Evaluation of Stable Chlorine and Bromine Isotopes in Sedimentary Formation Fluids
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Chlorine Stable Isotopes in Sedimentary Systems: Does Size Matter?
Chlorine stable isotopes in sedimentary systems: does size matter? Max Coleman Jet Propulsion Laboratory, Caltech, Pasadena, California, USA ABSTRACT: Stable isotope abundances vary because of size (atomic mass) differences. The chlorine stable isotope system was one of the first described theoretically, but had a slow, disappointment-strewn develop- ment, relative to other elements. Method improvement gave only small, but significant, differences (-1 %.) in compositions of geological materials. Eventually, brines and groundwater chlorides gave larger differences (-5%0). Physical processes like diffusion and adsorption, probably are the main controls of groundwater com- positions. In contrast, the processes producing brine compositions are still enigmatic and need further work for full understanding. Recent work on anthropogenic groundwater contaminants (chlorinated aliphatic hy- drocarbons and perchlorate) shows variations resulting from manufacturing processes; implying possibilities of tracing sources. However, they are subject to microbial degradation, producing much larger fractionations (115%0),but therefore offering better possibility of monitoring natural attenuation. So atomic size is important to give isotopic fractionation and the size of fractionation matters, allowing observation of otherwise unde- tectable processes. lecular and atomic weights by weighing the gases and relating them to the weight of hydrogen. All 1 INTRODUCTION atomic weights were integer multiples the weight of This paper aims to give a short and selective -
Redalyc.Chlorine in the Stratosphere
Atmósfera ISSN: 0187-6236 [email protected] Universidad Nacional Autónoma de México México VON CLARMANN, T. Chlorine in the stratosphere Atmósfera, vol. 26, núm. 3, 2013, pp. 415-458 Universidad Nacional Autónoma de México Distrito Federal, México Available in: http://www.redalyc.org/articulo.oa?id=56527859010 How to cite Complete issue Scientific Information System More information about this article Network of Scientific Journals from Latin America, the Caribbean, Spain and Portugal Journal's homepage in redalyc.org Non-profit academic project, developed under the open access initiative Atmósfera 26(3), 415-458 (2013) Chlorine in the stratosphere T. VON CLARMANN Karlsruhe Institute of Technology, IMK, POB 3640, 76021 Karlsruhe, Germany E-mail: [email protected] Received May 22, 2013; accepted June 21, 2013 RESUMEN Este artículo reseña varios aspectos de los compuestos clorados presentes en la estratosfera, que incluyen tanto su papel como agentes químicos como su función de trazadores de los procesos dinámicos. En la estratosfera, el cloro reactivo se libera a partir de los clorofluorocarbonos y otros gases orgánicos que contienen cloro. La mayor parte del cloro reactivo se convierte en compuestos inertes que almacenan cloro, como ClONO2 y HCl. La reactivación del cloro estratosférico ocurre principalmente por reacciones heterogéneas en vórtices polares invernales, en combinación con la luz solar. Los ciclos catalíticos de Cl, ClO, BrO, Cl2 O2 , ClO2 y otros compuestos como NO, NO2, OH y HO2 destruyen el oxígeno impar (ozono y oxígeno atómico) de la atmósfera. El ciclo del dímero de ClO es particularmente importante en la formación del agujero de ozono, mientras que en latitudes medias el HOCl tiene alguna relevancia. -
Global Sources and Distribution of Atmospheric Methyl Chloride
GLOBAL SOURCES AND DISTRIBUTION OF ATMOSPHERIC METHYL CHLORIDE A Dissertation Presented to The Academic Faculty By Yasuko Yoshida In Partial Fulfillment Of the Requirements for the Degree Doctor of Philosophy in the School of Earth and Atmospheric Sciences Georgia Institute of Technology August 2006 Global Sources and Distribution of Atmospheric Methyl Chloride Approved by: Dr. Yuhang Wang, Advisor Dr. Armistead Russell School of Earth and Atmospheric School of Civil and Environmental Sciences Engineering Georgia Institute of Technology Georgia Institute of Technology Dr. Robert Dickinson Dr. David Tan School of Earth and Atmospheric School of Earth and Atmospheric Sciences Sciences Georgia Institute of