Natural Weathering Rates Research Articles

Dissolution rate of borosilicate glass SON68: A method of quantification based upon interferometry and implications for experimental and natural weathering rates of glass

Rates of glass dissolution from laboratory and field studies are often considered to be irreconcilable, although potential causes for the difference, such as solution saturation state and increasing surface area from progressive weathering, have not been explored in depth. The dissolution rate of SON68 glass, the non-radioactive analog of the French R7T7 composition, was determined in a single-pass flow-through (SPFT) system at 90°C and pH 9 over a silica-saturation interval. Dissolution rates were determined on both powdered and monolithic specimens by assaying the concentration of elements released from glass to effluent solution. In addition, rates of 12 monolithic specimens were quantified using a Vertical Scanning Interferometry (VSI) method. The method entails measuring the difference in height between a reference and reaction surface. The height difference is proportional to the dissolution rate. By adjusting the relative position of the reacted surface to average surface roughness, the effects of surface area on the dissolution rate can be minimized. Values of the dissolution rate, based upon chemical assay of the effluent solution on the one hand, and VSI methods on the other, were compared. In general, rates determined by the two methods are within a factor of 2×. The difference in rates may be due to the presence of a reaction layer that develops on the glass surface, resulting in an underestimation of the height difference measurement. The dissolution rates of SON68 glass in silica-saturated solutions were then compared to rates previously determined on basalt glass in natural weathering environments (Gordon and Brady, 2002, Chem. Geol. 190, 113–122). When adjusted for differences in temperature and pH, the ranges of borosilicate and basalt glass dissolution rates overlap, indicating that laboratory and field rates can be reconciled and that the principal control on glass dissolution is solution saturation with respect to amorphous silica.

Carbon Dioxide Efficiency of Terrestrial Enhanced Weathering

Terrestrial enhanced weathering, the spreading of ultramafic silicate rock flour to enhance natural weathering rates, has been suggested as part of a strategy to reduce global atmospheric CO2 levels. We budget potential CO2 sequestration against associated CO2 emissions to assess the net CO2 removal of terrestrial enhanced weathering. We combine global spatial data sets of potential source rocks, transport networks, and application areas with associated CO2 emissions in optimistic and pessimistic scenarios. The results show that the choice of source rocks and material comminution technique dominate the CO2 efficiency of enhanced weathering. CO2 emissions from transport amount to on average 0.5-3% of potentially sequestered CO2. The emissions of material mining and application are negligible. After accounting for all emissions, 0.5-1.0 t CO2 can be sequestered on average per tonne of rock, translating into a unit cost from 1.6 to 9.9 GJ per tonne CO2 sequestered by enhanced weathering. However, to control or reduce atmospheric CO2 concentrations substantially with enhanced weathering would require very large amounts of rock. Before enhanced weathering could be applied on large scales, more research is needed to assess weathering rates, potential side effects, social acceptability, and mechanisms of governance.

Impact of nano-size weathering products on the dissolution rates of primary minerals

The natural weathering rates of primary minerals are often orders of magnitude lower than the rates of mineral dissolution measured in laboratory experiments. Primary dissolution rates are thought to be determined by the rate of secondary mineral precipitation, and in this paper we present a new approach to quantify the role played by interfacial energy, crystal size, and degree of supersaturation on precipitation kinetics in a population of crystals growing in a supersaturated fluid. We demonstrate that net mineral precipitation rates in systems that are close to equilibrium, and which possess a large number of micron and nanometer scale crystals, can be much lower than the rates predicted by standard kinetic equations. Moreover, when crystals are small enough, net dissolution dominates even when the system is supersaturated with respect to large crystals so that the standard reaction rate models used to describe bulk rates will no longer apply. Importantly, secondary minerals that form from the incongruent dissolution of primary phases are often submicron in size and field conditions are often far closer to equilibrium than those typically encountered in laboratory experiments. Thus, we propose that standard kinetic models – which ignore interfacial energy effects in small crystals – may be unsuitable to describe reaction kinetics in weathering systems.

