An experimental study of the solubility and speciation of the Rare Earth Elements (III) in fluoride- and chloride-bearing aqueous solutions at temperatures up to 300 °C

The solubility of REE(III) fluoride solids was determined in fluoride- and chloride-bearing solutions at 150, 200 and 250 °C and saturated water vapor pressure. These experimental data, together with experimental data from previously published studies, were used to evaluate formation constants for chloride- and fluoride-bearing aqueous species of the entire REE(III) group at temperatures up to 300 °C. The data show that the stability of these species differs significantly from that predicted theoretically. For example, contrary to the theoretical predictions, LREEF²⁺ species are more stable than HREEF²⁺ species at elevated temperature. The behavior of the chloride-bearing species is similar. Parameters for the Helgeson–Kirkham–Flowers (HKF) equation of state were determined for REEF²⁺, REECl²⁺ and REECl₂⁺ complexes using these experimental data and permit calculation of formation constants of these species at conditions not investigated experimentally. These data now permit the mobility of all REE in fluoride- and chloride-bearing hydrothermal systems to be reliably evaluated at intermediate temperatures and pressures.     

Holocene environments and climate in the Mongolian Altai reconstructed from the Hoton-Nur pollen and diatom records: a step towards better understanding climate dynamics in Central Asia

This study presents the results of the palynological and diatom analyses of the sediment core recovered in Hoton-Nur Lake (48°37′18″N, 88°20′45″E, 2083 m) in 2004. Quantitative reconstruction of the Holocene vegetation and climate dynamics in the semiarid Mongolian Altai suggests that boreal woodland replaced the primarily open landscape of northwestern Mongolia at about 10 kyr BP (1 kyr = 1000 cal yr) in response to a noticeable increase in precipitation from 200–250 mm/yr to 450–550 mm/yr. A decline of the forest vegetation and a return to a predominance of open vegetation types occurred after 5 kyr BP when precipitation sums decreased to 250–300 mm/yr. Prior to 11.5 kyr BP diatom concentrations are relatively low and the lake is dominated by planktonic Cyclotella and small Fragilariaceae, suggesting the existence of a relatively deep and oligotrophic/mesotrophic lake. The great abundance of Staurosirella pinnata from the beginning of the record until 10.7 kyr BP might imply intensified erosion processes in the catchment and this is fully consistent with the presence of scarce and dry vegetation and the generally arid climate during this period. From about 10.7 kyr BP, more planktonic diatom taxa appeared and increased in abundance, indicating that the lake became more productive as diatom concentration increased. This change correlates well with the development of boreal woodland in the catchment. Decrease in precipitation and changes in the vegetation towards steppe are reflected by the rapid increase in Aulacoseira distans from about 5 kyr BP. The Holocene pollen and diatom records do not indicate soil and vegetation cover disturbances by the anthropogenic activities, implying that the main transformations of the regional vegetation occurred as a result of the natural climate change. Our reconstruction is in agreement with the paleomonsoon records from China, demonstrating an abrupt strengthening of the summer monsoon at 12 kyr BP and an associated increase in precipitation and in lake levels between 11 and 8 kyr BP, followed by the stepwise attenuation of the monsoon circulation and climate aridization towards the modern level. The records from the neighboring areas of Kazakhstan and Russia, situated west and north of Hoton-Nur, demonstrate spatially and temporally different Holocene vegetation and climate histories, indicating that the Altai Mountains as a climate boundary are of pivotal importance for the Holocene environmental and, possibly, habitation history of Central Asia.     

Storage-discharge characteristics of an active rock glacier catchment in the Innere Ölgrube,Austrian Alps