Technology Georgia Institute of Technology Dr. Athanasios Nenes School of Earth and Atmospheric Date Approved: June 16, 2006 Sciences Georgia Institute of Technology To Ben and Ikuko ACKNOWLEDGEMENTS I would like to express my sincere appreciation to my faculty advisor, Dr. Yuhang Wang, for his direction, guidance and support throughout my PhD study. I would also like to thank my thesis committee members, Dr. Robert Dickinson, Dr. Athanasios Nenes, Dr. Armistead Russell, and Dr. David Tan, for their assistance. I thank Dr. David Erickson and Dr. Jose L. Hernandez for providing the UWM- COADS data and helpful comments. I also thank Dr. Donald Blake for his suggestions. Special thanks go to Dr. Derek Cunnold for providing us the AGAGE data. I am grateful to CMDL and Dr. Geoff Dutton for providing us their unpublished data. I am also indebted to Dr. Daniel Jacob and Dr. Colette Heald for their help. I would like to thank Dr. Louis Giglio for his helpful suggestions. -
12 Natural Isotopes of Elements Other Than H, C, O
12 NATURAL ISOTOPES OF ELEMENTS OTHER THAN H, C, O In this chapter we are dealing with the less common applications of natural isotopes. Our discussions will be restricted to their origin and isotopic abundances and the main characteristics. Only brief indications are given about possible applications. More details are presented in the other volumes of this series. A few isotopes are mentioned only briefly, as they are of little relevance to water studies. Based on their half-life, the isotopes concerned can be subdivided: 1) stable isotopes of some elements (He, Li, B, N, S, Cl), of which the abundance variations point to certain geochemical and hydrogeological processes, and which can be applied as tracers in the hydrological systems, 2) radioactive isotopes with half-lives exceeding the age of the universe (232Th, 235U, 238U), 3) radioactive isotopes with shorter half-lives, mainly daughter nuclides of the previous catagory of isotopes, 4) radioactive isotopes with shorter half-lives that are of cosmogenic origin, i.e. that are being produced in the atmosphere by interactions of cosmic radiation particles with atmospheric molecules (7Be, 10Be, 26Al, 32Si, 36Cl, 36Ar, 39Ar, 81Kr, 85Kr, 129I) (Lal and Peters, 1967). The isotopes can also be distinguished by their chemical characteristics: 1) the isotopes of noble gases (He, Ar, Kr) play an important role, because of their solubility in water and because of their chemically inert and thus conservative character. Table 12.1 gives the solubility values in water (data from Benson and Krause, 1976); the table also contains the atmospheric concentrations (Andrews, 1992: error in his Eq.4, where Ti/(T1) should read (Ti/T)1); 2) another category consists of the isotopes of elements that are only slightly soluble and have very low concentrations in water under moderate conditions (Be, Al). -
Anthropogenic Cycles of the Elements: a Critical Review Wei-Qiang Chen* and T
Critical Review pubs.acs.org/est Anthropogenic Cycles of the Elements: A Critical Review Wei-Qiang Chen* and T. E. Graedel Center for Industrial Ecology, School of Forestry and Environmental Studies, Yale University, New Haven, Connecticut 06511, United States *S Supporting Information ABSTRACT: A cycle is the quantitative characterization of the flows of a specific material into, within, and from a given system. An anthropogenic elemental cycle can be static (for a point in time) or dynamic (over a time interval). The about 350 publications collected for this review contain a total of 1074 individual cycle determinations, 989 static and 85 dynamic, for 59 elements; more than 90% of the publications have appeared since 2000. The cycles are of varying quality and completeness, with about 80% at country- or territory-level, addressing 45 elements, and 5% at global-level, addressing 30 elements. Despite their limitations, cycles have often been successful in revealing otherwise unknown information. Most of the elements for which no cycles exist are radioactively unstable or are used rarely and in small amounts. For a variety of reasons, the anthropogenic cycles of only perhaps a dozen elements are well characterized. For all the others, with cycles limited or nonexistent, our knowledge of types of uses, lifetimes in those uses, international trade, losses to the environment, and rates of recycling is quite limited, thereby making attempts to evaluate resource sustainability particularly problematic. 1. INTRODUCTION Thus, we exclude those biogeochemical cycles directed largely fl 2 As is now well-known, the human combustion of fossil fuels or completely at natural stocks and ows, as well as those that and the clearing of forest lands inject carbon dioxide into the are said to be anthropogenic cycles but actually only treat exchanges between the anthroposphere and the natural atmosphere. -
