Stable carbon isotopes of HCO3− in oil-field waters—implications for the origin of CO2

The δ¹³C values of dissolved HCO₃^? in 75 water samples from 15 oil and gas fields (San Joaquin Valley, Calif., and the Houston-Galveston and Corpus Christi areas of Texas) were determined to study the sources of CO₂ of the dissolved species and carbonate cements that modify the porosity and permeability of many petroleum reservoir rocks. The reservoir rocks are sandstones which range in age from Eocene through Miocene. The δ¹³C values of total HCO₃^? indicate that the carbon in the dissolved carbonate species and carbonate cements is mainly of organic origin.The range of δ¹³C values for the HCO₃^? of these waters is ?20–28 per mil relative to PDB. This wide range of δ¹³C values is explained by three mechanisms. Microbiological degradation of organic matter appears to be the dominant process controlling the extremely low and high δ¹³C values of HCO₃^? in the shallow production zones where the subsurface temperatures are less than 80°C. The extremely low δ¹³C values (< ?10 per mil) are obtained in waters where concentrations of SO₄^2? are more than 25 mg/l and probably result from the degradation of organic acid anions by sulfate-reducing bacteria (SO₄^2? + CH₃COO^? → 2HCO₃^? + HS^?). The high δ¹³C values probably result from the degradation of these anions by methanogenic bacteria (CH₃COO^? + H₂OaiHCO₃^? + CH₄).Thermal decarboxylation of short-chain aliphatic acid anions (principally acetate) to produce CO₂ and CH₄ is probably the major source of CO₂ for production zones with subsurface temperatures greater than 80°C. The δ¹³C values of HCO₃^? for waters from zones with temperatures greater than 100°C result from isotopic equilibration between CO₂ and CH₄. At these high temperatures, δ¹³C values of HCO₃^? decrease with increasing temperatures and decreasing concentrations of these acid anions.     

水-岩相互作用国际学术会议三十年

三十多年前(1974年9月9～14日),在捷克的布拉格召开了第一届水-岩相互作用(英文简写为WRI)国际学术会议,Tomas Paces博士担任该届会议的秘书长,来自21个国家的近150位会议代表参加了为期4 d的学术会议.     

Modeling the stochastic dependence of air pollution index data

The air pollution index (API) is a common tool, which is often used for determining the quality of air in the environment. In this study, a discrete-time Markov chain model is applied for describing the stochastic behaviour of API data. The study reported in this paper is conducted based on the data collected from Klang city in Malaysia for a period of 3 years (2012–2014). Based on the API data, we considered a five-state Markov chain for depicting the five different states of the air pollution. We identified the Markov chain is an ergodic Markov chain and determined the limiting distribution for each state of the air pollution. In addition, we have identified the mean first passage time from one state to another. Based on the limiting distribution and the mean return time, we found that the risk of occurrences for unhealthy events is small. However, the risk remains notably troubling. Therefore, the standard of air quality in Klang falls within a margin that is considered healthy for human beings.     

Serpentinites and their tectonic signature along the Northwest Zagros Thrust Zone, Kurdistan Region, Iraq

Two types of serpentinized peridotites are distinguished within the Northwest Zagros Thrust Zone (NW-ZTZ) in Kurdistan region of Iraq. One is found as lower members of ophiolite sequences, such as the Mawat and Penjwin ophiolites of the upper Cretaceous age. The other is represented by intraformational isolated serpentinite bodies in Betwat, Qaladeza, and Qalander areas within the Walash–Naopurdan volcano-sedimentary unit of the Paleocene to Eocene paleo-arc tectonic setting. Serpentinites within the NW-ZTZ consist mainly of lizardite and chrysotile, with subordinate amounts of syn-serpentinization magnetite, carbonates, chromium chlorite, tremolite, and talc as secondary minerals, and olivine, clinopyroxene, and chromian spinel as primary minerals. Minor antigorite is also found in the sheared serpentinites often found in ophiolite sequences. Petrological and geochemical studies of serpentinites from the NW-ZTZ show that, of the original protoliths of serpentinites, those associated with ophiolites are residual depleted harzburgite and dunite. The $ {\text{Cr}}\# \left( {{{ = {\text{ Cr}}} \mathord{\left/ {\vphantom {{ = {\text{ Cr}}} {\left( {{\text{Cr}} + {\text{Al}}} \right){\text{ atomic ratio}}}}} \right. \kern-0em} {\left( {{\text{Cr}} + {\text{Al}}} \right){\text{ atomic ratio}}}}} \right) $ of chromian spinel is more than 0.6, and the forsterite content of olivine is 91–92. On the other hand, the original protolith of isolated serpentinite bodies is less depleted harzburgite or depleted lherzolite, which has spinel with Cr# less than 0.6 and olivine with 90–91 forsterite contents. Whole rock chemistry of major, trace, and rare earth elements shows that the serpentinites of ophiolite sequences are depleted in CaO, Al₂O₃, and SiO₂, Sr, and Zr, and are enriched in MgO, Ni, and Cr, in comparison with the isolated serpentinites. Cr# of the disseminated unaltered chromian spinels indicates that the serpentinites of both types had been originated from the supra-subduction zone tectonic setting; the serpentinites of ophiolite sequences obducted and thrusted over the continental margin during the obduction of the Tethyth oceanic crust onto the Arabian continental margin during the upper Cretaceous period. Isolated serpentinite bodies represent serpentinized forearc mantle wedge peridotites emplaced by diapiric upwelling into non-accretionary forearc tectonic settings during the Paleocene to Eocene age.     

