 0.000 000 005 (Ho (holmium), 2017: from 164.930 33 ± 0.000 02 to 164.930 328 ± 0.000 007) Ho (holmium), 2021: from 164.930 328 ± 0.000 007 to 164.930 329 ± 0.000 005 Mn (manganese), 2017: from 54.938 044 ± 0.000 003 to 54.938 043 ± 0.000 002 Nb (niobium), 2017: from 92.906 37 ± 0.000 02 to 92.906 37 ± 0.000 01 Pa (protactinium), 2017: from 231.035 88 ± 0.000 02 to 231.035 88 ± 0.000 01 Pr (praseodymium), 2017: from 140.907 66 ± 0.000 02 to 140.907 66 ± 0.000 01 Rh (rhodium), 2017: from 102.905 50 ± 0.000 02 to 102.905 49 ± 0.000 02 Sc (scandium), 2021: from 44.955 908 ± 0.000 005 to 44.955 907 ± 0.000 004 (Tb (terbium), 2017: from 158.925 35 ± 0.000 02 to 158.925 354 ± 0.000 008) Tb (terbium), 2021: from 158.925 354 ± 0.000 008 to 158.925 354 ± 0.000 007 (Tm (thulium), 2017: from 168.934 22 ± 0.000 02 to 168.934 218 ± 0.000 006) Tm (thulium), 2021: from 168.934 218 ± 0.000 006 to 168.934 219 ± 0.000 005 (Y (yttrium), 2017: from 88.905 84 ± 0.000 02 to 88.905 84 ± 0.000 01) Y (yttrium), 2021: from 88.905 84 ± 0.000 01 to 88.905 838 ± 0.000 002

Pure and Applied Chemistry

IUPAC Periodic Table of the Elements and Isotopes (IPTEI) for the education community (IUPAC Technical Report)

The IUPAC (International Union of Pure and Applied Chemistry) Periodic Table of the Elements and Isotopes (IPTEI) was created to familiarize students, teachers, and non-professionals with the existence and importance of isotopes of the chemical elements. The IPTEI is modeled on the familiar Periodic Table of the Chemical Elements. The IPTEI is intended to hang on the walls of chemistry laboratories and classrooms. Each cell of the IPTEI provides the chemical name, symbol, atomic number, and standard atomic weight of an element. Color-coded pie charts in each element cell display the stable isotopes and the relatively long lived radioactive isotopes having characteristic terrestrial isotopic compositions that determine the standard atomic weight of each element. The background color scheme of cells categorizes the 118 elements into four groups: (1) white indicates the element has no standard atomic weight, (2) blue indicates the element has only one isotope that is used to determine its standard atomic weight, which is given as a single value with an uncertainty, (3) yellow indicates the element has two or more isotopes that are used to determine its standard atomic weight, which is given as a single value with an uncertainty, and (4) pink indicates the element has a well-documented variation in its atomic weight, and the standard atomic weight is expressed as an interval. An element-by-element review accompanies the IPTEI and includes a chart of all known stable and radioactive isotopes for each element. Practical applications of isotopic measurements and technologies are included for the following fields: forensic science, geochronology, Earth-system sciences, environmental science, and human health sciences, including medical diagnosis and treatment.

Pure and Applied Chemistry

Atomic weights of the elements. Review 2000 (IUPAC Technical Report)

A consistent set of internationally accepted atomic weights has long been an essential aim of the scientific community because of the relevance of these values to science and technology, as well as to trade and commerce subject to ethical, legal, and international standards. The standard atomic weights of the elements are regularly evaluated, recommended, and published in updated tables by the Commission on Atomic Weights and Isotopic Abundances (CAWIA) of the International Union of Pure and Applied Chemistry (IUPAC). These values are invariably associated with carefully evaluated uncertainties. Atomic weights were originally determined by mass ratio measurements coupled with an understanding of chemical stoichiometry, but are now based almost exclusively on knowledge of the isotopic composition (derived from isotope-abundance ratio measurements) and the atomic masses of the isotopes of the elements. Atomic weights and atomic masses are now scaled to a numerical value of exactly 12 for the mass of the carbon isotope of mass number 12. Technological advances in mass spectrometry and nuclear-reaction energies have enabled atomic masses to be determined with a relative uncertainty of better than 1 ×10−7 . Isotope abundances for an increasing number of elements can be measured to better than 1 ×10−3 . The excellent precision of such measurements led to the discovery that many elements, in different specimens, display significant variations in their isotope-abundance ratios, caused by a variety of natural and industrial physicochemical processes. While such variations increasingly place a constraint on the uncertainties with which some standard atomic weights can be stated, they provide numerous opportunities for investigating a range of important phenomena in physical, chemical, cosmological, biological, and industrial processes. This review reflects the current and increasing interest of science in the measured differences between source-specific and even sample-specific atomic weights. These relative comparisons can often be made with a smaller uncertainty than is achieved in the best calibrated “absolute ” (=SI-traceable) atomic-weight determinations. Accurate determinations of the atomic weights of certain elements also influence the values of fundamental constants such as the Avogadro, Faraday, and universal gas constants. This review is in two parts: the first summarizes the development of the science of atomic-weight determinations during the 20th century; the second summarizes the changes and variations that have been recognized in the values and uncertainties of atomic weights, on an element-by-element basis, in the latter part of the 20th century.

