TMKARPIŃSKI
ISSN 2084-3577 JBESAC 4(S1 ) 201 4
PUBLISHER
Supplement 1
Journal of Biology and Earth Sciences 1 2th Geochronological Conference "Dating of Minerals and Rocks XII" 1 st International Conference on Biology and Earth Sciences "Bio-Geo" UMCS, Lublin, 1 6-1 7.1 0.201 4 MNiSW 3 Index Copernicus 6.21 UIF 0.9802 http://www.journals.tmkarpinski.com/index.php/jbes http://jbes.strefa.pl e-mails: jbes@tmkarpinski.lh.pl jbes@interia.eu
i Journal of Biology and Earth Sciences Editor-in-Chief
Tomasz M. Karpiński, Poznań, Poland
List of Peer-Reviewers
http://www.journals.tmkarpinski.com/index.php/jbes/ pages/view/reviewers
Co-Editors
Artur Adamczak, Poznań, Poland - biology Miłosz Huber, Lublin, Poland - earth sciences Anna K. Szkaradkiewicz, Poznań, Poland - medicine
Statistical Editor
Paweł Zaprawa, Lublin, Poland
Language Editor
Dominik Piechocki, London, UK
Scientific Editorial Board
Tamara Bayanova, Apatity, Russia Alexander Ereskovsky, Marseille, France Ahmed El-Mekabaty, Mansoura, Egypt Agnieszka Gałuszka, Kielce, Poland Vittorio Gentile, Naples, Italy Stanisław Hałas, Lublin, Poland Afaf M. Hamada, Stockholm, Sweden Sven Herzog, Tharandt, Germany Liviu Holonec, ClujNapoca, Romania Shri Mohan Jain, Helsinki, Finland Wouter Kalle, Wagga Wagga, Australia Tomasz Klepka, Lublin, Poland Nikolaos Labrou, Athens, Greece Igor Loskutov, Sankt Petersburg, Russia Ákos Máthé, Sopron, Hungary Artem V. Mokrushin, Apatity, Russia Shahid M. Mukhtar, Birmingham, USA Robert Pal, Pécs, Hungary Amal K. Paul, Kolkata, India Rajiv Ranjan, Narkatia Ganj, India Antonio Tiezzi, Viterbo, Italy Timotej Verbovšek, Ljubljana, Slovenia Vladimir K. Zhirov, Apatity, Russia
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The Publisher and Editors cannot be held responsible for errors and any consequences arising from the use of information contained in this journal; the views and opinions expressed do not necessarily reflect those of the Publisher and Editors, neither does the publication of advertisements constitute any endorsement by the Publisher and Editors of the products advertised.
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Publisher and Editor's office: Tomasz M. Karpiński, ul. Szkółkarska 88B, 62-002 Suchy Las, Poland, e-mail: jbes@interia.eu All articles are open-access articles distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Journal of Biology and Earth Sciences 201 4; 4 (Suppl. 1 )
ii Aims and Scope
The aim of the Journal of Biology and Earth Sciences (JBES) is to provide the platform for exchange of scientific progress in the field of Biology, Medicine and Earth Sciences, and to do so at the highest possible level. The JBES also aims to facilitate the application of new scientific knowledge to the daily practice of the concerned disciplines and addresses both researchers and academics. The JBES publishes original contributions, case reports and review articles in the fields of biology, medicine and earth sciences. Its scope encompasses: 1 . in field of biology: botany, ecology, zoology, microbiology, molecular biology, cellular biology, genetics, taxonomy and allied, 2. in field of medicine: all medical aspects of human biology, 3. in field of earth sciences: geology, mineralogy, petrography, paleontology, geography, geophysics, soil sciences and allied.
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Journal of Biology and Earth Sciences 201 4; 4 (Suppl. 1 )
ii Journal of Biology and Earth Sciences is abstracted and/or indexed by the following services: ▪ Academic Journals Database ▪ AGRO ▪ Arianta ▪ Bielefeld Academic Search Engine (BASE) ▪ CABI - Abstracts on Hygiene and Communicable Diseases ▪ CABI - Agroforestry Abstracts ▪ CABI - Animal Production Database ▪ CABI - Animal Breeding Abstracts ▪ CABI - Animal Science Database ▪ CABI - Botanical Pesticides ▪ CABI - CAB Abstracts ▪ CABI - Crop Physiology Abstracts ▪ CABI - Crop Science Database ▪ CABI - Environmental Impact ▪ CABI - Environmental Science Database ▪ CABI - Field Crop Abstracts ▪ CABI - Forest Products Abstracts ▪ CABI - Forest Science Database ▪ CABI - Forestry Abstracts ▪ CABI - Global Health ▪ CABI - Grasslands and Forage Abstracts ▪ CABI - Helmintological Abstracts ▪ CABI - Horticultural Science Abstracts ▪ CABI - Horticultural Science Database ▪ CABI - InfoTree ▪ CABI - Nutrition Abstracts and Reviews Series A: Human and Experimental ▪ CABI - Nutrition and Food Sciences Database ▪ CABI - Parasitology Database ▪ CABI - Plant Breeding Abstracts ▪ CABI - Plant Genetic Resources Abstracts ▪ CABI - Plant Genetics and Breeding Database ▪ CABI - Plant Growth Regulator Abstracts ▪ CABI - Plant Protection Database ▪ CABI - Postharvest News and Information ▪ CABI - Review of Agricultural Entomology ▪ CABI - Review of Aromatic and Medicinal Plants (RAMP) ▪ CABI - Review of Medical and Veterinary Entomology ▪ CABI - Review of Medical and Veterinary Mycology ▪ CABI - Review of Plant Pathology (RoPP) ▪ CABI - Soil Science Database ▪ CABI - Soils and Fertilizers Abstracts ▪ CABI - TROPAG and RURAL ▪ CABI - Veterinary Bulletin ▪ CABI - Tropical Diseases Bulletin ▪ CABI - Veterinary Science Database ▪ CABI - Weed Abstracts ▪ CABI - Wheat, Barley and Triticale Abstracts ▪ Cite Factor ▪ Chemical Abstracts Service (CAS) ▪ Comsat ▪ Directory of Research Journals Indexing (DRJI)
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Journal of Biology and Earth Sciences 201 4; 4 (Suppl. 1 )
iii
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Journal of Biology and Earth Sciences 201 4; 4 (Suppl. 1 )
iv Instructions for authors cont. the observations can be critically evaluated and, if necessary, repeated. Case Reports must describe an individual phenomenon, uncommon case or a new or improved method. Reviews are selected for their broad general interest; should take a broad view of the field. 5. MANUSCRIPT FORMAT AND STRUCTURE 5.1 . Language The language of publications is English (in some cases we can publish in Polish). Authors whose native language is not English are strongly advised to have their manuscripts checked by a professional translator or a native speaker prior to submission. 5.2. Structure All articles should include Title Page, Abstract, and References and in addition sections on Source of Funding and Conflict of Interests. Figures, Figure Legends and Tables should be included where appropriate. Title Page: The title must contain no more than 1 00 characters including spaces. The title page should include a running title of no more than 40 characters; 5-1 0 key words, complete names of institutions for each author, and the name, address, telephone number, fax number and e-mail address for the corresponding author. Conflict of Interest and Source of Funding: Authors are requested to provide a statement concerning any commercial associations or patent licenses that might result in a conflict of interest with the work presented in the submitted paper. Author's conflict of interest (or the absence of conflicts of interest) and the sources of funding for the research will be published under a heading "Conflict of Interest and Source of Funding Statement". Abstract: is limited to 250 words in length and should not contain abbreviations or references. Acknowledgements: Under acknowledgements please specify contributors to the article other than the authors accredited.
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Journal of Biology and Earth Sciences 201 4; 4 (Suppl. 1 )
12th Geochronological Conference "Dating of Minerals and Rocks XII" 1st International Conference on Biology and Earth Sciences "Bio-Geo"
UMCS, Lublin, 16-17.10.2014
PREFACE
This volume contains the conferences program and abstracts prepared by the authors. The authors and participants are most warmly welcome at Maria Curie-Skłodowska University (UMCS) in Lublin, Poland. Present conference on Dating of minerals and Rocks XII joined for the first time Bio-Geo conference, according to postulated in previous conferences on Dating to include the use of stable isotopes in biogeochemical studies. This joined conference is organized in the 70th anniversary of UMCS, Lublin. It is worth to remain that the first all-Polish dating conference was organized at UMCS in the frame-work of celebration of 50th anniversary of UMCS in October 1994. At that time the only invited speaker was professor Jan Burchart from the Institute of Geological Sciences PAN, Warsaw. He was talking on advantages and drawbacks of the K-Ar method. In this conference we have a great opportunity to listen 4 invited talks: The first – is prepared by Prof. Burchart, who wrote with Dr. Jan Kráĺ from Slovakia excellent monograph entitled Isotopic Record of the Earth Past (in Polish an Slovakian). The second - by Dr. Ana Voica-Bojar from Austria, who coauthored the monograph on Isotopic Studies in Cretaceous Research, Geol. Soc. London 2013. The third – by Dr. Hans Eggenkamp from Holland, who wrote the monograph on Halogene Isotopes, Springer 2014, and the 4th – by Dr. Alexander Rocholl from German Centre in Potsdam, who works in a new SIMS facility applied for isotope geochronology and stable isotope research. The Organizing Committee wish to express sincere thanks for help in organization and financial support of this conference to the Lublin Division of the Polish Physical Society.
Yours sincerely,
Prof. dr hab. Stanisław Hałas
Dr hab. Tomasz Pieńkos
Dr eng. Miłosz A. Huber
Journal of Biology and Earth Sciences 2014; 4 (Suppl. 1): 1-51
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12th Geochronological Conference "Dating of Minerals and Rocks XII" 1st International Conference on Biology and Earth Sciences "Bio-Geo"
UMCS, Lublin, 16-17.10.2014
12th Geochronological Conference "Dating of Minerals and Rocks XII" 1st International Conference on Biology and Earth Sciences "Bio-Geo" UMCS, Lublin, 16-17.10.2014
Organizers: Mass Spectrometry Laboratory, Maria Curie-Skłodowska University in Lublin Earth Science and Spatial Management Faculty, Maria Curie-Skłodowska University in Lublin TMKarpiński Publisher Annales Universitatis Mariae Curie-Skłodowska, sectio “Physica”
Scientific Organizing Committee: Prof. dr hab. Stanisław Hałas, Chairman Dr eng. Miłosz A. Huber Dr hab. Tomasz M. Karpiński Dr Józef Adam Dąbek Dr Artur Wójtowicz
Patrons: Prof. dr hab. Jerzy Żuk, head of Polish Society of Physics in Lublin Prof. dr hab. Mieczysław Budzyński, director of Physics Institute in Lublin, UMCS Prof. dr hab. Radosław Dobrowolski, dean of Earth Science and Spatial Managment Faculty, UMSC Dr Przemysław Mroczek, head of Polish Society of Geology in Lublin
Journal of Biology and Earth Sciences 2014; 4 (Suppl. 1): 1-51
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12th Geochronological Conference "Dating of Minerals and Rocks XII" 1st International Conference on Biology and Earth Sciences "Bio-Geo"
UMCS, Lublin, 16-17.10.2014
PROGRAM OF CONFERENCES Time
Speaker
Title of presentation
16.10.2014. Physics Institute UMCS, Prof. Ziemecki hall, the 1st floor, 10 Radziszewskiego st. 15:30
Registration
16:00
Opening Ceremony
16:10
Ewa Krzeminska
16:50
Coffe break
17:15
Jan Burchart
18:00
Alexander Rocholl
18:50
Zbigniew Czupyt
20:00
Conferences dinner
The northwestern margin of the Sarmatia in the Lublin area (Poland) documented by SHRIMP U-Pb zircon micro-geochronological study Prof. Środoń (ING PAN Kraków) movie about origin of High Tatra Mts., entitled: “Jak Powstały Tatry i Podhale?” Isotope geochronology models vs. reality Capabilities of SIMS in geochronology and isotope geochemistry Solid state U-Pb isotope measurements on SHRIMP IIe ion microprobe - a window to the Early Earth Restaurant in Hotel Huzar, 9 Spadochroniarzy st.
