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Documentation of the WALDATEM-2003 Experiment April, 28th to August, 03rd 2003 (2004)

Christoph Thomas Johannes Ruppert Johannes Lüers Joel Schröter Jens-Christopher Mayer Theresa Bertolini

no abstract

Qualitätsbegutachtung komplexer mikrometeorologischer Messstationen im Rahmen des VERTIKO projects (2004)

Matthias Göckede Matthias Mauder Thomas Foken

keine Zusammenfassung

Documentation and Instruction Manual of the Eddy Covariance Software Package TK2 (2004)

Matthias Mauder Thomas Foken

no abstract

Freisetzung und Transport von polyzyklischen aromatischen Kohlenwasserstoffen aus / in kontaminiertem Bodenmaterial:Säulenversuche und Lysimeterstudie (2004)

Florian Storck

Polyzyklische aromatische Kohlenwasserstoffe (PAK) stellen ein besonderes Risiko für Mensch und Umwelt dar. Auf zahlreichen Flächen, vor allem ehemaligen Industriestandorten wie Gas- und Teerwerken, finden sich mit PAK kontaminierte Böden. Mit Hilfe von Säulen- und Lysimeterversuchen wird in dieser Arbeit der Einfluß der Temperatur sowie Fließgeschwindigkeit und Ionenstärke der Perkolationslösung auf die Freisetzung und den Transport von PAK unter wassergesättigten Bedingungen untersucht. Untersuchungsmaterial ist ein sandig-lehmiger Schluff, der mit Mineralöl und PAK belastet ist. In ihrem grundsätzlichen Aufbau entsprechen die Säulenversuche den Anforderungen der Vornorm prEN 14405 [CEN, 2002] und den Entwürfen DIN V 19736:2001-11 [DIN, 2001] sowie ISO/TC190WG6 [ISO, 2001]. Säulenexperimente wurden bei 15 und 25 °C mit zwei unterschiedlichen Fließgeschwindigkeiten und Flußunterbrechungen zur Identifizierung ratenlimierter Freisetzung durchgeführt. Um den Einfluß der Ionenstärke zu prüfen, wurde mit NaClO4-Lösung (0,02 mol/L, stellvertretend für eine Bodenlösung) und entsalztem Wasser (nach den Vorschriften der Normenentwürfe bzw. stellvertretend für Regenwasser) perkoliert. Die Lysimeterstudie stand unter natürlichem Temperaturregime des Versuchsortes Bayreuth. Von sonstigen atmosphärischen Einflüssen abgeschirmt, wurde das Lysimeter mit den gleichen Perkolationslösungen, die für die Säulenversuche Verwendung fanden, künstlich beregnet. Als bedeutsam für PAK-Transport und -Freisetzung erwies sich die Temperaturerhöhung um 10 °C. Bei hohen Fließgeschwindigkeiten stiegen die Konzentration im Eluat und die Quellstärke toxischer und cancerogener PAK um bis zu 500 % an. Damit erweist sich die in den Normentwürfen festgelegte Temperaturspanne für Säulenexperimente als zu groß. Noch weit stärker wirkt sich der Wechsel der Perkolationslösungen aus. Perkolation mit entsalztem Wasser führte bei hohen Fließgeschwindigkeiten, wie sie etwa bei Starkregenereignissen zu erwarten sind, zu einem Anstieg der Kolloidfreisetzung und der Eluatkonzentration und Quellstärke aller betrachteten PAK. Hervorzuheben ist hier die Zunahme von cancerogenem und für Wasserorganismen hochtoxischem BaPYR und Bbjk-FLA um den Faktor 400 bei hoher Fließgeschwindigkeit. Generell scheint sich mit höherer Fließgeschwindigkeit auch die Quellstärke zu erhöhen. Ergebnisse des Lysimeterversuches und der Säulenexperimente sprechen dafür, daß sich unter den gewählten experimentellen Bedingungen der PAK-Austrag fast ausschließlich auf Kolloide bzw. Partikel mit einem Durchmesser größer 0,7 Mikrometer beschränkt und DOC als Lösungsvermittler eine geringe Rolle spielt. Ratenlimitierte Freisetzung konnte in den Säulenexperimenten für DOC, nicht jedoch für PAK nachgewiesen werden.

