This thesis study is concerned with genetical investigation of Balikesir Balya Pb-Zn mineralization through the mineralogic-petrographic and geochemical examination of the core samples obtained from a total of 9 holes drilled by EczacibaSi ESAN Madencilik. The Pb-Zn mineralization in Balya is mainly of vein-type. Wall rocks hosting mineralizations are dacite, dacite porphyry and microdiorite. Major types of alteration are silicification, carbonatization and calc-silicate alteration, each of which is further subdivided into early and late stages and overprinted by argillic alteration of probable supergene origin. The ore minerals are mainly Zn- and Pb-sulphides and are hosted by the rocks with late calc-silicate alteration that underwent pervasive late silicification and late carbonatization. Sulfide mineralization is spatially and temporally associated with the late silicification and carbonatization stages. Lateral-vertical correlation of drill logs suggest that thickness of the ore zone tends to decrease towards north. The volcanic rocks hosting the mineralization have calc-alkaline nature. Major, trace and rare earth element (REE) geochemistry suggests either crustal contamination or subduction signature in the mantle source of the volcanics. Multi element patterns and discrimination diagrams collectively point to a post-collisional setting for their generation. Alteration geochemistry reveals that Fe2O3 and CaO are enriched during calc-silicate alteration in contrast to depletion of SiO2. Al2O3 and TiO2 are almost constant during late calc-silicate alteration. Enrichment of Fe2O3 and Na2O, and depletion of K2O characterize the silicified zones. Carbonatization is accompanied by strong enrichment of CaO and depletion of SiO2, Al2O3 and K2O.

Asphaltene precipitation, flocculation, and deposition in the reservoir and producing wells cause serious damages to the production equipment and possible failure to develop the reservoirs. From the field production prospective, predicting asphaltene precipitation, flocculation, and deposition in the reservoir and wellbore may avoid high expenditures associated with the reservoir remediation, well intervention techniques, and field production interruption. Since asphaltene precipitation, flocculation, and deposition strongly depend on the pressure, temperature, and composition variations (e.g. phase instability due to CO2 injection), it is important to have a model that can track the asphaltene behavior during the entire production system from the injection well to the production well, which is absent in the literature. Due to economic concerns for asphaltene related problems, companies spend a lot of money to design their own asphaltene inhibition and remediation procedures. However, due to the complexity and the lack of knowledge on the asphaltene problems, these asphaltene inhibition and remediation programs are not always successful. Near-wellbore asphaltene inhibition and remediation techniques can be divided into two categories: changing operating conditions, and chemical treatment of the reservoir. Although, the field applications of these procedures are discussed in the literature, a dynamic model that can handle asphaltene inhibition and remediation in the reservoir is missing. In this dissertation, a comprehensive non-isothermal compositional reservoir simulator with the capability of modeling near-wellbore asphaltene inhibition and remediation is developed to address the effect of asphaltene deposition on the reservoir performance. This simulator has many additional features compared to the available asphaltene reservoir simulators. We are able to model asphaltene behavior during primary, secondary, and EOR stages. A new approach is presented to model asphaltene precipitation and flocculation. Adsorption, entrainment, and pore-throat plugging are considered as the main mechanisms of the asphaltene deposition. Moreover, we consider porosity, absolute permeability, and oil viscosity reductions due to asphaltene. It is well known that the asphaltene deposition on the rock surface changes the wettability of the rock towards oil-wet condition. Although many experiments in the literature have been conducted to understand the physics underlying wettability alteration due to asphaltene deposition, a comprehensive mathematical model describing this phenomenon is absent. Based on the available experimental data, a wettability alteration model due to asphaltene deposition is proposed and implemented into the simulator. Furthermore, the reservoir simulator is coupled to a wellbore simulator to model asphaltene deposition in the entire production system, from the injection well to the production well. The coupled reservoir/wellbore model can be used to track asphaltene deposition, to diagnose the potential of asphaltene problems in the wellbore and reservoir, and to find the optimum operating conditions of the well that minimizes asphaltene problems. In addition, the simulator is capable of modeling near-wellbore asphaltene remediation using chemical treatment. Based on the mechanisms of the asphaltene-dispersant interactions, a dynamic modeling approach for the near-wellbore asphaltene chemical treatments is proposed and implemented in the simulator. Using the dynamic asphaltene remediation model, we can optimize the asphaltene treatment plan to reduce asphaltene related problems in a field. The results of our simulations show that asphaltene precipitation, flocculation, and deposition in the reservoir and wellbore are dynamic processes. Many parameters, such as oil velocity, wettability alteration, pressure, temperature, and composition variations influence the trend of these processes. In the simulation test cases, we observe that asphaltene precipitation, flocculation, and deposition can occur in primary production, secondary production, or EOR stages. In addition, our results show that the wettability alteration has the major effect on the performance of the reservoir, comparing to the permeability reduction. During CO2 flooding, asphaltene precipitation occurs mostly at the front, and asphaltene deposition is at its maximum close to the reservoir boundaries where the front velocity is at its minimum. In addition, the results of the coupled reservoir/wellbore simulator show that the behavior of asphaltene in the wellbore and reservoir are fully coupled with each other. Therefore, a standalone reservoir or wellbore simulator is not able to predict the asphaltene behavior properly in the entire system. Finally, we show that the efficiency of an asphaltene chemical treatment plan depends on the type of dispersant, amount of dispersant, soaking time, number of treatment jobs, and the time period between two treatment jobs. / text