17.10.2014. Earth Science and Spatial Protection Faculty, UMCS, 301 room, 2d Kraśnicka Rd 9:00
Ana-Voica Bojar
9:40
Hans Eggenkamp
10:20
Adrian Pacek
11:35
Miłosz A. Huber
11:50
Tomasz Pieńkos
Isotopic composition of Permian sulfate accumulations: examples from the North Calcareous Alps, Austria A closer look at chlorine and bromine isotopes: an approach to understand the similarities and differences Precise determination of isotopic composition of lithium in some Polish mineral waters by TIMS Stable isotope geochemistry of sulfides from old mafic intrusions in the Kola Peninsula (N Russia) A novel approach in the study of isotope anomalies (17O and Δ33S)
12:05 Coffee break and poster session Presenter
Poster title
Artur Michalik, Sabina Dołęgowska Sabina Dołęgowska, Artur Michalik
Local differentiation of groundwater chemistry using GIS and multivariate statistics Problems in assessment of uncertainty arising from environmental sampling
Journal of Biology and Earth Sciences 2014; 4 (Suppl. 1): 1-51
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12th Geochronological Conference "Dating of Minerals and Rocks XII" 1st International Conference on Biology and Earth Sciences "Bio-Geo"
UMCS, Lublin, 16-17.10.2014
Beata Gebus, Zbigniew Czupyt, Stanisław Hałas Beata Gebus, Andrzej Trembaczowski, Stanisław Chmiel, Stanisław Hałas Miłosz A. Huber, Lesia Lata, Stanisław Chmiel, Karolina Oszust, Karolina Oszust, Lesia Lata, Olga Jakowlewa Miłosz A. Huber, Stanisław Hałas, Lesia Lata, Yuri Neryadovskiy
A new preparation method of nitrates for simultaneous extraction of CO2 and N2 for δ18O and δ15N analysis The measurements of nitrates (δ15N, δ18O) and phosphates (δ18O) isotopic composition: a tool to identify the main pollution source of Zemborzycki Lake Geochemical–isotope characteristic of the waste metallurgical Zn-Pb ore from Ruda Śląska -Wirek heaps Stable isotopic and geochemical characteristics of surface water and soil from selected regions of the Kola Peninsula Study of δ13C and chemical composition of carbonates from the crystalline rocks from the Kola Peninsula (N Russia) Study of precipitates in the petroarchitecture detail samples from Bern, Switzerland
Miłosz A. Huber 12:50 Closing of Conference
Copyright: © The Author(s) 2014. Journal of Biology and Earth Sciences © 2014 Tomasz M. Karpiński. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. www.journals.tmkarpinski.com/index.php/jbes
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12th Geochronological Conference "Dating of Minerals and Rocks XII" 1st International Conference on Biology and Earth Sciences "Bio-Geo"
UMCS, Lublin, 16-17.10.2014
THE NORTHWESTERN MARGIN OF THE SARMATIA IN THE LUBLIN AREA (POLAND) DOCUMENTED BY SHRIMP U-Pb ZIRCON MICRO-GEOCHRONOLOGICAL STUDY Ewa Krzemińska 1, Leszek Krzemiński 1, Janina Wiszniewska 1, Ian S. Williams 2 1
Polish Geological Institute, National Research Institute, ul. Rakowiecka 4, 00-975 Warszawa, Poland; e-mails: ewa.krzeminska@pgi.gov.pl, leszek.krzeminski@pgi.gov.pl, janina.wiszniewska@pgi.gov.pl 2 Research School of Earth Sciences, The Australian National University, Canberra ACT 0200, Australia; e-mail: ian.williams@anu.edu.au
East European Craton (EEC) was formed by successive collision of the three large crustal blocks: Volgo-Uralia with Sarmatia and then with Fennoscandia. These blocks had their own independent prehistories of development and belonged to different lithospheric plates before final amalgamation at about 1.8 Ga (Bogdanova et al. 2006). Somewhere in the Lublin area in eastern part of Poland within a covered crystalline basement, the zone of the junction between Fennoscandia and Sarmatia (F-S) has been predicted. Supposed F-S suture (FSS) was inferred mainly from geophysical imaging, including regional magnetic and gravity maps and deep seismic profiles. The aim of this contribution is to report a first direct evidence of the Sarmatian crust recovered by deep drill holes and documented by U-Pb zircon age studies on the ion microprobe. The subject of micro-geochronological investigation were pink migmatitic rocks from Kaplonosy IG1 drill section (51°37'26"N, 23°21'21"E), that reached a basement on depth of 1877 m. Zircon from two part of drill section (samples from depth 1889 and 1896 m) was separated using the conventional heavy liquid and isodynamic techniques. Selected zircon grains were mounted in Struers epoxy resin together with the Temora 1 (206Pb/238U age = 416.8 Ma), OG1 (206Pb/207Pb age = 3465 Ma) and R33 (206Pb/238U age = 419.3 Ma) reference zircons and then polished to expose the internal crystal structure. Cathodoluminescence (CL), transmitted and reflected light images were obtained in order that analysis sites (core vs rim discrimination) could be precisely appointed. Zircon concentrates from two different depths and lithology provide a similar sets of relatively small particles <100 μm, with diverse forms. These are clearly a populations of detrital grains with a few types of measured grains. Metamorphic rims are always present, composing an uniform set of overgrowths, thus confirming the diagnosis that the so-called granitoid from Kaplonosy as well as banded garnet gneiss are the product of the migmatitisation of an older metaclastic rocks. U-Pb zircon dating was carried out at the Research School of Earth Sciences of Australian National University, in Canberra. Two spot sizes were applied according to the size of the target: 25 μm for the core of zircon grain and <20 μm for the metamorphic overgrowth. Over one hundred zircon grains were analyzed in the two samples selected. The international reference material of zircon Temora 1, used as isotope ratios standard was measured every 4 unknowns. Data reduction followed using Squid-2 and Isoplot 3.0 software. The 108 cores analyzed have low to moderate U and Th contents (120–706 and 102–800 ppm, respectively). Th/U ranges also from low to moderate (0.40–1.3). The clusters of zircon core analyses with concordant and close to concordant U-Pb ages can provide estimates of ages of zircon growth or/and recrystallization. The 207Pb/206Pb apparent ages range from ca. 2.99 to 1.85 Ga, but most of the cores (ca. 90%) have 207 206 Pb/ Pb ages in the narrow range 2.05–1.9 Ga. Moreover, there are a much smaller cluster of ages (ca.
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12th Geochronological Conference "Dating of Minerals and Rocks XII" 1st International Conference on Biology and Earth Sciences "Bio-Geo"
UMCS, Lublin, 16-17.10.2014
3%) in the range of 2.7–2.9 Ga and very limited number of cores (ca. 6%) in the range 1.87–1.89 Ga. Both samples have been metamorphically reworked at 1.79 Ga (n=16 zircon overgrowths and n=15 monazite U-Pb results). The prevailing cluster of zircon cores (n=104) demonstrates (Fig. 1) that the detritus was derived from Paleoproterozoic source mainly with age between 2.1 and 1.9 Ga (90% of data). Combining n=104 analyses of predominant group from the two samples yields a rough weighted mean 207Pb/206Pb age of 1965±33 Ma (MSWD=0.18, probability=1.000, 95% confidence). Moreover, the most coherent group of selected magmatic oscillatory zoned cores (n=40) defines most frequent age of source rock at 1927.25±6.5 Ma. data-point error symbols are 2σ
3600 Kaplonosy core ages merged samples 1889 1896 m 3200
AGE Pb 207/Pb 206
2800 2400 2000 1600 1200 800
Mean = 1965±33 [1.7%] 95% conf. Wtd by data-pt errs only, 0 of 104 rej.
400
MSWD = 0,18, probability = 1,000 (error bars are 2σ)
0
Fig. 1. The 207Pb/206Pb results of the predominant Paleoproterozoic population of detrital zircon cores showing a relatively uniform data set and defining a mean age of 1965±33 Ma.
No source rocks of this age (or older than 1.9 Ga) are known from south-easternmost part of the Fennoscandia, but comparable ages of a prominent magmatic events were primarily referred to youngest, westernmost part of the Sarmatia block, where main igneous activity was concentrated within NW-SE continental magmatic belt at 2.0–1.95 Ga and along more distant orogenic belt at 2.2–2.1 Ga (Bogdanova et al. 2006). The obtained ages (ca. 90% of data in range of 2.1–1.9 Ga) simply match the detrital zircon referenced for the extreme northwestern corner of the Sarmatia, where the similar crystallization ages of potential source rocks are known from two domains: Borisov–Ivanovo Zone (2.0–1.90 Ga) and Osnitsk– Mikashevichi Igneous Belt (2.02–1.96 Ga), which outlines an active continental margin of NW Sarmatia (Bogdanova et al., 2006). Zircon grains from the strongly metamorphosed at 1.79 Ga clastic rocks in the Lublin area (Kaplonosy) have a largely unimodal age distributions and are interpreted as being proximal clastic arc succession, attributed to be derived from the Sarmatian crust. High-grade metamorphism at 1.80–1.79 Ga was connected to the major Sarmatia–Fennoscandia collision and the eastward accretion, which led to the formation of the East European Craton (Skridlaite et al. 2014).
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UMCS, Lublin, 16-17.10.2014
These precise micro-geochronological data set on zircon grains selected from limited core material from the Kaplonosy IG1 deep drilling provide important constraints on deciphering the last stage of the gradual docking of both major crustal blocks within EEC: Fennoscandia and Sarmatia (Volgo-Sarmatia) as well as the potential site of the Fennoscandia-Sarmatia suture. This study was undertaken at the request of the Minister of the Environment, funded by the National Fund for Environmental Protection and Water Management, project no. 21.2101.0010, and under the auspices of a collaborative research agreement between the ANU and PGI-NRI. References: 1. Bogdanova S., Gorbatchev R., Grad M., Janik T., Guterch A., Kozlovskaya E., Motuza G., Skridlaite G., Starostenko I., Taran L., and Eurobridge and Polonaise working Group. 2006. EUROBRIDGE: new insight into the geodynamic evolution of East European Craton. In: Gee D.G., Stephenson R.A (eds) European Lithosphere Dynamics. Geol. Soc., London, Memoirs 32: 599-625. 2. Skridlaite G., Bogdanova S., Taran L. BagiĹ&#x201E;ski B. Recurrent high grade metamorphism recording a 300 Ma long Proterozoic crustal evolution in the western part of the East European Craton. Gondwana Research 2014; 25(2): 649-667.
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UMCS, Lublin, 16-17.10.2014
ISOTOPE GEOCHRONOLOGY: MODELS VERSUS REALITY Jan Burchart Institute of Geological Sciences Polish Academy of Sciences, Twarda 51/55, 00-818 Warszawa, e-mail:j.burchart1@upcpoczta.pl
Since its early days the principal aim of geochronology has been to date minerals and rocks. Numerous „radiometric clocks” have been introduced and tested in practice, analytical apparatus and techniques have been invented. We are able to examine our samples much more precisely. Nevertheless, more and more often we do not feel certain about what really we date. Laboratory determinations result in isotopic ratios – not „ages” – and they are converted to values expressed in years by means of some models. A calculated value represents an „age” provided that the model applied describes what really had happened in nature. Unfortunately the actual history of a rock is often much more complex than a simplistic model. The so called “uplift ages” and the rates of vertical movements in tectonic analyses of fission track data may serve as an example. The problem becomes serious when a model describes poorly understood processes, e.g. interactions between the mantle and the crust, origin of anorthosites, condensation of matter of the early solar system. Consequently, the term “the age of a rock” loses its straightforward meaning as understood by some geologists. Moreover, an agreement between the laboratory data and a model prediction does not constitute a definite proof (if the same set of data can be explained by some other model). Besides, often reported values of tCHUR or tDM should not be understood as the ages of rocks. Another problem of proper usage of isotopic data in geology is the magnitude of “errors”. The “±” values represent a confidence interval of uncertainty of laboratory determinations, the values based on many times repeated measurements. However, such a source of the real uncertainty represents only one of many sources. Among the other ones are: sampling pattern, contamination during crushing and grinding, homogeneity of the matter to be examined, contamination during chemical procedures, improper model used. Some of these sources of error, though difficult to be quantitatively evaluated, are often neglected and their importance grossly underestimated. The above problems and many others are discussed in the recently edited monograph “Izotopowy zapis przeszłości Ziemi”: Jan Burchart and Jan Kráĺ, Isotopic record of the Earth Past (in Polish an Slovakian), Mineralogical Society of Poland, Kraków (in press).
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12th Geochronological Conference "Dating of Minerals and Rocks XII" 1st International Conference on Biology and Earth Sciences "Bio-Geo"
UMCS, Lublin, 16-17.10.2014
A CLOSER LOOK AT CHLORINE AND BROMINE ISOTOPES; AN APPROACH TO UNDERSTAND THE SIMILARITIES AND DIFFERENCES Hans G.M. Eggenkamp Onderzoek & Beleving, Bussum, the Netherlands, e-mail: hans@eggenkamp.info
Chlorine and bromine are two, chemically relatively similar, elements that are found in group 17 (the halogens) of the periodic table. As both elements have two stable isotopes, 35Cl and 37Cl in the case of chlorine and 79Br and 81Br in the case of bromine it is possible for both elements to study their isotope chemistry. Being halogen elements both elements are present in natural environments preferably in the -I oxidation state as the chloride chloride or bromide ion. Due to the chemical similarity of both elements bromide minerals are hardly encountered, bromide is either incorporated in chloride minerals or it stays in the fluid from which these minerals are formed. Isotope fractionation has, for the first time, be studied theoretically by Harold Urey [1,2], in what perhaps still are the most important isotope papers that have ever been written. In these studies the theory of isotope fractionation was described and calculated for most light elements, including the halogens chlorine, bromine and iodine. The results of these calculations showed that large isotope fractionation is to be expected when there is exchange of isotopes between different oxidation states, and also that the fractionation between chlorine species is considerably larger than for bromine and iodine species (see Figure 1).
Fig. 1. Reduced partition coefficient ratios for the different oxidation states for chlorine, bromine and iodine (Urey, 1947).
Based on these data the expected natural variations for chlorine isotopes (expressed in per mil) should be approximately 5 to 6 times as large as for bromine isotopes if oxidation state transitions are studied. However, as the halogens on earth prefer to be present as as the halogenide (-I) ion it is also necessary to understand fractionation between different phases in which these ions are present.
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12th Geochronological Conference "Dating of Minerals and Rocks XII" 1st International Conference on Biology and Earth Sciences "Bio-Geo"
UMCS, Lublin, 16-17.10.2014
Equilibrium fractionation has for example been determined between salt minerals in solution and precipitation. The results of these experiments [3, 4] indicated that the equilibrium fractionation varied widely for each of the 17 salt minerals that were studied. Although these fractionation factors (defined as 103lnÎą) were on average smaller for the bromide minerals than for the chloride minerals the differences are not as large as perhaps expected and both positive and negative 103lnÎą values are encountered, indicating that the process of precipitation of salt from a brine is a complex process.
Fig. 2. Equilibrium fractionation between chloride and bromide salts and their saturated solutions.
On the other hand, kinetic fractionation, for example studied in the process of diffusion of chloride and bromide ions in solution [5] showed that chloride and bromide behave as expected and it was observed that the fractionation due to diffusion of the bromide ion was about half that of the chloride ion, which is in line with the ratio of the masses of the isotopes from these two elements. For that reason it came as a surprise that when the first stable bromine isotopes were analysed [6] that these effects were not seen. At that moment it was expected that the bromine isotope composition of a sample, compared to its chlorine isotope composition, would be more or less comparable but with a smaller numerical value. The first results however showed a completely different behaviour, with a negative, not very good correlation between the two isotope systems (Figure 3 [7])
Fig. 3. Relationship between Cl and Br isotopes in formation waters from the Oseberg Field (Norway) [7].