Response to the „Comment on ’Geoarchaeological and chronometrical evidence …’ ” by J.C. Carracedo et al. (2004)

Ludwig Zöller Hans von Suchodoletz Henrik Blanchard Dominik Faust Ulrich Hambach

This paper is a reply to the comments made by Carracedo et al. (Quaternary Science Reviews 23, 2045-2049) to the original paper by Zöller, L., Suchodoletz, H.von & N. Küster (2003): Geoarchaeological and chronometrical evidence of early human occupation on Lanzarote (Canary Islands), Quaternary Science Reviews 22, 1299-1307. The reply copes with comments concerning chronometrical dating, the origin of investigated material and geomorphologic and geoarchaeologic problems.

Effects of land-use changes on the properties of a Nitisol and hydrological and biogeochemical processes in different forest ecosystems at Munesa, south-eastern Ethiopia (2004)

Yeshanew Ashagrie

The effects of conversion of natural forest into different exotic tree species plantations and crop cultivation were investigated at Munesa, south-eastern Ethiopia with the objectives of (i) determining changes on soil physical and chemical properties, (ii) quantifying water and nutrient fluxes under the different forest ecosystems, and (iii) assessing nutrient dynamics in water flowing through the soil under the different forest ecosystems. Soil samples were taken from the organic layer and at 0-20, 20-40, 40-70, 70-100 cm depths from the mineral soil. Rainfall and throughfall were collected using plastic funnels mounted 1 m above the ground. Soil solutions were collected with zero-tension (organic layer) and tension (mineral soil at the depth of 20, 50 and 100 cm) lysimeters. After 26 years of cultivation, surface (20 cm depth) soil structure was deteriorated and total soil organic carbon (SOC) and N contents both in bulk soil and water stable aggregates were significantly reduced. Below 21 years old Eucalyptus plantation no significant changes on the above mentioned parameters could be identified, but significant reductions in SOC, N and S concentrations associated with the sand and silt separates were evident. There were also significant reductions both in quality and quantity of particulate organic matter (POM) due to cultivation and only in quality of POM due to 21 years Eucalyptus plantation. The organic layer mass under 21 years old Pinus patula, 21 years old Eucalyptus globulus and third rotation Eucalyptus globulus (established 42 yr ago) decreased by 43%, 57% and 15%, respectively, relative to the natural forest. There were also significant reductions in the organic layer C and N stocks (9 to 60% and 25 to 68%, respectively), being highest under Pinus and lowest under third rotation Eucalyptus. In the mineral soil, to 1 m depth, there was a significant (P<0.05) reduction (16 to 20%) in SOC stock after conversion of natural forest into forest plantations. The N stocks under the 21 years old Pinus and third rotation Eucalyptus plantations were significantly reduced amounting 27 and 20% respectively, whereas 21 years old Eucalyptus had nearly an equivalent amount of N as that of the natural forest, probably due to a dense forest floor vegetation, fixing N. The changes in the organic layer and mineral soil S stocks after plantation establishment were not significant. Of the total annual rainfall (1190 mm) recorded during the monitoring period (October 2001 to September 2002), about 47% and 18% were intercepted by the canopies of Cupressus and the natural forest, and Eucalyptus, respectively. Total annual nutrients (Ca, Cl, K, Mg, Na, NH4–N, NO3–N, PO4–P, SO4–S ) deposition by rainfall was 12 kg ha–1yr–1. Throughfall K, Mg, Ca and Cl fluxes were enriched relative to rainfall, whereas Na, NO3–N, NH4–N, PO4–P and SO4–S were depleted. Total annual throughfall nutrient inputs (Ca, Cl, K, Mg, Na, NH4–N, NO3–N, PO4–P, SO4–S) were 14 kg ha–1yr–1 under Cupressus, 21 kg ha–1yr–1 under the natural forest and 24 kg ha–1yr–1 under Eucalyptus. Water passing through the different forest floors differed only in K, Mg and NO3–N concentrations, the latter two being higher under the natural forest and Eucalyptus plantation than Cupressus. Potassium was greater under Eucalyptus than the natural forest and Cupressus. Except for NH4–N in the natural forest, forest floor leachate nutrient concentrations were enriched in all forest types in relation to throughfall. Most nutrient fluxes to the mineral soil decreased in relation to throughfall fluxes, whereas NO3–N fluxes increased by over 50% in all forest types. At all soil depths, the concentrations of most nutrients in the mineral soil solution decreased relative to the concentrations in the forest floor leachate, but Mg, Na and NO3–N at all depths in Cupressus plantation and SO4–S and Na at some soil depths in the natural forest and Eucalyptus plantation had increased. The vertical trends in soil solution nutrient concentrations showed a decreasing trend with depth increments for most of the nutrients, but the concentrations of Cl and Na in all forest types and Ca, Mg and NO3–N in Cupressus increased with increasing soil depth. At 1 m soil depth, the concentrations of Ca, Mg and NO3–N in Cupressus, respectively, were 8, 7 and 23 times higher than in the natural forest and 3, 4 and 81 times higher than in Eucalyptus indicating losses by leaching. Generally, the results of this study emphasize the importance of forest type, species composition and management in affecting carbon and nutrient storage, water and nutrient fluxes and dynamics.