Highly fractured carbonate reservoirs are a class of reservoirs characterized by high conductivity fractures surrounding low permeability matrix blocks. In these reservoirs, wettability alteration is a key method for recovering oil. Water imbibes into the matrix blocks upon water flooding if the reservoir rock is water-wet. However, many carbonate reservoirs are oil-wet. Surfactant solution was used to enhance spontaneous imbibition between the fractures and the matrix by both wettability alteration and ultra-low interfacial tensions. The first part of this study was devoted to determining the wettability of reservoir rocks using Amott-Harvey Index method, and also evaluating the performance of surfactants on wettability alteration, based on the contact angle measurement and spontaneous imbibition rate and ultimate oil recovery on oil-wet reservoir cores. The reservoir rocks have been found to be slightly oil-wet. One cationic surfactant BTC8358, one anionic surfactant and one ultra-low IFT surfactant formulation AKL-207 are all found to alter the wettability towards more water-wet and promote oil recovery through spontaneous imbibition. The second part of the study focused on the parameters that affect wettability alteration by surfactants. Some factors such as core dimension, permeability and heterogeneity of porous medium are evaluated in the spontaneous imbibition tests. Higher permeability leads to higher imbibition rate and higher ultimate oil recovery. Heterogeneity of core samples slows down the imbibition process if other properties are similar. Core dimension is critical in upscaling from laboratory conditions to field matrix blocks. The imbibition rate is slower in larger dimension of core. Further, we investigated the effects of EDTA in surfactant-mediated spontaneous imbibition. Since high concentration of cationic divalent ions in the aqueous solution markedly suppresses the surfactant-mediated wettability alteration, EDTA improved the performance of surfactant in the spontaneous imbibition tests. It is proposed in the thesis that surfactant/EDTA-enhanced imbibition may involve the dissolution mechanism. More experiments should be conducted to verify this mechanism. The benefits of using EDTA in the surfactant solution include but not limited to: altering the surface charge of carbonate to negative, producing the in-situ soap, reducing the brine hardness, decreasing the surfactant adsorption, and creating the water-wet area by dissolving the dolomite mineral. / text

The goal of this work is to change the wettability of a carbonate rock from oil wet-mixed-wet towards water-wet at high temperature and high salinity. Only simple surfactant systems (single surfactant, dual surfactants) in dilute concentration were tried for this purpose. It was thought that the change in wettability would help to recover more oil during secondary surfactant flood as compared to regular waterflood. Three types of surfactants, anionic, non-ionic and cationic surfactants in dilute concentrations (<0.2 wt%) were used. Initial surfactant screening was done on the basis of aqueous stability at these harsh conditions. Contact angle experiments on aged calcite plates were done to narrow down the list of surfactants and spontaneous imbibition experiments were conducted on field cores for promising surfactants. Secondary waterflooding was conducted in cores with and without the wettability altering surfactants. It was observed that barring a few surfactants, most were aqueous unstable by themselves at these harsh conditions. Dual surfactant systems, a mixture of a non-ionic and a cationic surfactant increased the aqueous stability of the non-ionic surfactants. One of the dual surfactant system, a mixture of Tergitol NP-10 and Dodecyl trimethyl ammonium bromide, proved very effective for wettability alteration and could recover 70-80% of OOIP during spontaneous imbibition. Secondary waterflooding with the wettability altering surfactant (without alkali or polymer) increased the oil recovery over the waterflooding without the surfactants (from 29% to 40% OOIP). Surfactant adsorption calculated during the coreflood showed an adsorption of 0.24 mg NP-10/gm of rock and 0.20 mg DTAB/gm of rock. A waterflood done after the surfactant flood revealed change in the relative permeability before and after the surfactant flood suggesting change in wettability towards water-wet. / text

Understanding climatic and water-mineral chemistry affecting hominin habitats duringthe period 1.92 to 1.80 Ma in Paleolake Olduvai basin, Tanzania is of social and scientific interest. Previous Olduvai research reported climate cycles in bulk sample mineral analyses. Xray diffraction, X-ray fluorescence, and color analyses of Locality 80 Tuff Bed I samples tested the null hypothesis: Alteration mineralogy of Central Basin volcanic Tuffs IA through IF reflect salinity/alkalinity cycles. Such cyclicity was not found. Several primary authigenic minerals were confirmed, but not as previously reported. Tuffs are thoroughly altered, mostly to potassium-feldspars, zeolites, and carbonates, plus other feldspars and clay minerals (clays not in this study). Nevertheless, other findings reveal there is more to be learned. Results imply a majorgeochemical shift around 1.869-1.857 Ma, from non-zeolite forming environments to zeolite forming environments. A newly developed age model could aid re-analysis of past work and assist future research.

