Geochemical detection of carbon dioxide in dilute aquifers

Background  

Carbon storage in deep saline reservoirs has the potential to lower the amount of CO₂ emitted to the atmosphere and to mitigate global warming. Leakage back to the atmosphere through abandoned wells and along faults would reduce the efficiency of carbon storage, possibly leading to health and ecological hazards at the ground surface, and possibly impacting water quality of near-surface dilute aquifers. We use static equilibrium and reactive transport simulations to test the hypothesis that perturbations in water chemistry associated with a CO₂ gas leak into dilute groundwater are important measures for the potential release of CO₂ to the atmosphere. Simulation parameters are constrained by groundwater chemistry, flow, and lithology from the High Plains aquifer. The High Plains aquifer is used to represent a typical sedimentary aquifer overlying a deep CO₂ storage reservoir. Specifically, we address the relationships between CO₂ flux, groundwater flow, detection time and distance. The CO₂ flux ranges from 10³ to 2 × 10⁶ t/yr (0.63 to 1250 t/m²/yr) to assess chemical perturbations resulting from relatively small leaks that may compromise long-term storage, water quality, and surface ecology, and larger leaks characteristic of short-term well failure.     

A contemporary appraisal of some key Fiskian concepts with emphasis on Holocene meander belt formation and morphology

Looking back five decades and reflecting on the contributions of Harold Fisk to Lower Mississippi Valley (LMV) geological knowledge, it is apparent that he was highly successful in making engineers aware of the critical role of glacial advance and retreat, sea level changes, valley slope and river gradient, and time in affecting geomorphic processes, sedimentary patterns, and river regimes. Perhaps his greatest contribution to river engineering was in recognizing and elaborating on the effects of bed and bank materials on stream meandering. Fisk, however, could only work within the prevailing geological theory and method of his time with regard to glacial chronology and stratigraphy and such matters as global structure and tectonics. Major advances in these areas with new concepts and techniques have shown his LMV glacial response model to be oversimplified and invalid in some respects. More cycles of valley filling and cutting are now known to be represented in the alluvial sequence and his concept of deep valley entrenchment as a direct response to sea level changes is untenable in light of substantial new data. The presence of a regional, rectilinear fracture pattern with a corresponding network of major fault zones has not been substantiated by subsurface data. The most widely known aspect of Fisk's work is his detailed interpretation and colorful depiction of the complex pattern of overlapping, cross cutting, and discontinuous Holocene meander belts and their hundreds of abandoned channels. However, it is now recognized that Fisk's elaborate chronological reconstruction is largely invalid both because of some incorrect basic assumptions and his lack of radiocarbon and other numerical dating techniques for precise control. A newly emerging model of meander belt formation is more generalized and relies heavily on archaeological evidence. It places emphasis on episodes of multiple active river courses (partial flow channels), frequent formation of distributary channels, and the significant influence of Mississippi River tributaries and minor basin drainage. Interesting regional variations over time in meander belt configurations and morphology may reflect climate changes, but at present broad-scale variations in the lithology of the Quaternary alluvial sequence appear to be the dominant control.     

Experimental studies At 5–12 GPa of the Ondermatjie hypabyssal kimberlite

Liquidus and sub-liquidus phase relationships are reported for melts formed from an aphanitic kimberlite composition crystallized at 5–12 GPa and 900–1400 °C. The liquidus phase over the pressure range investigated is forsteritic olivine. This is followed with decreasing temperature by olivine plus garnet as the initial sub-liquidus solid phase assemblage. Supra-solidus assemblages consist of olivine+garnet+clinopyroxene+Mg-ilmenite+liquid at 5–7 GPa or olivine+garnet+clinopyroxene+hematite–ilmenite solid solutions (+/−perovskite)+liquid at 8–12 GPa. Phlogopite forms as a near-solidus phase only at 900 °C and 6 GPa. Orthopyroxene does not form at any temperature and pressure. All garnets formed at 6–7 GPa are Ti-rich almandine–grossular–pyrope solid solutions and not Cr-pyrope, whereas garnets formed above 8 GPa are Ti- and Fe³⁺-rich and have no natural counterparts. Quenched liquids are represented by magnesite at 10–12 GPa and Mg–Ca-carbonates at lower pressures. In addition to forming discrete crystals, Mg-ilmenite and hematite–ilmenite solid solutions occur as lamellar intergrowths that are identical in texture to naturally occurring intergrowths. Mg-ilmenite compositions at 6–7 GPa are similar to those of the natural occurrences, whereas clinopyroxenes are richer in Ca. The effects of graphite versus platinum capsules on the oxygen fugacity of the experimental charges and the composition of the olivine, clinopyroxene, Fe–Ti-oxides and garnets formed are described. These experimental data are interpreted to indicate that kimberlite magmas are unlikely to be formed by very small degrees of partial melting of a simple homogeneous carbonated garnet lherzolite mantle. It is proposed that kimberlite magmas form by extensive partial melting of metasomatized mantle, i.e. mineralogically complex carbonate-bearing veins in a lherzolitic/harzburgitic substrate, and that lamellar ilmenite–clinopyroxene intergrowths represent the products of non-equilibrium growth in kimberlite magma.     

