Thermogravimetric Analysis of Carbonate Aggregate, HR-336, 1994

Research has shown that one of the major contributing factors in early joint deterioration of portland cement concrete (PCC) pavement is the quality of the coarse aggregate. Conventional physical and freeze/thaw tests are slow and not satisfactory in evaluating aggregate quality. In the last ten years the Iowa DOT has been evaluating X-ray analysis and other new technologies to predict aggregate durability in PCC pavement. The objective of this research is to evaluate thermogravimetric analysis (TGA) of carbonate aggregate. The TGA testing has been conducted with a TA 2950 Thermogravimetric Analyzer. The equipment is controlled by an IBM compatible computer. A "TA Hi-RES" (trademark) software package allows for rapid testing while retaining high resolution. The carbon dioxide is driven off the dolomite fraction between 705 deg C and 745 deg C and off the calcite fraction between 905 deg C and 940 deg C. The graphical plot of the temperature and weight loss using the same sample size and test procedure demonstrates that the test is very accurate and repeatable. A substantial number of both dolomites and limestones (calcites) have been subjected to TGA testing. The slopes of the weight loss plot prior to the dolomite and calcite transitions does correlate with field performance. The noncarbonate fraction, which correlates to the acid insolubles, can be determined by TGA for most calcites and some dolomites. TGA has provided information that can be used to help predict the quality of carbonate aggregate.

Compositional and Mechanical Properties of Carbonate Rocks, HR-110, 1967

The research project, HR-110, was begun in the fall of 1964 to further investigate the compositional and mechanical properties of some of the carbonate rocks used as aggregate in portland cement concrete. Samples were taken only from those portions of the quarries that are used as aggregate in portland cement concrete by the Iowa State Highway Commission except where designated by commission personnel for purposes of evaluation of potential aggregate sources. Where practical, the samples were taken from each bed recognized by the Highway Commission geologists, and in most instances, the thicker beds were sampled at the top, middle, and bottom to detect any lithologic changes that escaped megascopic observation.

Behavior of Carbonate Rocks as Concrete Aggregates, HR-15, 1962

The problem of determining the suitability of carbonate rocks as concrete aggregates is extremely complex and calls for more new data than has been available or obtainable from usual methods. Since 1955 the approach which has served as a primary basis for the project has been to gather as much new information as possible to apply to the problem. New information obtained by new and different techniques provides better understanding. This approach was decided on since, in all prior studies, a standard petrographic and petrologic approach correlated in many instances with standard engineering tests did not provide the answer in Iowa or elsewhere. One can theorize that concrete fails (excluding external causes such as traffic, foundation failure, etc.) because of stresses of internal origin. The stresses can be of a physical nature, such as frost action, or result from chemical activity such as the alkali aggregate reaction. If, as service records show, the aggregate is considered the cause of distress in concrete, it will without doubt be the manner in which an aggregate can create or contribute to stress of internal origin by physical or chemical means. Therefore the main emphasis was placed on studying physical and chemical properties of aggregates as well as the behavior of carbonate rocks in concrete environments. Although standard geologic and engineering methods were also utilized, the approach adopted required considerable effort in devising new techniques and methods. This report is intended to be a detailed summary of the research performed. Whenever possible, the work accomplished will be summarized and all pertinent data will be included. For further details, reference to the various theses and publications transmitted with this report or at previous times will be made wherever possible.

Compositional and Mechanical Properties of Carbonate Rocks, Progress Report, HR-110, 1965

This report briefly describes the progress of HR-110 of the Iowa Highway Research Board.

Origin of CO2 and carbonate veins in mantle-derived xenoliths in the Pannonian Basin

