Tesis sobre el tema "Carbonate weathering"

This study is the geochemical examination of mineral weathering and its path from hinterland, through sediment deposition and pedogenesis, to its dissolution and eventual uptake into plants or precipitation as carbonate minerals. The three papers examine the rate and character of carbonate and silicate mineral weathering over a wide range of climatic and tectonic regimes, time periods, and lithologies, and focus on very different questions. Examination of the 87Sr/86Sr ratios of architectural ponderosa pine in Chaco Canyon, New Mexico confirms a societally complex style of timber procurement from the 10th to the 12th centuries. In El Malpais National Monument, New Mexico, we measured the 87Sr/86Sr ratios in local bedrock and soils and compared them to the leaf/wood cellulose of four conifers (Pinus ponderosa, Pinus edulis, Juniperus monosperma, Juniperus scopulorum), a deciduous tree (Populus tremuloides), three shrubs (Chrysothamus nauseosus, Fallugia paradoxa, Rhus trilobata), and an annual grass (Bouteloua gracilis) and a lichen (Xanthoparmelia lineola). We found that plant 87Sr/86Sr ratios covaried with variations in plant physiognomy, life history, and rooting depth. In addition, the proportion of atmospheric dust and bedrock mineral contributions to soil water 87Sr/86Sr ratios varied predictably with landscape age and bedrock lithology. On the Himalayan floodplain, soils and paleosol silicate weathering intensities were measured along a climatic transect and through time. Overall, carbonate weathering dominates floodplain weathering. But, periods of more intense silicate weathering between 9 - 2 Ma, identified in soil profile and in the 87Sr/86Sr ratios of pedogenic carbonates, appear to be driven by changes in tectonic, rather than climatic, regime. All three papers are good examples of how 87Sr/86Sr isotopic tracer studies can shed light on pedogenic formation rates and internal processes. The complexity of each system warns against generalizations based on just one locale, one species or lithology, or a few isotopic ratios.

L'altération des lithologies himalayennes a potentiellement impacté le cycle global du carbone. Pour pouvoir contraindre et comprendre les processus qui se sont produits dans l'Himalaya et qui ont affecté ces cycles, nous devons être distinguer les signatures de l'altération du silicate et du carbonate dans la charge dissoute des fleuves de l'Himalaya. Des études antérieures ont tenté de le faire en utilisant diverses méthodes mais il n’existe toujours pas de consensus clair sur l’ampleur et le flux de l’altération du silicate dans l’Himalaya. Cette thèse propose l'utilisation du 40Ca comme traceur pouvant améliorer la quantification du flux d'altération du silicate et du carbonate dans la charge dissoute des rivières himalayennes. Des travaux antérieurs ont montré que le budget de l'eau de mer 40Ca est dominé par une source de manteau, de sorte que les carbonates marins ont une signature homogène de 40Ca indiscernable par rapport à la valeur du manteau. En revanche, la croûte supérieure de silicate devrait avoir développé une composition radiogénique. La différence entre la signature en Ca radiogénique des lithologies de carbonate et de silicate peut donc être utilisée pour différencier l’altération du carbonate et du silicate dans la charge dissoute des rivières. Nous présentons ici une étude géochimique comprenant des analyses de Ca radiogénique des rivières drainant les principales unités lithologiques de l'Himalaya, ainsi que des résultats provenant de sédiments, de substrat rocheux, de sol et de gravier. Nos résultats montrent que les carbonates de l’Himalaya ne présentent pas d’excès de 40Ca radiogénique malgré des signatures très variables 87Sr/86Sr, alors que les sédiments sont radiogènes (+0.9 à +4). Ceci suggère que pour Ca, contrairement à Sr, l'échange isotopique entre les lithologies silicate et carbonate a été minime. La composition en Ca radiogène de l'eau des rivières va de +0.1 dans les captages à prédominance carbonatée à +11 dans les rivières drainant des bassins versants silicatés. Pour les grandes rivières, les estimations du budget relatives à l’altération du silicate et du carbonate sur la base des éléments principaux et la composition en Ca radiogénique tendent à concorder. Cependant, pour certaines rivières plus petites, en particulier celles drainant des bassins à dominance silicatée dans les formations cristallines de HHC et du LH, certaines divergences sont observées. Celles-ci ne peuvent pas être attribuées à une définition imprécise de la composition chimique ou radiogénique en Ca des pôles de mélange utilisés pour la modélisation budgétaire, car les valeurs requises pour résoudre le modèle ne sont pas raisonnables. Ils ne peuvent pas non plus être expliqués par la précipitation de carbonates secondaires dans les rivières car la composition non radiogénique de carbonates suggère que ce processus n'est que mineur. Au contraire, ces différences peuvent être dues à la dissolution des traces de calcite radiogénique contenues dans les lithologies de silicate HHC et LH. Le vieillissement de ce matériau, qui ne représente qu'une infime partie de la surface du captage du silicate, pourrait produire une proportion substantielle du Ca radiogénique et pourrait ainsi avoir une influence significative sur le calcul des budgets de ces bassins à partir des données isotopiques. Néanmoins, comme cet effet est observé principalement dans les bassins à faible taux d’érosion des silicates, son influence sur les estimations du flux global de vieillissement du silicate sera mineure. Plus généralement, les résultats de cette thèse impliquent que le système 40Ca permet une résolution de problématiques qui ne peuvent pas être approfondies avec succès à l'aide d'isotopes Sr dans l'Himalaya. Des travaux supplémentaires sont nécessaires pour définir la gamme complète des compositions de Ca radiogénique dans l’Himalaya afin de répondre clairement aux questions concernant les flux d’altération des silicates
Weathering of Himalayan lithologies has had a potential impact on the global carbon cycle. To be able to constrain and understand the processes that occurred in the Himalayas that affected these cycles, we must be able to distinguish the signatures of silicate and carbonate weathering in the dissolved load of Himalayan rivers. Previous studies have attempted to do this using a variety of methods but there is still not a clear consensus on the magnitude and flux of silicate weathering in the Himalaya. This thesis proposes the use of 40Ca as a tracer that could improve the quantification of the silicate and carbonate weathering flux in the dissolved load of Himalayan rivers. Previous work has shown that the 40Ca budget of seawater is dominated by a mantle source, such that marine carbonates have a homogeneous 40Ca signature indistinguishable from the mantle value. In contrast, the upper silicate crust is expected to have developed a radiogenic composition. The difference between the radiogenic Ca signature of carbonate and silicate lithologies can be therefore used to differentiate between carbonate and silicate weathering in the dissolved load of rivers. Here, we present a geochemical survey, including radiogenic Ca analyses, of rivers draining the main lithological units of the Himalaya, as well as results from sediments, bedrock, soil and gravel. Our results show that Himalayan carbonates exhibit no radiogenic 40Ca excesses despite highly variable 87Sr/86Sr signatures, whereas sediments are variably radiogenic (+0.9 to +4). This suggests that for Ca, unlike for Sr, isotopic exchange between the silicate and carbonate lithologies has been minimal. The radiogenic Ca composition of river water ranges from +0.1 in carbonate dominated catchments to +11 in rivers draining silicate catchments. For large rivers, silicate and carbonate weathering budget estimates based on major elements and radiogenic Ca compositions tend to agree. However, for some smaller rivers, especially those draining silicate dominated basins in the HHC and LH formations, some discrepancies are observed. These cannot be attributed to poor definition of the chemical or radiogenic Ca composition of the endmembers used for budget modeling, as the values required to bring the estimates into agreement are unreasonable. They also cannot be explained by precipitation of secondary carbonates in the rivers as the non-radiogenic composition of the carbonate fraction of sediments suggests that this process is only minor. Rather, these discrepancies may be due to the dissolution/weathering of trace amounts of radiogenic calcite contained within HHC and LH silicate lithologies. The weathering of such material, which represents only a tiny fraction of the area of the silicate catchment, could yield a substantial proportion of the radiogenic Ca and may thus have a significant influence on the isotopically based weathering budgets of these basins. Nevertheless, as this effect is observed primarily in basins with low silicate erosion rates, its influence on estimates of the overall silicate weathering flux will be minor. More generally, the results of this thesis imply that the 40K–40Ca system can resolve issues that cannot be successfully addressed using Sr isotopes in the Himalaya. Further work is needed to define the full range of radiogenic Ca compositions in the Himalaya in order to clearly answer questions regarding silicate weathering fluxes