The active rock glacier “Innere Ölgrube” and its catchment area (Ötztal Alps, Austria) are assessed using various hydro(geo)logical tools to provide a thorough catchment characterization and to quantify temporal variations in recharge and discharge components. During the period from June 2014 to July 2018, an average contribution derived from snowmelt, ice melt and rainfall of 35.8%, 27.6% and 36.6%, respectively, is modelled for the catchment using a rainfall-runoff model. Discharge components of the rock glacier springs are distinguished using isotopic data as well as other natural and artificial tracer data, when considering the potential sources rainfall, snowmelt, ice melt and longer stored groundwater. Seasonal as well as diurnal variations in runoff are quantified and the importance of shallow groundwater within this rock glacier-influenced catchment is emphasized. Water derived from ice melt is suggested to be provided mainly by melting of two small cirque glaciers within the catchment and subordinately by melting of permafrost ice of the rock glacier. The active rock glacier is characterized by a layered internal structure with an unfrozen base layer responsible for groundwater storage and retarded runoff, a main permafrost body contributing little to the discharge (at the moment) by permafrost thaw and an active layer responsible for fast lateral flow on top of the permafrost body. Snowmelt contributes at least 1/3rd of the annual recharge. During droughts, meltwater derived from two cirque glaciers provides runoff with diurnal runoff variations; however, this discharge pattern will change as these cirque glaciers will ultimately disappear in the future. The storage-discharge characteristics of the investigated active rock glacier catchment are an example of a shallow groundwater aquifer in alpine catchments that ought to be considered when analysing (future) river runoff characteristics in alpine catchments as these provide retarded runoff during periods with little or no recharge.     

Role of reservoir regulation and groundwater feedback in a simulated ground-soil-vegetation continuum: A long-term regional scale analysis

The regional terrestrial water cycle is strongly altered by human activities. Among them, reservoir regulation is a way to spatially and temporally allocate water resources in a basin for multi-purposes. However, it is still not sufficiently understood how reservoir regulation modifies the regional terrestrial- and subsequently, the atmospheric water cycle. To address this question, the representation of reservoir regulation into the terrestrial component of fully coupled regional Earth system models is required. In this study, an existing process-based reservoir network module is implemented into NOAH-HMS, that is, the terrestrial component of an atmospheric–hydrologic modelling system, namely, the WRF-HMS. It allows to quantitatively differentiate role of reservoir regulation and of groundwater feedback in a simulated ground-soil-vegetation continuum. Our study focuses on the Poyang Lake basin, where the largest freshwater lake of China and reservoirs of different sizes are located. As compared to streamflow observations, the newly extended NOAH-HMS slightly improves the streamflow and streamflow duration curves simulation for the Poyang Lake basin for the period 1979–1986. The inclusion of reservoir regulation leads to major changes in the simulated groundwater recharges and evaporation from reservoirs at local scale, but has minor effects on the simulated soil moisture and surface runoff at basin scale. The performed groundwater feedback sensitivity analysis shows that the strength of the groundwater feedback is not altered by the consideration of reservoir regulation. Furthermore, both reservoir regulation and groundwater feedback modify the partitioning of the simulated evapotranspiration, thus affecting the atmospheric water cycle in the Poyang Lake region. This finding motivates future research with our extended fully coupled atmospheric–hydrologic modelling system by the community.     

Verification of tropical cyclone deposits with oxygen isotope analyses of coeval ostracod valves

Reconstruction of prehistoric tropical cyclone (TC) activity often relies on the identification of distinctive overwash deposits (tempestites) in coastal lagoon sediments. Similar sediment deposits, however, can result from high-energy events other than TCs. In this study we assessed the utility of using the geochemistry of ostracod valves, specifically their stable oxygen isotope composition (δ¹⁸O), as a potential validation variable that could reduce the chances of misidentifying an overwash deposit as having been generated by a TC, when in fact it formed from another high-energy depositional process (type 1 error). We applied this technique to a sediment core recovered from Laguna Alejandro, Dominican Republic, which had already been analyzed for other sedimentary TC proxies. Negative δ¹⁸O anomalies identified in the ostracod valve stable isotope record are associated with TC deposits and are most easily explained by large influxes of ¹⁸O-depleted meteoric waters typical of intense tropical storms. There is potential for this technique to be used to identify TC landfalls that are not represented by overwash deposits. We, however, propose a more conservative approach and suggest this technique be used to validate the origin of a storm deposit and reduce the odds of a type 1 error.     