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12th Geochronological Conference "Dating of Minerals and Rocks XII" 1st International Conference on Biology and Earth Sciences "Bio-Geo"
UMCS, Lublin, 16-17.10.2014
Later, when more bromine isotope measurements were done, it became obvious that there was no very clear relationship between chlorine and bromine isotope data in natural samples which are until now mostly very saline formation water samples [8,9,10]. One of the most interesting observations probably is the suggestion that the bromine isotope composition of evaporites is on average +0.60‰ [8,10,11], while based on experimental fractionation data the value should be very close to 0‰. Another very interesting observation was done by Shouakar-Stash [12] who observed that in formation waters from the Williston Basin (USA) the bromine isotopes of the samples showed larger variations than the chlorine isotopes. While average chlorine isotope data (per stratigraphic unit) range from -0.5 to +0.5‰ bromine isotope variations range from -1.0 to +2.5‰. To understand these differences there is need to take a closer look at the difference in chemical behaviour of chlorine and bromine. In inorganic chemistry the most striking difference is the difference in oxidation behaviour between chlorine and bromine, in the sense that it is just easier to oxidise bromine than it is chlorine. An effect that is actually used to separate bromine from chlorine if they need to be separated for isotope analysis. However, it is interesting if we look at natural biochemical reactions that involve chlorine or bromine. By now, it is well known that there are many processes in organisms that produce organohalogen compounds [13] and of the almost 3200 known that are naturally occurring more than 1600 these compounds, which thus is more than 50%, contain bromine [14]. Although the Br concentration in the oceans is about 650 times (mole/mole) lower than the Cl concentration the fact that it apparently is so much more easy to oxidise is the reason that an astounding array of organobromine metabolites is found in marine organisms. This effect is also known for inorganic halogens for example in the blood of higher animals where certain white blood cells prefer to oxidise bromide dissolved in the blood to hypobromite above the oxidation of chloride to attack certain parasites [15]. These biochemical reactions, both for chlorine and bromine, have effects on the isotope compositions of the reaction products. Although it may be expected that the isotope (equilibrium) fractionation for bromine is smaller than for chlorine the observed fractionation may be very much dependent on the reaction path, and there is not yet a clear overview of the effects on the isotope composition of organohalogen compounds [16]. Considering the fact that, in spite of the small concentrations of bromine compared to chlorine, bromine is so much present in natural organic compounds it may be suggested however that the isotope variation of natural bromine is for a larger amount than chlorine isotope variation dependent on isotope fractionation due to biochemical reactions. Although it is to be realised that all the mass balance calculations still have to be made, and isotope fractionation during formation of the most common organohalogen compounds, both equilibrium and kinetic, still has to be established in most environments these effects may for a large part be the reason that bromine isotope variations on earth are anomalously large when compared to chlorine isotope variations. References: 1. Urey H.C., Greiff L.J. 1935. Isotope exchange equilibria. J. Chem. Soc. Amer. 57:321-327. 2. Urey H.C. 1947. The thermodynamic properties of isotopic substances. J. Chem. Soc. 1947:562-581. 3. Eggenkamp H.G.M., Kreulen R., Koster van Groos A.F. 1995. Chlorine stable isotope fractionation in evaporites. Geochim. Cosmochim. Acta. 59:5169-5175. 4. Eggenkamp H.G.M., Bonifacie M., Ader M., Agrinier P. 2011. Fractionation of Cl and Br isotopes during precipitation of salts from their saturated solutions. 21th Annual V.M. Goldschmidt Conference. Prague, Czech Republic. Mineral. Mag. 75:798. 5. Eggenkamp H.G.M., Coleman M.L. 2009. The effect of aqueous diffusion on the fractionation of chlorine and bromine stable isotopes. Geochim. Cosmochim. Acta 73:3539-3548.
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6. 7. 8.
9. 10. 11.
12. 13. 14. 15. 16.
Eggenkamp H.G.M., Coleman M.L. 2000. Rediscovery of classical methods and their application to the measurement of stable bromine isotopes in natural samples. Chem. Geol. 167:393-402. Eggenkamp H.G.M., Coleman M.L. 1998. Heterogeneity of formation waters within and between oil fields by halogen isotopes. Proc. 9th Int. Symp. on Water-Rock Interaction Edt.: G.B. Arehart & J.R. Hulston 9;309-312. Shouakar-Stash O., Alexeev S.V., Frape S.K., Alexeeva L.P., Drimmie R.J. 2007. Geochemistry and stable isotope signatures, including chlorine and bromine isotopes, of the deep groundwaters of the Siberian Platform, Russia. Appl. Geochem. 22:589-605. Stotler R.L., Frape S.K., Shouakar-Stash O. 2010. An isotopic survey of δ81Br and δ37Cl of dissolved halides in the Canadian and Fennoscandian shields. Chem. Geol. 274:38-55. Boschetti T., Toscani L., Shouakar-Stash O., Iacumin P., Venturelli G., Mucchino C., Frape S.K. 2011. Salt Waters of the Northern Apennine Foredeep Basin (Italy): Origin and Evolution Aquat. Geochem. 17:71-108. Bagheri R., Nadri A., Raeisi E., Eggenkamp H.G.M., Kazemi G.A., Montaseri A. 2014. Hydrochemistry and isotope (δ18O, δ2H, 87Sr/86Sr, δ37Cl and δ81Br) applications: Clues to the origin of saline produced water in a gas reservoir. Chem. Geol. 384:62-75. Shouakar-Stash O. 2008. Evaluation of stable chlorine and bromine isotopes in sedimentary formation fluids. PhD Thesis University of Waterloo. Gribble G.W. 1998. Naturally occurring organohalogen compounds. Acc. Chem. Res. 31:141-152. Gribble G.W. 1999. The diversity of naturally occurring organobromine compounds. Chem. Soc. Rev. 28:335346. Mayeno A.N., Curran A.J., Roberts R.L., Foote C.S. 1989. Eosinophils preferentially use bromide to generate halogenating agents. J. Biol. Chem. 264:5660-5668. Eggenkamp H. 2014. The geochemistry of stable chlorine and bromine isotopes. Springer, Heidelberg. 172 pp.
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UMCS, Lublin, 16-17.10.2014
PRECISE DETERMINATION OF ISOTOPIC COMPOSITION OF LITHIUM IN SOME POLISH MINERAL WATERS BY THERMAL IONISATION MASS SPECTROMETRY (TIMS) Adrian Pacek, Stanisław Hałas Mass Spectrometry Laboratory, Institute of Physics, Maria Curie-Skłodowska University (UMCS), Lublin, Poland, e-mail: adrian.pacek@poczta.umcs.lublin.pl
The isotope ratio (7Li/6Li) of Lithium dissolved in groundwaters and surface waters has become nowadays important geochemical indicator of the origin of their mineralization (Tomascak 2004). In some mineral waters in Poland, Li concentration exceeds significantly that of seawater i.e. 0.1 mg/L, what makes the isotopic research easier. The development of a reproducible and inexpensive method of determining the isotopic ratio of lithium in natural waters is a problem, whose solution may have not only scientific, but also practical significance. The isotopic composition of Li in a sample is expressed as δ7Li (Chan 2004). By definition δ7Li is a relative difference between the ratio of sample and the ratio of the L-SVEC lithium carbonate standard with known 7Li/6Li = 12.173. So a higher δ7Li value indicates a higher concentration of heavy isotope. The isotope ratio strongly depends on the source of lithium (Rudnick & Nakamura 2004). We did lithium isotope analysis using Thermal Ionization Mass Spectrometry (TIMS). This method is convenient especially for elements of the first group of the Periodic Table, due to their relatively low ionization energy. To minimize the impact of the isotopic fractionation occurring during measurements on the results of measurements (Moriguti & Nakamura 1993, You & Chan 1996), we used a triple filament ion source. Our ion source comprises a central ionization Pt-Ir filament and two side evaporation Re filaments, which are parallel to the wider central one, oriented perpendicularly to the plane of the extraction slit. Due to the spatial separation of the vaporization and ionization processes and the use of relatively heavy molecules (Li3PO4) as the sample material loaded into evaporators, the mass discrimination effect (gradual increase of measured 7Li/6Li) is highly reduced (Xiao & Beary 1989). By far we analyzed lithium isotope ratios in lithium-abundant mineral waters from three geological regions of Poland: Carpathians Mts., Carpathian Foredeep and Holy Cross Mts. The results obtained for Carpathian Mts. waters (Paleogene-Neogene in age) fall into a low range of marine pore waters, e.g. Zuber is lower in δ7Li by 20‰ than modern seawater. Two other Carpathian waters from Wysowa Spa contain Li with much lower delta values. Extremely positive δ7Li shows Jurassic brine from the Holy-Cross region (Busko Spa). The values of δ7Li for the samples of natural waters by TIMS method is achieved with reproducibility of about a few permil or better. This method of lithium isotope determination requires neither complicated chemical preparation of the investigated samples, nor large quantities of material, thus being one of the simplest methods. The method of sample preparation and the obtained results will be presented in details during the conference. Keywords: lithium isotopes, thermal ionization mass spectrometry (TIMS), mineral waters.
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References: 1. Chan L.-H. (2004), Chapter 6 in: de Groot P. A. (editor). Handbook of Stable Isotope Analytical Techniques. vol. 1, Elsevier, Amsterdam. 2. Moriguti T., Nakamura E. (1993) Precise Lithium Isotopic Analysis by Thermal Ionization Mass Spectrometry Using Lithium Phosphate as an Ion Source Material, Proc. Japan Acad., vol.69 Ser. B, pp. 123-128. 3. Rudnick R.L., Nakamura E. (2004) Preface to „Lithium isotope geochemistry”, Chem. Geol. Vol. 212, pp. 1-4. 4. Tomascak P. B. (2004) Developments in the Understanding and Application of Lithium Isotopes in the Earth and Planetary Sciences, Reviews in Mineralogy & Geochemistry Vol. 55, pp. 153-195. 5. Xiao, Y. K., Beary, E. S. (1989) High-precision isotopic measurement of lithium by thermal ionization mass spectrometry Int. J. Mass Spectrom. Ion Processes, vol. 94, pp. 101-114. 6. You C.F., Chan L.H. (1996) Precise determination of lithium isotopic composition in low concentration natural samples. Geochim. Cosmochim. Acta, 60: 909–915.
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UMCS, Lublin, 16-17.10.2014
CAPABILITIES OF SECONDARY ION MASS SPECTROMETRY IN GEOCHRONOLOGY AND ISOTOPE GEOCHEMISTRY – FIRST EXPERIENCES FROM THE POTSDAM SIMS FACILITY Alexander Rocholl, Michael Wiedenbeck, Frédéric Couffignal Helmholtz Zentrum Potsdam, GFZ German Research Centre for Geosciences, 14473 – Potsdam, Germany; e-mails: rocholl@gfz-potsdam.de, wiedenbeck@gfz-potsdam.de, couffig@gfz-potsdam.de
Thanks to its extremely fine sampling size, Secondary Ion Mass Spectrometry (SIMS) is one of the most powerful methods available to the analytical geochemist. State-of-the-art SIMS instrumentation can determine precise isotope ratios at the < 200 pg scale and can provide high quality U-Pb data from e.g., zircons at total sampling masses under 5 ng. In late 2013 the Helmholtz Zentrum Potsdam completed installation of a Cameca 1280-HR instrument, which is to operate as an open user facility. This instrument is to server the global user community by providing access to top-quality SIMS infrastructure in as simple and uncomplicated means as possible. The Potsdam 1280-HR instrument is equipped with a five trolley multi-collection ion detection system that enables isotope ratio determinations (e.g., δ11B, δ18O, δ34S) with repeatabilities at or below ± 0.2 ‰ (1sd) on major elements. We can equip the multi-collector with both electron multipliers or Faraday cups, and the system is flexible permitting both types of two ion detection methods to be combined, as is best optimize for a given application. During a typical 24 hour operating cycles between 250 and 35 analyses can be produced. Other applications such as U-Pb geochronology, depth profiling and the quantification of volatile element cycles will also be major research themes in the Potsdam facility. We also have a major focus on the precaution of a new suite of reference materials for calibrating both SIMS and other microanalytical methods, and here we benefit from a large consortium of interested universities and research facilities within the Berlin/Potsdam region. Along side our SIMS tool we are also supported by an extensive range of peripheral instrumentation. This includes a fully motorized optical microscope for sample documentation, a white light optical profilometer for determining crater dimensions at the sub-micron scale and a polychromatic cathode luminescence chamber. Additionally, the GFZ can provide access to a complete sample preparation facility along with other large instruments such as a field emission (FE) scanning electron microscope for backscattered electron and monochromatic CL imaging, a FE electron microprobe for major element determinations, a dual-beam FIB instrument and a Raman spectrometer. During the planning of the Potsdam SIMS facility detailed consideration was given to the design of our laboratory space. Our 1280-HR is housed in a room which has 2 autonomous air handling systems. Temperature within the majority of the room is dynamically controlled to maintain an air temperature stability within a 0.5 C° range, regardless of variations in heat load into the laboratory. Air supply is provided from below floor level and the heat is extracted at ceiling level. The air in the room is completely exchanged every 2 minutes with relative humidity maintained at below 72 % relative. In order to further assure the maximum stability of the instrument there is a second, independent air supply operating at a constant temperature and flow rate which delivers air to the main electronics rack from beneath floor level. The electronics rack has its own heat extraction hood to extract the thermal output immediately from the laboratory. The Cameca 1280-HR can operate autonomously for up to 45 minutes using an uninterruptable power supply, which also acts as a line conditioner. In order to fully minimize disturbances to laboratory
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12th Geochronological Conference "Dating of Minerals and Rocks XII" 1st International Conference on Biology and Earth Sciences "Bio-Geo"
UMCS, Lublin, 16-17.10.2014
environment the actual machine operation is conducted from an adjoining office. All superfluous heat sources, such as a vacuum-capable drying oven and sample coater, have been removed to a dedicated sample preparation room, which also adjoins the SIMS laboratory. We have already completed a number of projects, and here we will show some of the performance capabilities of our instrument. Further information about our facility and its activities can be found at our facilityâ&#x20AC;&#x2122;s web site: www.gfzpotsdam.de/SIMS/.