The use of 10Be surface exposure dating of erratic boulders in the reconstruction of the late Pleistocene glaciation history of mountainous regions, with examples from Nepal and Central Asia (2004)

Uwe Abramowski

Be-10 surface exposure dating (SED) of erratic boulders is an innovative approach in Quaternary geochronology. It proves to be an excellent tool for the reconstruction of the glacial history of mountainous regions, which is an important part of climate change research. In the course of this work, I have 1) installed the analytical procedure to extract in-situ produced Be-10 from quartz-bearing rock surface samples in the laboratory of the Institute of Soil Science and Soil Geography at the University of Bayreuth; 2) developed and calibrated the program TEBESEA for quick calculation of Be-10 surface exposure ages with fully propagated errors, thereby evaluating the existing procedures; 3) deduced a new interpretation scheme for exposure age distributions from several stratigraphically related moraines in an area; 4) provided 37 new Be-10 exposure ages for the Nepal Himalaya, complementing earlier soil geographic studies in the Langtang Valley and the Macha Khola Valley; and finally 5) provided 108 new Be-10 exposure ages for the Pamir, and the Alay- and Turkestan Ranges, defining a new glacial chronology for Central Asia. The analytical procedure used to extract Be-10 from quartz-bearing rocks and to prepare it for measurement closely followed the one established at the ETH Zurich, where all Be-10 measurements have been done. The accuracy of the analytical work in Bayreuth was confirmed by preparation of five calibration samples from the Koefels landslide, Oetz Valley, Austria. The traditional scaling system of Lal (1991) as modified by Stone (2000) still proves to be the most suitable one to be used in Be-10 exposure age calculations. For this procedure, I have calibrated a total standard production rate at sea level, high latitude of 5.35 ± 0.15 atoms/(g a), using a contribution of capture of slow negative muons of 1.2%, and including all possible corrections. The altitude dependency of Be-10 production used in the scaling systems of Dunai (2001) and Desilets & Zreda (2003) is as yet not convincing, given the existing calibration data, but suggests that ages calculated for sites above 2000-3000 m a.s.l. in High Asia may be overestimates. Detailed error propagation shows that the uncertainties of Be-10 surface exposure ages at present are dominated by the errors of the scaling factor, the erosion rate, and the tectonic uplift rate. As long as surface erosion and tectonic uplift rates cannot be constrained to within 10%, however, exposure ages older than 30-40 ka have uncertainties of 20% or more and can be no more than rough approximations. For exposure age distributions from a set of stratigraphically related moraines, a new interpretation scheme is presented, which is able to detect ages older than the deposition age of the moraine (Be-10 inheritance), and to interpret age clusters younger than the deposition age, which may be synchronous on several moraines (phases of regionally enhanced surface activity). In the Nepal Himalaya, glacier advances in the Macha Khola Valley have occurred 70-100, 20-23, 11-12 and around 3 cal. ka B.P. Glacier advances in the Langtang Valley are dated to 14-15, 8-9 and ~3.5 cal. ka B.P. Late Pleistocene and Holocene glacial activity in the Nepal Himalaya seems to be controlled by the Indian monsoon rather than the westerly circulation. Only in the MIS 2, the westerly jetstream appears to have shifted as far south as to affect glaciation all over the Himalaya. During the Younger Dryas, the eastern limit of the influence of the westerly circulation on Himalaya glaciation may have been situated between the Manaslu and Langtang Himal. Glacial advances in the Pamir and in the Alay and Turkestan Ranges have occurred >93->136, ~60-80, (40-55), ~27-25, ~22-20, ~18, ~15.5, ~14.3, and 10.5 cal. ka B.P. The most extensive late Pleistocene glaciation occurred during the MIS 5-3, and is characterized by ELA depressions of ~370-380 m in the eastern Pamir, as well as 600 m and >750 m, in the Alay and Turkestan Ranges, respectively. Late Pleistocene glacier advances in northwestern High Asia, were triggered by climatic cold phases rather than by monsoonal maxima. Climate in the region seems to have been mostly under the influence of the westerly circulation and the Siberian anticyclone. Asynchrony of Central Asian and western hemisphere glacier advances is due to increasing aridity in Central Asia in the course of the last glacial cycle. High altitude glaciers seem to have reached their maximum extent earlier (MIS 5-4) than low altitude glaciers (first half of MIS 3). Some indirect monsoonal influence in the eastern Pamir may be responsible for the existence of some of the lateglacial moraine stages in this area.

Aerob-thermophile Reinigung mineralölkontaminierter Abwässer (2004)

