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At least 469 records · Page 26Linked to original sources

Transient changes in shallow groundwater chemistry during the MSU ZERT CO2 injection experiment

Food-grade CO 2 was injected into a shallow aquifer through a perforated pipe placed horizontally 1–2 m below the water table at the Montana State University Zero Emission Research and Technology (MSU-ZERT) field site at Bozeman, Montana. The possible impact of elevated CO 2 levels on groundwater quality was investigated by analyzing 80 water samples taken before, during, and following CO 2 injection. Field determinations and laboratory analyses showed rapid and systematic changes in pH, alkalinity, and conductance, as well as increases in the aqueous concentrations of trace element species. The geochemical data were first evaluated using principal component analysis (PCA) in order to identify correlations between aqueous species. The PCA findings were then used in formulating a geochemical model to simulate the processes likely to be responsible for the observed increases in the concentrations of dissolved constituents. Modeling was conducted taking into account aqueous and surface complexation, cation exchange, and mineral precipitation and dissolution. Reasonable matches between measured data and model results suggest that: (1) CO 2 dissolution in the groundwater causes calcite to dissolve. (2) Observed increases in the concentration of dissolved trace metals result likely from Ca +2 -driven ion exchange with clays (smectites) and sorption/desorption reactions likely involving Fe (hydr)oxides. (3) Bicarbonate from CO 2 dissolution appears to compete for sorption with anionic species such as HAsO 4 −2 , potentially increasing dissolved As levels in groundwater.

Conference Paper↗

Changes in the chemistry of acidified Adirondack streams from the early 1980s to 2008

Lakes in the Adirondack region of New York have partially recovered in response to declining deposition, but information on stream recovery is limited. Here we report results of Adirondack stream monitoring from the early 1980s to 2008. Despite a 50% reduction in atmospheric deposition of sulfur, overall increases in pH of only 0.28 and ANC of 13 μeq L −1 were observed in 12 streams over 23 years, although greater changes did occur in streams with lower initial ANC, as expected. In the North Tributary of Buck Creek with high dissolved organic carbon (DOC) concentrations, SO 4 2 − "> SO42− concentrations decreased from 1999 to 2008 at a rate of 2.0 μmol L −1 y −1 , whereas in the neighboring South Tributary with low DOC concentrations, the decrease was only 0.73 μmol L −1 y −1 . Ca 2+ leaching decreased in the North Tributary due to the SO 4 2 − "> SO42− decrease, but this was partially offset by an increase in Ca 2+ leaching from increased DOC concentrations.

New York↗

The global variation in the iron isotope composition of marine hydrogenetic ferromanganese deposits: Implications for seawater chemistry?

The iron (Fe) isotope compositions of 37 hydrogenetic ferromanganese deposits from various oceans have been analysed by MC-ICPMS; they permit the construction of a global map of Fe isotopic values. The isotopic compositions range between -1.2 and -0.1??? in ??57FeIRMM14. Averages for the Atlantic and the Pacific are -0.41 and -0.88???, but their standard deviations are identical (0.27, 1 ??) and the data very largely overlap. No correlation is found with Pb or Nd isotope compositions and there is no evidence that the observed oceanic Fe isotopic heterogeneity is directly controlled by variations in continental sources. The small quantities of Fe that can be introduced from hydrothermal sources render as unlikely the possibility that the isotopic variations reflect variable proportions of continental and hydrothermal Fe, as recently proposed. The more likely explanation is that the variations are induced locally within the ocean. The exact sources of fractionation remain unclear. Likely possibilities are the dissolution and reprecipitation processes that liberate Fe from sediments during anoxic events, dissolution in surface waters or processes occurring during growth of the crusts. ?? 2004 Elsevier B.V. All rights reserved.