Measurement of the Reactive Surface Area of Clay Minerals Using Solid-State NMR Studies of a Probe Molecule

Understanding the surface reactivity of clay minerals is necessary for accurate prediction of natural weathering rates due to the ubiquity of clays in the environment as weathering products of primary minerals. However, the reactivity of the heterogeneous surfaces of a clay can be difficult to characterize as clay mineral edge sites often react at different rates or via different mechanisms than sites on the basal planes. Ultimately, a method is needed to probe quantitatively the reactive surface sites in order to predict clay mineral dissolution rates. In this study, solid-state NMR spectroscopy has been utilized to investigate surface hydroxyl species and their relation to clay surface reactivity. The surfaces of two kaolinite samples (KGa-1b and KGa-2) and two montmorillonite samples (STx-1b and SWy-2) were reacted with the probe molecule (3,3,3-trifluoropropyl)dimethylchlorosilane (TFS), which binds selectively to reactive non-hydrogen bonded Q3Si hydroxyl sites. Quantification of 19F spins in the TFS...

The durability of rocks--Developing a test of rock resistance to chemical weathering

Dissolution rates of 39 rock-forming minerals were determined at 20 °C and 100 °C and different pH values, using experimental set-ups which achieve near-zero cation concentrations. Weathering rates in nature for rock above surface were estimated from data in this study and data in the literature. Extraction in a Soxhlet extractor with boiling 2.5 m acetic acid causes an acceleration of such estimated natural weathering rates by a factor of 0.25 × 103 to 7 × 104 for nearly all important rock-forming minerals, including the carbonates. The applicability of such a comparative test for rock resistance to chemical weathering was corroborated by testing 32 different rocks and building stones. Run times of only one to four days were needed for a reliable result.

Influence of surface-area estimation on rates of plagioclase weathering determined from naturally weathered 3400 y old Hawaiian basalt

AbstractDimensions of plagioclase (An65) crystals in a polished thin section of naturally weathered 3400 y old Hawaiian basalt were measured by scanning electron microscopy (in backscattered electron imaging mode). The three-dimensional shape, size, volume and surface area of the plagioclase crystals were then estimated using the method of Morgan and Jerram (2006). The weathering rate of plagioclase (mass loss divided by initial geometric surface area during 3400 y) is –12.116 log10 mol m–2 s–1. This weathering rate represents a time span (3.4 ka) intermediate between laboratory experimental timescales and the ages of regoliths in field studies of natural weathering rates. Weathering rates of the same plagioclase are recalculated using different assumptions concerning the method of estimating surface area, including simple geometric surface area and geometric surface area adjusted for surface roughness. Varying assumptions about surface area result in variations of up to two orders of magnitude in rates estimated from the same basic crystal geometry. The slowest rate estimated here approaches but does not fall within the range of previously determined field rates of plagioclase weathering.

Predicting the impact of land use on the major element and nutrient fluxes in coastal Mediterranean rivers: The case of the Têt River (Southern France)

This study presents a detailed discrimination between the natural and anthropogenic sources of dissolved major elements in the Têt River, a typical small coastal river in the south of France. The main objectives were to quantify the materials that were released by human activities in the basin, and to determine the specific element inputs for the major land use forms. The dissolved material fluxes were estimated by weekly monitoring over a hydrological year (2000–2001) along the major water gauging stations, and the flux relationships were examined in the context of anthropogenic and natural basin characteristics as determined by a Geographical Information System (GIS). Intensive agricultural land use in the form of fruit tree cultures and vineyards has a strong control on the dissolved element fluxes in the river. Area specific element releases for these cultures are greatest for SO 4, with an estimated average of about 430 ± 18 keq km −2 a −1. This is ⩾11 times the natural SO 4 release by rock weathering. Also for K, NO 3, PO 4 and Mg, the specific releases were ⩾6 times the natural weathering rates (respectively about 44, 60, 4 and 265 keq km −2 a −1). Waste-waters are the other major source of anthropogenic elements in the river. They have an important role for the fluxes of inorganic P and N, but they are also a considerable source of Cl and Na to the river. For example, the average annual release of Cl is around 150 moles/inhabitant in the rural basin parts. Further downstream, however, where population density strongly increases, industrial effluents can enhance this value (>300 moles/inhabitant). The waste-waters contribute more than 70% of the dissolved inorganic N export to the sea, although their contribution to the average DOC export is almost negligible (3%).