The North Caribou Terrane forms the core of Superior Province and records a protracted history of crustal growth and modification. At the centre of the North Caribou Terrane, lies the North Caribou greenstone belt, which is surrounded by granitoids of diverse compositions and ages. This study reports whole-rock geochemistry, zircon and titanite geochronology, and hornblende geobarometry on these plutonic rocks. Although zircons as old as 3132 ± 7 Ma were found, the main magmatic pulse occurred between 2880 and 2830 Ma, and geobarometry indicates tectonic thickening during this period. This was followed by widespread hydrothermal alteration and limited magmatism from 2760 to 2680 Ma, and shallow, brittle-ductile intrusions at circa 2630 Ma. From 2730 to 2630 Ma, intrusions were emplaced at increasingly shallow crustal levels. All of the rocks, except for the youngest pegmatitic intrusions, show similar patterns in major and trace elements, with a general trend toward more evolved compositions through time. These patterns indicate that the granitoids record mostly reworking of early intrusions, which is also consistent with patterns observed in the geochronology.

This thesis documents hydrothermal alteration patterns exposed along major fault scarps at Pito Deep, a tectonic window into the upper ocean crust formed at the very fast-spreading (>140 mm/yr) East Pacific Rise. Two main study areas were examined, each covering at least five lateral kms across the sheeted dike complex, exposing > four km of relief. and revealing >70,000 years of spreading history. Hydrothermal alteration patterns reveal vertical and lateral variation in the degree of alteration, dominant secondary mineral assemblages, peak temperatures of alteration, and metal depletion on the scale of 10s to 100s of meters. Amphibole and chlorite are the most common secondary minerals and replace clinopyroxene, interstitial zones, and plagioclase. Mineral assemblages indicate alteration temperatures of 250-450°C were common throughout most of the sheeted dike complex. Geothermometry indicates a range in alteration temperatures from 902-505°C and 350-60°C for amphibole-plagioclase and chlorite thermometry respectively. The highest temperatures are recorded in both deformed and undeformed dikes indicating that deformation was not always synchronous with peak alteration temperatures.

The Palaeoproterozoic Dannemora inlier is situated in the north-eastern Bergslagen region. The inlier consists of primary and reworked volcanic deposits, stromatolitic limestone and skarn that have been subjected to upper greenschist facies metamorphism. Thicknesses of the different volcanic deposits indicate deposition within a caldera, where syn-volcanic alkali alteration was strong. The deposition was submarine and below wave base in the eastern part of the inlier, but above wave base in the central part where erosion channels together with cross-bedding occurs frequently. The Dannemora Formation is the volcanosedimentary succession of the inlier. Two borehole profiles, a northern and a southern, cover the whole Formation and show different alteration patterns. A strong depletion of Na2O and enrichment of K2O dominate in the southern profile, whereas this pattern is not as evident in the northern profile. The uppermost section of the totally eight constituting the Formation, is intercalated with ore-bearing dolomitic limestone and skarn, and has experienced at least two episodes of alteration. An anticline has been established lithogeochemically from immobile element ratios and the reoccurrence of an accretionary lapilli bed. Numerous altered sub-alkaline, calc-alkaline and basaltic dykes have been recorded in the Dannemora inlier. They are the result of mixing and fractionation of at least three magmatic sources and carry a mixed signature of subduction zone and within-plate volcanic tectonic setting. A seismic profile across the Dannemora inlier images a strong reflector package that dips c. 50° E to the east of the inlier. This package coincides with the polyphase, E-up reverse, brittle-ductile Österbybruk deformation zone (ÖDZ). Yet another steep reflector in the Dannemora ore-field extends to a depth of more than two kilometres. This reflector might represent either a deep-seated iron deposit or a fluid-bearing fault zone.