With rising atmospheric CO2 concentrations, a detailed understanding of processes that impact atmospheric CO2 fluxes is required. While a sink of atmospheric carbon from the continents to the ocean from carbonate mineral weathering is, to some degree, offset by carbonate mineral precipitation in the oceans, efforts are underway to make direct measurements of these fluxes. Measurement of the continental sink has two parts: 1) measurement of the dissolved inorganic carbon (DIC) flux leaving a river basin, and 2) partitioning the inorganic carbon flux between the amount removed from the atmosphere and the portion from the bedrock. This study attempted to improve methods to measure the DIC flux using existing data to estimate the DIC flux from carbonate weathering within the limestone karst region of south central Kentucky. The DIC flux from the Barren River drainage basin upstream from Bowling Green in southern Kentucky and northern Tennessee, and the upper Green River drainage basin, upstream from Greensburg, Kentucky, was measured, each for a year, using U.S.G.S. discharge data and water-chemistry data from municipal water plants. A value of the (DIC) flux, normalized by time and area of carbonate rock, of 4.29 g km-3 day-1 was obtained for the Barren River, and 4.95 kg km-3 for the Green. These compared favorably with data obtained by Osterhoudt (2014) from two nested basins in the upper Green River with values of 5.66 kg km-3 day-1 and 5.82 kg km-3 day-1 upstream from Greensburg and Munfordville, respectively. Additional normalization of the values obtained in this study by average precipitation minus evapotranspiration over the area of carbonate rock, or water available for carbonate dissolution, resulted in values of 5.61x107 g C (km3 H20)- 1 day-1 (grams of carbon per cubic kilometer of water, per day) for the Barren, and 7.43x107g C (km3 H20)-1 day-1 for the Green River. Furthermore, a statistical relationship between the total DIC flux and time-volume of water available for dissolution has been observed, yielding an r2 value of 0.9478. This relationship indicates that the primary variables affecting DIC flux for these drainage basins are time and the volume of water available for dissolution.

Although karst processes in south central Kentucky have been studied extensively, the Haney Limestone Member of the Golconda Formation has not been studied in detail in contrast to limestones stratigraphically below it that are thicker. In addition, the relationship between petrographic features of the Haney Limestone and the formation of caves and karst features has not been studied extensively compared to lithographic, petrographic, or structural variables Petrographic data were collected using core and surface exposures across the study area of south central Kentucky from northern Logan and Warren counties up toward the Rough Creek Graben region, and stratigraphic columns were constructed. Twenty-three petrographic thin-sections were made from samples collected at these sites, described, and photo documented. These studies have revealed that grain size and silica content play a role in how the Haney weathers both in surface exposure and in a cave setting. Petrographic thin-section analysis suggests that the Haney possesses a complex diagenetic history that involves several generations of calcite cementation, dolomitization, silicification, and pressure-dissolution features in the form of microstylolites and stylolites. A basal shale in the Big Clifty occurs commonly at the Big Clifty/Haney contact and acts as a confining hydrogeologic unit, which is favorable for the development of springs and caves. Studying the Haney Limestone petrographically provides an opportunity not only to study a lesser known unit, but also in the context of relating petrographic influences or controls on the morphology of Haney cave-passage development under both vadose and phreatic hydrologic regimens. Heretofore, the vast majority of cave morphological studies have only linked the hydrologic regimen to formation of cave passages, but such studies have not considered petrographic variance. This study not only relates karst features to petrographic variance, but also provides a petrographical description of the Haney across south central Kentucky, whereas many previous studies focused on Illinois and Indiana. Understanding Haney petrographic characteristics also provides context for potential carbonate hydrocarbon reservoirs and groundwater resources in the Illinois Basin region.

Kentucky’s Upper Green River Basin has received significant attention due to the area’s high biodiversity and spectacular karst development. While carbonate bedrock is present throughout the watershed, it is more extensive and homogenous along the river between Greensburg and Munfordville than upstream from Greensburg where the geology is more heterogeneous. This research quantitatively evaluated how lithological differences between the two catchment areas impact hydrochemistry and inorganic carbon cycling. This first required correcting catchment boundaries on previous US Geological Survey Hydrologic Unit Maps to account for areas where the boundaries cross sinkhole plains. Basin boundaries using existing Kentucky Division of Water dye trace data differed from the earlier versions by as much as three kilometers. The river at the downstream site is more strongly influenced by carbonate mineral dissolution, reflected in higher specific conductance (SpC) and pH. The SpC at Munfordville ranges from 0.9 to 4.8 times that at Greensburg, averaging 2.0 times higher. Although rainfall is impacted by sulfuric acid from coal burning, river pH is buffered at both sites. The pH is higher at Munfordville 91% of the time, by an average of 0.28 units. Diurnal, photosynthetic pH variations are damped out downstream suggesting interactions between geologic and biological influences on river chemistry. River temperature differences between the two sites are at least 4oC higher at Greensburg under warm season conditions, but there is a clear trend of temperature differences diminishing as the river cools through the fall and winter. This results from a relatively stable temperature at Munfordville, impacted by large spring inputs of groundwater within the karst region downstream. Although weak statistical relationships between SpC and HCO3 - create uncertainties in high resolution carbon flux calculations, measurement of these fluxes is more highly impacted by discharge variations than concentration variations, which resulted in average daily atmospheric flux estimates within 34% between the two basins using weekly concentration data (3.3x108 vs. 2.2x108 gkm-2 d-1, where km2 is the outcrop area of carbonate rocks), and within only 12% using 15-minute concentration data from regressions (2.6x108 vs. 2.3x108 gkm-2 d-1) for Greensburg and Munfordville, respectively.

The Savannah River Site (SRS) deposits in the Southeastern US between 30-45 m of depth are calcium carbonate-rich, marine-skeletal, Eocene-aged sediments with varying clastic content and extensive diagenetic alteration, including meter-sized caves that coexist with brittle and hard limestone. An experimental investigation including geotechnical (P- and S-wave velocities, tensile strength, porosity) and geochemical (EDS, XRD, SEM, N2-adsorption, stable isotopes, K-Ar age dating, ICP-assisted solubility, groundwater) studies highlighted the contrast between hard and brittle limestones, their relationship with cave formation, and allowed calculation of parameters for geochemical modeling. Results demonstrate that brittle and hard limestones bear distinct geochemical signatures whereby the latter exhibits higher crystallinity, lower clastic load, and freshwater-influenced composition. Results also reveal carbonate diagenesis pathways likely driven by geologic-time seawater/freshwater cycles, microorganism-driven micritization, and freshwater micrite lithification. The second section of this investigation dealt with SRS surface soils which are largely coarse-grained and rich in iron oxides with various degrees of maturity. These soils were simulated in the laboratory using Ottawa sands that were chemically coated with goethite and hematite. Surface (SEM, AFM, N2-adsorption) and geotechnical properties (fabric, small-strain stiffness, shear strength) were investigated on the resulting "soil analog". Results indicate that iron-oxide coated sands bear distinct inherent fabric and enhanced small-strain stiffness and critical state parameters when compared to uncoated sands. Contact mechanics analyses suggest that iron oxide coatings yield an increased number of grain-to-grain contacts, higher surface roughness, and interlocking, which are believed to be responsible for the observed properties.

