Carbon isotopic fractionation between CO2 vapour,silicate and carbonate melts: an experimental study to 30 kbar

The carbon isotopic fractionation between CO₂ vapour and sodamelilite (NaCaAlSi₂O₇) melt over a range of pressures and temperatures has been investigated using solid-media piston-cylinder high pressure apparatus. Ag₂C₂O₄ was the source of CO₂ and experimental oxygen fugacity was buffered at hematite-magnetite by the double capsule technique. The abundance and isotopic composition of carbon dissolved in sodamelilite (SM) glass were determined by stepped heating and the ¹³C of coexisting vapour was determined directly by capsule piercing. CO₂ solubility in SM displays a complex behavior with temperature. At pressures up to 10 kbars CO₂ dissolves in SM to form carbonate ion complexes and the solubility data suggest slight negative temperature dependence. Above 20 kbars CO₂ reacts with SM to form immiscible Na-rich silicate and Ca-rich carbonate melts and CO₂ solubility in Na-enriched silicate melt rises with increasing temperature above the liquidus. Measured values for carbon isotopic fractionation between CO₂ vapour and carbonate ions dissoived in sodamelilite melt at 1200°–1400° C and 5–30 kbars average 2.4±0.2, favouring¹³C enrichment in CO₂ vapour. The results are maxima and are independent of pressure and temperature. Similar values of 2 are obtained for the carbon isotopic fractionation between CO₂ vapour and carbonate melts at 1300°–1400° C and 20–30 kbars.     

Modelling weathering processes at the catchment scale: The WITCH numerical model

A numerical model of chemical weathering in soil horizons and underlying bedrock (WITCH) has been coupled to a numerical model of water and carbon cycles in forest ecosystems (ASPECTS) to simulate the concentration of major species within the soil horizons and the stream of the Strengbach granitic watershed, located in the Vosges Mountains (France). For the first time, simulations of solute concentrations in soil layers and in the catchment river have been performed on a seasonal basis. The model is able to reproduce the concentrations of most major species within the soil horizons, as well as catching the first-order seasonal fluctuations of aqueous calcium, magnesium and silica concentrations. However, the WITCH model underestimates concentrations of Mg²⁺ and silica at the spring of the catchment stream, and significantly underestimates Ca²⁺ concentration. The deficit in calculated calcium can be compensated for by dissolution of trace apatite disseminated in the bedrock. However, the resulting increased Ca²⁺ release yields important smectite precipitation in the deepest model layer (in contact with the bedrock) and subsequent removal of large amount of silica and magnesium from solution. In contrast, the model accurately accounts for the concentrations of major species (Ca, Mg and silica) measured in the catchment stream when precipitation of clay minerals is not allowed. The model underestimation of Mg²⁺ and H₄SiO₄ concentrations when precipitation of well crystallized smectites is allowed strongly suggests that precipitation of well crystallized clay minerals is overestimated and that more soluble poorly crystallized and amorphous materials may be forming. In agreement with observations on other watersheds draining granitic rocks, this study indicates that highly soluble trace calcic phases control the aqueous calcium budget in the Strengbach watershed.     

Genesis of monazite and Y zoning in garnet from the Black Hills, South Dakota

The paragenesis of monazite in metapelitic rocks from the contact aureole of the Harney Peak Granite, Black Hills, South Dakota, was investigated using zoning patterns of monazite and garnet, electron microprobe dating of monazite, bulk-rock compositions, and major phase mineral equilibria. The area is characterized by low-pressure and high-temperature metamorphism with metamorphic zones ranging from garnet to sillimanite zones. Garnet porphyroblasts containing euhedral Y annuli are observed from the garnet to sillimanite zones. Although major phase mineral equilibria predict resorption of garnet at the staurolite isograd and regrowth at the andalusite isograd, textural and mass balance analyses suggest that the formation of the Y annuli is not related to the resorption-and-regrowth of garnet having formed instead during garnet growth in the garnet zone. Monazite grains in Black Hills pelites were divided into two generations on the basis of zoning patterns of Y and U: monazite 1 with low-Y and -U and monazite 2 with high-Y and -U. Monazite 1 occurs in the garnet zone and persists into the sillimanite zone as cores shielded by monazite 2 which starts to form in the andalusite zone. Pelites containing garnet porphyroblasts with Y annuli and monazite 1 with patchy Th zoning are more calcic than those with garnet with no Y annuli and monazite with concentric Th zoning. Monazite 1 is attributed to breakdown of allanite in the garnet zone, additionally giving rise to the Y annuli observed in garnet. Monazite 2 grows in the andalusite zone, probably at the expense of garnet and monazite 1 in the andalusite and sillimanite zones. The ages of the two different generations of monazite are within the precision of chemical dating of electron microprobe. The electron microprobe ages of all monazites from the Black Hills show a single ca. 1713 Ma population, close to the intrusion age of the Harney Peak Granite (1715 Ma). This study demonstrates that Y zoning in garnet and monazite are critical to the interpretation of monazite petrogenesis and therefore monazite ages.     

Sources of Sediment in Lake Pepin on the Upper Mississippi River in Response to Holocene Climatic Changes

Sediments from Lake Pepin on the Mississippi River, southeastern Minnesota, are used as provenance tracers to assess variations in hydrology and sediment-transport during the middle Holocene. Three rivers contribute sediment to Lake Pepin, and each catchment is characterized by a distinctly different geologic terrain. The geochemical fingerprint for each drainage basin was determined from the elemental composition of heavy minerals in the silt-sized fraction of modern sediment samples. Down-core elemental abundances were compared with these fingerprints by use of a chemical-mass-balance model that apportions sediment to the source areas. We observed a decreased contribution from the Minnesota River during the interval ~6700–5500 ¹⁴C yr BP, which we attribute to decreased discharge of the Minnesota River, likely controlled by a combination of precipitation, snow melt, and groundwater input to the river. This hydrologic condition coincides with the mid-Holocene prairie period recorded by fossil pollen data. The occurrence of this feature in a proxy record for hydrologic variations supports the hypothesis that the mid-Holocene prairie period reflects drier conditions than before or after in midwestern North America.     

Identifying and quantifying urban recharge: a review

The sources of and pathways for groundwater recharge in urban areas are more numerous and complex than in rural environments. Buildings, roads, and other surface infrastructure combine with man-made drainage networks to change the pathways for precipitation. Some direct recharge is lost, but additional recharge can occur from storm drainage systems. Large amounts of water are imported into most cities for supply, distributed through underground pipes, and collected again in sewers or septic tanks. The leaks from these pipe networks often provide substantial recharge. Sources of recharge in urban areas are identified through piezometry, chemical signatures, and water balances. All three approaches have problems. Recharge is quantified either by individual components (direct recharge, water-mains leakage, septic tanks, etc.) or holistically. Working with individual components requires large amounts of data, much of which is uncertain and is likely to lead to large uncertainties in the final result. Recommended holistic approaches include the use of groundwater modelling and solute balances, where various types of data are integrated. Urban recharge remains an under-researched topic, with few high-quality case studies reported in the literature. Electronic Publication