Earth and Planetary Science Letters↗

Comment on “Particle fluxes in groundwater change subsurface rock chemistry over geologic time”

Over the last decade, studies at the Shale Hills Critical Zone Observatory (Shale Hills) have greatly expanded knowledge of weathering in previously understudied, shale-mantled terrains, as well as Earth's Critical Zone as a whole. Among the many discoveries made was the importance of redistribution and losses of micron-sized particles during development of shale-derived soils. A geochemical fingerprint of this process for Al and Fe was illustrated quantitatively by Jin et al. (2010). Subsequent papers, too numerous to list in a Comment, built upon this new recognition by evaluating the spatial and temporal aspects element mobilization. Recently, Kim et al. (2018) examined the composition of suspended, generally micron-sized particles in the Shale Hills stream, along with the dissolved load, across seasons and ranges of discharge. One prominent conclusion from Kim et al. (2018) is that Zr is essentially immobile at Shale Hills. Such a broad conclusion is in direct contradiction with one from Bern and Yesavage (2018) that Zr has been mobilized from soils at Shale Hills, and the losses relative to soil parent material are significant (median 41%). The point is important, because assuming Zr immobility is necessary to index gains and losses of other elements using the open-chemical-system transport function ( τ ). Both papers draw upon patterns and calculations using elemental concentration data from Shale Hills and attempt to construct conceptual frameworks to explain the results. Here, the argument is made that the understanding of substantial Zr mobility from soils at Shale Hills described by Bern and Yesavage (2018) is more accurate. Additionally, issues with adaptations of the standard τ equations used in Kim et al. (2018) and some previous papers are also addressed.

Pennsylvania↗

Traveling around Cape Horn: Otolith chemistry reveals a mixed stock of Patagonian hoki with separate Atlantic and Pacific spawning grounds

Trace element fingerprints of edge and core regions in otoliths from 260 specimens of Patagonian hoki, Macruronus magellanicus L??nnberg, 1907, were analyzed by LA-ICPMS to reveal whether this species forms one or more population units (stocks) in the Southern Oceans. Fish were caught on their spawning grounds in Chile and feeding grounds in Chile and the Falkland Islands. Univariate and multivariate analyses of trace element concentrations in the otolith edges, which relate to the adult life of fish, could not distinguish between Atlantic (Falkland) and Pacific (Chile) hoki. Cluster analyses of element concentrations in the otolith edges produced three different clusters in all sample areas indicating high mixture of the stocks. Cluster analysis of trace element concentrations in the otolith cores, relating to juvenile and larval life stages, produced two separate clusters mainly distinguished by 137 Ba concentrations. The results suggest that Patagonian hoki is a highly mixed fish stock with at least two spawning grounds around South America. ?? 2009 Elsevier B.V.

Fisheries Research↗

The relation of harvesting intensity to changes in soil, soil water, and stream chemistry in a northern hardwood forest, Catskill Mountains, USA

Previous studies have shown that clearcutting of northern hardwood forests mobilizes base cations, inorganic monomeric aluminum (Al im ), and nitrate (NO 3 - - N) from soils to surface waters, but the effects of partial harvests on NO 3 - - N have been less frequently studied. In this study we describe the effects of a series of partial harvests of varying proportions of basal area removal (22%, 28% and 68%) on Al im , calcium (Ca 2+ ), and NO 3 - - N concentrations in soil extracts, soil water, and surface water in the Catskill Mountains of New York, USA. Increases in NO 3 - - N concentrations relative to pre-harvest values were observed within a few months after harvest in soils, soil water, and stream water for all three harvests. Increases in Al im and Ca 2+ concentrations were also evident in soil water and stream water over the same time period for all three harvests. The increases in Al im , Ca 2+ , and NO 3 - - N concentrations in the 68% harvest were statistically significant as measured by comparing the 18-month pre-harvest period with the 18-month post-harvest period, with fewer significant responses in the two harvests of lowest intensity. All three solutes returned to pre-harvest concentrations in soil water and stream water in the two lowest intensity harvests in 2–3 years compared to a full 3 years in the 68% harvest. When the results of this study were combined with those of a previous nearby clearcut and 40% harvest, the post-harvest increases in NO 3 - - N concentrations in stream water and soil water suggest a harvesting level above which the relation between concentration and harvest intensity changes; there was a greater change in concentration per unit change in harvest intensity when basal area removal was greater than 40%. These results indicate that the deleterious effects on aquatic ecosystems previously demonstrated for intensive harvests in northern hardwood forests of northeastern North America that receive high levels of atmospheric N deposition can be greatly diminished as harvesting intensity decreases below 40?8%. These results await confirmation through additional incremental forest harvest studies at other locations throughout the world that receive high levels of atmospheric N deposition.