Over millions of years, atmospheric CO2 concentrations, and Earth’s climate, are regulated by continental silicate weathering and associated marine carbonate deposition. On this geological timescale, carbonate weathering has no net effect on CO2 drawdown. However, over the coming decades-to-centuries, accelerated weathering of carbonate rocks may provide a sink for anthropogenic CO2 emissions and increase alkalinity flux to the oceans to counteract ocean acidification. Recent experimental evidence strongly supports trees and their associated mycorrhizal fungi as key drivers of silicate mineral weathering; however, their role in the context of carbonate weathering is largely unknown. Carbonate lithology is abundant globally and underlies many boreal and temperate forest ecosystems in the northern hemisphere. If biological enhancement of carbonate weathering by forests occurs, this might presents a new opportunity for CO2 sequestration. This thesis presents results from a 14-month field experiment at the UK's national pinetum investigating carbonate rock weathering under a common climate. Overall, I find original evidence for biotic enhancement of calcite- and dolomite weathering by an evolutionary diverse range of trees that host either arbuscular (AM) or ectomycorrhizal (EM) root-associating fungal symbionts. Recent soil analyses are integrated with a re-interpretation of historic data to provide an 85-year record of in-situ soil development under different forestry species. This study challenges the classic dogma that divergence of properties is driven by the major tree functional groups, angiosperms and gymnosperms. Instead, we find that over decades, mycorrhizal functional type plays a dominant role in determining soil physico- chemical characteristics, and conditions generated by EM fungi are likely to enhance mineral weathering. Field trials next investigated the impact of tree-mycorrhizal functional group on weathering of the four main carbonate rock types (chalk, limestone, marble and dolomite) and a quartz silicate. Under EM trees carbonate rock grain dissolution was 12 times faster that silicate weathering. In the initial 3 months, calcite weathering intensity increased from gymnosperm to angiosperm species and from AM to later, but independently-evolved EM fungal partnerships. More extensive weathering after 6 months, especially within EM forest soils, confirms the importance of these fungi for carbonate mineral dissolution and nutrient mobilisation. This effect is linked to rhizosphere acidification by EM fungi and is confirmed by a parallel study of tree species’ influence on soil chemistry. Both AM and EM fungi facilitate the mobilisation of nutrient elements, which are provided to their host plants in exchange for carbon from photosynthesis. I applied a suite of nanoscale surface analysis techniques (VSI, SEM) to quantify mineral alteration and provide direct evidence for mycorrhizal involvement in carbonate weathering in the field. Fungal hyphae preferentially colonised chalk and quartz silicate grains, which contained the highest concentrations of phosphorus (P), a growth limiting elemental nutrient. P was selectively depleted from silicate grains, especially in EM forest soils, but accumulated on carbonates. Although the origin of this accumulated P remains uncertain, extensive analyses of different potential P-pools indicated it is likely to be inorganic, but accumulated via active microbial import. These findings lead to new insights linking carbonate weathering with phosphorus biogeochemical cycling in soils. Results show that P from the surrounding environment is concentrated on carbonate grains and this potentially provides a renewable P resource accessible to host trees. Overall, this thesis builds new support for the role of mycorrhizal partnerships in shaping soil properties important for accelerating carbonate rock weathering (Chapter 2); presenting the first field-based evidence for the enhancement of carbonate dissolution by tree roots and their associated mycorrhizal partners (Chapters 3-5) and generating new insights into biogeochemical P cycling in soils (Chapter 4). More broadly, these findings suggest targeted reforestation/afforestation with EM-tree taxa on carbonate-rich terrain as a possible regional-scale land management strategy for promoting short-term anthropogenic CO2 sequestration and perhaps helping ameliorate ocean acidification.

Rising atmospheric CO2 concentrations have motivated efforts to better quantify reservoirs and fluxes of Earth’s carbon. Of these fluxes from the atmosphere, one that has received relatively little attention is the atmospheric carbon sink associated with carbonate mineral dissolution. Osterhoudt (2014) and Salley (2016) explored new normalization techniques to improve and standardize a process for measuring this flux over large river basins. The present research extends this work to the 490,600 km2 Ohio River drainage basin and 11 subbasins. The study estimated the DIC flux leaving these basins between October 1, 2013, and September 30, 2014, based on secondary hydrogeochemical, geologic, and climatic data. The total annual DIC flux for the Ohio River basin was estimated to be 7.54 x 1012 g carbon (C). The time-volume normalized value of DIC flux for the Ohio basin was 3.36 x 108 g C/km3 day, where the km3 refers to the amount of water available during the year. This was within 71.4% agreement with the Barren River data (Salley, 2016) and within 63.9% agreement with the Green River data (Osterhoudt, 2014). In general, normalized DIC flux values of sub-basins containing at least modest amounts (more than 8%) of exposed carbonates (Tennessee, Cumberland, Green, Kentucky, Licking, Monongahela, and Allegheny) were in strong agreement with the normalized DIC flux of the Ohio River basin, whereas inclusion of basins with little or no near surface carbonates (Wabash, Great Miami, Scioto and Kanawha) yielded poor agreement. Regression analysis yielded strong agreement between DIC flux and the normalization parameters for the carbonate-bearing sub-basins (R2 = 0.97, p =

Reports an investigation of the effects of chemical and physical weathering on submerged karst surfaces that pairs laboratory studies with computer modeling studies. The first study attempts to quantify the production of carbonate fines; soluble sediments produced by the incomplete dissolution of karst minerals during chemical weathering. Results show carbonate fine production in relation to dissolutional action; Chalk: 42.8%; Coquina: 2.6%; Dolomite: 3.1%; Gray Limestone: 4.8%; Ocala Limestone: 3.1%; Shell Limestone: 6.1%; Travertine: 8.6%. Due to the use of hydrochloric acid as opposed to carbonic acid these results may not be fully valid for application to natural speleogenic processes. The Limestone Weathering Model, a numerical-computer model, was developed using these experimental findings as minimal values compared with published rates. Reported as the actual volume of rock mass lost to both dissolution and to carbonate fine production, the rates for carbonate fine production ranged from 5.8% to 10.9% (year 1- 5.8%, year 2- 8.5%, year 3- 9.7%, year 4-10.3%, year 5- 10.9%), with a mean value for carbonate fine production of 9%, but a continuing rate after five years approaching 11%. The second study uses metrological laser scanning to measure the erosive loss due hydraulic shearing force and corrasion on submerged limestone surfaces. The rates for material removed using increasing velocity values (0.3m/s, 0.5m/s, 1.0m/s, 1.5m/s, 2.0 m/s, 2.5m/s) during flow durations of less than 6 minutes duration were : 1) Hydraulic shearing force- 0.3µm/s, 0.5µm/s, 0.4-1.7µm/s, 2.5 µm/s, 5.5 µm/s, 2) Corrasion- 0.3 µm/s, 0.7 µm/s, 1.5 µm/s, 1.5-1.8 µm/s, 8.9 µm/s, 8.1 µm/s. The study model was modified to return these rates for hydraulic shearing force limited by the depth of the chemical corrosion of the surface. The model returns % rock volume lost to hydraulic shearing force compared to dissolutional rate (1mm/y) for 3 flow velocities (0.03m/s<, 1.0m/s<, 2.5m/s<) on 4 timing schedules: Annual 7.8,14.3,19.6, Semiannual 21.1,21.1,69.7, Quarterly- 32.8,43.6, 70.9, Monthly- 80.0, 109.3, 200.3. Model demonstrates significant effect (7.8% to 200% over dissolutional rate) on speleogenic rates from even infrequent, moderate changes in flow velocities due to storm events. Study’s results support the significance of chemical weathering by disaggregation and physical weathering by hydraulic shearing force as major factors in the processes of karst speleogenesis.