锚喷网支护法在中远两湾城(一期)B14基坑护壁工程中的应用

中远两湾城（一期）B14基坑采用锚喷网（土钉）支护法获得成功。施工中通过动态监测反馈到施工过程，及时调整支护参数；对于深五米以上地段增加了竖向注浆锚管以防止深部滑移；最大限度地缩短各分层的支护施工时间，从而有效控制各阶段边壁的变形，确保基坑边壁整体稳定。同时对基坑内进行轻型井点抽水和明排水，以保持施工作业过程的干燥。     

Seasonal variations in the composition of mine drainage-contaminated groundwater in Dalarna, Sweden

Groundwater down-gradient from a mine rock dump in Dalarna, Sweden was sampled from the onset of snowmelt runoff (April) until October in order to investigate seasonal variations in groundwater composition. The results demonstrate that considerable variation in solute concentration (Al, Cu, Fe, SO₄²⁻, Zn) and acidity occurs in groundwater; the greatest change in solute concentrations occurs during the melting of the snow cover, when sulfide oxidation products are flushed from the rock dump. During this period, groundwater flow is concentrated near the soil surface with an estimated velocity of 1 m/day. Groundwater acidity varied by a factor of four closest to the rock dump during the sampling period, but these variations were attenuated with distance from the rock dump. Over a distance of 145 m, groundwater pH increases from 2.5 to 4.0 and acidity decreases from 3–13 to 0.8–1.1 meq/L, which is the combined effect of ferric iron precipitation and aluminosilicate weathering. As a result of flushing from the upper soil horizons, peaks in total organic carbon and ammonium concentrations in groundwater are observed at the end of snowmelt. In soils impacted by acidic surface runoff, the sequential extraction of C horizon soils indicates the accumulation of Cu in well-crystallized iron oxyhydroxides in the upper C horizon, while Cu, Fe, Ni and Zn accumulate in a well-crystallized iron oxyhydroxide hardpan that has formed 2.5m below the ground surface. Surface complexation modeling demonstrates that SO₄²⁻ and Cu adsorb to the abundant iron oxyhydroxides at pH < 4, while Zn adsorption in this pH range is minimal.     

Hornblende–garnet–plagioclase thermobarometry: a natural assemblage calibration of the thermodynamics of hornblende

Calibrations are presented for an independent set of four equilibria between end-members of garnet, hornblende, plagioclase and quartz. Thermodynamic data from a large internally-consistent thermodynamic dataset are used to determine the ΔG° of the equilibria. Then, with the known mixing properties of garnet and plagioclase, the non-ideal mixing in amphibole is derived from a set of 74 natural garnet–amphibole–plagioclase–quartz assemblages crystallised in the range 4–13 kbar and 500–800 °C. The advantage of using known thermodynamic data to calculate ΔG° is that correlated variations of composition with temperature and pressure are not manifested in fictive derived entropies and volumes, but are accounted for with non-ideal mixing terms. The amphibole is modelled using a set of ten independent end-members whose mixing parameters are in good agreement with the small amount of data available in the literature. The equilibria used to calibrate the amphibole non-ideal mixing reproduce pressures and temperatures with average absolute deviations of 1.1 kbar and 35 °C using an average pressure–temperature approach, and 0.8 kbar with an average pressure approach. The mixing data provide not only a basis for thermobarometry involving additional phases, but also for calculation of phase diagrams in complex amphibole-bearing systems. Received: 8 November 1999 / Accepted: 7 July 2000     

NEW SET OF LOW CONCENTRATION STANDARDS FOR LA, CE, SM, YB, LU, Y, SC, V, NB AND TA IN SILICATES

We have developed a set of four synthetic standards for the rare earth and high field strength elements designed for use in the determination of those elements in silicates. The base material is a glass nominally at the eutectic of the MgO-Al₂O₃-SiO₂ ternary system. The nominal doping level was 2 wt% of the elements as oxides. To avoid problems associated with peak interference, the elements were doped in four separate glasses.     