New York↗

Organic nitrogen chemistry during low-grade metamorphism

Most of the organic nitrogen (Norg) on Earth is disseminated in crustal sediments and rocks in the form of fossil nitrogen-containing organic matter. The chemical speciation of fossil Norg within the overall molecular structure of organic matter changes with time and heating during burial. Progressive thermal evolution of organic matter involves phases of enhanced elimination of Norg and ultimately produces graphite containing only traces of nitrogen. Long-term chemical and thermal instability makes the chemical speciation of Norg a valuable tracer to constrain the history of sub-surface metamorphism and to shed light on the subsurface biogeochemical nitrogen cycle and its participating organic and inorganic nitrogen pools. This study documents the evolutionary path of Norg speciation, transformation and elimination before and during metamorphism and advocates the use of X-ray photoelectron spectroscopy (XPS) to monitor changes in Norg speciation as a diagnostic tool for organic metamorphism. Our multidisciplinary evidence from XPS, stable isotopes, traditional quantitative coal analyses, and other analytical approaches shows that at the metamorphic onset Norg is dominantly present as pyrrolic and pyridinic nitrogen. The relative abundance of nitrogen substituting for carbon in condensed, partially aromatic systems (where N is covalently bonded to three C atoms) increases exponentially with increasing metamorphic grade, at the expense of pyridinic and pyrrolic nitrogen. At the same time, much Norg is eliminated without significant nitrogen isotope fractionation. The apparent absence of Rayleigh-type nitrogen isotopic fractionation suggests that direct thermal loss of nitrogen from an organic matrix does not serve as a major pathway for Norg elimination. Instead, we propose that hot H, O-containing fluids or some of their components gradually penetrate into the carbonaceous matrix and eliminate Norg along a progressing reaction front, without causing nitrogen isotope fractionation in the residual Norg in the unreacted core of the carbonaceous matrix. Before the reaction front can reach the core, an increasing part of core Norg chemically stabilizes in the form of nitrogen atoms substituting for carbon in condensed, partially aromatic systems forming graphite-like structural domains with delocalized ??-electron systems (nitrogen atoms substituting for "graphitic" carbon in natural metamorphic organic matter). Thus, this nitrogen species with a conservative isotopic composition is the dominant form of residual nitrogen at higher metamorphic grade. ?? 2007 Elsevier Ltd. All rights reserved.

Geochimica et Cosmochimica Acta↗

Mg isotope constraints on soil pore-fluid chemistry: Evidence from Santa Cruz, California

Mg isotope ratios ( 26 Mg/ 24 Mg) are reported in soil pore-fluids, rain and seawater, grass and smectite from a 90 kyr old soil, developed on an uplifted marine terrace from Santa Cruz, California. Rain water has an invariant 26 Mg/ 24 Mg ratio (expressed as δ26 Mg> δ26 Mg ) at −0.79 ± 0.05‰, identical to seawater δ26 Mg> δ26 Mg . Detrital smectite (from the base of the soil profile, and therefore unweathered) has a δ26Mg"> δ26Mg value of 0.11‰, potentially enriched in 26 Mg by up to 0.3‰ compared to the bulk silicate Earth Mg isotope composition (although within the range of all terrestrial silicates). The soil pore-waters show a continuous profile with depth for δ26 Mg> δ26 Mg , ranging from −0.99‰ near the surface to −0.43‰ at the base of the profile. Shallow pore-waters (<1 m) have δ26 Mg> δ26 Mg values that are similar to, or slightly lower than the rain waters. This implies that the degree of biological cycling of Mg in the pore-waters is relatively small and is quantified as <32%, calculated using the average Mg isotope enrichment factor between grass and rain ( δ26 Mggrass- δ26 Mgrain> δ26 Mggrass- δ26 Mgrain ) of 0.21‰. The deep pore-waters (1–15 m deep) have δ26 Mg> δ26 Mg values that are intermediate between the smectite and rain, ranging from −0.76‰ to −0.43‰, and show a similar trend with depth compared to Sr isotope ratios. The similarity between Sr and Mg isotope ratios confirms that the Mg in the pore-waters can be explained by a mixture between rain and smectite derived Mg, despite the fact that Mg and Sr concentrations may be buffered by the exchangeable reservoir. However, whilst Sr isotope ratios in the pore-waters span almost the complete range between mineral and rain inputs, Mg isotopes compositions are much closer to the rain inputs. If Mg and Sr isotope ratios are controlled uniquely by a mixture, the data can be used to estimate the mineral weathering inputs to the pore-waters, by correcting for the rain inputs. This isotopic correction is compared to the commonly used chloride correction for precipitation inputs. A consistent interpretation is only possible if Mg isotope ratios are fractionated either by the precipitation of a secondary Mg bearing phase, not detected by conventional methods, or selective leaching of 24 Mg from smectite. There is therefore dual control on the Mg isotopic composition of the pore-waters, mixing of two inputs with distinct isotopic compositions, modified by fractionation. The data provide (1) further evidence for Mg isotope fractionation at the surface of the Earth and (2) the first field evidence of Mg isotope fractionation during uptake by natural plants. The coherent behaviour of Mg isotope ratios in soil environments is encouraging for the development of Mg isotope ratios as a quantitative tracer of both weathering inputs of Mg to waters, and the physicochemical processes that cycle Mg, a major cation linked to the carbon cycle, during continental weathering.