Anthropogenic disruptions in the form of hydrological alterations, such as dam construction and the associated water diversions are a cause of much upheaval to local and regional ecosystems. Lake 626 within the Experimental Lakes Area of north-west Ontario, along with its downstream wetlands, 626A and 626B are one such system. Construction of a dam at the L626 inflow has completely restricted water flow, reducing and reshaping the watershed, increasing water retention time, and decreasing outflow into the wetlands. This study investigates the state of each wetland through physical and geochemical characterization during the first year following the diversion. Previous studies have found that hydrological diversions in wetlands can lower water table levels, altering soil chemistry and producing a shift in floral and faunal communities. Ultimate consequences involve significant loss of wetland area through conversion to upland habitat. This provides a model for climatic warming scenarios, wherein sustained drought conditions can produce the same result. Boreal wetlands are surprising fragile ecosystems that store massive quantities of carbon and are at risk of releasing it in such situations. One study showed that an extended summer drought in an otherwise average year with above average precipitation produced losses of 90 g C/m2 over the course of the year. Maintenance of reduced-flow in wetlands 626A and 626B is expected to convert the system into a carbon source and reduce overall wetland area. Radiocarbon dating has revealed that following deglaciation, both 626A and 626B basins were open water wetlands, depositing limnic peat for about 3200 and 1300 years respectively. Each site then transitioned into open sedge dominated fen – 626B to the present and 626A until about 2.5 ka BP when Sphagnum began to develop. Wetland 626B is decidedly an open shrub/sedge fen, supporting Myrica gale, Chamaedaphne calyculata and Carex rostrata / lasiocarpa communities. Wetland 626A is a bog/fen complex, sharing similar communities in the fen areas, but housing a large, centrally located bog of shrub species overlying Sphagnum hummocks. Tritium values in 626A were similar to cosmic background levels, indicating that recharge of basal pore water has not occurred in at least 60 years. Tritium in 626B was much higher, suggesting a substantial difference in hydrology or peat hydraulic conductivity between the basins. Measurement of DOC profiles showed high concentrations in near-surface water, reaching over 80 mg/L, and dropping to about 20 mg/L at maximum depths. An opposite trend was seen for DIC and CH4 profiles which increased concentration with depth (25 – 70 mg/L DIC; 75 – 700 μmol/L CH4). Isotopically however, 13C signatures from basal DIC were more positive while signatures from CH4 were typically more negative (-6 ‰ to +4 ‰ DIC; -57 ‰ to -73 ‰ CH4). Breakdown of DOC by LC-OCD showed high concentrations of humic substances and low molecular weight neutrals. The origin of humic substances in surface water became more pedogenic with increasing distance from the L626 outflow, indicating the influence of decaying wetland vegetation on the DOC of adjacent water. A comparison between contemporary and future characterization of boreal peatlands under drought-like conditions will provide a better understanding of the impacts suffered by wetlands during hydrological alterations. The high sensitivity of wetlands to changing hydrology should also provide a measure for gauging the effects of long term climate warming. This will assist in the development of environmental policies to better govern both the establishment of water diversions and the multitude of other practices leading to climate change.

Tracking and quantifying hydrologic change in urbanizing watersheds is a complex problem which can vary spatially and temporally throughout the effective catchment area as change occurs. Hydromodification due to urbanization usually results in a larger peak event stream discharge, a change in typical event volume, a reduced lag time between rainfall and stream discharge events, and a more complex falling hydrograph. Recently extracted Environment Canada data have allowed the creation of a high resolution instantaneous stream flow dataset dating to the late 1960s for many Ontario gauge stations. Hydrometric data were obtained for fifteen urban and semi-urban catchments within Southern Ontario ranging in size from ~50km² to 300 km² with urbanized land use assemblages varying from <5% to 80%. Utilizing automated methods, each individual runoff event from the hydrographic record was identified and characterized. Temporal changes to urban land area, land use, and road length were quantified for each watershed from aerial photography spanning the period of record at approximately 8 year intervals allowing identified trends in event hydrograph parameters to be correlated quantitatively with the alteration of the catchment over time. <br> Increasing trends in event peak discharge were identified in all but one study catchment. Event volume was found to be consistently increasing in most of the urban watershed, while trends in event duration were observed but with no clear increasing or decreasing trend. The lack of consistent trends in the timing and distribution of flow during runoff events suggest that build-out, drainage network design, and stormwater management systems play differing roles in the neighbouring urban catchments. Changes to flood recurrence intervals through the period of urbanization were also investigated; peak magnitude of high frequency events is affected to a greater extent than low frequency or flood events. The relative change in return frequency distribution is not consistent between catchments, also the degree of alteration can differ between various recurrence intervals at a gauge. Peak discharge of some return periods appeared to decrease with urban development suggesting that the increased detention brought with urban stormwater management systems have effectively offset the increased runoff due to additional impervious area and improved drainage efficiency. A consistent relationship defining the change in geomorphically significant return periods (i.e. channel forming flow) with urbanization was identified in neighbouring urban catchments.