Acid deposition forms when emission-derived sulfur dioxide and nitrogen oxides interact with precipitation and was particularly severe in the northeastern US. Effects of acid deposition include declining soil quality due to low pH and base cation leaching, which subsequently altered the composition of soil solution, ground water (GW) and eventually stream water. Because of the high buffering capacity of carbonates, watersheds underlain by carbonate rich rocks have received limited attention in acid deposition studies, however, carbonate weathering by strong anthropogenic acids can increase atmospheric CO2 levels. Emission reductions due to the Clean Air Act and Amendments has led to a substantial reduction of acid deposition and many ecosystems are now recovering and stream water exports contain lower concentrations of acid anions and base cations. However, the effects of recovery on watershed soil, soil solution, and GW composition, which potentially varies with landscape position, are not well constrained. The objective of this study was therefore to investigate links between soils and water composition in a watershed with important carbonate contents in the underlying rock, the Sleepers River Research Watershed (SRRW), using long-term datasets that span the recovery period. Temporal trends (1991-2015) for acid anions (sulfate and nitrate), pH, base cations (Ca, Na) and Si were investigated for stream water and trends with time, depth, and landscape position (hilltop, hillslope, and riparian zone) for the same solutes were assessed in GW and soil solution (2004-2013). Furthermore, soil elemental composition and mineralogy in archived (1996) and modern (2017) soil samples were analyzed to investigate changes in soil composition due to base cation leaching and carbonate weathering with time and landscape position. Results indicate that SRRW is indeed recovering from acidification as evidenced by declining sulfate content and rising pH in stream water, GW, and soil solution. Additionally, Ca typically derived from carbonate weathering decreased progressively with time in GW and showed signs of decreasing in soil solution at various landscape positions due to reduced leaching. However, Ca in stream water shows slight increases, likely due to Ca released from riparian soil stores. Spatial heterogeneity is especially pronounced in headwater catchments with steep topography as evidenced by changes in solution and soil composition along hillslopes. In addition to the paper submitted for publication (Chapter 2) to Frontiers in Earth Science – Biogeochemistry this thesis includes i) a background and literature review to inform the reader on pertinent topics, ii) an appendix containing additional soil data with figures, iii) and an appendix with additional aqueous phase data with figures.

Dans le domaine andin du bassin amazonien, les zones karstiques jouent un rôle prépondérant sur la géochimie du fleuve Amazone et sur la consommation de CO2 liée aux processus d’altération, malgré la faible surface qu’elles couvrent (<1% du bassin de l’Amazone). Le Pérou concentre près de 90% de ces zones karstiques andines, qui s’étagent des sommets de la cordillère (à plus de 5000 m d’altitude) jusqu’au piedmont amazonien (400 m), dans une grande variété d’écosystèmes tropicaux. Bien que ces zones représentent une source majeure de matières dissoutes exportées par l’Amazone, elles n’ont jamais été étudiées dans le but de caractériser le fonctionnement hydrogéologique de ces systèmes karstiques, et d’estimer leurs contributions en termes de flux dissous. Afin d’identifier les facteurs de contrôle des dynamiques de production et de transfert de matières dissoutes depuis le domaine carbonaté jusqu’à l’Amazone, le fonctionnement hydrogéologique des aquifères du massif karstique de l’Alto Mayo, situé sur le versant oriental des Andes du Nord du Pérou, a été analysé. Les trois principales sources du massif ont été équipées de sondes enregistreuses à haute fréquence CTD (Conductivity, Température and Depth), et des jaugeages périodiques ont été réalisés afin d’évaluer leur débit. Un prélèvement bimensuel a été effectué pour l’analyse des paramètres hydrogéochimiques (éléments majeurs et en trace, Carbone Organique Total et isotopes stables de l’eau) entre 2016 et 2018. La variabilité temporelle des débits et des concentrations a été calculée par le rapport (en pourcentage) entre l'écart-type et la moyenne mensuelle. La principale source de ce massif (Rio Negro, débit moyen = 22 m3s-1) est à ce jour la plus importante source karstique d’Amérique du Sud. Cette résurgence majeure présente une faible variabilité du débit au cours du cycle hydrologique (variabilité temporelle des débits de 17%) et une faible réponse impulsionnelle aux précipitations, qui indiquent un fort amortissement du signal par le système karstique. Une faible réactivité hydrologique aux précipitations est également observée sur la source du Rio Aguas Claras (variabilité temporelle des débits de 59%). La source du Rio Tío Yacu présente quant à elle une réponse impulsionnelle plus marquée ainsi qu’une variabilité hydrologique plus élevée (variabilité temporale des débits de 67%). La signature hydrogéochimique des eaux souterraines de l’ensemble des sources est fortement dominée par l’altération des carbonates (Ca2+ et HCO3-). La charge totale dissoute au pas de temps journalier est estimée à partir de la relation entre la conductivité électrique et les TDS des sources karstiques péruviennes étudiées dans ce travail, et de celles du réseau français du SNO Karst. Cette TDS journalière affiche une variabilité relativement faible au cours du cycle hydrologique (12%, 7% et 9% pour les résurgences de Rio Negro, d’Aguas Claras et de Tio Yacu respectivement) par rapport à celle du débit. Ces résultats indiquent que la dynamique de production du matériel dissous, pour les sources du massif karstique du l’Alto Mayo, est contrôlée principalement par la variabilité des débits malgré l’hétérogénéité des comportements hydrodynamiques. Ce comportement «chemostatique» est observé dans de nombreux contextes à l’échelle globale et à des échelles spatiales très contrastées, pouvant être attribué à l’hypothèse que les fluides s’approchent rapidement de l'équilibre chimique. Cependant, la source de Rio Negro présente une faible variabilité des flux de TDS, en raison de la faible variabilité du débit. Ceci est conditionné par son comportement hydrogéologique (plus inertiel), qui implique de faibles réponses hydrodynamiques et hydrochimiques après les précipitations. En conséquence, nos résultats caractérisent la sensibilité de l’altération des zones karstiques, aux variabilités hydroclimatiques dans les milieux andins tropicaux. L'altération des zones karstiques andines représente [...]
In the Andean area of the Amazon Basin, karst areas play a major role in the geochemistry of the Amazon River and in the CO2 consumption associated with weathering processes despite the small surface they cover (<1% of the basin of the Amazon basin). Amazon). Peru concentrates nearly 90% of these Andean karst areas, which stretch from the peaks of the Cordillera (at more than 5000 m altitude) to the Amazon piedmont (400 m) in a wide variety of tropical ecosystems. Although these areas represent a major source of dissolved materials exported by the Amazon, they have never been studied for characterizing the hydrogeologic functioning of these karstic systems and estimate their contributions in term of dissolved fluxes. To identify the control factors of the dynamics of production and transfer of dissolved matter from the carbonated domain to the Amazon, the hydrogeological functioning of aquifers of the karst massif of Alto Mayo, located on the eastern slope of the Andes Northern Peru, has been analyzed. The three main karst springs of the massif were equipped with CTD (Conductivity, Temperature and Depth) and periodic gauging was carried out to evaluate their flow. A bi-monthly sampling was carried out for the analysis of geochemical parameters (major and trace elements, Total Organic Carbon and stable isotopes of water). The temporal variability of flow rates and concentrations was calculated by the ratio of the standard deviation to the monthly mean percentage. The main spring of this massif (Río Negro, average flow = 22 m3s-1) is currently the most important karstic spring of South America. This major spring presents a low discharge variability during the hydrology cycle (the temporal variability of the discharge is 17%) and a weak impulse response to the precipitations, which indicate a strong damping signal by the karstic system. Low hydrological reactivity to rainfall is also observed at the Río Aguas Claras spring (temporal variability of flows of 59%). The Río Tío Yacu spring has a higher impulse response and a higher hydrological variability (temporal variability of flow rates of 67%). The hydrogeochemical signature of the groundwaters from all springs is highly dominated by the carbonate rocks weathering (Ca2+ et HCO3-). Daily total dissolved solid (TDS) was estimated by the relationship between electrical conductivity and TDS of the peruvian karstic springs studied in this work, and those of the French network of SNO Karst. This daily TDS has a relatively low variability during the hydrologic cycle (12%, 7% and 9% for Rio Negro, Aguas Claras and Tio Yacu springs, respectively) compared to that of the discharge. These results indicate that the dynamics of production of dissolved material, in the karstic spring of the Alto Mayo, is mainly controlled by the variability of flows despite the heterogeneity of the hydrodynamic behaviors. This “chemostatic’’ behavior has been observed in many contexts at the global scale and can be attributed to the fast kinetics of carbonate weathering. However, Rio Negro spring shows a weak variability of TDS fluxes, as a result of low discharge variability. This is conditioned by his hydrogeological behavior (more inertial), which involves weak hydrodynamic and hydrochemical responses after rainfall events. As a result, our results characterize the sensitivity of carbonate rocks weathering to hydroclimatic variability in tropical Andean environments. The weathering of Andean karstic areas represents 50% of the total of the dissolved fluxes exported by the Marañón River, the principal affluent of the Amazon river