California↗

Temperature-dependent variations in mineralogy, major element chemistry and the stable isotopes of boron, lithium and chlorine resulting from hydration of rhyolite glass: Constraints from hydrothermal experiments at 150 to 350°C and 25 MPa

Rhyolite-hosted hydrothermal systems in the continental crust contain valuable energy and mineral resources that make them of special interest across several scientific disciplines. Despite extensive research on these systems, the temperature-dependence of chemical reactions between host rocks and aqueous-rich fluids and the mineralogical transformations resulting from these reactions are not well quantified. To expand our understanding of the controlling processes operating in these systems, we carried out seven laboratory experiments in which rhyolite was reacted with deionized water at 150 °C to 350 °C and 25 MPa. An additional experiment at 200 °C was carried out to examine the effect of dissolved CO 2 on the reactions. The overarching goal of this experimental study was to provide new insights on the temperature-dependence of water-rock interaction in continental hydrothermal systems. We applied a wide range of chemical, isotopic and mineralogical methods to analyze the reacted rhyolite and waters, and the major observations are: (1) the rhyolite progressively hydrates with increasing temperature between 150 °C to a maximum of 8.2 wt% H 2 O at 275 °C; hydration then decreases until 350 °C in conjunction with the destruction of the rhyolite glass and crystallization of secondary mineral phases; (2) the ratio of molecular water (H 2 O m ) to hydroxyl (OH − ) of the water that is dissolved in the reacted rhyolite decreases from ∼7 at 150 °C to ∼4 at 250 °C; (3) the main secondary minerals formed are the zeolite ferrierite (T ≥ 275 °C); biotite, albite and cristobalite mainly form at higher experimental temperatures (T ≥ 300 °C); (4) the reacted waters are nearly saturated with respect to amorphous silica; (5) at temperatures ≥ 275 °C nearly all the chlorine is leached into solution; (6) fluorine leaching from the rhyolite gradually increases between 150 °C and 250 °C, but then gradually decreases at higher temperatures and is incorporated into a secondary mineral phase; (7) dissolved CO 2 in the water enhances alkali metal cation leaching from the rhyolite; and (8) calculated Na-K and silica geothermometer temperatures differ from the experimental temperatures by varying amounts. In addition, apart from some small lithium isotope fractionation at temperatures ≤ 250 °C, the stable isotopes of boron, lithium and chlorine do not fractionate during rhyolite-water reactions, and the stable isotope compositions of these species in the reacted water are similar to those in the reactant rhyolite. These results provide new insights for a broad range of applications, including quantifying processes involving rhyolite glass hydration (obsidian hydration dating, perlite formation and discriminating secondary from magmatic water in rhyolitic matrix-glass of volcanic pyroclasts), for geothermal energy and mineral deposit exploration and for monitoring volcanoes.

Geochimica et Cosmochimica Acta↗

An important biogeochemical link between organic and inorganic carbon cycling: Effects of organic alkalinity on carbonate chemistry in coastal waters influenced by intertidal salt marshes