Pure and Applied Chemistry

Comprehensive inter-laboratory calibration of reference materials for δ18O versus VSMOW using various on-line high-temperature conversion techniques

Internationally distributed organic and inorganic oxygen isotopic reference materials have been calibrated by six laboratories carrying out more than 5300 measurements using a variety of high-temperature conversion techniques (HTC) in an evaluation sponsored by the International Union of Pure and Applied Chemistry (IUPAC). To aid in the calibration of these reference materials, which span more than 125‰, an artificially enriched reference water ( δ 18 O of +78.91‰) and two barium sulfates (one depleted and one enriched in 18 O) were prepared and calibrated relative to VSMOW2 and SLAP reference waters. These materials were used to calibrate the other isotopic reference materials in this study, which yielded: Reference material δ 18 O and estimated combined uncertainty IAEA-602 benzoic acid +71.28 ± 0.36‰ USGS35 sodium nitrate +56.81 ± 0.31‰ IAEA-NO-3 potassium nitrate +25.32 ± 0.29‰ IAEA-601 benzoic acid +23.14 ± 0.19‰ IAEA-SO-5 barium sulfate +12.13 ± 0.33‰ NBS 127 barium sulfate +8.59 ± 0.26‰ VSMOW2 water 0‰ IAEA-600 caffeine −3.48 ± 0.53‰ IAEA-SO-6 barium sulfate −11.35 ± 0.31‰ USGS34 potassium nitrate −27.78 ± 0.37‰ SLAP water −55.5‰ The seemingly large estimated combined uncertainties arise from differences in instrumentation and methodology and difficulty in accounting for all measurement bias. They are composed of the 3-fold standard errors directly calculated from the measurements and provision for systematic errors discussed in this paper. A primary conclusion of this study is that nitrate samples analyzed for δ 18 O should be analyzed with internationally distributed isotopic nitrates, and likewise for sulfates and organics. Authors reporting relative differences of oxygen-isotope ratios ( δ 18 O) of nitrates, sulfates, or organic material should explicitly state in their reports the δ 18 O values of two or more internationally distributed nitrates (USGS34, IAEA-NO-3, and USGS35), sulfates (IAEA-SO-5, IAEA-SO-6, and NBS 127), or organic material (IAEA-601 benzoic acid, IAEA-602 benzoic acid, and IAEA-600 caffeine), as appropriate to the material being analyzed, had these reference materials been analyzed with unknowns. This procedure ensures that readers will be able to normalize the δ 18 O values at a later time should it become necessary. The high-temperature reduction technique for analyzing δ 18 O and δ 2 H is not as widely applicable as the well-established combustion technique for carbon and nitrogen stable isotope determination. To obtain the most reliable stable isotope data, materials should be treated in an identical fashion; within the same sequence of analyses, samples should be compared with working reference materials that are as similar in nature and in isotopic composition as feasible.

Rapid Communications in Mass Spectrometry

Guidelines and recommended terms for expression of stable-isotope-ratio and gas-ratio measurement results

To minimize confusion in the expression of measurement results of stable isotope and gas-ratio measurements, recommendations based on publications of the Commission on Isotopic Abundances and Atomic Weights of the International Union of Pure and Applied Chemistry (IUPAC) are presented. Whenever feasible, entries are consistent with the Système International d'Unités, the SI (known in English as the International System of Units), and the third edition of the International Vocabulary of Basic and General Terms in Metrology (VIM, 3rd edition). The recommendations presented herein are approved by the Commission on Isotopic Abundances and Atomic Weights and are designed to clarify expression of quantities related to measurement of isotope and gas ratios to ensure that quantity equations instead of numerical value equations are used for quantity definitions. Examples of column headings consistent with quantity calculus (also called the algebra of quantities) and examples of various deprecated usages connected with the terms recommended are presented.