Alexandra Oberthür

Unter aeroben Bedingungen ist der thermophile Mikroorganismus Geobacillus thermoleovorans im Labor- und Pilotmaßstab fähig, verschiedene mit Mineralölen kontaminierte Abwässer als einzige Kohlenstoffquelle zu nutzen. Die Verwertbarkeit eines synthetischen Dieselöls sowie eines Kühlschmierstoffs standardisierter Zusammensetzung durch die Kultur wurde untersucht. Des Weiteren wurden Kühlschmieremulsionen aus Kfz-Produktionsstätten und Spüllösungen zum Reinigen von Lackleitungen auf deren biologische Abbaubarkeit hin geprüft. Der Nachweis von Metaboliten erfolgte an einem GC-FID-System (Gaschromatograph mit Flammenionisationsdetektor). Im Vergleich zum Standardsubstrat Olivenöl wurden ähnliche, in Einzelfällen sogar höhere Wachstumsraten und Zelldichten erzielt. Hierbei wurde nachgewiesen, dass die Initialisierung der Lipaseexpression durch Triglyceride Voraussetzung für den effizienten Abbau von Mineralölkohlenwasserstoffen (MKW) durch Geobacillus thermoleovorans ist. Da MKW in der Praxis nahezu ausschließlich in Verbindung mit einer Vielzahl von Additiven gebraucht werden, wurde der Einfluss verschiedener Zusatzstoffe auf die Mikroorganismen erforscht. Als Kohlenstoffquelle diente das synthetische Dieselöl, als Zusatzstoffe wurden insbesondere Tenside, Flockungsmittel, Komplexbildner und Entschäumer verwendet. Es zeigte sich, dass alle eingesetzten anionischen Tenside (Natrimlaurylsulfat = SDS, Natriumlaurylbenzolsulfonat = SDBS) und nichtionischen Tenside (Tergitol NPX, Triton X 100) in Konzentrationen unterhalb der kritischen Mizellenbildungskonzentration (CMC, engl. Critical Micelle Concentration) nachweislich das Wachstum der Kultur durch die Verbesserung der Substrat-Bioverfügbarkeit stimulieren. Oberhalb der CMC fördern anionische Tenside das Wachstum der Kultur; nichtionische Tenside wirken mit ansteigender Konzentration zunehmend inhibierend. Triton X 100 unterdrückt in Konzentrationen oberhalb der CMC die extrazelluläre Lipaseaktivität vollständig. Positive und negative Effekte auf das Wachstumsverhalten der Kultur sind gleichermaßen das Resultat von Tensid-Membran-Interaktionen. Durch Einlagerung in die Zellmembranen erhöhen die Tenside die Permeabilität der Membranen für Enzyme, was wiederum zu einer Beschleunigung des MKW-Abbaus führt. Der inhibierende Einfluss von Triton X 100 hingegen kann auf die Konformation