Mit dem Grundwasserwiederanstieg in Braunkohleabraumkippen werden die aus der Pyritverwitterung resultierenden Stoffausträge an Sulfat-, Eisen-, Schwermetall- und H+-Ionen gelöst. Im Rahmen dieser Dissertation wurde eine Methodik entwickelt, mit deren Hilfe Problembereiche ausgehalten und somit Maßnahmen im aktiven mitteldeutschen Tagebaubetrieb ergriffen werden können, um die zukünftige Beeinflussung der umgebenden Grund- und Oberflächenwasserkörper zu minimieren. An Vorfeldsedimenten konnten in Feld-eluaten, Stoßbeprobungen und Verwitterungsversuchen geochemische Eigenschaften ermittelt werden. In resultierenden Pufferungsversuchen aus karbonathaltigen Geschiebe-mergeln und Hauptaciditätsträgern konnte eine langfristige Minderung der Aciditätswirkung nachgewiesen werden und ein adaptierter Regelkippenaufbau mit laminaren, alterierenden Sichtaufbau begründet werden. In umliegenden Altkippengrundwässern sind Pufferung und Sulfatreduktion als Wiederfestlegungsprozesse der AMD-Problemstoffe belegt worden
For lignite mining extensive overburden masses have to be moved. Due to the ventilation of the overburden by atmospheric oxygen, there is a weathering of mostly tertiary sulfides. The rebound of groundwater in future tippings dissolves sulfate, iron, heavy metal and H+ ions, resulting from the pyrite weathering. The partial mobilization of overburden sulfides are opposed to hydrogeochemical buffer reactions e.g. the buffering by carbonates as the first step of buffering. Therefore, there are the questions to the mining operators of the measures that can be taken to minimize the geochemical influence of the surrounding ground and surface water bodies. Object of this PhD-thesis is to lead a methodology that helps to characterize the future tilting substrates to find technological and strategic measures for minimizing the acid water formation in the active open pit operation. In Field eluates and weathering tests in the laboratory and in the field, sediments from dry drill holes in the forefront of open pits “Schleenhain” and “Peres” it could be shown that the geological facies formation of sediments has a decisive influence on geochemical characteristics. As the main acidifying sediment the tertiary aquifer number 2 (lying part) and number 3 can be identified with their high sulfur contents. With increasing time of oxygen exposure sulfate, iron, heavy metal and H + ions released massively. Furthermore, it appears that carbonate buffer essentially are available as glacial till only in cohesive Quaternary. With the resulting buffering experiments from glacial till and the most acidic aquifer sediments a long-term retention of iron, heavy metal and H + - ion and a reduction of sulfate release can be shown, if there is a share of at least 40% glacial till to the lying aquifer number 2 sediments or 20% glacial till to the aquifer number 3. The groundwater quality monitoring of unstructured resaturated old dumps near to the active open pits is comparable to a field test. In addition to weathering zones with high levels of pollutants in the presence of carbonates, buffering processes and sulfate reduction with precipitation of problematic substances in secondary mineral phases can be detected. Blending the research results of geological and geochemical data, an important, in principle selectively recoverable, buffer potential already exists. The determined mixing ratio from 80-60 mass-% acidic sediments to 20-40 mass-% buffering sediment from the buffering experiments can be realized in tilting. In the open pit “Schleenhain” the missing buffering material can be compensated by mass offset from the open pit “Peres”. With the use of the already existing equipment, it is possible to establish a laminar, alternately tipping body with good geochemical and geotechnical conditions

Cette thèse explore l'influence des orogenèses sur le climat de la Terre à travers l'étude quantitative des interactions entre dynamique climatique, érosion des continents, taux d'altération chimique des roches silicatées et cycle géologique du carbone. Le premier chapitre détaille les mécanismes par lesquels les reliefs affectent la circulation atmosphérique et océanique, l'emphase est mise sur la circulation thermohaline. Le second chapitre compare les effets des changements de dynamique climatique et d'érosion liés à la présence de montagnes sur l'altérabilité des continents. Le troisième chapitre développe un modèle dynamique de régolithe applicable à l'échelle globale et étudie son comportement en régime transitoire, ainsi que la réponse du cycle du carbone à un dégazage de CO2. Enfin, le quatrième chapitre s'attache à modéliser le cycle isotopique continental du lithium, potentiel traceur de l'altération dans le passé de la Terre. Ce modèle est appliqué au cas du bassin amazonien
This thesis explores how orogenies may affect the Earth climate through the quantification of the interactions between climate dynamics, continental erosion, silicate rock weathering rate and geological carbon cycle. The first chapter describes the mechanisms linking the continental topography and its impacts on the atmospheric and oceanic circulations, with emphasis on the thermohaline circulation. The second chapter compares the effects on continental weatherability of climate dynamics and erosional changes related to the presence of mountains. The third chapter describes a dynamic model of regolith designed for global scale simulations, and describes its transient behavior, as well as its response to a CO2 degassing. Finally, the last chapter presents a numerical model of the continental isotopic cycle of lithium, so that its reliability as a proxy of the past weathering can be tested. The model explores the case study of the Amazon lithium cycle

La contribution, dans le cycle supergène, du carbone organique fossile (COF), issu de l'érosion des roches sédimentaires, est aujourd'hui une inconnue majeure du cycle du carbone. Le présent travail, initié dans le cadre du GIS Draix "étude de l'érosion en montagne », s'est intéressé au devenir de la matière organique contenue dans les "terres noires" (marnes jurassiques) des bassins versants de Draix (Alpes de haute Provence, France). Ceci a nécessité : - la mise en évidence de la contribution de COF au sein des compartiments supergènes (sols, particules fluviatiles, altérites) à travers une approche pluri-analytique (investigations géochimiques, optiques, isotopiques). - l'estimation de la part de COF disparue lors de son transfert d'un compartiment à un autre obtenue grâce au développement d'une nouvelle méthode analytique (palynofacies quantitatif) et en couplant approches terrain et expérimentale. - l'estimation et la modélisation des flux de COF libérés par les altérations mécaniques et chimiques des terres noires à l'échelle des bassins étudiés. Les résultats obtenus permettent : - 1) de confirmer la résistance du COF, dont les pertes n'excèdent pas 30 % et ne concernent que la part libérée par l'altération chimique; - 2) de rappeler la pluralité du COF, dont les familles réagissent différemment face aux différents types d'altérations ; - 3) de hiérarchiser les facteurs contrôlant les flux de COF (couvert végétal, pentes, précipitations) ; - 4) de mettre en évidence l'importance du COF libéré, exprimé en t/ha/an, par les « terres noires » aux échelles locales et régionales.