Complex interplay between depositional and petrophysical environments in Holocene tidal carbonates (Al Ruwais,Qatar)

Carbonate rocks can be classified in terms of those properties relating to the pore system of lithified sediments, so‐called ‘petrophysical rock types’, or ‘depositional rock types’ which are categorized based on characteristics directly reflecting their original depositional environment. Whereas petrophysical rock types are typically used to identify and distribute rock bodies within a reservoir with similar flow characteristics, depositional rock types ignore pore types and capture sedimentary structures, lithology and fossils. Both classification systems are extensively used to describe reservoir rocks, but the degree of plurality between them remains poorly understood and is the motivation for this study. To examine the degree of congruency between the two classification schemes, a field assessment was conducted for a 175 km² area situated offshore Al Ruwais, northern Qatar, encompassing depositional environments spanning supratidal, intertidal, shallow subtidal and open marine conditions. A total of 350 surficial sediment samples were collected along 24 shore‐normal transects. Each sample was assigned a ‘petrophysical rock type’ class based on analysis of sedimentary texture (grain size and sorting). ‘Depositional rock type’ classes, by contrast, were defined with reference to faunal content and, in turn, classes of mineralogy were delimited by weighting this content against the mineralogy of each faunal category. Of course, the samples studied correspond to unconsolidated sediments and not to indurated rocks. However, considering only primary porosity and permeability preservation, it is reasonable to assume that the classified sediments would become petrophysical rock types and depositional rock types when consolidated, following their primary grain size, sorting and grain type distribution. Therefore, the term ‘rock type’ is retained here for ease of terminology but, for clarity, these are sediment samples. The discrete samples were interpolated into continuous surfaces describing the distribution of depositional rock types, petrophysical rock types and mineralogy, and spatial correspondence between those surfaces was statistically evaluated. In order to link these parameters with environment of deposition, their correlation with water depth (as audited from airborne light detection and ranging) and ecological habitat (mapped from DigitalGlobe satellite imagery) was also assessed. The data reveal that spatial distributions of sedimentary faunal, petrographic and mineralogical properties do not show exactly congruent patterns. Other meaningful trends do exist, however. For example, the occurrence of certain depositional rock types is indicative of particular petrophysical rock types, and vice versa. Further, connections between petrophysical rock types and mineralogy are emphasized and offer insight as to how the evolution of matrix porosity might be predicted via diagenetic models tuned to specific sediment textures. Useful relationships are also identified between the occurrence of petrophysical rock types and depositional rock types, and both ecological habitat and water depth. The potential of such dualities is two‐fold. Firstly, they can be applied to more realistically distribute petrophysical rock types and depositional rock types by environment of deposition in reservoir models and, secondly, the use of modern carbonate systems as subsurface analogues might be enhanced.     

Changes in the chemistry of shallow groundwater related to the 2008 injection of CO2 at the ZERT field site, Bozeman, Montana

Approximately 300 kg/day of food-grade CO₂ was injected through a perforated pipe placed horizontally 2–2.3 m deep during July 9–August 7, 2008 at the MSU-ZERT field test to evaluate atmospheric and near-surface monitoring and detection techniques applicable to the subsurface storage and potential leakage of CO₂. As part of this multidisciplinary research project, 80 samples of water were collected from 10 shallow monitoring wells (1.5 or 3.0 m deep) installed 1–6 m from the injection pipe, at the southwestern end of the slotted section (zone VI), and from two distant monitoring wells. The samples were collected before, during, and following CO₂ injection. The main objective of study was to investigate changes in the concentrations of major, minor, and trace inorganic and organic compounds during and following CO₂ injection. The ultimate goals were (1) to better understand the potential of groundwater quality impacts related to CO₂ leakage from deep storage operations, (2) to develop geochemical tools that could provide early detection of CO₂ intrusion into underground sources of drinking water (USDW), and (3) to test the predictive capabilities of geochemical codes against field data. Field determinations showed rapid and systematic changes in pH (7.0–5.6), alkalinity (400–1,330 mg/l as HCO₃), and electrical conductance (600–1,800 μS/cm) following CO₂ injection in samples collected from the 1.5 m-deep wells. Laboratory results show major increases in the concentrations of Ca (90–240 mg/l), Mg (25–70 mg/l), Fe (5–1,200 ppb), and Mn (5–1,400 ppb) following CO₂ injection. These chemical changes could provide early detection of CO₂ leakage into shallow groundwater from deep storage operations. Dissolution of observed carbonate minerals and desorption-ion exchange resulting from lowered pH values following CO₂ injection are the likely geochemical processes responsible for the observed increases in the concentrations of solutes; concentrations generally decreased temporarily following four significant precipitation events. The DOC values obtained are 5 ± 2 mg/l, and the variations do not correlate with CO₂ injection. CO₂ injection, however, is responsible for detection of BTEX (e.g. benzene, 0–0.8 ppb), mobilization of metals, the lowered pH values, and increases in the concentrations of other solutes in groundwater. The trace metal and BTEX concentrations are all significantly below the maximum contaminant levels (MCLs). Sequential leaching of core samples is being carried out to investigate the source of metals and other solutes.     