The origin and evolution of CO2 inclusions and calcite veins in peridotite xenoliths of the Pannonian Basin, Hungary, were investigated by means of petrographic investigation and stable isotope analyses. The fluid inclusions recovered in paragenetic olivine and clinopyroxene belong to distinct populations: type A (texturally early) inclusions with regular shapes (often with negative crystal forms) forming intragranular trails, type B (texturally late) inclusions defining randomly oriented trails that reach grain boundaries Type B inclusions are often associated with silicate melt (type C) inclusions Stable carbon isotope compositions in inclusion-hosted CO2 were obtained by vacuum crushing followed by conventional dual inlet as well as continuous flow mass spectrometry in order to eliminate possible lab artifacts. Olivines, clino- and orthopyroxenes of the host peridotite have oxygen isotope compositions from 5.3 to 6.0 parts per thousand (relative to V-SMOW). without any relationship with xenolith texture. Some of the xenoliths contained calcite in various forms veins and infillings in silicate globules in veins, secondary carbonate veins filling cracks and metasomatic veins with diffuse margins The former two carbonate types have delta C-13 values around -13 parts per thousand (relative to V-PDB) and low Sr contents (<05 wt %), whereas the third type,veins with high-temperature metasomatic features have a delta C-13 value of -5 0 parts per thousand and high Sr contents up to 34 wt.% In spite of the mantle-like delta C-13 value and the unusually high Sr content typical for mantle-derived carbonate, trace element compositions have proven a crustal origin. This observation supports the conclusions of earlier studies that the carbonate melt droplets found on peridotite xenoliths in the alkaline basalts represent mobilized sedimentary carbonate. The large delta C-13 range and the C-12-enrichment in the carbonates can be attributed to devolanlization of the migrating carbonate or infiltration of surficial fluids containing C-12-rich dissolved carbon Carbon isotope compositions of inclusion-hosted CO2 range from -17 8 to -4.8 parts per thousand (relative to V-PDB) with no relation to the amount of CO2 released by vacuum crushing. Low-delta C-13 values measured by stepwise heating under vacuum suggest that the carbon component is pristine and not related to surficial contamination, and that primary mantle fluids with delta C-13 values around -5 parts per thousand were at least partly preserved in the xenoliths Tectonic reworking and heating by the basaltic magma resulted in partial CO2 release and local C-13-depletion. (C) 2010 Elsevier B V All rights reserved

The lower Triassic anachronistic carbonate facies in space and time

The end-Permian mass extinction greatly affected the sedimentary record, but the sedimentary response was not limited to the Permian-Triassic boundary interval. This transformation extended to sedimentation that spanned the entire Early Triassic. Calcimicrobialites play an important role throughout this time interval, and at least four main events of anomalous carbonate deposition can be shown. A post-extinction calcimicrobial unit occurs above the extensive Permian skeletal carbonate platform exposed in the Taurus Mountains (southern Turkey), in south Armenia, north-west north and Central Iran along the Zagros Mountains. The calcimicrobial unit formed during the flooding of the platform that took place during the earliest Triassic. A similar calcimicrobialite formed during late Griesbachian to Dienerian time atop the shallow Permian skeletal carbonate platform largely exposed in south China. A third event occurred during the Early Olenekian on the first Mesozoic isolated pelagic plateau (Baid seamount, Oman Mountains). Here the change in carbonate sedimentation is reflected in the occurrence of thrombolites and carbonate seafloor fans. Near the end of Early Triassic time, unusual carbonate deposition is recorded both on an isolated pelagic plateau of the Western Tethys (Halstatt limestone of Dobrogea, Romania) and on the eastern Panthalassa margin of the western United States. In the western United States, the event is represented by stromatolites and thrombolites in the Virgin Limestone of the Moenkopi Formation and by seafloor fans in the middle and upper members of the Union Wash Formation. These unusual episodes of anomalous carbonate deposition illustrate a fundamental change in sedimentation that occurred in the aftermath of the end-Permian mass extinction.

Relationship of Carbonate Aggregates to Concrete Aging, HR-116, 1967

HR-116 is concerned with the relationship of carbonate aggregate to aging of highway concrete. The ultimate purpose of the research is to provide the Materials Department with better criteria for selection of carbonate aggregates for use in highway concrete. The research stems from the problem in Iowa which relates durability of highway concrete to use of certain aggregates. Service records of certain highways have shown that concrete deterioration is related to the source of coarse carbonate aggregate. Research on this problem in projects HR-15 and HR-86 helped define three broad areas of the problem in more detail: 1. The problem of evaluation of rocks which pass current specifications but have poor service records 2. The basic problem of how rocks contribute to distress in concrete 3. The problem of how concrete ages or weathers.