Rapid Communications in Mass Spectrometry

Normalization of stable isotope data for carbonate minerals: implementation of IUPAC guideline

Carbonate minerals provide a rich source of geochemical information because their δ 13 C and δ 18 O values provide information about surface and subsurface Earth processes. However, a significant problem is that the same δ 18 O value is not reported for the identical carbonate sample when analyzed in different isotope laboratories in spite of the fact that the International Union of Pure and Applied Chemistry (IUPAC) has provided reporting guidelines for two decades. This issue arises because (1) the δ 18 O measurements are performed on CO 2 evolved by reaction of carbonates with phosphoric acid, (2) the acid-liberated CO 2 is isotopically fractionated (enriched in 18 O) because it contains only two-thirds of the oxygen from the solid carbonate, (3) this oxygen isotopic fractionation factor is a function of mineralogy, temperature, concentration of the phosphoric acid, and δ 18 O value of water in the phosphoric acid, (4) researchers may use any one of an assortment of oxygen isotopic fractionation factors that have been published for various minerals at various reaction temperatures, and (5) it sometimes is not clear how one should calculate δ 18 O VPDB values on a scale normalized such that the δ 18 O value of SLAP reference water is −55.5 ‰ relative to VSMOW reference water. To enable researchers worldwide to publish the same δ 18 O value (within experimental uncertainty) for the same carbonate sample, we have re-evaluated reported acid fractionation factors for calcite at 25, 50, and 75 °C and propose a revised relation for the temperature dependence of oxygen isotopic acid fractionation factor, α CO 2 ( ACID ) -calcite αCO2(ACID)-calcite , of 1000ln α CO 2 ( ACID ) -calcite=3.48(10 3 /T)-1.47 1000lnαCO2(ACID)-calcite=3.48(103/T)-1.47 Turn MathJax on where T is temperature in kelvin. At 25 °C, α CO 2 ( ACID ) -calcite=1.01025 αCO2(ACID)-calcite=1.01025 , the most commonly accepted value for this quantity. We propose a normalization protocol in which (1) the internationally distributed carbonate isotopic reference materials NBS 18 and NBS 19 are interspersed among carbonate samples analyzed by treatment with phosphoric acid, (2) the δ 18 O values of the calcite reference materials and the carbonate samples are calculated, respectively, by using the α CO 2 ( ACID ) -calcite αCO2(ACID)-calcite relation above and oxygen-isotope acid fractionation factors appropriate for the sample mineralogy and reaction temperature, (3) the δ 18 O values of solid carbonate samples are determined on the VPDB scale ( δ 18 O VPDB ) with IUPAC-recommended scale expansion such that the δ 18 O of SLAP reference water is −55.5 ‰ relative to VSMOW reference water by normalizing δ 18 O values of carbonate samples with 2014-IUPAC-recommended δ 18 O values of NBS 18 and NBS 19, and (4) δ 18 O values on the VPDB scale are converted to δ 18 O values on the VSMOW-SLAP scale by using IUPAC recommendations. To ease calculations in the protocol, a software application titled “Carbon and Oxygen Isotopic Normalization Tool for Carbonates” is available that relies upon IUPAC-recommended δ 13 C and δ 18 O values of carbonate isotopic reference materials ( http://isotopes.usgs.gov/research/topics/carbonatesnormalizationtool.html ).

Geochimica et Cosmochimica Acta

Clarifying atomic weights: A 2016 four-figure table of standard and conventional atomic weights

To indicate that atomic weights of many elements are not constants of nature, in 2009 and 2011 the Commission on Isotopic Abundances and Atomic Weights (CIAAW) of the International Union of Pure and Applied Chemistry (IUPAC) replaced single-value standard atomic weight values with atomic weight intervals for 12 elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, magnesium, silicon, sulfur, chlorine, bromine, and thallium); for example, the standard atomic weight of nitrogen became the interval [14.00643, 14.00728]. CIAAW recognized that some users of atomic weight data only need representative values for these 12 elements, such as for trade and commerce. For this purpose, CIAAW provided conventional atomic weight values, such as 14.007 for nitrogen, and these values can serve in education when a single representative value is needed, such as for molecular weight calculations. Because atomic weight values abridged to four figures are preferred by many educational users and are no longer provided by CIAAW as of 2015, we provide a table containing both standard atomic weight values and conventional atomic weight values abridged to four figures for the chemical elements. A retrospective review of changes in four-digit atomic weights since 1961 indicates that changes in these values are due to more accurate measurements over time or to the recognition of the impact of natural isotopic fractionation in normal terrestrial materials upon atomic weight values of many elements. Use of the unit “u” (unified atomic mass unit on the carbon mass scale) with atomic weight is incorrect because the quantity atomic weight is dimensionless, and the unit “amu” (atomic mass unit on the oxygen scale) is an obsolete term: Both should be avoided.