des Tensids zurückgeführt werden, die entweder die Ausscheidung von Enzymen behindert oder Zellmembran oder Enzyme direkt schädigt. Die experimentell ermittelten CMC im aerob-thermophilen System betrugen 50 mg/L für SDS und SDBS, 90 mg/L für Tergitol NPX® und 108 mg/L für Triton X 100. Darüber hinaus wurde nachgewiesen, dass SDBS in Anwesenheit von MKW metabolisiert wird. In Abwesenheit anderer Kohlenstoffquellen kann auch SDS von Geobacillus thermoleovorans verwertet werden. Ein Abbau nichtionischer Tenside wurde hingegen nicht beobachtet. Die Anwesenheit nichtionischer Tenside ist daher, wie nach der Durchführung einer Diskriminanzanalyse bestätigt wurde, das wichtigste Entscheidungskriterium bzgl. der Anwendbarkeit des Verfahrens zur Reinigung bislang nicht experimentell untersuchter MKW-haltiger Abwässer. Basierend auf den versuchsbegleitend erhobenen Wachstumsparametern wurde ein Vorhersagemodell zur Übertragbarkeit des aerob-thermophilen Verfahrens entwickelt. Geobacillus thermoleovorans weist eine hohe Resistenz gegenüber Bioziden, Schwermetallen und weiteren in Reinigungs- und Schmiermitteln eingesetzten Zusatzstoffen auf. Erst in Konzentrationen ab 1.500 mg/L bewirkt Antimon(III)oxid eine Inhibierung des Wachstums. Eine Anreicherung der genannten Substanzen im Abstrom der Anlage ist daher zu erwarten. Weiterer Forschungsbedarf besteht hinsichtlich der Aufklärung der Metabolisierungspfade von Geobacillus thermoleovorans in Bezug auf (Poly-)Ether und Biozide. Bei der weiteren Verfahrensoptimierung ist insbesondere die Reduktion des Energiebedarfs der Anlage anzustreben. Darüber hinaus empfiehlt sich der Einsatz des Verfahrens in (sub)tropischen Ländern sowie die Ausnutzung von Prozesswärme. Die Entsorgung metallbelasteter Schlämme und anderer nicht abbaubarer Feststoffe ist sicher zu stellen. Bei der Behandlung von Kühlschmierstoffen und ähnlich hoch CSB-belasteten Abwässern (CSB: Chemischer Sauerstoffbedarf) ist die Bereitstellung von Verdünnungswasser notwendig, da eine Raumlast von 13 kg CSB/m -3 d -3 die Belastungsobergrenze für das Verfahren darstellt. Aufgrund der hohen Prozess-Stabilität, der kurzen Anlaufzeiten, der hohen Wachstumsraten und der einfachen Betreuung ist das Verfahren sehr flexibel und vielfältig einsetzbar. Eine weitere Vertiefung dieses innovativen Ansatzes in der Abwasserreinigung ist von daher wünschenswert.