Geospatial Information and Environmental Isotopes for Hydrogeological Evaluation: Ras Alam El Rum,Northwestern Coast of Egypt

The present study demonstrates the potential of the geospatial information as well as isotopes and chemical analyses to elucidate the hydrogeological setting of the study area. The main objective of this research is to identify factors affecting the occurrence and quality of groundwater in the study area. The Ras Alam El Rum is the pilot area chosen in the northwestern coast of Egypt to evaluate the carbonate aquifer with emphasis on the Middle Miocene aquifer, which has been explored recently. The average of annual precipitation and surface runoff amounts were estimated to indicate possibility of groundwater recharge, where the water-bearing rocks are mainly fractured. The isotope data indicate that the groundwater was derived from rainwater, the recharge source is local precipitation, and no indication of seawater intrusion was recorded. The salinity of the groundwater is attributed to interaction between the water and aquifer rocks represented by limestone, dolomitic limestone, and marl. The mineral indices obtained from the geochemical model reveal that the groundwater is over-saturated with aragonite, calcite, dolomite, strontianite, and barite. The hydrogeological evaluation of the study area led to recommendations to determine of the suitable areas for exploration of the Middle Miocene aquifer and to protect groundwater from deterioration.     

Integrated remote sensing and GIS for surface water development. Case study: Ras El Hekma area, northwestern coast of Egypt

The surface water development can help to address the growing demand for water resources and the effects of stormwater flooding on the local environment. The study area was chosen according to its special conditions where it represents one of the main headlands along the southern Mediterranean coast and receives amount of rainfall during the winter season. The main objective of this paper is to monitor and record data about the current surface water status as well as to have a systematic understanding of the water resources base in the study area, and this assessment will contribute in the exploitation of the surface water. The current research is integration between geomorphology, geology, remote sensing, and the applications of geographical information system. The total amount of annual rainfall and surface runoff are estimated (annual rainfall is 23.345 million m³ and surface runoff is 1.167 million m³). On the other hand, the surface runoff which has been resulted from one event (storm) is also estimated to be 483,000 m³/day. The present study introduce some recommendations; the cisterns should be established in the vicinities of the watersheds and on the downstream of the drainage basins to store water before draining to the sea, the dug should be in oolitic limestone to reduce drilling costs, the water reservoirs should be established to store large amount of surface water (from 2,000 to 3,000 m³). Dams are necessary to protect the agriculture activities from any flash hazard which is expected any time.     

Sedimentology and stratigraphy of Geli Khana Formation (Anisian–Ladinian), a contourite depositional system in the northeastern passive margin of Arabian plate,northern Iraq-Kurdistan region

The Middle Triassic Geli Khana Formation of the northeastern part of the Arabian plate marks the establishment of the Neo-Tethys passive margin. The indication of bottom-current activities, within the lower and middle parts of the formation, gives the opportunity to study Middle Triassic facies and depositional settings in northern Iraq. Three sections (two outcrops and one subsurface) were selected to study the sedimentology and stratigraphy of Geli Khana succession. Petrographic investigations of the carbonate and siliciclastic beds on 140 thin sections show both skeletal and non-skeletal grains. The skeletal grains reveal deposition in deep open marine and in shallow warm water, within a gently slope ramp setting. Twelve microfacies were recognized. In the northern thrust zone, these facies were subdivided, according to their environmental interpretation, into three basic types of facies associations: outer ramp/basinal, middle ramp/slope, and inner ramp/lagoon (open and restricted). Restricted lagoon and tidal flat facies association is suggested for the Geli Khana Formation in Well Jabal Kand-1. Typical contourite deposits associated with turbidites are recognized for the first time in the Middle Triassic Geli Khana Formation in the northern thrust zone, northern Iraq, Kurdistan region. The contourites are characterized by thin beds and occasional lenses of sandy limestones, siltstones to fine-grained sandstones with current ripples, laminations (planar and cross), and erosional surfaces. These current structures are associated with thin-bedded (5–25 cm) limestones and shales. Deformation structures are characteristic feature of the formation inferring syndepositional slumping and turbidite influence too.