03B Risk Assessment and Cycling of Natural Organochlorines
FOCS Focus on Chlorine Science Edition 2013 ISSUE 03B Risk assessment and the cycle of natural To investigate potential chlorination rates, conifer- Rapid and extensive natural chlorination & 36 ous forest soil from the organic horizon with Clin dechlorination of soil organic matter was amended, and over time the amounts of 36Cl subsequently present as chloride (Clin) and non- David Bastviken (Stockholm University, Sweden) extractable organic chlorine were monitored (Clorg; using water and 0.1M potassium nitrate as extract- Co-authors of the original paper: Frida Thomsen, Teresia ants). Three different experiments were per- Svensson, Susanne Karlsson, Per Sandén, George Shaw, formed. Miroslav Matucha and Gunilla Öberg. In the first, transformation of Cl over 133 days un- During recent decades, the extent to which soil der oxic conditions was studied. This experiment organic matter can be chlorinated by natural pro- 36 showed a rapid initial increase in Clorg and after cesses has been debated. The amounts of organi- 36 eight days, 23% of the added Clin had been trans- cally bound chlorine (Clorg) in soils are often as 36 36 36 formed into Clorg. The proportion of Cl as Clorg large as or greater than the quantities of inorganic remained at this level until day 20. After that, the chlorine (chloride; Clin). Such high levels of Clorg 36 fraction of Clorg started to decrease and reached a even in very remote areas imply that its presence plateau at 8% by day 133. The decline in 36Cl af- cannot be explained by anthropogenic emissions org 36 ter day 20 can only be explained by substantial alone. -
Chlorine Cycling and the Fate of Cl in Terrestrial Environments
Environmental Science and Pollution Research (2021) 28:7691–7709 https://doi.org/10.1007/s11356-020-12144-6 REVIEW ARTICLE Chlorine cycling and the fate of Cl in terrestrial environments Teresia Svensson1 & Henrik Kylin1,2 & Malin Montelius3 & Per Sandén1 & David Bastviken1 Received: 14 July 2020 /Accepted: 16 December 2020 / Published online: 5 January 2021 # The Author(s) 2021 Abstract Chlorine (Cl) in the terrestrial environment is of interest from multiple perspectives, including the use of chloride as a tracer for water flow and contaminant transport, organochlorine pollutants, Cl cycling, radioactive waste (radioecology; 36Cl is of large concern) and plant science (Cl as essential element for living plants). During the past decades, there has been a rapid development towards improved understanding of the terrestrial Cl cycle. There is a ubiquitous and extensive natural chlorination of organic matter in terrestrial ecosystems where naturally formed chlorinated organic compounds (Clorg) in soil frequently exceed the abundance of chloride. Chloride dominates import and export from terrestrial ecosystems while soil Clorg and biomass Cl can dominate the standing stock Cl. This has important implications for Cl transport, as chloride will enter the Cl pools resulting in prolonged residence times. Clearly, these pools must be considered separately in future monitoring programs addressing Cl cycling. Moreover, there are indications that (1) large amounts of Cl can accumulate in biomass, in some cases representing the main Cl pool; (2) emissions of volatile organic chlorines could be a significant export pathway of Cl and (3) that there is a production of Clorg in tissues of, e.g. plants and animals and that Cl can accumulate as, e.g. -
Accelerator Mass Spectrometry of 36Cl and 129I Analytical Aspects and Applications