Investigation of Rapid Thermal Analysis Procedures for Prediction of the Service Life of PCCP Carbonate Coarse Aggregate, HR-337, 1993

The major objective of this research project was to use thermal analysis techniques in conjunction with x-ray analysis methods to identify and explain chemical reactions that promote aggregate related deterioration in portland cement concrete. Twenty-two different carbonate aggregate samples were subjected to a chemical testing scheme that included: • bulk chemistry (major, minor and selected trace elements) • bulk mineralogy (minor phases concentrated by acid extraction) • solid-solution in the major carbonate phases • crystallite size determinations for the major carbonate phases • a salt treatment study to evaluate the impact of deicer salts Test results from these different studies were then compared to information that had been obtained using thermogravimetric analysis techniques. Since many of the limestones and dolomites that were used in the study had extensive field service records it was possible to correlate many of the variables with service life. The results of this study have indicated that thermogravimetric analysis can play an important role in categorizing carbonate aggregates. In fact, with modern automated thermal analysis systems it should be possible to utilize such methods on a quality control basis. Strong correlations were found between several of the variables that were monitored in this study. In fact, several of the variables exhibited significant correlations to concrete service life. When the full data set was utilized (n = 18), the significant correlations to service life can be summarized as follows ( a = 5% level): • Correlation coefficient, r, = -0.73 for premature TG loss versus service life. • Correlation coefficient, r, = 0.74 for relative crystallite size versus service life. • Correlation coefficient, r, = 0.53 for ASTM C666 durability factor versus service life. • Correlation coefficient, r, = -0.52 for acid-insoluble residue versus service life. Separation of the carbonate aggregates into their mineralogical categories (i.e., calcites and dolomites) tended to increase the correlation coefficients for some specific variables (r sometimes approached 0.90); however, the reliability of such correlations was questionable because of the small number of samples that were present in this study.

Carbonate Rock Pore Size Distribution Determination through Iowa Pore Index Testing, MLR-15-01, 2015

The Iowa Pore Index (IPI) measures the pore system of carbonate (limestone and dolomite) rocks using pressurized water to infiltrate the pore system. This technique provides quantitative results for the primary and capillary (secondary) pores in carbonate rocks. These results are used in conjunction with chemical and mineralogical test results to calculate a quality number, which is used as a predictor of aggregate performance in Portland cement concrete (PCC) leading to the durability classification of the aggregate. This study had two main objectives: to determine the effect different aggregate size has on IPI test results and to establish the precision of IPI test and test apparatus. It was found that smaller aggregate size fractions could be correlated to the standard 1/2”-3/4” size sample. Generally, a particle size decrease was accompanied by a slight decrease in IPI values. The IPI testing also showed fairly good agreement of the secondary pore index number between the 1/2”-3/4”and the 3/8”-1/2” fraction. The #4-3/8” showed a greater difference of the secondary number from the 1/2”-3/4” fraction. The precision of the IPI test was established as a standard deviation (Sr) of 2.85 (Primary) and 0.87 (Secondary) with a repeatability limit (%r) of 8.5% and 14.9% for the primary and secondary values, respectively.

Organic geochemistry of Jurassic-Cretaceous source rocks and oil seeps from the profile across the Adriatic-Dinaric carbonate platform

Organic geochemical and stable isotope investigations were performed to provide an insight into the depositional environments, origin and maturity of the organic matter in Jurassic and Cretaceous formations of the External Dinarides. A correlation is made among various parameters acquired from Rock-Eval, gas chromatography-mass spectrometry data and isotope analysis of carbonates and kerogen. Three groups of samples were analysed. The first group includes source rocks derived from Lower Jurassic limestone and Upper Jurassic ``Leme'' beds, the second from Upper Cretaceous carbonates, while the third group comprises oil seeps genetically connected with Upper Cretaceous source rocks. The carbon and oxygen isotopic ratios of all the carbonates display marine isotopic composition. Rock-Eval data and maturity parameter values derived from biomarkers define the organic matter of the Upper Cretaceous carbonates as Type I-S and Type II-S kerogen at the low stage of maturity up to entering the oil-generating window. Lower and Upper Jurassic source rocks contain early mature Type III mixed with Type IV organic matter. All Jurassic and Cretaceous potential source rock extracts show similarity in triterpane and sterane distribution. The hopane and sterane distribution pattern of the studied oil seeps correspond to those from Cretaceous source rocks. The difference between Cretaceous oil seeps and potential source rock extracts was found in the intensity and distribution of n-alkanes, as well as in the abundance of asphaltenes which is connected to their biodegradation stage. In the Jurassic and Cretaceous potential source rock samples a mixture of aromatic hydrocarbons with their alkyl derivatives were indicated, whereas in the oil seep samples extracts only asphaltenes were observed.