Fig. 1. The frequency histograms show B-isotope composition of tourmaline in different samples from the Barberton Greenstone Belt, South Africa as analysed by SIMS. δ11B values in permil. Images on the right-hand side are microprobe element maps of Cr for two tourmaline grains with extreme internal variations (SIMS spots and values shown). Project Farber, Dziggel, Meyer (RWTH Aavchen) and Trumbull (GFZ Potsdam).
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UMCS, Lublin, 16-17.10.2014
Zircon RM 91500 δ18O = 9.86 ± 0.11‰ (1 sd) VSMOW (Wiedenbeck et al., 2004) Fig. 2. U-Pb ages of quality-control materials zircons Plesovice, Temora-2 and FC-1. Indicated is also the relative difference between SIMS and TIMS ages. RSD: relative standard deviation [%].
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12th Geochronological Conference "Dating of Minerals and Rocks XII" 1st International Conference on Biology and Earth Sciences "Bio-Geo"
UMCS, Lublin, 16-17.10.2014
Fig. 3. Drift corrected δ 18O variation in zircon RM 91500, obtained by 230 analyses of seven zircon fragments. Repeatibility: 0.20 ‰. Mean in-run precision: 0.12 ‰ (1 sdm, N=20).
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12th Geochronological Conference "Dating of Minerals and Rocks XII" 1st International Conference on Biology and Earth Sciences "Bio-Geo"
UMCS, Lublin, 16-17.10.2014
THE MEASUREMENTS OF NITRATES (Δ15N, Δ18O) AND PHOSPHATES (Δ18O) ISOTOPIC COMPOSITION: A TOOL TO IDENTIFY THE MAIN POLLUTION SOURCE OF ZEMBORZYCKI LAKE Beata Gebus 1, Andrzej Trembaczowski 1, Stanisław Chmiel 2, Stanisław Hałas 1 1
Maria Curie-Sklodowska University,Mass Spectrometry Laboratory, pl. M. Curie-Skłodowskiej 1, 20-31Lublin, Poland, e-mail: beata.gebus@poczta.umcs.lublin.pl 2 Maria Curie-Sklodowska University, Department of Hydrology, Al. Kraśnicka 2, 20-718 Lublin, Poland
Zemborzycki Lake is a relatively small (area: 280 ha) retention reservoir on Bystrzyca river, located in southern part of Lublin city. This reservoir since the late 90’s has a problem with quickly progressive eutrophication, resulting in life-threatening water degradation quality of some living species. The reason for this phenomenon is the increase of nutrients content in surface waters, mainly the compounds of nitrogen and phosphorus (Vollenweider, 1968; O'Neill, 1997). To determine the origin of nitrates, one of nutrients components, in Zemborzycki Lake waters, we use the isotopic methods. The measurements of NO3concentration and isotopic compositions analysis of nitrate (δ15N, δ18O) allow to specify whether the main source of their impact to reservoir are atmospheric nitrate deposition, fertilizers, sewage and manure or nitrate derived from nitrification in soils (Mayer et al., 2002). For determination of nitrate concentration in Zemborzycki Lake we use micro ion selective electrode (Model ISM-146NOXM, Lazar Research Laboratories, Inc., USA), whilst for extraction of NO3- ions from water samples we use procedure described by Silva et al. (2000). The water sample is introduced into a column containing an anion exchange resin AG1-X8, NO3- ions are eluted with 15 ml of 3M HCl. Subsequently the obtained HNO3 is neutralized by adding about 8 g Ag2O, whereas the precipitated AgCl is removed on 0.2 µm policarbonate membrane filters. Clean, freeze-dried AgNO3 is used in the next preparation step, developed in Mass Spectrometry Laboratory of Maria Curie-Skłodowska University, in which gaseous decomposition products are converted into CO2 and N2 (Gebus et al., 2012). For extraction of phosphates from water we used method developed by Gruau et al. (2005). PO43- ions adsorbed on anion exchange resin IRN-78 where eluted and then converted to Ag3PO4. Silver phosphate was thermally decomposed in vacuum system to CO2, which isotopic composition (δ18O) were measured on a dual inlet and triple-collector mass spectrometer (Pelc & Hałas, 2011). References: 1. Gebus B., Czupyt Z., Hałas S. (2012). Simultaneous preparation of N2 and CO2 for stable isotope analysis from nitrate samples, Mineralogia – Special papers, 39, 44-45. 2. Mayer B., Boyer E.W., Goodale C., Jaworski N.A., Van Breemen N., Howarth R.W., Seitzinger S., Billen G., Lajtha K., Nadelhoffer K., Van Dam D., Heitling L.J., Nosal M., Paustian K. (2002). Sources of nitrate in rivers draining sixteen watersheds in the northeastern U.S.: Isotopic constraints. Biogeochemistry, 57/58, 171-197. 3. O’Neill P. (1993) in: Environmental chemistry, Polish Edition (1997), PWN, Warsaw 4. Silva, S. R.; Kendall, C.; Wilkison, D. H.; Ziegler, A. C.; Chang, C. C. Y. and Avancino, R. J.(2000). A New Method for Collection of Nitrate from Fresh Water and the Analysis of Nitrogen and Oxygen Isotope Ratios. Journal of Hydrology, Nr 1-2, t. 228, 22-36. 5. Vollenweider R.A. (1968). The scientific basis of lake and stream eutrophication, with particular reference to phosphorus and nitrogen as eutrophication factors. Technical Report OAS/DSI/68.27. Organization for Economic Cooperation and Development, Paris.
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UMCS, Lublin, 16-17.10.2014
A NEW PREPARATION METHOD OF NITRATES FOR SIMULTANEOUS EXTRACTION OF CO2 AND N2 FOR Δ18O AND Δ15N ANALYSIS Beata Gebus 1, Zbigniew Czupyt 1,2, Stanisław Hałas 1 1
Mass Spectrometry Laboratory, Institute of Physics, UMCS, pl. Marii Curie-Skłodowskiej 1, 20-031 Lublin, e-mail: beata.gebus@umcs.pl 2 Polish Geological Institute – National Research Institute, ul. Rakowiecka 4, 00-975 Warszawa
Isotopic composition of δ15N and δ18O in NO3- dissolved in water are valuable source of information in hydrology and geochemistry. Isotope composition studies of NO3- in water reservoirs allow the identification of anthropogenic contaminants (Vitousek et al., 1997; Piatek et al., 2005). This is especially important in the case of water reservoirs with concentrations above the acceptable level of NO3-, which is dangerous to life and health of living organisms (O’Neill, 1993; Price, 1998). Studies of δ15N and δ18O are useful tool for water quality monitoring and they allow to observe changes in the biogeochemical processes of nitrogen cycle (Delwiche, 1981; Jaffe, 1992; Casciotti, 2009). Our new preparation method of nitrates allows simultaneous extraction of N2 and CO2 gases for mass spectrometrical δ15N and δ18O analysis. The reaction is performed in a vacuum line at high temperatures to decompose of AgNO3 to Ag, NO2 and O2. Subsequently NO2 and O2 are reduced with spectrally pure graphite in presence of PtIr catalyst. The optimum weight ratio AgNO3:C was found to be 4:1. We have studied conversion process to CO2 and N2 in temperature range from 650°C to 900°C with different reaction times. References: 1. Delwiche C.C. (1981). The Nitrogen Cycle and Nitrous Oxide. [In:] Delwiche C.C. (ed.) Denitryfication, Nitryfication and Atmospheric Nitrous Oxide, John Wiley, New York, 1-15. 2. Jaffe D.A. (1992). The Nitrogen Cycle. [In:] Butcher S.S., Charlson R.J., Orians G.H., Wolfe G.V. (eds.) Global Biogeochemical Cycles. Academic Press Inc., San Diego, 263-284. 3. O’Neill P. (1993) Environmental Chemistry, 2nd Ed. Chapman & Hall. London, 96-113. 4. Piatek K.B., Mitchell M.J., Silva S.R., Kendall C. (2005). Sources of nitrate in snowmelt discharge: evidence from water chemistry and stable isotopes of nitrate; Water, Air, and Soil Pollution, 165, 13–35. 5. Price D. (1998) Methemoglobinemia, 6th Ed. Goldfrank’s Toxicologic Emergiences, 1507-1522. 6. Vitousek P.M., Aber J., Howarth R.W., Likens G.E., Matson P.A., Schindler D.W., Schlesinger W.H., Tilman G.D. (1997). Human Alteration of the Global Nitrogen Cycle: Causes and Consequences, Issues in Ecology, 1, 1-16. 7. Casciotti K.L. (2009). Inverse kinetic isotope fractionation during bacterial nitrite oxidation, Geochimica et Cosmochimica Acta, 73, 2061–2076.
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UMCS, Lublin, 16-17.10.2014
ISOTOPIC COMPOSITION OF PERMIAN SULFATE ACCUMULATIONS: EXAMPLES FROM THE NORTHERN CALCAREOUS ALPS, AUSTRIA Ana-Voica Bojar 1,2, Stanislaw Halas 3, Hans-Peter Bojar 2, Andrzej Trembaczowski 3 1
2
Department of Geology, Salzburg University, Salzburg, Austria Department of Geoscience, Studienzentrum Naturkunde, Universalmuseum Joanneum, Graz, Austria 3 Mass Spectrometry Laboratory, Institute of Physics, UMCS, 20-031 Lublin, Poland e-mail: ana-voica.bojar@sbg.ac.at
Sulfur and oxygen stable isotope composition of evaporites are controlled by global cycles through geological times as well as by local environmental factors. Thus, isotopic investigations on sulphur and oxygen from sulfate accumulations combined with mineralogical investigations may offer information regarding the origin of fluids, pH and/or eH of fluids, inflows, restricted conditions, evaporative effects, recrystallization or bacterial processes (Longinelli and Craig, 1967; Holser et al., 1979; Ohmoto, 1986; Halas, 1987; Raab and Spiro, 1991; Machel et al., 1995; Seal et al., 2000; Canfield, 2001; Kucha et al., 2010; Peryt et al., 2010). While sulphur isotope measurements where done on sulfates from austrian Permian-Triassic deposits (Pak, 1974, 1981; Spöttl & Pak, 1996) oxygen data are missing. The mineralogical data and the additional set of isotope composition for evaporite sulphates and associated sulphides will provide information regarding the condition of formation and subsequent history. Geology and mineralogy of investigated sulphate deposits The Eastern Alps are characterised by the presence of three main tectonic units, such as the Lower, Middle and Upper Austroalpine, which overlie the Penninicum (Tollmann, 1977). The Upper Austroalpine unit consists of the Northern Calcareous Alps (NCA) overlying the Greywacke zone and corresponding to the Graz Paleozoic, Murau Paleozoic and the Gurktal Nappe. Evaporitic rocks are lacking in the later ones. The Northern Calcareous Alps are a detached fold and thrust belt. The sedimentation started in the Late Carboniferous or Early Permian, the age of the youngest sediments being Eocene. The NCA are divided into the Bajuvaric, Tirolic and Juvavic nappe complexes. The evaporitic Haselgebirge Formation occurs in connection with the Juvavic nappe complex at the base of the Tirolic units (Leitner et al., 2013). The Haselgebirge Formation consists mainly of salt, shales, gypsum and anhydrite and includes the oldest sediments of the NCA. The age of the Haselgebirge Formation, established by using spors and geochronological data, is Permian to Lower Triassic (Klaus, 1965; Tollmann 1977; Pak and Schausberger 1981; Flügel and Neubauer 1984; Schausberger, 1986; Spötl 1988; Spötl, 1989; Weber et al., 1997; Schorn et al. 2013; Leitner et al., 2014;). For the Northern Calcareous Alps, the mineralogy of sulphate accumulations consists mainly of gypsum and anhydrite and subordonates of carbonates. The carbonates as magnesite, dolomite and calcite can be found either as singular crystals (Niedermayr et al., 1983; Kirchner, 1987) or as small accumulations within the hosting gypsum. Sulfides (sphalerite, galena, pyrite), sulfarsenides (enargite, baumhauerite) and native sulphur enrichments are known from several deposits (Kirchner, 1987; Postl, 1990).