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 1 Accelerator Mass Spectrometry of 36Cl and 129I Analytical Aspects and Applications BY VASILY ALFIMOV ACTA UNIVERSITATIS UPSALIENSIS ISSN 1651-6214 UPPSALA ISBN 91-554-6124-7 2005 urn:nbn:se:uu:diva-4725 Dissertation presented at Uppsala University to be publicly examined in Häggsalen, The Ång- ström Laboratory, Uppsala, Friday, January 21, 2005 at 10:15 for the Degree of Doctor of Philosophy. The examination will be conducted in English. Abstract Alfimov, V. 2005. Accelerator Mass Spectrometry of 36Cl and 129I: Analytical Aspects and Applications. Acta Universitatis Upsaliensis. Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 1. 81 pp. Uppsala. ISBN 91-554-6124-7 36 129 Two long-lived halogen radionuclides ( Cl, T1/2 = 301 kyr, and I, T1/2 = 15.7 Myr) have been studied by means of Accelerator Mass Spectrometry (AMS) at the Uppsala Tandem Labo- ratory. The 36Cl measurements in natural samples using a medium-sized tandem accelerator (∼1 MeV/amu) have been considered. A gas-filled magnetic spectrometer (GFM) was proposed for the separation of 36Cl from its isobar, 36S. Semi-empirical Monte-Carlo ion optical calculations were conducted to define optimal conditions for separating 36Cl and 36S. A 180° GFM was constructed and installed at the dedicated AMS beam line. 129I has been measured in waters from the Arctic and North Atlantic Oceans. Most of the 129I currently present in the Earth’s surface environment can be traced back to liquid and gaseous releases from the nuclear reprocessing facilities at Sellafield (UK) and La Hague (France). -
Technical and Regulatory Guidance Environmental Molecular Diagnostics
Technical and Regulatory Guidance Environmental Molecular Diagnostics New Site Characterization and Remediation Enhancement Tools April 2013 Prepared by The Interstate Technology & Regulatory Council Environmental Molecular Diagnostics Team ABOUT ITRC The Interstate Technology and Regulatory Council (ITRC) is a public-private coalition working to reduce bar- riers to the use of innovative environmental technologies and approaches so that compliance costs are reduced and cleanup efficacy is maximized. ITRC produces documents and training that broaden and deepen technical knowledge and expedite quality regulatory decision making while protecting human health and the envir- onment. With private and public sector members from all 50 states and the District of Columbia, ITRC truly provides a national perspective. More information on ITRC is available at www.itrcweb.org. ITRC is a pro- gram of the Environmental Research Institute of the States (ERIS), a 501(c)(3) organization incorporated in the District of Columbia and managed by the Environmental Council of the States (ECOS). ECOS is the national, nonprofit, nonpartisan association representing the state and territorial environmental commissioners. Its mission is to serve as a champion for states; to provide a clearinghouse of information for state envir- onmental commissioners; to promote coordination in environmental management; and to articulate state pos- itions on environmental issues to Congress, federal agencies, and the public. DISCLAIMER This material was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any war- ranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or use- fulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. -
Biological Chlorine Cycling in the Arctic Coastal Plain
Biological chlorine cycling in the Arctic Coastal Plain Jaime E. Zlamal, Theodore K. Raab, Mark Little, Robert A. Edwards & David A. Lipson Biogeochemistry An International Journal ISSN 0168-2563 Biogeochemistry DOI 10.1007/s10533-017-0359-0 1 23 Your article is protected by copyright and all rights are held exclusively by Springer International Publishing AG. This e-offprint is for personal use only and shall not be self- archived in electronic repositories. If you wish to self-archive your article, please use the accepted manuscript version for posting on your own website. You may further deposit the accepted manuscript version in any repository, provided it is only made publicly available 12 months after official publication or later and provided acknowledgement is given to the original source of publication and a link is inserted to the published article on Springer's website. The link must be accompanied by the following text: "The final publication is available at link.springer.com”. 