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Fluid injection monitoring using electrical resistivity tomography — five years of injection at Ketzin,Germany

Between the years 2008 and 2013, approximately 67 kilotons of CO₂ have been injected at the Ketzin site, Germany. As part of the geophysical monitoring programme, time‐lapse electrical resistivity tomography has been applied using crosshole and surface‐downhole measurements of electrical resistivity tomography. The data collection of electrical resistivity tomography is partly based on electrodes that are permanently installed in three wells at the site (one injection well and two observation wells). Both types of ERT measurements consistently show the build‐up of a CO₂‐related resistivity signature near the injection point. Based on the imaged resistivity changes and a petrophysical model, CO₂ saturation levels are estimated. These CO₂ saturations are interpreted in conjunction with CO₂ saturations inferred from neutron‐gamma loggings. Apart from the CO₂–brine substitution response in the observed resistivity changes, significant imprints from the dynamic behaviour of the CO₂ in the reservoir are observed.     

Investigating groundwater flow components in an Alpine relict rock glacier (Austria) using a numerical model

Relict rock glaciers are complex hydrogeological systems that might act as relevant groundwater storages; therefore, the discharge behavior of these alpine landforms needs to be better understood. Hydrogeological and geophysical investigations at a relict rock glacier in the Niedere Tauern Range (Austria) reveal a slow and fast flow component that appear to be related to the heterogeneous structure of the aquifer. A numerical groundwater flow model was used to indicate the influence of important internal structures such as layering, preferential flow paths and aquifer-base topography. Discharge dynamics can be reproduced reasonably by both introducing layers of strongly different hydraulic conductivities or by a network of highly conductive channels within a low-conductivity zone. Moreover, the topography of the aquifer base influences the discharge dynamics, which can be observed particularly in simply structured aquifers. Hydraulic conductivity differences of three orders of magnitude are required to account for the observed discharge behavior: a highly conductive layer and/or channel network controlling the fast and flashy spring responses to recharge events, as opposed to less conductive sediment accumulations sustaining the long-term base flow. The results show that the hydraulic behavior of this relict rock glacier and likely that of others can be adequately represented by two aquifer components. However, the attempt to characterize the two components by inverse modeling results in ambiguity of internal structures when solely discharge data are available.     

Detrital zircon U–Pb ages and whole-rock geochemistry of the Neoproterozoic Paulistana and Santa Filomena complexes,Borborema Province,northeastern Brazil: implications for source area composition,provenance, and tectonic setting

The Paulistana and Santa Filomena Complexes are situated in the southern part of the Borborema Province (northeastern Brazil), in the Riacho do Pontal Orogen, and represent meta-volcano-sedimentary sequences. We present compositional variations in the metasedimentary rocks and new U–Pb detrital zircon data. Major and trace elements indicate that the metasedimentary rocks from the Paulistana and Santa Filomena Complexes are composed mostly of immature to mature sediments derived from felsic-intermediate sources with moderate to slightly high chemical weathering. The geochemical signatures of the sediment protoliths for both complexes are characteristic of continental magmatic arc settings with minor contribution from recycled sediment sources. The source area for the Paulistana Complex rocks follow the compositional trend between calc-alkaline granites and granodiorites, whereas the Santa Filomena Complex rocks have a more restricted composition trending to more granodioritic sources. For the Paulistana Complex, two main source ages were identified: (1) Tonian (ca. 950 Ma – sample RPE-58) and Tonian–Stenian (ca. 1.0 Ga – sample RPE-103). These data coupled with geochemical information suggest that the Cariris Velhos arc system was the main source area for the Paulistana Complex. Regarding the Santa Filomena metasedimentary rocks, potential source-areas include: (1) Neoarchaean rocks (~2.6 Ga) represented by the adjacent basement rocks of the Riacho do Pontal Orogen; (2) Rhyacian–Orosirian rocks (2.2–2.0 Ga) of the Riacho do Pontal Orogen and the Pernambuco–Alagoas terrain, which include an augen-gneiss with arc-related geochemical signature; (3) Statherian granites (1.7–1.6 Ga); and (4) Cariris Velhos crust (1000–920 Ma). The metasedimentary rocks of the Paulistana Complex were deposited in a rift stage (ca. 900 Ma), which is related to the break-up of the Rodinia supercontinent. The metasedimentary rocks of the Santa Filomena Complex most probably were deposited in another rift stage (ca. 750–700 Ma) and could be correlatives of the rift formation of the Canindé Domain (Sergipano Orogen).