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Methods The isotope ratios of sulfates (δ34S and δ18O) and sulfides (δ34S) were determined by measuring the isotopic composition of resulting SO2 and CO2 gases on dual inlet and triple collector mass spectrometer (Halas and Szaran, 2001, 2004; Mizutani, 1971; Halas et al., 2007). Delta values were normalized to the CDT and the SMOW scales by analysis of the NBS-127. For carbonate samples, the δ13C and δ18O values were determined as well. CO2 gas was extracted from calcite at 25°C by reaction with H3PO4 (McCrea,1950) and measured on an IRMS with dual-inlet system. Standard deviations of measurements for NBS19 international standard were better than 0.1‰. Delta values were normalized to PDB. Results The investigated samples were selected from various gypsum and halite rich deposits of the Northern Calcareous Alps. A total of 23 sulfates were investigated, and oxygen and sulfur isotopic composition were determined for anhydrite, gyps, polyhalite, blödite and langbeinite. The δ34S values vary between 10.1 to 14 ‰ (CDT), with three values higher than 14 ‰. The δ18O values show a range from 9 to 23 ‰ (SMOW). The sulfur isotopic compositon of 14 sulfides as galena, sphalerite, pyrite and native sulfure were determined as well, with values ranging between -17.5 and 2.8 ‰ (CDT). The δ13C and δ18O values were determined for 5 carbonates as well. Discussions At low temperatures, isotopic exchange between dissolved sulphate and water has slow exchange rates (Chiba and Sakai, 1985). Accordingly, the sulfur and oxygen isotopic composition of sulphates should reflect the composition of the dissolved sulphates, and not that of water. However some of the investigated deposits from the Northern Calcareous Alps were overprint during burial at higher temperatures (Leitner et al., 2013; Schorn et al., 2013). Dissolved sulfate in modern seawater has a δ34S value of +21‰ (Rees et al., 1978; Longinelli, 1983; Böttcher et al., 2007), but its composition largely varied in the ocean history related to the bacterial reduction and continental weathering (Claypool et al., 1980). The δ34S of the sea water sulfate is approx. 1.7‰ less than that of the precipitated mineral (Thode and Monster, 1965), the sulfur fractionation between sulfate minerals and aqueous sulfates being small (Holser and Kaplan, 1966; Sakai, 1968). The δ18O values of the present-day dissolved marine sulfate is approx. ~9.5‰ (Longinelli and Craig, 1967; Rafter and Mizutani, 1967; Longinelli, 1983), the values of precipitated sulfate being with 3.5 ‰ heavier than the dissolved sulfate (Gonfiantini and Fontes, 1963; Lloyd, 1968). For the investigated sulfates, the δ34S values show generally low values, which are characteristic for the late Permian (Claypool et al., 1980; Kampschulte and Strauss, 2004; Peryt et al., 2010). The broad distribution of sulfide δ34S values point toward bacterial reduction, fact also reflected by some higher δ34S values of sulfates. The δ18O values show a larger scatter from 9 to 23‰, which is even larger than that found for the Zechstein anhydrites of northern Germany, north-eastern Italian Alps or western Poland (Kampschulte et al., 1988; Longinelli and Flora, 2007; Peryt et al., 2010) The histogram of data show a maximum between 11 and 15‰, the large scatter suggesting also subsequent bacterial reduction. The associated carbonates, as calcite, dolomite and magnesite are in disequilibrium with the sulfates indicating rather primary marine isotopic signature than re-equlibration with the sulfates at higher temperatures. Further refinements include association of the data with microstructures, age, type of deposit and documented thermal overprint.
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References: 1. Canfield D.E. 2001. Biogeochemistry of Sulphur Isotopes. In: Valley J.W., Cole D.R., (eds.): Stable Isotope geochemistry. Reviews in Mineralogy & Geochemistry, 43, 579-606. 2. Flügel H.W., Neubauer F. 1984. Steiermark Geologie der österreichischen Bundesländer in kurzgefassten Einzeldarstellungen. Geologische Bundesanstalt, Vienna, 127 S. 3. Halas S. 1987. Oxygen and Sulphur Isotope Ratios of Sulphate Minerals. Isotopenpraxis, 23/7, 282-283. 4. Halas S., Szaran J. 2004. Use of Cu2O-NaPO3 mixtures for SO2 extraction from BaSO4 for sulphur isotope analysis. Isotopes Environ. Health Studies, 40, 229–231. 5. Halas S., Szaran J., Czarnacki M., Tanweer A. 2007. Refinements in BaSO4 to CO2 preparation and 18O calibration of the sulphate standards NBS-127, IAEA SO-5 and IAEA SO-6. Geostandard Geoanalyse Research, 31, 61–68. 6. Holser W.T., Kaplan I.R., Sakai H., Zak I. 1979. Isotope geochemistry of oxygen in the sedimentary sulfate cycle. Chemical Geology 25, 1-17. 7. Kampschulte A., Buhl D., Strauss H. 1998. The sulfur and strontium isotopic compositions of Permian evaporites from theZechstein basin, northern Germany. Geol. Rundsch., 87, 192-199. 8. Kirchner E. 1987: Die Mineral- und Gesteinsvorkommen in den Gipslagerstätten der Lammermasse, innerhalb der Hallstattzone, Salzburg. Jahrbuch Haus der Natur. 10, 156-167. 9. Klaus W. 1965. Zur Einstufung alpiner Salztone mittels Sporen. Verhandlungen der Geologischen Bundesanstalt, Sonderheft, 228-292. 10. Kucha H., Schroll E., Raith J.G., Halas S. 2010. Microbial sphalerite formation in carbonate-hosted zn-pb ores, bleiberg, austria: micro- to nanotextural and sulfur isotope evidence. Economic Geology, 105, 1005-1023. 11. Leitner C., Neubauer F., Genser J., Borojevic-Sostaric B., Rantitsch G. 2013. 40Ar/39Ar ages of recrystallization of rock-forming polyhalite in Alpine rocksalt deposits. In: Jordan F., Mark D.F., Verati C. (eds.) Advances in 40 Ar/39Ar Dating: from Archaeology to Planetary Sciences. Geological Society, London, Special Publications, 378, 207-244. 12. Niedermayr G., Beran A., Brandstätter F. 1983. Diagenetic type magnesits in the Permo-Scythian rocks of the Eastern Alps, Austria. In: Möller P. (ed.) Magnesite Geology, Mineralogy, Geochemistry, Formation of MgCarbonates, Monograph Series on Mineral Deposits, Gebrüder Bornträger Berlin Stuttgart, 35-59. 13. Longinelli A., Flora O. 2007. Isotopic composition of gypsum samples of Permian and Triassic age from the north-eastern Italian Alps. Palaeoenvironmental implications. Chemical Geology, 245, 275-284. 14. Machel H.G., Krouse H.R., Sassen R. 1995. Products and distinguishing criteria of bacterial and thermochemical sulphate reduction. Applied Geochemistry 110, 373–379. 15. McCrea J.M. 1950. On the isotopic geochemistry of carbonates and a paleotemperature scale. Journal of Chemical Physics, 18, 849-857. 16. Mizutani Y. 1971. An improvement in the carbon reduction method for the isotopic analysis of sulfates. Geochem. J. 5, 69–67. 17. Ohmoto H. 1986. Stable isotope geochemistry of ore deposits. In: Valley J.W., Taylor H.P. Jr., O’Neil J.R. (eds.) Stable Isotopes in High Temperature Geological Processes. Reviews in Mineralogy, 16, 491–560. 18. Pak E. 1974. Schwefelisotopenuntersuchungen am Institut für Radiumforschung und Kernphysik I. Anzeiger der Akademie der Wissenschaften mathematisch-naturwissenschaftliche Klasse, 166-174. 19. Pak E. 1981. Schwefelisotopenuntersuchungen am Institut für Radiumforschung und Kernphysik III. Anzeiger der Akademie der Wissenschaften mathematisch-naturwissenschaftliche Klasse, 187-198. 20. Peryt T.M., Halas S., Hryniv S.P. 2010. Sulphur and oxygen isotope signatures of late Permian Zechstein anhydrites, West Poland: seawater evolution and diagenetic constraints. Geological Quarterly, 54/4, 387-400. 21. Postl W. 1990. Enargit und Parnauit aus dem Gips- und Anhydritbergbau Tragöß-Oberort, Steiermark. In: Niedermayr G. et al. 1990. Neue Mineralfunde aus Österreich XXXIX. Carinthia II, 180/100, 277. 22. Raab M., Spiro B. 1991. Sulfur isotopic variations during seawater evaporation with fractional crystallization. Chemical Geology, 86, 323–333. 23. Schorn A., Neubauer F., Genser J., Bernroider M. 2013. The Haselgebirge evaporitic mélange in central Norhtern Calcareous Alps (Austria): part of the Permian to Lower Triassic rift of the Meliata ocean? Tectonophysics, 583, 28-48.
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24. Seal R.R., Alpers C.N., Rye R.O. 2000. Stable isotope systematics of sulfate minerals. In: Alpers C.N., Jambor J.L., Nordstrom D.K. (eds.), Sulphate minerals: crystallography, geochemistry, and environmental significance. Reviews in Mineralogy & Geochemistry, 40, 541-593. 25. Spötl C. 1988. Schwefelisotopendatierung und fazielle Entwicklung permoskythischer Anhydrite in den Salzbergbauen von Dürnberg (Hallein) und Hallstatt (Österreich). Mitt. Ges. Geol. Bergbaustud. Österr., 34/35, 209-229. 26. Spötl C. 1989. The Alpine Haselgebirge Formation, Northern Calcareous Alps (Austria): Permo-Scythian evaporites in an alpine thrust system. Sedimentary Geology, 65, 113-125. 27. Spötl C., Pak E. 1996. A strontium and sulfur isotopic study of Permo-Triassic evaporites in the Northern Calcareous Alps. Geology, 219-234. 28. Tollmann A. 1977. Geologie von Österreich. Band 1. Die Zentralalpen. Deuticke, Wien, 766 pp. 29. Weber C. (Hrsg.) 1997. Handbuch der Lagerstätten der Erze, Industrieminerale und Energierohstoffe Österreichs. Archiv für Lagerstättenforschung, Band, 19, 607 pp.
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STUDY OF δ13C AND CHEMICAL COMPOSITION OF CARBONATES FROM THE CRYSTALLINE ROCKS FROM THE KOLA PENINSULA (N RUSSIA) Miłosz A. Huber 1, Stanisław Hałas 2, Lesia Lata 1, Yuri Neryadovskiy 3 1
Maria Curie-Skłodowska University, Earth Science and Spatial Managmenent Faculty, 2 cd Kraśnicka St., 20-718 Lublin, Poland; 2 Maria Curie-Skłodowska University, Mass Spectrometry Laboratory, Institute of Physics, Lublin, 1 M. Curie-Skłodowska Sq., 20-031 Lublin, Poland. e-mail: miloh@interia.pl 3 Geological Institute of the Kola Science Center of Russian Academy of Science, 14 Fersman Str., 184209 Apatity, Russia.
In this study we report new data on the δ13C of carbonates from proterozoic Ni-Cu deposits and Kovdor and Khibina alkaline intrusive rocks from Kola Peninsula of the northern part of Baltic Shield. The selected ore minerals were analyzed with optical and electron microscopy (Hitachi SU6600 with EDS attachment), whereas the δ13C was approach was determined in the Mass Spectrometry Laboratory, Maria Curie-Skłodowska University. These carbonates were analyzed by ICP MS in Department of Soil Science in order to figure out typical metallic concentrations. It was studied a samples of carbonates from mafic rocks from Granulite Belt from Kandalaksha on the White Sea and the Cu-Ni deposits of Piechenga (Fig. 1), Monchepluton, alkaline massif of Khibina and carbonatites from the Kovdor.
a
b
d c
Fig. 1. Microphotographs of the typical carbonate samples from Piechenga with sulphide mineralization (thin section, reflected light a, b, cross light c, d, crossed pollars b, c, d).
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UMCS, Lublin, 16-17.10.2014
The carbonate minerals were observed in the mineral veins cutting the mafic rocks in old massifs. The carbonates in Kovdor are basic component in the phoscorite rocks. The K/Ar age of carbonate massifs is a 350 Ma. The carbonate from Kovdor was formed in the active zone of continental type of hot spot plutonism in the Kola Peninsula. The carbonate from the mafic rocks from old proterosoic massifs indicate the regional character of magmatic processes in whole East European Province included the Kola Peninsula. Keywords: geochemistry, stable isotope analysis, Kola Penisula, mafic rocks, carbanatites.
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12th Geochronological Conference "Dating of Minerals and Rocks XII" 1st International Conference on Biology and Earth Sciences "Bio-Geo"
UMCS, Lublin, 16-17.10.2014
STABLE ISOTOPE GEOCHEMISTRY OF SULFIDES FROM OLD MAFIC INTRUSIONS IN THE KOLA PENINSULA (N RUSSIA) Miłosz A. Huber 1, Stanisław Hałas 2, Lesia Lata 1, Felix P. Mitrofanov 3, Yuri N. Neryadovski 3, Tamara B. Bayanova 3 a
Maria Curie-Skłodowska University, Earth Science and Spatial Managmenent Faculty, 2 cd Kraśnicka St., 20-718 Lublin, Poland; b Maria Curie-Skłodowska University, Mass Spectrometry Laboratory, Institute of Physics, Lublin, 1 M. Curie-Skłodowska Sq., 20-031 Lublin, Poland. e-mail: miloh@interia.pl c Geological Institute of the Kola Science Center of Ruusian Academy of Science, 14 Fersman Str., 184209 Apatity, Russia.
The sulfides from old mafic intrusion rocks from the Kola Peninsula were analyzed on stable sulfur isotopes. These samples were dated by the Sm-Nd method. These sulfide samples were evaluated upon a geochemical compositions by ICP-MS and compared to subject REE analysis. The sulfide samples were selected from the main ore-bearing rocks of the layered Fedorovo-Pansky intrusion, Monchetundra massif and Pilguyarvi (Pechenga) deposit (Fig 1, 2). The analyzed sulfides formed several generations of mineralization in the above mentioned fields associated with primary and hydrothermal stage of formation of the deposits. Isotopic studies confirm a few consecutive stages of mineralization, which already was particularly well described in the case of sulfides from Fiodoro-Pansky deposit. These data were compared with the results of Sm-Nd dating of sulfide mineralization. These results were compared with previously obtained U-Pb ages for zircon and baddeleyite. The studied sulfides with some mafic intrusions of the Kola deposits indicate a multistage mineralization. This is due to the processes of their formation and also imposed factors metamorphic and hydrothermal processes occurring in these rocks. The results of geochemical and geochronological studies indicate a complementarity in the context of determining the mineralization stages.
Fig. 1. Microphotographs of samples of sulfide mineralization in gabrroides from Monchegorsk (in left) and peridotites from Piechenga (right), reflected light.
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UMCS, Lublin, 16-17.10.2014
Fig. 2. BSE microfotograph of the sample of Cu-Ni sulphide from Monchegorsk (in left), and Fe-Ni sulphides in Piechenga (right).
Keywords: geochemistry, geochronology, stable isotope analysis, sulfides, Kola Penisula, mafic rocks.