Comprendre le fonctionnement hydrochimique de la Zone Critique reste un enjeu fort de ces décennies, notamment en ce qui concerne les interactions entre les cycles de l’eau, du carbone et de l’azote. Le bassin versant agricole du Montoussé à Auradé (Gers) soumis à des fortes pressions anthropiques et climatiques sur ces cycles, est l’un des dispositifs pérennes d’observation à long terme de l’infrastructure de recherche OZCAR, en charge de surveiller la zone critiques en milieu agricole. Ce bassin versant carbonaté est soumis à une climat semi-aride marqué par une forte évapotranspiration et des périodes de hautes eaux en hiver et au printemps, caractéristiques confirmées par les signatures isotopiques de l’eau. Une analyse des variations temporelles des eaux des précipitations atmosphériques et des eaux du ruisseau, à long- (sur 15 et 30 ans), moyen- (annuel et saisonnier) et court-terme (journalier et nycthéméral), et à haute fréquence (10mn) a mis en évidence : (i) l’origine des éléments dans les précipitations ; (ii) l’effet de l’augmentation des débits et de la fréquence des crues sur la diminution des concentrations en éléments majeurs, (iii) K et COD comme indicateurs de l’érosion des matières organiques des sols, favorisées par une amélioration des pratiques agricoles et une augmentation des températures; (iv) les processus de précipitation de la calcite, de nitrification, d’évapotranspiration et de prélèvement par la végétation. Une analyse spatiale de la composition chimique des eaux des ruisseaux du bassin versant, couplée aux signatures isotopiques de C et N, a permis de préciser les sources d’éléments, les processus en jeu tant hydrologiques que géochimiques associés aux perturbations de l’altération. Le découpage des hydrogrammes de crue, les relations concentration-débit et l’analyse des isotopes stables (δ15N, δ17O et δ18O) ont permis de mettre en évidence un contrôle des nitrates par des processus de dénitrification, une voie préférentielle de transfert des ions dans l’écoulement hypodermique, alors que les matières en suspensions (MES) sont transportées par le ruissellement. La contribution des crues aux flux exportés représente 93% pour les MES et 30-47% pour les éléments majeurs dissous. Les bilans nets (entrée-sortie) des éléments majeurs exportés sont très dépendants des quantité d’eau drainées. L’export des éléments majeurs se situe dans la moyenne des bassins versants du Sud-Ouest de la France tandis que les flux de MES sont similaires à ceux de bassins versants semi-arides du Maghreb. Enfin, l’apport de fertilisants azotés contribue à acidifier les sols, modifie la dissolution naturelle des carbonates et augmente l’altération chimique, induisant une perte de CO2 consommé de l’ordre de 15% au regard d’une dissolution naturelle des carbonates. Les sols du bassin versant du Montoussé ne sont pas en équilibre, puisque l’érosion mécanique est en moyenne deux fois supérieure à l’altération chimique. Le changement climatique et les pratiques agricoles auront donc des implications fortes sur la dynamique des cycles de l’azote et du carbone dans les années à venir. Les observatoires de la Zone Critique ont donc un rôle essentiel de surveillance et de compréhension de ces perturbations dans les prochaines décennies, et ils jouent aussi un rôle majeur dans l’aide à la gestion de ces bassins agricoles
Understanding the hydrochemical functioning of the Critical Zone is a major issue of these decades, especially for water, nitrogen and carbon cycles interactions. The Montoussé agricultural catchment at Auradé (Gers, France) undergoes strong anthropic and climatic pressure on these cycles, and is one of the long-term perennial observatory of the OZCAR research infrastructure in charge of monitoring the Critical Zone in an agricultural context. This carbonate catchment suffers semi-arid-climate characterized by a strong evapotranspiration and high water flow conditions during spring, as confirmed by water isotopic data. The investigation of the temporal evolution of atmospheric rainfall and stream water discharge at long-term (15 and 30 years), middle-term (seasonal and annual) and short-term (nycthemeral land daily), and at a high frequency (10 minutes), revealed: (i) the origin of elements in the precipitations; (ii) the influence of increasing discharge and of flood frequency on the decrease of major element concentration; (iii) K and DOC, as indicators of soil organic matter erosion, favored by improved agricultural practices and increasing air temperature; (iv) calcite precipitation, nitrification, evapotranspiration and vegetation uptake processes. A spatial investigation of stream water chemical composition at the catchment scale, coupled with carbon and nitrogen isotopic signature, allowed to identify the origin of the elements and the hydrological and geochemical processes associated with weathering perturbations. Separation of stromflow hydrograph, discharge-concentration relationships and stables isotopes analyses (15N, 17O and 18O) highlighted the nitrate control by denitrification process, a preferential way of ion transfer by sub-surface water flow, whereas suspended particulate matter (SPM) was transported by runoff. The flood events contribution to total flux exportation represented 93% for SPM and 30- 47% for dissolved major elements. The major elements mass-balance (inputs-outputs) was dependent upon drainage. The net major elements exportation was close to the average of other catchments of the southwest of France, whereas SPM fluxes were close to those of Maghreb semi-arid catchments. Nitrogen fertilizer inputs contributed to soil acidification, have modified the natural carbonate dissolution and have increased the chemical weathering rate, inducing a 15% loss of consumed CO2 compared natural conditions. The soils from the Montoussé catchment are not currently in balance since mechanical erosion is two times stronger than chemical weathering. In the coming years, climate Change and agricultural practices will have strong implication for the carbon and nitrogen cycle dynamic. The Critical Zone observatories will thus have an essential role in the survey and the understanding of these perturbations in the next decades, as well as in supporting agricultural catchment management

abstract: Chemical and physical interactions of flowing ice and rock have inexorably shaped planetary surfaces. Weathering in glacial environments is a significant link in biogeochemical cycles – carbon and strontium – on Earth, and may have once played an important role in altering Mars’ surface. Despite growing recognition of the importance of low-temperature chemical weathering, these processes are still not well understood. Debris-coated glaciers are also present on Mars, emphasizing the need to study ice-related processes in the evolution of planetary surfaces. During Earth’s history, subglacial environments are thought to have sheltered communities of microorganisms from extreme climate variations. On Amazonian Mars, glaciers such as lobate debris aprons (LDA) could have hosted chemolithotrophic communities, making Mars’ present glaciers candidates for life preservation. This study characterizes glacial processes on both Earth and Mars. Chemical weathering at Robertson Glacier, a small alpine glacier in the Canadian Rocky Mountains, is examined with a multidisciplinary approach. The relative proportions of differing dissolution reactions at various stages in the glacial system are empirically determined using aqueous geochemistry. Synthesis of laboratory and orbital thermal infrared spectroscopy allows identification of dissolution rinds on hand samples and characterization of carbonate dissolution signals at orbital scales, while chemical and morphological evidence for thin, discontinuous weathering rinds at microscales are evident from electron microscopy. Subglacial dissolution rates are found to outpace those of the proglacial till plain; biologically-mediated pyrite oxidation drives the bulk of this acidic weathering. Second, the area-elevation relationship, or hypsometry, of LDA in the midlatitudes of Mars is characterized. These glaciers are believed to have formed ~500 Ma during a climate excursion. Hypsometric measurements of these debris-covered glaciers enable insight into past flow regimes and drive predictions about past climate scenarios. The LDA in this study fall into three major groups, strongly dependent on basal elevation, implying regional and climatic controls on ice formation and flow. I show that biologically-mediated mineral reactions drive high subglacial dissolution rates, such that variations within the valley can be detected with remote sensing techniques. In future work, these insights can be applied to examining Mars’ glacial regions for signs of chemical alteration and biosignatures.
Dissertation/Thesis
Doctoral Dissertation Geological Sciences 2015