Organic acid charge groups in dissolved organic carbon (DOC) contribute to total alkalinity (TA), i.e. organic alkalinity (OrgAlk). Its effect is often ignored or treated as a calculation uncertainty in many aquatic CO2 studies. This study evaluated the variability, sources, and characteristics of OrgAlk in estuarine waters exchanged tidally with a groundwater-influenced salt marsh in the northeast USA. Importantly, OrgAlk was found to serve as a biogeochemical medium linking organic and inorganic carbon cycling through its effects on pH, CO2 system speciation, and buffering capacity (H = -(∂pH/∂[H+])-1). Both the concentrations and characteristics of the identified organic acid charge groups, as well as water pH, influenced the magnitude and sign of the OrgAlk effects. The two main charge groups identified include carboxylic and phenolic or amine groups, with concentrations and pK values varying across tides and seasons. OrgAlk and DOC in the tidal creek were highly variable over tidal and seasonal cycles, and may be sourced from both terrestrial groundwater and in situ production in salt marsh sediments. OrgAlk seems to be more preserved over DOC in groundwater, although DOC and OrgAlk largely covaried in marsh tidal water, but with variable OrgAlk:DOC ratios. This highlights the insufficiency of using a fixed proportion of DOC to account for organic acid charge groups. OrgAlk was found to affect H+ concentrations by ~ 1 – 40 nmol kg-1 (equivalent to a pH change of ~ 0.03 – 0.26), pCO2 by ~ 30 – 1590 atm and buffering capacity by ~ 0.00 – 0.14 mmol kg-1 at relative OrgAlk contributions of 0.9 – 4.3% of TA observed in the marsh-influenced tidal water. Thus OrgAlk may have a significant influence on coastal inorganic carbon cycling. Further theoretical calculations confirm that these concentrations of OrgAlk would have sizable impacts on both carbonate speciation and, ultimately, air-sea CO2 fluxes in different coastal environments, ranging from estuarine to shelf waters. A new conceptual model linking organic and inorganic carbon cycling for coastal waters is proposed to highlight the sources and sinks of organic acid charge groups, as well as their biogeochemical behaviors and mechanistic control on the CO2 system.

Geochimica et Cosmochimica Acta↗

A reactive transport approach to modeling cave seepage water chemistry I: Carbon isotope transformations

The majority of Critical Zone research has emphasized silicate lithologies, which are typified by relatively slow rates of reactivity and incongruent weathering. However, the relatively simpler weathering of carbonate-dominated lithology can result in secondary mineral deposits, such as speleothems, which provide a long-term archive for Critical Zone processes. In particular, carbon isotopic variability in speleothems has the potential to provide records of changes in vegetation, soil respiration, carbon stabilization in deep soils, and/or chemical weathering in the host rock. Despite this opportunity to reconstruct many Critical Zone processes, multiple influences can also make interpretion of these speleothem carbon isotope records challenging. The integration of observational data and simulations specific to karst systems offers an interpretive framework for these unique time-averaged records accumulated through the evolution of carbonate landscapes. Here, we present a forward and process-based reactive transport simulation based on a multi-year monitoring study of Blue Spring Cave in central Tennessee, USA. The simulations describe the fluid-driven weathering of limestone including explicit tracking of dissolved calcium, stable carbon, and radiocarbon isotope ratios based on reaction rates calibrated through laboratory batch reaction data. We find that calcium concentrations and radiocarbon isotope ratios are strongly influenced by the combination of fluid flow rate and soil CO 2 content, and require rapid gas phase communication between the overlying soil boundary condition and interior karst to sustain both elevated limestone weathering rates and relatively modern radiocarbon signatures. Stable carbon isotopes are largely dictated by temperature-dependent equilibrium fractionation among contemporaneous species. These simulations are extended to a wide range of parameter space to demonstrate the environmental factors that these isotope proxies record.

Geochimica et Cosmochimica Acta↗

Chemistry of diagenetic features analyzed by ChemCam at Pahrump Hills, Gale crater, Mars

The Curiosity rover's campaign at Pahrump Hills provides the first analyses of lower Mount Sharp strata. Here we report ChemCam elemental composition of a diverse assemblage of post-depositional features embedded in, or cross-cutting, the host rock. ChemCam results demonstrate their compositional diversity, especially compared to the surrounding host rock: (i) Dendritic aggregates and relief enhanced features, characterized by a magnesium enhancement and sulfur detection, and interpreted as Mg-sulfates; (ii) A localized observation that displays iron enrichment associated with sulfur, interpreted as Fe-sulfate; (iii) Dark raised ridges with varying Mg- and Ca-enriched compositions compared to host rock; (iv) Several dark-toned veins with calcium enhancement associated with fluorine detection, interpreted as fluorite veins. (v) Light-toned veins with enhanced calcium associated with sulfur detection, and interpreted as Ca-sulfates. The diversity of the Pahrump Hills diagenetic assemblage suggests a complex post-depositional history for fine-grained sediments for which the origin has been interpreted as fluvial and lacustrine. Assessment of the spatial and relative temporal distribution of these features shows that the Mg-sulfate features are predominant in the lower part of the section, suggesting local modification of the sediments by early diagenetic fluids. In contrast, light-toned Ca-sulfate veins occur in the whole section and cross-cut all other features. A relatively late stage shift in geochemical conditions could explain this observation. The Pahrump Hills diagenetic features have no equivalent compared to targets analyzed in other locations at Gale crater. Only the light-toned Ca-sulfate veins are present elsewhere, along Curiosity's path, suggesting they formed through a common late-stage process that occurred at over a broad area.