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UMCS, Lublin, 16-17.10.2014
STUDY OF PRECIPITATES IN THE PETROARCHITECTURE DETAIL SAMPLES FROM BERN, SWITZERLAND Miłosz A. Huber Geology and Lithosphere Protection Department, Earth Science and Spatial Management Faculty, Maria Curie-Skłodowska University in Lublin, 2d/108 Kraśnicka rd. 20-718 Lublin, Poland, email: miloh@interia.pl
In the Swiss capital, Bern, are the centuries-old city buildings representing different architectural styles and forms associated with the development of urbanization of the city. At the confluence of the promontory of the peninsula on which is located the old town there is a crossing bridge "Nydeggbrücke". The bridge is connecting the banks of the Aare river. The bridge on both sides of the lining encased in flysch sandstone (Fig. 1). As a result of infiltration of the sandstone by aqueous solutions derived directly from the road embankment there was a precipitation of sulfate efflorescence on the surface of sandstone. The precipitates have concentric circles form along with the original laminae of the sandstone. The study of these precipitates using optical and electron microscopy clearly shows that the two dominant sulfate phases are gypsum (calcium and magnesium sulfate) and mirabilite (sodium sulfate), Fig. 2. The appearance of Ca and Mg rich precipitates suggests the dissolution of carbonates contained in the binder sandstone. The sulfates may be associated with natural marine salt inclusions contained in the specified shoals.
Fig. 1. Precipitates on the surface of sandstone bedding.
Fig. 2. SE Macrophotograph with mirabilit crystals.
Keywords: petroarchitercture, precipitates, gypsum, mirabilite, microscopy analysis.
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12th Geochronological Conference "Dating of Minerals and Rocks XII" 1st International Conference on Biology and Earth Sciences "Bio-Geo"
UMCS, Lublin, 16-17.10.2014
GEOCHEMICAL–ISOTOPE CHARACTERISTIC OF THE WASTE METALLURGICAL Zn-Pb ORE FROM RUDA ŚLĄSKA-WIREK HEAPS Miłosz A. Huber 1, Lesia Lata 1, Stanisław Chmiel 1, Karolina Oszust 2 1
Maria Curie-Skłodowska University, Earth Science and Spatial Managmenent Faculty, 2 cd Kraśnicka St., 20-718 Lublin, Poland; 2 Institute of Agrophysics Polish Academy of Sciences, ul. Doswiadczalna 4, 20-290 Lublin, Poland, e-mail: miloh@interia.pl
Studied metallurgical Zn-Pb ores located in the city of Ruda Śląska – Wirek. These wastes are byproduct material obtained in the process when metals are mixed with other types of waste such as coal output, which were stored on the heap. Today, after more than 100 years since the closure of steel plants ZnPb ores in Ruda Śląska heaps are located in the city center, which since that time have been expanded. These samples were examined by means of microscopic, chemical (ICP) and isotope methods. These heaps due to the presence of metals Zn-Pb pose a significant threat to the environment. These are found to be a lead-zinc mineralization in the form of base metals, oxides (zincite) and hydroxides and silicates (willemite, Fig. 1). Minerals are accompanied by iron oxides and hydroxides and sulfides (primary mineralization) and sulfates and carbonates (secondary mineralization). For this purpose, samples were taken from the surface of the heap of the pre-pits, and in the field. Apart from the typical metals such as Zn and Pb ore characteristic, and Fe and Mn-related both to the primary process and the subsequent infiltration of water are also elements such as Cu, Ti and Ni, As, Cd and Ba. While zinc silicates such as willemite detected are as stable phases of the back (zincite), carbonates (cerussite, smithsonite) and sulfides (galenite) and sulfate (barites) may be more sensitive.
Fig. 1. BSE Microphotographs with marked results of the phase. Crystals zincite (ZnO) on the background of willemite (Zn2SiO4) and carbonates and sulfate (left) crystals of hematite (Fe2O3) on the background of galenite (PbS) against a barite (BaSO4, right).
Keywords: Ruda Śląska-Wirek, Zn-Pb slaks, geochemistry, stable isotopic analysis.
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UMCS, Lublin, 16-17.10.2014
SOLID STATE U-PB ISOTOPE MEASUREMENTS ON SHRIMP IIE ION MICROPROBE - A WINDOW TO THE EARLY EARTH Zbigniew Czupyt, Ewa Krzemińska Ion Microprobe Section Micro-area Analysis Laboratory Polish Geological Institute - National Research Institute, 4 Rakowiecka St., 00-975 Warszawa, Poland. e-mails: zbigniew.czupyt@pgi.gov.pl ewa.krzeminska@pgi.gov.pl
Over one hundred years ago British geologist Arthur Holmes published his famous book “The Age of the Earth” in which he applied uranium/lead chemical measurements to the quantification of geologic time. Then researchers were beginning to realize that the same way hold promise for assessing the Earth's age. The century since then the measuring methods have been significantly improved, reducing technical limitations, modernizing the counting methods to full potential of U-Pb technique be realized. U-Pb system currently received a reputation as a most broadly reliable. Measurements can now be performed using a several types of facilities and new generation of the mass spectroscopes including secondary ion mass spectrometry (SIMS). The SIMS technique makes in situ isotopic and chemical 'surface' analysis of solid targets on the scale of a few micrometers by bombarding the sample on a very fine scale, and eliminate the difficult, timeconsuming, labour-intensive and potentially hazardous aspects of sample preparation for conventional mass spectrometer. Minerals may be analyzed directly either as grain mounts or in thin sections. Quantitative isotopic data from SIMS technique must be derived by comparing measurements of unknowns to well characterized matrix-matched reference materials. One of the best a high precision equipment of SIMS class, primarily designed for isotopic geochronology is SHRIMP - Sensitive High Resolution Ion Microprobe ion microprobe. The newest large radius, multi-collector SHRIMP ion microprobe has been just installed in PGI-NRI, Warsaw and now Window to the Early Earth secrets is within easy reach. SHRIMP allowed to detect oldest rocks of the Earth > 4.Ga (Acasta Gneiss Complex, Canada, and Jack Hills Australia), which have survived the remnants of the first 500 million years of Earth's history (Hadean). Until now, SHRIMP IIe has been applied to a variety of geological and geochemical purposes including U-Th-Pb geochronology of uranium bearing minerals, but also stable isotopes analyses (eg carbon, sulphur and oxygen) in biogenic and inorganic materials; and to diagnosis isotope anomalies in meteorites and lunar soil. SHRIMP is the most productive geochemical instrument of its class. It is designed for continuous round-the-clock data acquisition in order to maximize scientific returns. The simple ion optics and robust design results in ease of operation and instrumental setup compared to other ion probes. It is a highly versatile workhorse for a wide range of geochemical and geochronological investigations, including: • Unravelling the history of complex metamorphic terranes. • Tracing crustal growth and recycling through geologic time. • Examining stellar nucleosynthesis. • Tracing climate change on geological timescales via oxygen isotope analysis. • Calibrating the Palaeozoic time-scale. • Dating of the Earth’s oldest crust. • Examining the oldest zircons in the solar system. • Measuring trace elements in diamond inclusions. • Investigating Ti isotopic ratios in meteorites.
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• • •
Determining Pb isotopic composition of lunar granites. Analysis of microscopic samples of nuclear fuels to determine fuel history. With the Alphachron, identifying the source of kimberlite pipes through ‘hot’ zircons.
The SHRIMP IIe/MC can be used for any sort of SIMS application. Depth profiling and trace elemental analyses are occasionally performed. For example, SHRIMP analysis has been applied to numerous problems in trace element geochemistry, such as: • Measurements of the concentration and distribution of trace elements within individual grains, and mineral inclusions. • Measurement of chemical and isotopic diffusion rates. • Partitioning of elements between phases, and dissolution rates of minerals.
The SHRIMP II table of elements.
SHRIMP IIe/MC in Polish Geological Institute - National Research Institute.
Nevertheless, there are two main types of analysis which dominate current SHRIMP usage. These are uranium-lead geochronology, and isotope ratio determination. These analytical techniques can be used to solve a wide variety of geological, environmental, or technological problems.
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SHRIMP facility offers high-spatial resolution analyses using either a focused ion beam to sputter a volume of sample. The technique is relatively non-destructive, allowing multiple analyses to be performed within single grains or thin zones within grains. Typical volume of zircon analyzed by an ion-probe is cylindrical, 20-30 μm or less in diameter and up to 1 μm deep. It allows isotopic data to be correlated with other geochemical information in spatial context with textures and imaging. SHRIMP using high mass resolution to reduce interferences to levels where the corrections required are minimal. The SHRIMP instrument revolutionized the field of U-Pb geochronology accessory minerals by permitting spatially controlled dating (Williams, 1998).
Schematic layout of the SHRIMP IIe/MC.
The SHRIMP instrument broadly consists of a primary ion column to generate a tightly focused beam of oxygen (or cesium) primary ions, a sample holding and exchange system to present the sample to the ion beam, a secondary extraction optical chain to collect the ions sputtered from the sample, followed by a double focusing mass spectrometer (simultaneous energy and mass refocussing) with a very large turning radius (magnet radius is 1 m, electrostatic analyzer radius is 1.27 m). The resulting instrument has a beam line over 7 m long and weighs more than 12 tons but such large electromagnet sector enable to achieve a high mass dispersion. The secondary ions are gathered using electrostatic lenses, by which they are separated according to their relative masses. The quality of the instrument can be assessed by its sensitivity (ability to detect trace elements present in the target at low concentrations) and mass resolution (ability to distinguish between ions of very similar mass). The entire instruments is kept under Ultra-High Vacuum. SHRIMP II the achieves resolution > 5000 (1% definition) with flat-tops for 80 µm source slit and 100 µm collector slit and for those conditions the sensitivity is better than 18 cps/ppm for 206Pb. References 1. Holmes A. (1913). The age of the earth 1913, Harper & Brothers, 2nd edition 1927, 3rd edition, 1937. 2. Williams I.S. U-Th-Pb geochronology by ion microprobe. In: McKibben A., Shanks W.C. (eds) Applications of microanalytical techniques to understanding mineralizing processes, Reviews in Economic Geology 1998; 7: 1-35.
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A NOVEL APPROACH IN THE STUDY OF ISOTOPE ANOMALIES (Δ17O AND Δ33S) Tomasz Pieńkos, Artur Wójtowicz, Andrzej Pelc, Stanisław Hałas Mass Spectrometry Laboratory, Institute of Physics, Maria Curie-Sklodowska University, 20-031 Lublin, Poland
By term “isotope anomalies” they are understand the deviations of δ17O and δ33S from respective values of 0.52δ18O and 0.52δ34S predicted by the mass-dependent theory (Urey 1947, Bigeleisen & Mayer 1947). These anomalies, denoted as Δ17O and Δ33S, are encountered to be large in meteorites and stratospheric trace gases (O3, CO2, H2O2, SO4, CO), but they are very small at Earth surface level. The major source of the Δ17O anomaly is atmospheric ozone and CO2, whilst that of Δ33S noticed in Precambrian sulfide and sulfate minerals were most likely due to ionization phenomena of SO2 and H2S in ancient Earth atmosphere. The distinct anomaly of stratospheric CO2 is diluted with isotopically normal CO2 when it enters the troposphere, hence at the ground level CO2 shows a little anomaly. Hoag et al. (2005) predicted Δ17O = +0.15 ‰ only for tropospheric CO2. For this reason the isotope anomalies were not well recognized by far at Earth surface level due to severe analytical difficulties of isotope analysis of δ17O and δ33S by isotope ratio mass spectrometry (IRMS). In this research we plan to overcome the most crucial difficulties by applying negative ion mass spectrometry. With the proposed developments we will attack the problem of study of minor variations of Δ17O and Δ33S. Necessary precision of δ17O determination should be enhanced several times in comparison to attained nowadays. Inasmuch as the isotope anomalies received a great attention nowadays (Thiemens 2006, Eiler et al. 2014) we have proposed their study using a novel approach. We will try to enhance the precision of isotope ratios determination by mass spectrometry on one hand, and on the other hand, we will increase the efficiency of isotope determinations by simplification of the sample preparation procedures. These goals will be achieved by a significant reconstruction and modernization of an old model of mass spectrometer (manufactured by Nuclide, Pennsylvania, in 70's of XX century) which we owned 2 years ago. This IRMS will be redesigned for measurements the negative ions O- and S- produced from being easily prepared gases CO2, CO and SO2. Such measurements (made on an IRMS used for routine isotope analysis of the C, N, O, and S elements in the Mass Spectrometry Laboratory) yielded very promising results regarding the intensity of the negative ion beam of oxygen (O-) which was generated from CO gas at the resonance electron energy of 11 eV (Hałas 2002). In dependence on the achievement degree of the outlined goals, we would be able to investigate smaller or larger isotopic anomalies recorded in various types of terrestrial carbonates, sulfates and sulfides and perhaps some components dissolved in waters. This will be rather exploring study of rock samples of different geological age, from Precambrian to Quaternary. We will put major effort to study isotopic anomalies in times of global crisis like those encountered in Permian/Triassic and K/T boundaries. In those boundaries great variations of δ18O and δ13C have been already recorded in sedimentary carbonates (Gruszczyński et al. 1989) and δ34S and δ18O in marine sulfates (Holser 1977, Claypool et al. 1980). Since start of this project we have completely rebuilt the whole vacuum system, the ion source and its electronic controller (Fig. 1). Preliminary tests made with single Faraday collector indicate excellent ion transmission and resolving power for our purposes (Fig. 2).
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Fig.1. Photo of the reconstructed IRMS.
O2+
N2+ Fig. 2. A mass spectrum obtained for air gases on positive ions. It is seen from major peaks of mass 28 and 32 that the resolving power M/â&#x2C6;&#x2020;M determined from half peak width is about 70.
Acknowledgements: This project is funded by NCN (a Polish government agency National Science Center) according to the decision no DEC-2013/11/B/ST10/00250. We are grateful to Dr. Keith Hackley from Illinois State Geological Survey for his kind assistance in donation procedures and the shipment of the old Nuclide IRMS designated for scrapping.