Adoption of footprint methods for the quality control of eddy-covariance measurements (2004)

Mathias Göckede

Footprint models determine the spatial context of a measurement by defining a transfer function between sources or sinks of the signal and the sensor position. The resulting source area provides an important quality control tool to improve the interpretation of micrometeorological data sets. However, to date no approaches have been presented in the literature that provide a standardised footprint-based methodology that allows observers to include terrain characteristics into quality assessment and quality control strategies. One problem in this context is the small number of studies that concentrate on the validation of footprint models under the non-ideal conditions in which they are frequently being used. Therefore, for many applications, the accuracy of the source areas computed by the footprint models cannot be evaluated. To further increase the acceptance of footprint-based studies, a stronger focus on footprint validation studies for a wide variety of experimental designs is needed. This dissertation focuses on the development of a footprint-based evaluation tool for complex measurement sites that allows the combination of quality assessment results for micrometeorological measurements with characteristics of the surrounding terrain. The standardised method is easy-to-use in order to encourage its application on a large number of sites. To improve the interpretation of the obtained results, a second objective of this thesis was to develop and test approaches to validation experiments for footprint models. Göckede et al. (2004) presented an approach for the evaluation of micrometeorological measurement sites in complex terrain, which combined a method for quality assessment of eddy-covariance measurements with an analytic footprint model. Their software package provided micrometeorologists a practical tool for determining the average flux contributions from the land use type intended to observe at a specific site, or to identify footprint areas for which a high data quality could be assumed. Rebmann et al. (2005) proved the efficiency of this evaluation approach for extensive studies on a large number of sites organised in a network. Their results may serve as a tool for an improved determination of yearly sums of the net ecosystem exchange, because fluxes originating from sectors of minor quality could be excluded from the analysis. Because of these important contributions to quality control, Foken et al. (2004) integrated the site evaluation approach into a comprehensive survey on micrometeorological post-field data quality control techniques. The experiences obtained during the extensive study by Rebmann et al. (2005) allowed us identification of the major weak points of the approach, which we were able to improve in subsequent studies. Using remote sensing methods Reithmaier et al. (2005) studied the influence of the characteristics of the land use maps and different roughness length assignment schemes on the performance of the site evaluation approach. Finally, Göckede et al. (2005a) developed an updated version of the site evaluation approach, which improved the basic method by replacing the analytic footprint model with a Lagrangian stochastic footprint model that is more suitable for studies above high vegetation, and by applying a more sophisticated microscale flux aggregation method for the determination of areally-averaged roughness lengths. Although the implemented models are far more sophisticated than in the original version, the approach by Göckede et al. (2005a) still permits a practical application that allows for comparative studies of a large number of sites. With respect to the development of validation methods for footprint models using natural tracer measurements from field scale experiments, Göckede et al. (2005b) presented two different experimental approaches. Firstly, a comparison of measured flux differences and modelled land use differences for pairs of measurement positions revealed general correlations between measurement data and model results. Secondly, Göckede et al. (2005b) tested a correlation analysis between measured and modelled parameters using reference measurements and footprint results. This approach resulted in an objective quantitative evaluation of the accuracy of the footprint model. The study by Reth et al. (2005) could not be employed for footprint validation purposes because of a large systemic scatter between these measurement systems. Overall, both the paper by Göckede et al. (2005b) and by Reth et al. (2005) provided successful methods to testing the suitability of natural tracer experiments in the validation of footprint models. Although experimental deficits prevented the working out of significant differences between the results of the employed footprint models, their studies developed an improved design for natural tracer experiments that are especially designed for footprint validation purposes.