Early Variscan HP metamorphism in the western Iberian Allochthon—A 390 Ma U–Pb age for the Bragança eclogite (NW Portugal)

HP rocks (eclogites and granulites) occur in the upper unit of the western Iberian allochthonous complexes in Spain and Portugal. This HP metamorphism was considered as Early Variscan or Ordovician in Spain and Precambrian in Portugal. We have dated eclogites retrogressed into granulites in the Bragança massif in NE Portugal by U–Pb on rutile and zircon. The upper intercept of the discordia gives 390±4 Ma that we consider as the age of the HP/HT metamorphism.     

160 Ma of magmatic/hydrothermal and metamorphic activity in the Gällivare area: Re–Os dating of molybdenite and U–Pb dating of titanite from the Aitik Cu–Au–Ag deposit, northern Sweden

Host rocks to the Aitik Cu–Au–Ag deposit in northern Sweden are strongly altered and deformed Early Proterozoic mica(-amphibole) schists and gneisses. The deposit is characterised by numerous mineralisation styles, vein and alteration types. Four samples were selected for Re–Os molybdenite dating and 12 samples for U–Pb titanite dating in order to elucidate the magmatic/hydrothermal and metamorphic history following primary ore deposition in the Aitik Cu–Au–Ag deposit. Samples represent dyke, vein and alteration assemblages from the ore zone, hanging wall and footwall to the deposit. Re–Os dating of molybdenite from deformed barite and quartz veins yielded ages of 1,876±10 Ma and 1,848±8 Ma, respectively. A deformed pegmatite dyke yielded a Re–Os age of 1,848±6 Ma, and an undeformed pegmatite dyke an age of 1,728±7 Ma. U–Pb dating of titanite from a diversity of alteration mineral associations defines a range in ages between 1,750 and 1,805 Ma with a peak at ca. 1,780 Ma. The ages obtained, together with previous data, bracket a 160-Ma (1,890–1,730 Ma) time span encompassing several generations of magmatism, prograde to peak metamorphism, and post-peak cooling; events resulting in the redistribution and addition of metals to the deposit. This multi-stage evolution of the Aitik ore body suggests that the deposit was affected by several thermal events that ultimately produced a complex ore body. The Re–Os and U–Pb ages correlate well with published regional Re–Os and U–Pb age clusters, which have been tied to major magmatic, hydrothermal, and metamorphic events. Primary ore deposition at ca. 1,890 Ma in connection with intrusion of Haparanda granitoids was followed by at least four subsequent episodes of metamorphism and magmatism. Early metamorphism at 1,888–1,872 Ma overlapping with Haparanda (1,890–1,880 Ma) and Perthite-monzonite (1,880–1,870 Ma) magmatism clearly affected the Aitik area, as well as late metamorphism and Lina magmatism at 1,810–1,774 Ma and TIB1 magmatism at 1,800 Ma. The 1,848 Ma Re–Os ages obtained from molybdenite in a quartz vein and pegmatite dyke suggests that the 1,850 Ma magmatism recorded in parts of northern Norrbotten also affected the Aitik area.     

A 560-Year Record of Santa Ana Fires Reconstructed from Charcoal Deposited in the Santa Barbara Basin, California

Microscopic charcoal from varved Santa Barbara Basin sediments was used to reconstruct a 560-yr record (A.D. 1425 to 1985) of Santa Ana fires. Comparison of large (>3750 μm²) charcoal with documented fire records in the Santa Barbara Ranger District shows that high accumulations correspond to large fires (>20,000 ha) that occurred during Santa Ana conditions. The charcoal record reconstructed a minimum of 20 large fires in the Santa Barbara region during the study period. The average time between fires shows no distinct change across three different land use periods: the Chumash period, apparently characterized by frequent burning, the Spanish/Early American period with nominal fire control, and the 20th century with active fire suppression. Pollen data support the conclusion that the fire regime has not dramatically changed during the last 500 yr. Comparison of large charcoal particle accumulation rates and precipitation reconstructed from tree rings show a strong relationship between climate and fire history, with large fires consistently occurring at the end of wet periods and the beginning of droughts.