Icarus↗

Geochemical modeling of changes in shallow groundwater chemistry observed during the MSU-ZERT CO2 injection experiment

A field experiment involving the release of carbon dioxide (CO 2 ) into a shallow aquifer was conducted near Bozeman, Montana, during the summer of 2008, to investigate the potential groundwater quality impacts in the case of leakage of CO 2 from deep geological storage. As an essential part of the Montana State University Zero Emission Research and Technology (MSU-ZERT) field program, food-grade CO 2 was injected over a 30 day period into a horizontal perforated pipe a few feet below the water table of a shallow aquifer. The impact of elevated CO 2 concentrations on groundwater quality was investigated by analyzing water samples taken before, during, and following CO 2 injection, from observation wells located in the vicinity of the injection pipe, and from two distant monitoring wells. Field measurements and laboratory analyses showed rapid and systematic changes in pH, alkalinity, and conductance, as well as increases in the aqueous concentrations of naturally occurring major and trace element species. The geochemical data were evaluated using principal component analysis (PCA) to (1) understand potential correlations between aqueous species, and (2) to identify minerals controlling the chemical composition of the groundwater prior to CO 2 injection. These evaluations were used to assess possible geochemical processes responsible for the observed increases in the concentrations of dissolved constituents, and to simulate these processes using a multicomponent reaction path model. Reasonable agreement between observed and modeled data suggests that (1) calcite dissolution was the primary pH buffer, yielding increased Ca +2 concentrations in the groundwater, (2) increases in the concentrations of most major and trace metal cations except Fe could be a result of Ca +2 -driven exchange reactions, (3) the release of anions from adsorption sites due to competitive adsorption of carbonate could explain the observed trends of most anions, and (4) the dissolution of reactive Fe minerals (presumed ferrihydrite and fougerite, from thermodynamic analyses) could explain increases in total Fe concentration. Highlights ► Because the possibility of CO 2 leakage cannot be completely ruled out, the potential impact of CO 2 intrusion on the quality of fresh water aquifers overlying CO 2 storage sites needs to be investigated. ► Geochemical data from a field experiment involving the release of carbon dioxide (CO 2 ) into a shallow aquifer were evaluated. ► Geochemical model used to assess possible geochemical processes responsible for the observed increases in the concentrations of dissolved constituents. ► Reasonable agreement between observed and modeled data suggests that increases in the concentrations of most major and trace metal cations except Fe could be a result of Ca +2 -driven exchange reactions and the release of anions from adsorption sites due to competitive adsorption of carbonate could explain the observed trends of most anions.

Montana↗

Comparative mineral chemistry and textures of SAFOD fault gouge and damage-zone rocks

Creep in the San Andreas Fault Observatory at Depth (SAFOD) drillhole is localized to two foliated gouges, the central deforming zone (CDZ) and southwest deforming zone (SDZ). The gouges consist of porphyroclasts of serpentinite and sedimentary rock dispersed in a foliated matrix of Mg-smectite clays that formed as a result of shearing-enhanced reactions between the serpentinite and quartzofeldspathic rocks. The CDZ takes up most of the creep and exhibits differences in mineralogy and texture from the SDZ that are attributable to its higher shearing rate. In addition, a ∼0.2-m-wide sector of the CDZ at its northeastern margin (NE-CDZ) is identical to the SDZ and may represent a gradient in creep rate across the CDZ. The SDZ and NE-CDZ have lower clay contents and larger porphyroclasts than most of the CDZ, and they contain veinlets and strain fringes of calcite in the gouge matrix not seen elsewhere in the CDZ. Matrix clays in the SDZ and NE-CDZ are saponite and corrensite, whereas the rest of the CDZ lacks corrensite. Saponite is younger than corrensite, reflecting clay crystallization under declining temperatures, and clays in the more actively deforming portions of the CDZ have better equilibrated to the lower-temperature conditions.