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References: 1. Claypool GC, Holser WT, Kaplan IR, Sakai H, Zak I. 1980. The age curves of sulfur and oxygen isotopes in marine sulfate and their mutual interpretation. Chem. Geol. 28: 199-260. 2. Eiler J. M., Bergquist B., Bourg I., Cartigny P., Farquhar J., Gagnon A., Guo W., Halevy I., Hofmann A., Larson T. E., Levin N., Schauble E. A. and Stolper D. 2014. Frontiers of stable isotope geosciences, Chemical Geology 327: 119-143. 3. Gruszczyński M, Hałas S, Hoffman A. & Małkowski K. 1989. A brachiopoid record of the oceanic carbon and oxygen isotope shifts at the Permiam/Triassic transition, Nature 337: 64-68 4. Halas S. 2002. Źródła jonów ujemnych w spektrometrach mas. Prace Naukowe Politechniki Warszawskiej, z. 143: 53-63. 5. Hoag KJ, Still CJ, Fung IY, & Boering KA. 2005. Triple oxygen isotope composition of tropospheric carbon dioxide as a tracer of terrestrial gross carbon fluxes. Geophysical Research Letters 32: 5. 6. Holser WT. 1977. Catastrphic chemical events in the history of ocean, Nature 267: 399-403. 7. Thiemens MH. 2006. History and applications of mass-independent isotope effects. Annu. Rev. Earth Planet. Sci. 34:217–62. 8. Urey HC. 1947. The thermodynamic properties of isotopic substances. J. Chem. Soc. London. 1947:562–581.
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STUDY OF PRINTED MATERIALS USING OPTICAL (POLARIZING) AND ELECTRON MICROSCOPY Anna Synajewska–Przybyś 1, Tomasz Sidor 1, Olga Jakowlewa 2, Miłosz A. Huber 2 1
2
Office of Forensic Expertises, Traugutta 17a, 20-454 Lublin Maria Curie-Skłodowska University, Earth Science and Spatial Managmenent Faculty, 2 cd Kraśnicka St., 20-718 Lublin, Poland, e-mail: mhuber@umcs.lublin.pl
Prints, old prints and securities studied in the context of their performance and plotted them changes at a later date by other persons (eg. in order to falsification). The study of these documents are usually nondestructive. The aim of the analysis is to present the order applied layers of pigment and (not infrequently) to determine their chemical composition, which can serve as an answer to indicate the technique and the time frame of marks performed. With this type of study comes analysis using SEM-EDS and optical microscopy. In the first of these through the use of high magnifications can get detailed information about how to print application on the map, font style in determining its chemical composition. It is also important information to determine the type of paper on which the map was made. Studies using of optical microscopy in connection with image analysis (by spectroscopic techniques) allow for execution of a numerous of specific print photographs, letters, in order to determine the sequence of the imposition of the various layers of the pigment. These methods are not destructive, can thus be performed on valuable specimens of historic documents without the risk of interference with them. The studied sample prints using the technique of optical polarizing microscopy and confocal and electron allowed to put forward a number of proposals on how to order the application and printing paper invoices, status, and secondary processes. In addition, were able to determine this technique changes the nature of additions and counterfeiting. These methods are not fully destructive, can thus be performed on valuable specimens of historic documents without the risk of interference with them. The studied sample prints using the technique of optical polarizing microscopy and confocal and electron allowed to put forward a number of proposals on how to order the application and printing paper invoices, status, and secondary processes. In addition, were able to determine this technique changes the nature of additions and counterfeiting. Studies with EDS addition also allowed the determination of the chemical composition of the test ink. All these methods are non-destructive, allowing for multiple, repeatable, and accurate analysis of samples tested for their performance. Range of methods shown above does not include image processing, which can further consequence expose the differences observed in research using of optical microscopy. These tests are an important tool in the description of the behavior and the identification of printed materials found application in both historical and engineering issues, forensics, etc.
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STABLE ISOTOPIC AND GEOCHEMICAL CHARACTERISTICS OF SURFACE WATER AND SOIL FROM SELECTED REGIONS OF THE KOLA PENINSULA Karolina Oszust 1, Lesia Lata 2, Olga Jakowlewa 3 1
Institute of Agrophysics Polish Academy of Sciences, Doswiadczalna 4, 20-290 Lublin, Poland; 2 Maria Curie-Skłodowska University, Earth Science and Spatial Managmenent Faculty, 2 cd Kraśnicka St., 20-718 Lublin, Poland; 3 Maria Curie-Skłodowska University, Institute of Slavic Philology, Faculty of Humanities, Plac Marii Curie Skłodowskiej 4, 20-718 Lublin; e-mail: OlgaJ@interia.eu
The Kola Peninsula is the northern part of Scandinavia and is almost entirely located above the North Arctic Circle. Therefore is in the polar climate zone, strongly alleviated by the current Norwegian, which ends in the Murmansk region (causing that there is the northernmost ice-free port). Therefore the Kola Peninsula has quite a lot of rainfalls, temperatures normally reach 10ºC in July, and -3ºC in January. This has an impact on growing season, which are very short, however very intense. In these area is present numerous deposits with Ni, Cr, Fe, Ti, Al mineralization. It also contributes to other environmental conditions, resulting in a much smaller distribution of pollutants. Water and soil samples were collected in 2012, field observations were made and in 1999, along with photo documentation and phytology research (conducted in 2000-2004). The goal of this study was to resolve the problem concerning the impact of geological and anthropogenic factors and to mention their origin. Selected components were tested, necessary for the functioning of living, among others: zinc, copper and iron, calcium, magnesium, etc., and on the other hand toxic for organisms. These were cadmium, lead, nickel, etc. The study showed that soil and water samples from various areas of the Kola Peninsula were characterized by great diversity. Dopant elements like P, F, Cl, Ti, Fe, Mn and Cu, Ni, S are normally associated with ground rock in which they are located. These are areas rich in alkaline syenite of mineralization apatit-nefelin-titanite (the Khibiny, Fig. 1, 2, Lovoziero) and sulphide mineralization gabbroids of iron-nickel-copper (Cr-doped, Monchegorsk).
Fig. 1. Panorama of the Maly Vudyavr lake in the Khibiny Mts.
Fig. 2. Typical regolith samples in Khibiny Mts.
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Near Murmansk city metamorphosed granite occurred very often and explicit admixture of iron (especially in the migration zone of the solutions at faults). The appearance of metals such as Zn, Pb, Cr in settlers, urban areas, rivers come from industrial plants may be already associated with anthropogenic activity. Similarly, in the case of dopant elements such as P, S, Cd. Trend was confirmed according obtained from the graphical analysis identified number of elements (Cr and Cd co-existence, and Fe and Cr, Zn and Pb). Keywords: geochemistry, stable isotope analysis, surface water, soil, Kola Penisula.
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UMCS, Lublin, 16-17.10.2014
OPTICAL AND ELECTRON MICROSCOPY APPLICATION IN BIOMEDICAL RESEARCH Eliza Blicharska 1, Tomasz M. Karpiński 2, Bożena Muraczyńska 3 1
Medical University of Lublin, Chair of Chemistry, Department of Analytical Chemistry, 20-059 Lublin, Chodźki 4A str.,Poland, e-mail: bayrena@tlen.pl 2 Poznań University of Medical Sciences, Department of Medical Microbiology, Wieniawskiego 3, 61-712 Poznań, e-mail: tkarpin@interia.pl 3 Department of Surgery and Surgical Nursing, Faculty of Nursing and Health Sciences, Medical University of Lublin, Al. Racławickie 1, 20-950 Lublin, bmska@interia.pl
Modern biomedical research is based largely on the analysis of the microscale. Analysis of optically active materials can examine and change the orientation property of pathogenic preparations by optical microscopy in transmission and reflection. Research in the light of the optical drive allows experiment "in vivo" with the ability to track significant changes and their documentation. The test is particularly important in the case of pathological changes of various tissues, is an important factor where capturing and analyzing these changes. The inclusion of heavy metals into the food chain can be serious consequences for living organisms. Ideally, this tool seems to be optical and electron microscopy. The advantage of this method is to rapidly identify the elemental composition that allows you to make a decision about the need for any further research on the quantitative level using other analytical methods. In order to accurately depict phenomena have long been used SEM technique that allows to obtain high magnification for detailed documentation of test items. Appetizers with electron microscope such as EDS allow to perform simple measurements of the chemical composition, helping to identify and variability of elements in the microscale eg. cells compositions, bacteria (Figs. 1 and 2) and viruses, results of biochemical reactions. Modern technology enables us to obtain the map of elements in spatial distribution and in many cases it is necessary to study certain properties of the formulations. Crystalline materials, in turn, can be studied using EBSD camera to obtain information on the spatial distribution and orientation of the crystals in the sample.
Fig. 1. Lactobacillus spp. in the optical microscopy (Gram staining, magn. x1000)
Fig. 2. Lactobacillus spp. in the electron microscopy (magn. x6000)
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MAIN EDIBLE WILD PLANTS OF KOLA PENINSULA (RUSSIA) Artur Adamczak 1, Olga Jakowlewa 2, Miłosz A. Huber 3, Tomasz M. Karpiński 4 1
Institute of Natural Fibres and Medicinal Plants, Department of Botany, Breeding and Agricultural Technology, Kolejowa 2, 62-064 Plewiska, e-mail: artur.adamczak@iwnirz.pl 2 Maria Curie-Skłodowska University, Institute of Slavic Philology, Faculty of Humanities, Maria Curie-Skłodowska Square 4, 20-718 Lublin; e-mail: OlgaJ@interia.eu 3 Maria Curie-Skłodowska University, Department of Geology and Protection of Lithosphere, Kraśnickie Avenue 2cd/107, 20-718 Lublin; e-mail: miloh@interia.pl 4 Poznań University of Medical Sciences, Department of Medical Microbiology, Wieniawskiego 3, 61-712 Poznań, e-mail: tkarpin@interia.pl
Kola Peninsula is a part of the Scandinavian Peninsula and it covers an area of approximately 100 000 km , mostly outside the Arctic Circle. The capital city of this region is Murmansk (about 300 000 inhabitants), located on the Barents Sea. Climate of Kola Peninsula is moderated by the warm Norwegian Current, but it is still harsh. The average annual temperature, measured in the Botanical Garden in Kirovsk (Khibiny Mountains, Fig. 1) is -0,5oC, the average temperature for July is 12,5oC and listed minimum is -42,5oC. On mountaintops, the average annual temperature is -3oC. Low temperatures and short growing season limit the possibilities of fruit and vegetable cultivation. There are no fruit trees, while tomatoes and cucumbers grow only in small greenhouses. Cultivation in the ground can be carried out for such vegetables as potatoes and onion. Among the fruit species, currants and special cultivars of strawberry are planted. In this context, harvesting of wild edible plants becomes important, because they are a valuable source of vitamins. 2
Fig. 1. Khibiny Mountains.
Kola Peninsula is covered by taiga. Tundra develops only in the north, along the coast of the Barents Sea. Vascular plant flora is poor in species, but individual taxa grow in large number. Berry plants from Ericaceae family belong to this group. There are: bilberry (Vaccinium myrtillus, Fig. 2),
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lingonberry (V. vitis-idaea), bog bilberry (V. uliginosum) and cranberry (Oxycoccus palustris) – all very often harvested for juices, jams or liqueur (cranberry). Another common species – crowberry (Empetrum hermaphroditum) is rarely collected due to the small and less tasty fruit. Also cloudberry (Rubus chamaemorus, Fig. 3) represents a frequent species, which fruits are used for making jam, and leaves – for brewed tea. From other common plants, birch juice is collected as well as fruits of rowanberry (for tinctures) and dandelion inflorescences (for confitures) too.
Fig. 2. Vaccinium myrtillus L.
Fig. 3. Rubus chamaemorus L.
Key words: Murmansk, Khibiny Mountains, taiga, arctic tundra, berry plants.
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GEOTOURISTIC ATTRACTIONS OF THE KHIBINY AND LOVOZIERO MASSIF ON THE KOLA PENINSULA IN NORTHERN RUSSIA Olga Jakowlewa 1, Miłosz A. Huber 2 1
Maria Curie-Skłodowska University, Institute of Slavic Philology, Faculty of Humanities, Plac Marii Curie Skłodowskiej 4, 20-718 Lublin; e-mail: OlgaJ@interia.eu 2 Maria Curie-Skłodowska University, Department of Geology and Protection of Lithosphere, Al. Kraśnickie 2cd/107, 20-718 Lublin; e-mail: miloh@interia.pl
This study is dedicated to the twin intrusions of alkaline rocks, which are located in the center part of the Kola Peninsula (with age about 360 million years). These rocks are the youngest (after the quaternary) and highest elevations in the region. Their presence is associated with Eastern European province of alkaline intrusions involving distributed on the Scandinavian Peninsula. Young sculpture mountains related to their age relative to the surrounding rocks and imposed forms of post-glacial gives them alpine character. In addition, location of the Northern Arctic Circle causes that make up these incredibly beautiful landscape. In the mountains the vegetation is variable reaching the floor of the Arctic wilderness, visible especially in the upper parts of the mountains, which are flattened and form a plateau. Lovoziero Massif due to its location to the east of Khibiny is less landscaped by human. In the mountains of these deserve special attention also numerous locations occurrences of rare minerals, such as murmanite, lorenzenite, narsarsukite, villiaumite or eudialyte, arfvedsonite and many others. Some of them are known from the few instances in the world and the others are only here. The place is very attractive offering contact with wild arctic nature which reveals its beauty especially during the short Arctic summer, when the polar day prevails here.
Fig. 1. Kukisvumchorr slopes and valley in the Khibiny Mountains.
Key Words: Geotouristic attractions, Khibina, Lovoziero, Kola Peninsula, Arctic Russia.