A macroscopic and microscopic investigation of the magnesite – otavite solid soluition (2004)

Fiona Bromiley

The magnesite (MgCO3) – calcite (CaCO3) system is the most geologically important of the carbonate minerals. At intermediate compositions a distinct ordered phase exists, dolomite [MgCa(CO3)2], which has symmetry. A complete, disordered ( c symmetry) solid solution exists, but at temperatures in excess of 1400°C. Unmixing and ordering processes that occur at high temperatures in the magnesite – calcite system make experimental work difficult. However, the use of an analogue system allows syntheses under more accessible experimental conditions. The effects of cation substitution and ordering in the magnesite (MgCO3) – otavite (CdCO3) solid solution have, therefore, been investigated using X-ray powder diffraction and Hard Mode Infrared Spectroscopy (HMIS). The results from Rietveld refinements of the X-ray powder diffraction data show that the variation of the a-axis is linear as a function of composition and is not affected by different degrees of order at intermediate compositions. However, the c-axis shows a positive deviation from linearity as a function of composition for the 800°C series. The observed deviation decreases with increasing degree of order for samples of composition Mg0.5Cd0.5CO3. Oxygen-carbon-oxygen bond angles for samples with symmetry showed a decrease in bond angle from 120° (constrained by symmetry in samples with the c structure) with increase in degree of order. Site occupancies were used to determine the long-range order parameter, Q, for samples with symmetry. The square of the order parameter varies linearly as a function of temperature, suggesting a second-order phase transition, and a critical transition temperature of Tc = 719°C. Intensity ratios between reflections present only in the low symmetry phase and reflections present in both the low and high symmetry phases can be used to determine a value proportional to the square of the long-range order parameter, Q. Intensity ratios, between the (101) and (202) reflections for samples of composition Mg0.5Cd0.5CO3, were determined from X-ray powder diffraction patterns and show a linear variation as a function of temperature, with a critical transition temperature, Tc = 716°C. The local mixing and ordering behaviour of the magnesite – otavite solid soluition has been characterised using infrared powder absorption spectroscopy. Phonon bands due to cadmium-oxygen translations, and magnesium-oxygen translations were both observed in the IR spectra for samples of intermediate composition. Band positions for cadmium-oxygen translations remained constant as a function of composition, whereas band positions for magnesium-oxygen translations showed a decrease in wavenumber as a function of composition. Vibrational bands in other spectral regions (libration and translation of carbonate groups and doubly degenetrate in-plane bending and out-of-plane bending of carbonate groups) vary linearly as a function of composition and no effect of order on band position is observed. At high frequencies the samples with c symmetry (800°C series) show a linear shift in band position as a function of composition, whereas, samples in the cadmium dolomite stability field, with symmetry, show a marked increase in frequency compared to their c symmetry counterparts. Cation substitution, or disordering causes broadening of IR vibrational bands for a given material. In this study an alternative method was used, which makes use of the autocorrelation function to establish average line widths for six spectral regions. The autocorrelation results, delta corr, can be interpreted in terms of local strain fields present in the structure due to cation substitution and disordering. In the low frequency region, the delta corr values show a positive deviation from linearity as a function of composition. For samples of composition Mg0.5Cd0.5CO3 the delta corr values are virtually all the same, independent of the degree of order. Over all the spectral regions, the addition of 10mol% MgCO3 (1 Mg atom every 2 unit cells) to the otavite results in a large increase in line width. It is, therefore, suggested that the strain fields surrounding the substituting magnesium atoms into the otavite structure are on the order of 30Å. In the low MIR and at a composition of Mg0.5Cd0.5CO3, an effect of order is observed as a reduction in delta corr values with respect to the sample with c symmetry. The difference in delta corr values between the ordered and disordered samples was used to determine the local-order parameter, q, which scales linearly with the long-range order parameter, Q.

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