California↗

Source and fate of inorganic solutes in the Gibbon River, Yellowstone National Park, Wyoming, USA. II. Trace element chemistry

The Gibbon River in Yellowstone National Park receives inflows from several geothermal areas, and consequently the concentrations of many trace elements are elevated compared to rivers in non-geothermal watersheds. Water samples and discharge measurements were obtained from the Gibbon River and its major tributaries near Norris Geyser Basin under the low-flow conditions of September 2006 allowing for the identification of solute sources and their downstream fate. Norris Geyser Basin, and in particular Tantalus Creek, is the largest source of many trace elements (Al, As, B, Ba, Br, Cs, Hg, Li, Sb, Tl, W, and REEs) to the Gibbon River. The Chocolate Pots area is a major source of Fe and Mn, and the lower Gibbon River near Terrace Spring is the major source of Be and Mo. Some of the elevated trace elements are aquatic health concerns (As, Sb, and Hg) and knowing their fate is important. Most solutes in the Gibbon River, including As and Sb, behave conservatively or are minimally attenuated over 29 km of fluvial transport. Some small attenuation of Al, Fe, Hg, and REEs occurs but primarily there is a transformation from the dissolved state to suspended particles, with most of these elements still being transported to the Madison River. Dissolved Hg and REEs loads decrease where the particulate Fe increases, suggesting sorption onto suspended particulate material. Attenuation from the water column is substantial for Mn, with little formation of Mn as suspended particulates.

Wyoming↗

The structure and volume of large geysers in Yellowstone National Park, USA and the mineralogy and chemistry of their silica sinter deposits

Siliceous sinter is formed by biogenic and abiogenic opal deposition around hot springs and geysers. Using Structure-from-Motion photogrammetry we generated three-dimensional models of Giant and Castle Geysers from the Upper Geyser Basin of Yellowstone National Park. We use these models to calculate an approximate mass of sinter for each (~2 and ~ 5 kton, respectively) and estimate a range of plausible long-term deposition rates for Castle Geyser (470 to 940 kg·yr −1 ). We estimate ~2% of the silica discharged from Castle Geyser is deposited as sinter in the cone and proximal terraces. We collected 15 sinter samples following the stratigraphy of each geyser from an older terrace to a younger cone and examined them using a variety of analytical methods. We find that young opaline sinter with a water content of <12 wt% (from loss on ignition) contains higher concentrations of major and trace elements, notably As, Sb, Rb, Ga and Cs, relative to older dehydrated sinter. Rare earth element (REE) concentrations in sinter are 2–3 orders of magnitude higher than in the thermal water from which they are deposited. Sinter deposits are enriched in light REE, Gd and Yb when normalized to concentrations in thermal water and enriched in Eu, Tm, and Yb when normalized to the underlying rhyolite. Sinter samples with the highest REE concentrations are also enriched in organic material, implying either microbial uptake of REE, or that organic molecules are efficient ligands that form metal complexes.

Wyoming↗

Chemistry and petrography of early 19th century basaltic andesites and basalts from the Kamakaiʻa Hills in the Southwest Rift Zone of Kīlauea volcano, Hawaiʻi