Journal of Chemical Education

Description, Properties, and Degradation of Selected Volatile Organic Compounds Detected in Ground Water--A Review of Selected Literature

This report provides abridged information describing the most salient properties and biodegradation of 27 chlorinated volatile organic compounds detected during ground-water studies in the United States. This information is condensed from an extensive list of reports, papers, and literature published by the U.S. Government, various State governments, and peer-reviewed journals. The list includes literature reviews, compilations, and summaries describing volatile organic compounds in ground water. This report cross-references common names and synonyms associated with volatile organic compounds with the naming conventions supported by the International Union of Pure and Applied Chemistry. In addition, the report describes basic physical characteristics of those compounds such as Henry's Law constant, water solubility, density, octanol-water partition (log Kow), and organic carbon partition (log Koc) coefficients. Descriptions and illustrations are provided for natural and laboratory biodegradation rates, chemical by-products, and degradation pathways.

Open-File Report

Compilation of minimum and maximum isotope ratios of selected elements in naturally occurring terrestrial materials and reagents

Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope abundance variations potentially are large enough to result in future expansion of their atomic weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope-abundance variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio. There are no internationally distributed isotopic reference materials for the elements zinc, selenium, molybdenum, palladium, and tellurium. Preparation of such materials will help to make isotope ratio measurements among laboratories comparable. The minimum and maximum concentrations of a selected isotope in naturally occurring terrestrial materials for selected chemical elements reviewed in this report are given below: Isotope Minimum mole fraction Maximum mole fraction -------------------------------------------------------------------------------- 2H 0 .000 0255 0 .000 1838 7Li 0 .9227 0 .9278 11B 0 .7961 0 .8107 13C 0 .009 629 0 .011 466 15N 0 .003 462 0 .004 210 18O 0 .001 875 0 .002 218 26Mg 0 .1099 0 .1103 30Si 0 .030 816 0 .031 023 34S 0 .0398 0 .0473 37Cl 0 .240 77 0 .243 56 44Ca 0 .020 82 0 .020 92 53Cr 0 .095 01 0 .095 53 56Fe 0 .917 42 0 .917 60 65Cu 0 .3066 0 .3102 205Tl 0 .704 72 0 .705 06 The numerical values above have uncertainties that depend upon the uncertainties of the determinations of the absolute isotope-abundance variations of reference materials of the elements. Because reference materials used for absolute isotope-abundance measurements have not been included in relative isotope abundance investigations of zinc, selenium, molybdenum, palladium, and tellurium, ranges in isotopic composition are not listed for these elements, although such ranges may be measurable with state-of-the-art mass spectrometry. This report is available at the url: http://pubs.water.usgs.gov/wri014222.

Water-Resources Investigations Report

Correction for the 17O interference in δ(13C) measurements when analyzing CO2 with stable isotope mass spectrometry

Measurements of δ( 13 C) determined on CO 2 with an isotope-ratio mass spectrometer (IRMS) must be corrected for the amount of 17 O in the CO 2 . For data consistency, this must be done using identical methods by different laboratories. This report aims at unifying data treatment for CO 2 IRMS by proposing (i) a unified set of numerical values, and (ii) a unified correction algorithm, based on a simple, linear approximation formula. Because the oxygen of natural CO 2 is derived mostly from the global water pool, it is recommended that a value of 0.528 be employed for the factor λ, which relates differences in 17 O and 18 O abundances. With the currently accepted N( 13 C)/N( 12 C) of 0.011 180(28) in VPDB (Vienna Peedee belemnite) reevaluation of data yields a value of 0.000 393(1) for the oxygen isotope ratio N( 17 O)/N( 16 O) of the evolved CO 2 . The ratio of these quantities, a ratio of isotope ratios, is essential for the 17 O abundance correction: [N( 17 O)/N( 16 O)]/[N( 13 C)/N( 12 C)] = 0.035 16(8). The equation [δ( 13 C) ≈ 45 δ VPDB-CO2 + 2 17 R/ 13 R ( 45 δ VPDB-CO2 – λ 46 δ VPDB-CO2 )] closely approximates δ( 13 C) values with less than 0.010 ‰ deviation for normal oxygen-bearing materials and no more than 0.026 ‰ in extreme cases. Other materials containing oxygen of non-mass-dependent isotope composition require a more specific data treatment. A similar linear approximation is also suggested for δ( 18 O). The linear approximations are easy to implement in a data spreadsheet, and also help in generating a simplified uncertainty budget.