Chemical weathering in a tropical watershed, Luquillo Mountains, Puerto Rico III: quartz dissolution rates

The paucity of weathering rates for quartz in the natural environment stems both from the slow rate at which quartz dissolves and the difficulty in differentiating solute Si contributed by quartz from that derived from other silicate minerals. This study, a first effort in quantifying natural rates of quartz dissolution, takes advantage of extremely rapid tropical weathering, simple regolith mineralogy, and detailed information on hydrologic and chemical transport. Quartz abundances and grain sizes are relatively constant with depth in a thick saprolite. Limited quartz dissolution is indicated by solution rounding of primary angularity and by the formation of etch pits. A low correlation of surface area (0.14 and 0.42 m 2 g −1) with grain size indicates that internal microfractures and pitting are the principal contributors to total surface area. Pore water silica concentration increases linearly with depth. On a molar basis, between one and three quarters of pore water silica is derived from quartz with the remainder contributed from biotite weathering. Average solute Si remains thermodynamically undersaturated with respect to recently revised estimates of quartz solubility (<180 μM) but exceeds estimated critical saturation concentrations controlling the initiation of etch pit formation (>17–81 μM). Etch pitting is more abundant on grains in the upper saprolite and is associated with pore waters lower in dissolved silica. Rate constants describing quartz dissolution increase with decreasing depth (from 10 −14.5–10 −15.1 mol m −2 s −1), which correlate with both greater thermodynamic undersaturation and increasing etch pit densities. Unlike for many aluminosilicates, the calculated natural weathering rates of quartz fall slightly below the rate constants previously reported for experimental studies (10 −12.4–10 −14.2 mol m −2 s −1). This agreement reflects the structural simplicity of quartz, dilute solutes, and near-hydrologic saturation.

Global tectonics and agriculture: A geochemical perspective

The global distribution of regions of sustained productive agriculture shows that an ample supply of fresh rock residues is vital to soil fertility. Once such rock debris is removed soil degradation will be evident in falling yields and trends within the clay fraction from chemically diverse smectite clays towards impoverished kaolinite-gibbsite soils. Increased erosion will follow the clay degradation. Reliance on N, P and K and organic residues alone will not be sufficient to counteract this trend unless Nature, through geological forces, or Man, through the application of appropriate rock dusts, intervenes to restore nutrient balance and a better clay spectrum. The geological evidence of natural weathering rates, and soil evidence of leaching rates, points to applications only of the order of 1 ton ha −1 year −1 being the amount of fresh rock replenishment required to hold the soil in balance for agriculture. Failure to achieve this makes way for a progressive trend towards soil degradation accelerating, as changes induced in the nature of the clay fraction enhance the leaching effect of the aerial environment. On a world scale these effects can best be seen by comparing the enhanced fertility of soils that have benefited from volcanic renewal near active plate boundaries or the fresh rock enrichment arising from the rock grinding involved in glaciation, with the almost ‘impossible’ soils typical of geologically quiescent areas, such as the Amazon and Congo basins where, merely to fertilise with N, P and K alone so impoverishes the soils of their critically limited supplies of other essential nutrients, that disaster is inevitable.

Weathering processes and pickeringite formation in a sulfidic schist: A consideration in acid precipitation neutralization studies

Extremely low abrasion pH values (2.8–3.3) characterize the weathering products of the Partridge Formation, a Middle-Ordovician metamorphosed, black, sulfidic shale. The local occurrence is observed of two sulfates that are rare in the Northeast: pickeringite and jarosite. X-ray diffraction studies of the weathering residues and the sulfate efflorescences have also identified dioctahedral and trioctahedral illite, kaolinite, vermiculite, and an 11–12 A phase, thought to be a type of randomly-interstratified biotite-vermiculite. From the mineralogical studies, qualitative weathering processes for the schist are formulated. A probable mechanism for the intense chemical weathering of the schist appears to be oxidation of iron sulfides to form iron oxide-hydroxides, sulfates, and sulfuric acid. This natural weathering process is proposed as an analog to anthropogenic low pH rock weathering resulting from acid precipitation. In the Northeast,natural weathering rates, may, in places, significantly affect the water chemistry and mineralogy used to quantify total (natural plus anthropogenic) weathering and leaching rates.