Mit dem Grundwasserwiederanstieg in Braunkohleabraumkippen werden die aus der Pyritverwitterung resultierenden Stoffausträge an Sulfat-, Eisen-, Schwermetall- und H+-Ionen gelöst. Im Rahmen dieser Dissertation wurde eine Methodik entwickelt, mit deren Hilfe Problembereiche ausgehalten und somit Maßnahmen im aktiven mitteldeutschen Tagebaubetrieb ergriffen werden können, um die zukünftige Beeinflussung der umgebenden Grund- und Oberflächenwasserkörper zu minimieren. An Vorfeldsedimenten konnten in Feld-eluaten, Stoßbeprobungen und Verwitterungsversuchen geochemische Eigenschaften ermittelt werden. In resultierenden Pufferungsversuchen aus karbonathaltigen Geschiebe-mergeln und Hauptaciditätsträgern konnte eine langfristige Minderung der Aciditätswirkung nachgewiesen werden und ein adaptierter Regelkippenaufbau mit laminaren, alterierenden Sichtaufbau begründet werden. In umliegenden Altkippengrundwässern sind Pufferung und Sulfatreduktion als Wiederfestlegungsprozesse der AMD-Problemstoffe belegt worden.:Versicherung 3 Zusammenfassung 8 1 Aktualität und Bedeutung der gesteuerten Abraumverkippung 10 2 Theoretische Grundlagen, Ziele, Aufgaben und Technik 15 2.1 Das System Kippe mit Verwitterungsstufen und Stufen der Gegenmaßnahmen 16 2.1.1 Phasen der Tagebauentwicklung in Bezug auf die Sauerwasserbildung 16 2.1.2 Systematik der Gegenmaßnahmen 18 2.2 Pyritbildung, Verwitterung, Pufferung und Wiederfestlegung 22 2.2.1 Pyritbildung 22 2.2.2 Pyritverwitterung 22 2.2.3 Pufferreaktionen 24 2.2.4 Wiederfestlegung durch autochthone mikrobielle Sulfatreduktion 26 2.2.5 Wiederfestlegung durch technisch- biologisch forcierte Sulfatreduktion 28 2.3 Geochemische Verhältnisse der Kippen Zwenkau und Witznitz 30 2.4 Geräteeinsatz im Tagebau des Untersuchungsgebietes 33 3 Ableitung einer Untersuchungsmethodik 35 3.1 Bearbeitungsziel und Ableitung der notwendigen Methoden 35 3.1.1 Geologisches Modell 36 3.1.2 Geochemisches Modell 38 3.1.3 Gewinnungstechnologisches Modell 39 3.2 Vorfeldbohrungen, Korngrößenbestimmung, stoffliche Charakterisierung und RFA 41 3.2.1 Vorfeldbohrungen 41 3.2.2 Lagerung und Probenahme 42 3.2.3 Körnungsanalyse und Wassergehaltsbestimmung 43 3.2.4 Feststoffcharakterisierung Kohlenstoff / Schwefel mittels CS-Mat 44 3.2.5 Röntgenfluoreszenzanalytik 44 3.3 Feldeluate, HCl-Test und organoleptische Ansprache 46 3.3.1 Feldelution 46 3.3.2 Salzsäure-Test (HCl-Test) 47 3.3.3 Organoleptische Ansprache 47 3.3.4 Hydrolytische Acidität 48 3.4 Verwitterungsversuche 49 3.5 Stoßbeprobung 51 3.6 Pufferungsversuche 52 3.7 Kippengrundwassermonitoring 54 3.7.1 Grundwassermessstellen und Probenahmeequipment 54 3.7.2 Feldanalytik 55 3.7.3 Laboranalytik 56 3.7.4 Hydrogeochemische Modellierung 56 4 Grundlagen und geologische Beschreibung des Untersuchungsgebietes 58 4.1 Untersuchungsgebiet 58 4.2 Tertiäre Einheiten 59 4.3 Quartäre Einheiten 61 4.4 Abgrenzung und Festlegung der Auswerteeinheiten 61 4.5 Vorfeldbohrungen 62 5 Anwendung der Methodik für den Tagebau Vereinigtes Schleenhain 65 5.1 Baufeld Schleenhain 65 5.1.1 Vorfeldbohrungen und Feldeluate 65 5.1.2 Stoffliche C/S-Charakterisierung 69 5.1.3 Verwitterungsversuche 72 5.1.4 Stoßbeprobung 85 5.1.5 Pufferungsversuche 90 5.1.6 Körnungsanalyse und Verwitterungszugänglichkeit 99 5.2 Baufeld Peres 103 5.2.1 Feldeluate 103 5.2.2 Vorfeldbohrungen und stoffliche Charakterisierung 105 5.2.3 Verwitterungsversuche 107 5.2.4 Pufferungsversuche 113 5.3 Beschaffenheit der Kippengrundwässer 114 5.3.1 Grundlegende hydrogeochemische Charakterisierung 115 5.3.2 Verwitterungszonen 117 5.3.3 Spurenmetallgehalte 118 5.3.4 Wirksamkeit der geogenen Puffer 119 5.3.5 Kennzeichnung der Sulfatreduktion als natürlicher Rückhalteprozess 121 5.3.6 Hydrochemische Modellierung 124 5.4 Fehlerdiskussion 126 6 Übertragung der Ergebnisse, Bewertung und Schlussfolgerung 127 6.1 Geologisches Modell und technische Verschnittmöglichkeiten 127 6.1.1 Geologisch-genetische Charakteristik der Auswerteeinheiten 127 6.1.2 Verbreitung und Mächtigkeit wesentlicher Auswerteeinheiten im Tagebau „Vereinigtes Schleenhain“ 128 6.1.3 Tagebautechnologische Verschnittmöglichkeiten 130 6.2 Geochemische Möglichkeiten bei der Umstellung der Tagebautechnologie – Massenversatz und Mischung 132 6.2.1 Gewinnungsscheiben 132 6.2.2 Regelkippenaufbau 134 6.2.3 „Schnelle Fahrweise“ und (Zwischen-) Abdeckung 134 6.2.4 Einmischung der Sedimente 135 6.3 RFA-Analytik und Bewertung von Sedimenteigenschaften 137 7 Zusammenfassung und weiterer Handlungsbedarf 139 7.1 Zusammenfassung - Ergebnisse Vorfeldbohrungen 139 7.2 Zusammenfassung – Verwitterungsversuche Labor und Feld 139 7.3 Zusammenfassung – Pufferungsversuche Schleenhain und Peres 141 7.4 Zusammenfassung – Gütemonitoring Kippengrundwässer 141 7.5 Zusammenfassung – Geologisches Modell/ Verschnitt/Technologie 142 7.6 Nachweis der Anwendbarkeit der Methode 144 7.7 Ausblick und weiterer Handlungsbedarf 145 Literatur und Quellen 146 Tabellenverzeichnis 151 Abbildungsverzeichnis 151 Abkürzungsverzeichnis 157 Anlagen 159
For lignite mining extensive overburden masses have to be moved. Due to the ventilation of the overburden by atmospheric oxygen, there is a weathering of mostly tertiary sulfides. The rebound of groundwater in future tippings dissolves sulfate, iron, heavy metal and H+ ions, resulting from the pyrite weathering. The partial mobilization of overburden sulfides are opposed to hydrogeochemical buffer reactions e.g. the buffering by carbonates as the first step of buffering. Therefore, there are the questions to the mining operators of the measures that can be taken to minimize the geochemical influence of the surrounding ground and surface water bodies. Object of this PhD-thesis is to lead a methodology that helps to characterize the future tilting substrates to find technological and strategic measures for minimizing the acid water formation in the active open pit operation. In Field eluates and weathering tests in the laboratory and in the field, sediments from dry drill holes in the forefront of open pits “Schleenhain” and “Peres” it could be shown that the geological facies formation of sediments has a decisive influence on geochemical characteristics. As the main acidifying sediment the tertiary aquifer number 2 (lying part) and number 3 can be identified with their high sulfur contents. With increasing time of oxygen exposure sulfate, iron, heavy metal and H + ions released massively. Furthermore, it appears that carbonate buffer essentially are available as glacial till only in cohesive Quaternary. With the resulting buffering experiments from glacial till and the most acidic aquifer sediments a long-term retention of iron, heavy metal and H + - ion and a reduction of sulfate release can be shown, if there is a share of at least 40% glacial till to the lying aquifer number 2 sediments or 20% glacial till to the aquifer number 3. The groundwater quality monitoring of unstructured resaturated old dumps near to the active open pits is comparable to a field test. In addition to weathering zones with high levels of pollutants in the presence of carbonates, buffering processes and sulfate reduction with precipitation of problematic substances in secondary mineral phases can be detected. Blending the research results of geological and geochemical data, an important, in principle selectively recoverable, buffer potential already exists. The determined mixing ratio from 80-60 mass-% acidic sediments to 20-40 mass-% buffering sediment from the buffering experiments can be realized in tilting. In the open pit “Schleenhain” the missing buffering material can be compensated by mass offset from the open pit “Peres”. With the use of the already existing equipment, it is possible to establish a laminar, alternately tipping body with good geochemical and geotechnical conditions.:Versicherung 3 Zusammenfassung 8 1 Aktualität und Bedeutung der gesteuerten Abraumverkippung 10 2 Theoretische Grundlagen, Ziele, Aufgaben und Technik 15 2.1 Das System Kippe mit Verwitterungsstufen und Stufen der Gegenmaßnahmen 16 2.1.1 Phasen der Tagebauentwicklung in Bezug auf die Sauerwasserbildung 16 2.1.2 Systematik der Gegenmaßnahmen 18 2.2 Pyritbildung, Verwitterung, Pufferung und Wiederfestlegung 22 2.2.1 Pyritbildung 22 2.2.2 Pyritverwitterung 22 2.2.3 Pufferreaktionen 24 2.2.4 Wiederfestlegung durch autochthone mikrobielle Sulfatreduktion 26 2.2.5 Wiederfestlegung durch technisch- biologisch forcierte Sulfatreduktion 28 2.3 Geochemische Verhältnisse der Kippen Zwenkau und Witznitz 30 2.4 Geräteeinsatz im Tagebau des Untersuchungsgebietes 33 3 Ableitung einer Untersuchungsmethodik 35 3.1 Bearbeitungsziel und Ableitung der notwendigen Methoden 35 3.1.1 Geologisches Modell 36 3.1.2 Geochemisches Modell 38 3.1.3 Gewinnungstechnologisches Modell 39 3.2 Vorfeldbohrungen, Korngrößenbestimmung, stoffliche Charakterisierung und RFA 41 3.2.1 Vorfeldbohrungen 41 3.2.2 Lagerung und Probenahme 42 3.2.3 Körnungsanalyse und Wassergehaltsbestimmung 43 3.2.4 Feststoffcharakterisierung Kohlenstoff / Schwefel mittels CS-Mat 44 3.2.5 Röntgenfluoreszenzanalytik 44 3.3 Feldeluate, HCl-Test und organoleptische Ansprache 46 3.3.1 Feldelution 46 3.3.2 Salzsäure-Test (HCl-Test) 47 3.3.3 Organoleptische Ansprache 47 3.3.4 Hydrolytische Acidität 48 3.4 Verwitterungsversuche 49 3.5 Stoßbeprobung 51 3.6 Pufferungsversuche 52 3.7 Kippengrundwassermonitoring 54 3.7.1 Grundwassermessstellen und Probenahmeequipment 54 3.7.2 Feldanalytik 55 3.7.3 Laboranalytik 56 3.7.4 Hydrogeochemische Modellierung 56 4 Grundlagen und geologische Beschreibung des Untersuchungsgebietes 58 4.1 Untersuchungsgebiet 58 4.2 Tertiäre Einheiten 59 4.3 Quartäre Einheiten 61 4.4 Abgrenzung und Festlegung der Auswerteeinheiten 61 4.5 Vorfeldbohrungen 62 5 Anwendung der Methodik für den Tagebau Vereinigtes Schleenhain 65 5.1 Baufeld Schleenhain 65 5.1.1 Vorfeldbohrungen und Feldeluate 65 5.1.2 Stoffliche C/S-Charakterisierung 69 5.1.3 Verwitterungsversuche 72 5.1.4 Stoßbeprobung 85 5.1.5 Pufferungsversuche 90 5.1.6 Körnungsanalyse und Verwitterungszugänglichkeit 99 5.2 Baufeld Peres 103 5.2.1 Feldeluate 103 5.2.2 Vorfeldbohrungen und stoffliche Charakterisierung 105 5.2.3 Verwitterungsversuche 107 5.2.4 Pufferungsversuche 113 5.3 Beschaffenheit der Kippengrundwässer 114 5.3.1 Grundlegende hydrogeochemische Charakterisierung 115 5.3.2 Verwitterungszonen 117 5.3.3 Spurenmetallgehalte 118 5.3.4 Wirksamkeit der geogenen Puffer 119 5.3.5 Kennzeichnung der Sulfatreduktion als natürlicher Rückhalteprozess 121 5.3.6 Hydrochemische Modellierung 124 5.4 Fehlerdiskussion 126 6 Übertragung der Ergebnisse, Bewertung und Schlussfolgerung 127 6.1 Geologisches Modell und technische Verschnittmöglichkeiten 127 6.1.1 Geologisch-genetische Charakteristik der Auswerteeinheiten 127 6.1.2 Verbreitung und Mächtigkeit wesentlicher Auswerteeinheiten im Tagebau „Vereinigtes Schleenhain“ 128 6.1.3 Tagebautechnologische Verschnittmöglichkeiten 130 6.2 Geochemische Möglichkeiten bei der Umstellung der Tagebautechnologie – Massenversatz und Mischung 132 6.2.1 Gewinnungsscheiben 132 6.2.2 Regelkippenaufbau 134 6.2.3 „Schnelle Fahrweise“ und (Zwischen-) Abdeckung 134 6.2.4 Einmischung der Sedimente 135 6.3 RFA-Analytik und Bewertung von Sedimenteigenschaften 137 7 Zusammenfassung und weiterer Handlungsbedarf 139 7.1 Zusammenfassung - Ergebnisse Vorfeldbohrungen 139 7.2 Zusammenfassung – Verwitterungsversuche Labor und Feld 139 7.3 Zusammenfassung – Pufferungsversuche Schleenhain und Peres 141 7.4 Zusammenfassung – Gütemonitoring Kippengrundwässer 141 7.5 Zusammenfassung – Geologisches Modell/ Verschnitt/Technologie 142 7.6 Nachweis der Anwendbarkeit der Methode 144 7.7 Ausblick und weiterer Handlungsbedarf 145 Literatur und Quellen 146 Tabellenverzeichnis 151 Abbildungsverzeichnis 151 Abkürzungsverzeichnis 157 Anlagen 159