Genesis of the Jurassic carbonate-hosted Pb-Zn deposits of Jebel Ressas (North-eastern Tunisia): Evidence from mineralogy, petrography and trace metal contents and isotope (O, C, S, Pb) geochemistry

The Jebel Ressas Pb-Zn deposits in North-Eastern Tunisia occur mainly as open-space fillings (lodes, tectonic breccia cements) in bioclastic limestones of the Upper Jurassic Ressas Formation and along the contact of this formation with Triassic rocks. The galena-sphalerite association and their alteration products (cerussite, hemimorphite, hydrozincite) are set within a calcite gangue. The Triassic rocks exhibit enrichments in trace metals, namely Pb, Co and Cd enrichment in clays and Pb, Zn, Cd, Co and Cr enrichment in carbonates, suggesting that the Triassic rocks have interacted with the ore-bearing fluids associated with the Jebel Ressas Pb-Zn deposits. The delta(18)O content of calcite associated with the Pb-Zn mineralization suggests that it is likely to have precipitated from a fluid that was in equilibrium with the Triassic dolostones. The delta(34)S values in galenas from the Pb-Zn deposits range from -1.5 to +11.4%, with an average of 5.9% and standard deviation of 3.9%. These data imply mixing of thermochemically-reduced heavy sulfur carried in geothermal- and fault-stress-driven deep-seated source fluid with bacterially-reduced light sulfur carried in topography-driven meteoric fluid. Lead isotope ratios in galenas from the Pb-Zn deposits are homogenous and indicate a single upper crustal source of base-metals for these deposits. Synthesis of the geochemical data with geological data suggests that the base-metal mineralization at Jebel Ressas was formed during the Serravallian-Tortonian (or Middle-Late Miocene) Alpine compressional tectonics.

Detection and characterization of hydraulically active fractures in a carbonate aquifer: Results from self-potential, temperature and fluid conductivity logging along a 260-m-deep borehole in the Combioula hydrothermal system in the southwestern Swiss Alps

A geophysical and geochemical study has been conducted in a fractured carbonate aquifer located at Combioula in the southwestern Swiss Alps with the objective to detect and characterize hydraulically active fractures along a 260-m-deep borehole. Hydrochemical analyses, borehole diameter, temperature and fluid electrical conductivity logging data were integrated in order to relate electrokinetic self-potential signals to groundwater flow inside the fracture network. The results show a generally good, albeit locally variable correlation of variations of the self-potential signals with variations in temperature, fluid electrical conductivity and borehole diameter. Together with the hydrochemical evidence, which was found to be critical for the interpretation of the self-potential data, these measurements not only made it possible to detect the hydraulically active fractures but also to characterize them as zones of fluid gain or fluid loss. The results complement the available information from the corresponding litholog and illustrate the potential of electrokinetic self-potential signals in conjunction with temperature, fluid electrical conductivity and hydrochemical analyses for the characterization of fractured aquifers, and thus may offer a perspective for an effective quantitative characterization of this increasingly important class of aquifers and geothermal reservoirs.

Investigation of Rapid Thermal Analysis Procedures for Prediction of the Service Life of PCCP Carbonate Coarse Aggregate: Phase I, Progress Report, HR-337, 1992

The major objective of this research project is to utilize thermal analysis techniques in conjunction with x-ray analysis methods to identify and explain chemical reactions that promote aggregate related deterioration in Portland cement concrete. The first year of this project has been spent obtaining and analyzing limestone and dolomite samples that exhibit a wide range of field service performance. Most of the samples chosen for the study also had laboratory durability test information (ASTM C 666, method B) that was readily available. Preliminary test results indicate that a strong relationship exists between the average crystallite size of the limestone (calcite) specimens and their apparent decomposition temperatures as measured by thermogravimetric analysis. Also, premature weight loss in the thermogravimetric analysis tests appeared to be related to the apparent decomposition temperature of the various calcite test specimens.