Kīlauea is a frequently active, open-system volcano on the Island of Hawaiʻi known for erupting olivine-dominated tholeiitic basalt compositions. On rare occasions it erupts more differentiated magmas (<1% of erupted volume), such as basaltic andesites and andesites, from its rift zones. These differentiated magmas offer an opportunity to understand better the petrology, magma storage, magma mixing, and eruptive triggers that occur in Kīlauea's rift zone reservoirs. This study focuses on an eruption from the Southwest Rift Zone of Kīlauea, which is dominantly basaltic andesite with subordinate basalt. This eruption originated at the Kamakaiʻa Hills during the early 19th century and has two eruptive phases: 1) an early ‘a‘ā phase that is primarily exposed in the eastern part of the flow field, with minor western lobes, and 2) a late pāhoehoe phase that makes up most of the western part of the flow field. The early ‘a‘ā phase covers at least 5.8 km 2 with an erupted volume of ∼150 × 10 6 m 3 and consists of uniform composition basaltic andesites with 3.72–4.15 wt% MgO over its ∼7 km flow length. The late pāhoehoe phase reached >10 km from its vent, covers an area of ∼7.1 km 2 , has a volume of ∼100 × 10 6 m 3 , and initially erupted basaltic andesite near its vent (4.50–5.64 wt% MgO extending to 3.8 km from vent) with channel and tube-fed basalt (6.21–12.38 wt% MgO sampled at >3.8 km from vent) emplaced during its waning stages. Most Kamakaiʻa Hills lavas are crystal-poor, containing ≤1.5% glomerocrysts and individual phenocrysts of plagioclase + clinopyroxene + Fe Ti oxides ± orthopyroxene, as well as olivine in lavas with >6 wt% MgO. Major-oxide and trace-element concentrations throughout the Kamakaiʻa Hills lavas demonstrate the involvement of three distinct magmatic processes. First, the basaltic andesites of the early ‘a‘ā phase are the products of fractionation of plagioclase + clinopyroxene + Fe Ti oxides ± orthopyroxene, indicative of magmas that have been stored in rift zone reservoirs for decades or longer. Second, the near-vent (within ∼400 m of vent) basaltic andesites of the late pāhoehoe phase yield chemical concentrations that indicate magma mixing with a more differentiated magma (of a similar evolved composition to basaltic andesites at ∼55–56 wt% SiO 2 and ∼3.4–4.1 wt% MgO that erupted in the lower East Rift Zone in 2018). Third, the progressively more mafic magma (containing olivine + plagioclase + clinopyroxene) that continued to erupt throughout the waning stages of activity suggests an eruptive triggering process whereby an intruding summit or uprift reservoir basalt overpressurized and forced out the stored, differentiated magma of the Kamakaiʻa Hills rift zone reservoir.

Hawaiʻi↗

Mineral chemistry perspective on remobilization of stored magma at Kamakai'a Hills, Southwest Rift Zone of Kilauea, Island of Hawai'i, USA

Differentiated magmas stored in the rift zones of Kīlauea have received more attention in recent years following eruption of andesite during the early phase of 2018 lower East Rift Zone activity. Despite this growing interest, some of the most voluminous eruptions of differentiated rift zone magmas remain poorly studied. One such eruption, and the most voluminous exposed differentiated flow field at Kīlauea, is the Kamakaiʻa Hills. This eruption took place in the Southwest Rift Zone of Kīlauea, a region that is hypothesized to contain a long-lived rift zone reservoir. The Kamakaiʻa Hills flow field encompasses >250 × 10 6 m 3 of basaltic andesite and basalt compositions with a mineral assemblage of orthopyroxene + clinopyroxene + plagioclase during its early ʻaʻā phase and clinopyroxene + plagioclase + olivine during its late pāhoehoe phase. To better understand storage conditions and magma accumulation, this study focuses on major, minor, and trace elements from the mineral assemblage present within the early ʻaʻā and late pāhoehoe phases. The diversity of clinopyroxene and plagioclase compositions within the early ʻaʻā and late pāhoehoe phases, as well as diverse compositions of plagioclase and orthopyroxene within the early ʻaʻā phase, suggest multiple magma bodies and limited pre-eruption magma mixing within the broader Kamakaiʻa Hills reservoir. Oscillatory zoning patterns (particularly in clinopyroxene) imply processes such as recharge events, magma mixing or mingling, or convection within a differentially cooling, chemically stratified reservoir over protracted time intervals, whereas only limited resorbed mineral textures indicate incomplete mixing of heat and chemically distinct magmas during the dike intrusion that triggered the eruption. Mineral-mineral and mineral-melt thermobarometry indicate predominantly shallow (≤2.5 km depth) crustal storage conditions of the cooled, differentiated magma (∼1100 °C and cooler for the basaltic andesites) to hotter temperatures for the basalts (all >1100 °C). Despite the known large standard errors estimated for mineral-melt and mineral-mineral barometry (10s to >100 MPa), the calculated pressures and depths broadly correspond with earthquake swarm depths beneath the Kamakaiʻa Hills, and drill core and fluid inclusion barometry storage depths of differentiated magmas within the lower East Rift Zone. The Kamakaiʻa Hills differentiated magmas have H 2 O contents (∼0.5 wt%, using plagioclase-melt hygrometry) equivalent to typical Kīlauea basalts. Our data and interpretations demonstrate a complex, long-lived rift zone storage system that consisted of multiple magma bodies and was mobilized into eruption through intrusion of a hotter and more primitive summit-derived (uprift) magma.

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