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LOCAL DIFFERENTIATION OF GROUNDWATER CHEMISTRY USING GIS AND MULTIVARIATE STATISTICS Artur Michalik, Sabina Dołęgowska Jan Kochanowski University, Institute of Chemistry, Świętokrzyska 15G St., 25-406 Kielce, Poland, e-mail Artur.Michalik@ujk.edu.pl
Groundwater is a very important source of drinking water in many countries including Poland. There are many research and monitoring programs that focus on groundwater quality. These programs generate huge data sets which are often very difficult to interpret. This is the reason why obtaining useful information from raw data poses many problems. The most important statistical issues in environmental studies encompass the use of proper hydrogeochemical classification and finding similarities in large data sets. The hydrogeochemical classifications employ only main cations and anions. In another approach researchers use local regulations for drinking water quality or some other standards and recommendations. Most of these techniques utilize only few parameters, or a “parameter by parameter” classification, which is far from a holistic approach used in hydrogeochemistry. At this point, the application of chemometrics seems to be the best option (Mallick et al., 2014). This can be defined as a chemical discipline that uses mathematical and statistical methods to: design or select optimal measurement procedures and experiments, and to provide maximum chemical information by analyzing chemical data. In the analysis of groundwater the second approach is commonly used. Of the different chemometric methods, pattern recognition is widely employed including such techniques as: Principal Components Analysis, and Supervised and Unsupervised Pattern Recognition (Brereton, 2003). Another problem that is often overlooked in presenting the results of environmental analysis is to link them with the spatial distribution. Geographic information system (GIS) is a powerful tool for handling spatial data and decision making in several areas, including hydrogeology and environmental fields (Stafford, 1991). Hydrogeochemical information can be easily input to a GIS environment for integration with other types of data, followed by analysis (Jha et al., 2007). The use of GIS enables a quantitative assessment of hydrogeochemical results over a broad range of spatial and temporal scales. The groundwater samples were collected in three areas: Świętokrzyski National Park (springs) and in two remote administrative districts: Tarłów and Morawica (wells). Cluster analysis was used to divide the groundwater outflows and wells into groups (Michalik, 2008). These groups were connected with land development, water discharge, the use and construction of wells. For example, in the ŚNP springs with highest yield (PN-20, 13, 1) were grouped in cluster 1 – Figure 1. It should be noted that the spring discharges were not included in statistical calculations. The GIS was used to create a thematic layer for different parameters and coefficients for the study area. These thematic maps could be very useful for fast the interpretation and presentation of raw data and results of statistical calculation. The pH values from the Tarłów district was presented as a contour map (Fig. 2). Both methods are ideal tools for a fast and reliable groundwater analysis. The statistical approach allows us to determine the internal structure of different data sets using the same algorithm. This gives an opportunity to compare different datasets. The GIS systems are indispensable in combining the results of chemical analysis and geographical data. These methods allow us to separate areas characterized by different
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groundwater chemistry and to link them with various natural and anthropogenic factors. These results may be imported into one of the GIS systems and presented as a thematic maps.
Fig. 4. Dendrogram showing clustering of springs in Świętokrzyski National Park derived from chemical analyses of waters.
Fig. 5. Analysis of pH values in the Tarłów district.
References: 1. Brereton R.G. 2003. Chemometrics: Data Analysis for the Laboratory and Chemical Plant. John Wiley & Sons, Ltd. 2. Mallick J., Singh C.K., Al-Wadi H., Ahmed M., Rahman A., Shashtri S., Mukherjee S. 2014. Geospatial and geostatistical approach for groundwater potential zone delineation. Hydrological Processes, doi:10.1002/hyp.10153
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3. 4.
5.
Michalik A. 2008. The Use of Chemical and Cluster Analysis for Studying Spring Water Quality in Ĺ&#x161;wiÄ&#x2122;tokrzyski National Park. Polish J. Environ. Stud. 17(3): 357 362. Jha M.K., Chowdhury A., Chowdary V.M., Peiffer S. 2007. Groundwater management and development by integrated remote sensing and geographic information systems: prospects and constraints. Water Resour. Manage. 21: 427-467. Stafford D.B. 1991. Civil Engineering Applications of Remote Sensing and Geographic Information Systems. ASCE, New York.
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PROBLEMS IN ASSESSMENT OF UNCERTAINTY ARISING FROM ENVIRONMENTAL SAMPLING Sabina Dołęgowska, Artur Michalik Jan Kochanowski University, Institute of Chemistry, Świętokrzyska 15G St., 25-406 Kielce, Poland, e-mail Sabina.Dolegowska@ujk.edu.pl
The only way to achieve a satisfactory accuracy in environmental studies is the proper sampling. All errors generated during this step should be well recognized and the whole process should be optimized to minimalize the possibility of unrepresentative sampling. Different factors may influence element concentrations and a level of uncertainty. Nowadays, the estimation of the total uncertainty, which includes both geochemical and measurement variance, has become a routine step in analytical procedures. It is calculated as:
where:
The measurement uncertainty is defined as the interval around the results of measurement that contains the true value with high probability. When it contributes less than 20% of the total variance the measurement technique can be considered as a fit for the purpose and it could be used to describe the variation between samples. But when this assumption is violated the sampling and/or analytical methodology should be modified (Ramsey et al. 2001). The sampling uncertainty can be calculated using the following methods: classical analysis of variance (ANOVA); robust analysis of variance (RANOVA) and range statistic method. In these methods the uncertainty is given as the standard deviation of measurement, so they are based on the assumption that the population is normally distributed. It should be stressed that in environmental studies the assumption of normality is usually unfulfilled. In proper sampling a lack of normality may be linked with heterogeneity of sampling area and/or with errors during homogenization. Different element concentrations in heterogeneous material strongly influence statistical distribution of results. It is always difficult to predict and avoid. When the assumption of normality is violated a data transformation is applied. In practice, several sets of transformed data should be checked and the transformation that gives the closest to normally distributed dataset should be selected. The transformation methods, such as: square root or logarithm are typical in statistical calculations, but these transformations very often fail to restore normality (Reimann, Filzmoser 2000). In environmental studies with plant samples (e.g. biominitoring studies) the factors that may change the bioaccumulative properties of organisms, such as: type of forest community, population density, seasonal fluctuations, topographic, climatic, edaphic and hydrologic conditions (type and amount of precipitation, rosewind), age and part of plant that was collected must be always considered. It has been confirmed (Schröder et al. 2008) that all these factors affect a wide variety of plant metabolic processes, growth rate,
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12th Geochronological Conference "Dating of Minerals and Rocks XII" 1st International Conference on Biology and Earth Sciences "Bio-Geo"
UMCS, Lublin, 16-17.10.2014
the rate of assimilation and physiological activity, but no precise information has been given on how these factors affect the sampling step and the total uncertainty level. Nowadays, most of works concern optimization of economic aspects and financial costs of sampling and analysis (Ramsey et al. 2001, Lyn et al. 2003). Because inexpensive sampling is one of the main advantages of environmental studies (e.g. biomonitoring studies), these considerations may seem to be unnecessary. More important is to find the answers for the following questions: 1) how heterogeneity of sampling area contributes to sampling uncertainty; 2) how to select the appropriate transformation when the typical transformation methods fail to restore normality; 3) when the plant samples should be collected to avoid variability in accumulative properties of organisms; 4) how the type of community (e.g. forest community) affects the population density and processes of accumulation. The lack of unequivocal information about error sources induced by sampling may have a significant effect on interpretation and comparison of analytical results. References: 1. Ramsey M.H., Lyn J.A., Wood R. 2001. Optimised uncertainty at minimum overall cost to achieve fitness-forpurpose in food analysis. Analyst 126: 1777-1783, 2. Lyn J.A., Ramsey M.H., Wood R. 2003. Multi-analyte optimisation of uncertainty in infant food analysis. Analyst 128: 379-388. 3. Reimann C., Filzmoser P. 2000. Normal and log-normal data distribution in geochemistry: death of a myth. Consequences for the statistical treatment of geochemical and environmental data. Environ. Geol. 39: 1001-1014, 4. Schröder W., Pesch R., Englert C., Harmens H., Suchara I., Zechmeister H.G., Thöni L., Maňkovská B., Jeran Z., Grodzińska K., Alber R. 2008. Metal accumulation in mosses across national boundaries: Uncovering and ranking causes of spatial variation. Environ. Pollut. 151: 377-388.
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12th Geochronological Conference "Dating of Minerals and Rocks XII" 1st International Conference on Biology and Earth Sciences "Bio-Geo"
UMCS, Lublin, 16-17.10.2014
Contents
Pages i-ii
Editorial pages
iii-iv
Instructions for Authors
1
Preface
3
Program of Conference
5 8 9
13
15
19
20
21
25
27
29
The northwestern margin of the Sarmatia in the Lublin area (Poland) documented by SHRIMP U-Pb zircon micro-geochronological study Ewa Krzemińska, Leszek Krzemiński, Janina Wiszniewska, Ian S. Williams Isotope geochronology: models versus reality Jan Burchart A closer look at chlorine and bromine isotopes; an approach to understand the similarities and differences Hans G.M. Eggenkamp Precise determination of isotopic composition of lithium in some Polish mineral waters by Thermal Ionisation Mass Spectrometry (TIMS) Adrian Pacek, Stanisław Hałas Capabilities of Secondary Ion Mass Spectrometry in geochronology and isotope geochemistry – first experiences from the Potsdam SIMS Facility Alexander Rocholl, Michael Wiedenbeck, Frédéric Couffignal The measurements of nitrates (δ15N, δ18O) and phosphates (δ18O) isotopic composition: a tool to identify the main pollution source of Zemborzycki Lake Beata Gebus, Andrzej Trembaczowski, Stanisław Chmiel, Stanisław Hałas A new preparation method of nitrates for simultaneous extraction of CO2 and N2 for δ18O and δ15N analysis Beata Gebus, Zbigniew Czupyt, Stanisław Hałas Isotopic composition of Permian sulfate accumulations: examples from the Northern Calcareous Alps, Austria Ana-Voica Bojar, Stanislaw Halas, Hans-Peter Bojar, Andrzej Trembaczowski Study of δ13C and chemical composition of carbonates from the crystaline rocks from the Kola Peninsula (N Russia) Miłosz A. Huber, Stanisław Hałas, Lesia Lata, Yuri Neryadovskiy Stable isotope geochemistry of sulfides from old mafic intrusions in the Kola Peninsula (N Russia) Miłosz A. Huber, Stanisław Hałas, Lesia Lata, Felix P. Mitrofanov, Yuri N. Neryadovski, Tamara B. Bayanova Study of precipitates in the petroarchitecture detail samples from Bern, Switzerland Miłosz A. Huber
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12th Geochronological Conference "Dating of Minerals and Rocks XII" 1st International Conference on Biology and Earth Sciences "Bio-Geo"
UMCS, Lublin, 16-17.10.2014
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31 34 37 38 40 41 43 44 47
Geochemical–isotope characteristic of the waste metallurgical Zn-Pb ore from Ruda ŚląskaWirek heaps Miłosz A. Huber, Lesia Lata, Stanisław Chmiel, Karolina Oszust Solid state U-Pb isotope measurements on SHRIMP IIe ion microprobe - a window to the Early Earth Zbigniew Czupyt, Ewa Krzemińska A novel approach in the study of isotope anomalies (Δ17O and Δ33S) Tomasz Pieńkos, Artur Wójtowicz, Andrzej Pelc, Stanisław Hałas Study of printed materials using optical (polarizing) and electron microscopy Anna Synajewska–Przybyś, Tomasz Sidor, Olga Jakowlewa, Miłosz A. Huber Stable isotopic and geochemical characteristics of surface water and soil from selected regions of the Kola Peninsula Karolina Oszust, Lesia Lata, Olga Jakowlewa Optical and electron microscopy application in biomedical research Eliza Blicharska, Tomasz M. Karpiński, Bożena Muraczyńska Main edible wild plants of Kola Peninsula (Russia) Artur Adamczak, Olga Jakowlewa, Miłosz A. Huber, Tomasz M. Karpiński Geotouristic attractions of the Khibiny and Lovoziero Massif on the Kola Peninsula in northern Russia Olga Jakowlewa, Miłosz A. Huber Local differentiation of groundwater chemistry using GIS and multivariate statistics Artur Michalik, Sabina Dołęgowska Problems in assessment of uncertainty arising from environmental sampling Sabina Dołęgowska, Artur Michalik
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12th Geochronological Conference "Dating of Minerals and Rocks XII" 1st International Conference on Biology and Earth Sciences "Bio-Geo"
UMCS, Lublin, 16-17.10.2014
Index of Authors
Adamczak Artur, 41 Bayanova Tamara B., 27 Blicharska Eliza, 40 Bojar Ana-Voica, 21 Bojar Hans-Peter, 21 Burchart Jan, 8 Chmiel Stanisław, 19, 30 Couffignal Frédéric, 15 Czupyt Zbigniew, 20, 31 Dołęgowska Sabina, 44, 47 Eggenkamp Hans G.M., 9 Gebus Beata, 19, 20 Hałas Stanisław, 13, 19, 20, 21, 25, 27, 34 Huber Miłosz A., 25, 27, 29, 30, 37, 41, 43 Jakowlewa Olga, 37, 38, 41, 43 Karpiński Tomasz M., 40, 41 Krzemińska Ewa, 5, 31 Krzemiński Leszek, 5 Lata Lesia, 25, 27, 30, 38 Michalik Artur, 44, 47 Mitrofanov Felix P., 27 Muraczyńska Bożena, 40 Neryadovskiy Yuri, 25, 27 Oszust Karolina, 30, 38 Pacek Adrian, 13 Pelc Andrzej, 34 Pieńkos Tomasz, 34 Rocholl Alexander, 15 Sidor Tomasz, 37 Synajewska–Przybyś Anna, 37 Trembaczowski Andrzej, 19, 21 Wiedenbeck Michael, 15 Williams Ian S., 5 Wiszniewska Janina, 5 Wójtowicz Artur, 34
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