1 23 Author's personal copy Biogeochemistry DOI 10.1007/s10533-017-0359-0 Biological chlorine cycling in the Arctic Coastal Plain Jaime E. Zlamal . Theodore K. Raab . Mark Little . Robert A. Edwards . David A. Lipson Received: 1 April 2017 / Accepted: 30 July 2017 Ó Springer International Publishing AG 2017 Abstract This study explores biological chlorine compounds (Clorg) were correlated with organic matter cycling in coastal Arctic wet tundra soils. While many content, with a steeper slope in older soils. The previous chlorine-cycling studies have focused on concentration and chemical diversity of Clorg increased contaminated environments, it is now recognized that with soil development, with Clorg in younger soils more chlorine can cycle naturally between inorganic and closely resembling that of vegetation, and older soils organic forms in soils. -
Chlorine in the Stratosphere
Atmósfera 26(3), 415-458 (2013) Chlorine in the stratosphere T. VON CLARMANN Karlsruhe Institute of Technology, IMK, POB 3640, 76021 Karlsruhe, Germany E-mail: [email protected] Received May 22, 2013; accepted June 21, 2013 RESUMEN Este artículo reseña varios aspectos de los compuestos clorados presentes en la estratosfera, que incluyen tanto su papel como agentes químicos como su función de trazadores de los procesos dinámicos. En la estratosfera, el cloro reactivo se libera a partir de los clorofluorocarbonos y otros gases orgánicos que contienen cloro. La mayor parte del cloro reactivo se convierte en compuestos inertes que almacenan cloro, como ClONO2 y HCl. La reactivación del cloro estratosférico ocurre principalmente por reacciones heterogéneas en vórtices polares invernales, en combinación con la luz solar. Los ciclos catalíticos de Cl, ClO, BrO, Cl2 O2 , ClO2 y otros compuestos como NO, NO2, OH y HO2 destruyen el oxígeno impar (ozono y oxígeno atómico) de la atmósfera. El ciclo del dímero de ClO es particularmente importante en la formación del agujero de ozono, mientras que en latitudes medias el HOCl tiene alguna relevancia. También los eventos de protones solares pueden alterar la química del cloro estratosférico, aunque su efecto de activación o desactivación depende de las condiciones de iluminación. La vida media atmosférica de los clorofluorocarbonos determina la disponibilidad de las sustancias que destruyen el ozono en la estratosfera y depende de la circulación de Brewer-Dobson, que a su vez establece a qué altitudes y por cuánto tiempo está expuesta una porción de aire a la fotoquímica. Por su parte, los gases orgánicos clorados pueden usarse como trazadores para estimar la edad del aire estratosférico y así examinar la circulación de Brewer-Dobson. -
The Isotope Effect: Prediction, Discussion, and Discovery
1 The isotope effect: Prediction, discussion, and discovery Helge Kragh Centre for Science Studies, Department of Physics and Astronomy, Aarhus University, 8000 Aarhus, Denmark. ABSTRACT The precise position of a spectral line emitted by an atomic system depends on the mass of the atomic nucleus and is therefore different for isotopes belonging to the same element. The possible presence of an isotope effect followed from Bohr’s atomic theory of 1913, but it took several years before it was confirmed experimentally. Its early history involves the childhood not only of the quantum atom, but also of the concept of isotopy. Bohr’s prediction of the isotope effect was apparently at odds with early attempts to distinguish between isotopes by means of their optical spectra. However, in 1920 the effect was discovered in HCl molecules, which gave rise to a fruitful development in molecular spectroscopy. The first detection of an atomic isotope effect was no less important, as it was by this means that the heavy hydrogen isotope deuterium was discovered in 1932. The early development of isotope spectroscopy illustrates the complex relationship between theory and experiment, and is also instructive with regard to the concepts of prediction and discovery. Keywords: isotopes; spectroscopy; Bohr model; atomic theory; deuterium. 1. Introduction The wavelength of a spectral line arising from an excited atom or molecule depends slightly on the isotopic composition, hence on the mass, of the atomic system. The phenomenon is often called the “isotope effect,” although E-mail: [email protected]. 2 the name is also used in other meanings.