Weathering of silicate rocks releases cations and anions which are transported to the oceans by rivers where calcium carbonate precipitates from the seawater. This process results in the net consumption of atmospheric CO2 and has regulated the Earth’s surface temperature over geological timescales. These marine carbonates along with other sediments are eventually subducted resulting in mantle heterogeneity, which is subsequently sampled by mantle-derived magmas. This thesis investigates the geochemical and isotopic effects of weathering of silicate rocks on the surface of the Earth and the role of recycled crustal components in the petrogenesis of unique mantle-derived carbonate mineral-bearing igneous rocks called carbonatites. In the first part of the thesis, the geochemical and isotopic variability of a ~ 2.47 billion years old spheroidally weathered diabase has been studied. The variations in the major and trace element compositions of the weathered rindlets are explained by selective weathering of the rock-forming minerals plagioclase and clinopyroxene. Significant variations observed in the 87Sr/86Sr and 143Nd/144Nd ratios of the weathered rindlets have been used to estimate the timing of the peakweathering event which took place ~1.2-1.3 billion years ago, coinciding with the break-up of the supercontinent Columbia. It has also been shown that selective weathering of plagioclase and clinopyroxene can generate large variations in the stable Ca isotopic composition (δ44/40Ca) in a weathered diabase. These results have important implications for interpreting the δ44/40Ca variability observed in global rivers draining basalts. In the second part of the thesis, major, trace element and Nd, Sr and Ca isotopic compositions of globally distributed carbonatites (wholerock and acid-leached carbonate fractions) have been studied to investigate the role of recycled carbonates in the mantle-source of carbonatites. The δ44/40Ca values of carbonatites of widely varying eruption ages from different geographical locations show a large variability (~0.8 ‰). This variability is explained in terms of mantle mineralogy, recycling of carbonates into the mantle as well as contamination with the continental crust during magma emplacement. Additionally, the δ44/40Ca values of a wide-range of mantle-derived minerals like clinopyroxene, orthopyroxene, garnet, amphibole and phlogopite have been determined. The variation in δ44/40Ca of co-existing mantle minerals has implications for estimating the δ44/40Ca value of the bulk silicate earth (BSE). The acetic acid leached carbonate and non-carbonate fractions of carbonatites show different Nd, Sr and Ca isotopic compositions compared to the corresponding whole-rock samples which is interpreted in terms of isotopic disequilibrium between the coexiting carbonate and non-carbonate phases. Carbonatites and silicate rocks from the ~65 million years old Ambadongar carbonatite complex and the adjacent Phenai Mata region of western India were studied for their geochemical and isotopic compositions to understand the genetic link of these carbonatites with the spatially and temporally associated silicate rocks. The variability in the δ44/40Ca values of these rocks is interpreted in terms of continental crustal contamination, role of subducted carbonates and mantle mineralogy (phlogopite versus amphibole). The Ca isotopic data suggests that the Ambadongar carbonatites are derived from a deeper phlogopite-bearing mantle source whereas the silicate rocks are derived from a relatively shallow amphibole-bearing mantle source.