Pure and Applied Chemistry

Atomic weights of the elements 2011 (IUPAC Technical Report)

The biennial review of atomic-weight determinations and other cognate data has resulted in changes for the standard atomic weights of five elements. The atomic weight of bromine has changed from 79.904(1) to the interval [79.901, 79.907], germanium from 72.63(1) to 72.630(8), indium from 114.818(3) to 114.818(1), magnesium from 24.3050(6) to the interval [24.304, 24.307], and mercury from 200.59(2) to 200.592(3). For bromine and magnesium, assignment of intervals for the new standard atomic weights reflects the common occurrence of variations in the atomic weights of those elements in normal terrestrial materials.

Pure and Applied Chemistry

Atomic weights of the elements 1999

The biennial review of atomic-weight, Ar(E), determinations and other cognate data have resulted in changes for the standard atomic weights of the following elements: Presented are updated tables of the standard atomic weights and their uncertainties estimated by combining experimental uncertainties and terrestrial variabilities. In addition, this report again contains an updated table of relative atomic-mass values and half-lives of selected radioisotopes. Changes in the evaluated isotopic abundance values from those published in 1997 are so minor that an updated list will not be published for the year 1999. Many elements have a different isotopic composition in some nonterrestrial materials. Some recent data on parent nuclides that might affect isotopic abundances or atomic-weight values are included in this report for the information of the interested scientific community.

Pure and Applied Chemistry

Workshop 3.5: Closing the gap between exposure and effects in monitoring studies

A major challenge to contaminant monitoring programs is the selection of an appropriate suite of measurements for assessing exposure and effects. Early monitoring programs relied solely on residue analysis to detect the organochlorine compounds that were in use at that time. A shift to the use of more transient, less persistent chemicals required that a new set of tools be developed to determine if an organism had been exposed. This led to the development of cellular and biochemical assays that could indicate the presence of these types of chemicals in biota and the environment. However, it was recognized that measures of contaminant presence alone were insufficient to assess the health of biota. As a result, considerable research began to be directed toward development of diagnostic tools for measuring chemical effects in fish and wildlife. Today, contaminant monitoring programs follow a paradigm for study design that emphasizes not only the use of measures of exposure, but also measures of effect. Using data from our monitoring and research studies for hormonally active substances, we discuss a variety of metrics of exposure and effects and their application to specific chemicals, and the current information gaps. We conclude that although several bioindicators of exposure and effect have been promoted and used, to date there continues to be a poor association between cause and effect for endocrine active substances. In part, this is due to the limited number of diagnostic tools that are available and to a lack of basic toxicological information concerning toxicokinetics and mechanisms of action of hormonally active chemicals in fish and wildlife species. In the foreseeable future, both tissue and environmental residue data, despite the many limitations, will continue to be an important component of monitoring programs for hormonally active chemicals as we continue to develop and validate more specific bioindicators of exposure and effects.

Pure and Applied Chemistry

Variation in the terrestrial isotopic composition and atomic weight of argon

The isotopic composition and atomic weight of argon (Ar) are variable in terrestrial materials. Those variations are a source of uncertainty in the assignment of standard properties for Ar, but they provide useful information in many areas of science. Variations in the stable isotopic composition and atomic weight of Ar are caused by several different processes, including (1) isotope production from other elements by radioactive decay (radiogenic isotopes) or other nuclear transformations (e.g., nucleogenic isotopes), and (2) isotopic fractionation by physical-chemical processes such as diffusion or phase equilibria. Physical-chemical processes cause correlated mass-dependent variations in the Ar isotope-amount ratios ( 40 Ar/ 36 Ar, 38 Ar/ 36 Ar), whereas nuclear transformation processes cause non-mass-dependent variations. While atmospheric Ar can serve as an abundant and homogeneous isotopic reference, deviations from the atmospheric isotopic ratios in other Ar occurrences limit the precision with which a standard atomic weight can be given for Ar. Published data indicate variation of Ar atomic weights in normal terrestrial materials between about 39.7931 and 39.9624. The upper bound of this interval is given by the atomic mass of 40 Ar, as some samples contain almost pure radiogenic 40 Ar. The lower bound is derived from analyses of pitchblende (uranium mineral) containing large amounts of nucleogenic 36 Ar and 38 Ar. Within this interval, measurements of different isotope ratios ( 40 Ar/ 36 Ar or 38 Ar/ 36 Ar) at various levels of precision are widely used for studies in geochronology, water–rock interaction, atmospheric evolution, and other fields.

Pure and Applied Chemistry