Suitability of Existing Numerical Model Codes and Thermodynamic Databases for the Prognosis of Calcite Dissolution Processes in Near-Surface Sediments Due to a CO2 Leakage Investigated by Column Experiments

Among the risks of CO₂ storage is the potential of CO₂ leakage into overlaying formations and near-surface potable aquifers. Through a leakage, the CO₂ can intrude into protected groundwater resources, which can lead to groundwater acidification followed by potential mobilisation of heavy metals and other trace metals through mineral dissolution or ion exchange processes. The prediction of pH buffer reactions in the formations overlaying a CO₂ storage site is essential for assessing the impact of CO₂ leakages in terms of trace metal mobilisation. For buffering the pH-value, calcite dissolution is one of the most important mechanisms. Although calcite dissolution has been studied for decades, experiments conducted under elevated CO₂ partial pressures are rare. Here, the first study for column experiments is presented applying CO₂ partial pressures from 6 to 43 bars and realising a near-natural flow regime. Geochemical calculations of calcite dissolution kinetics were conducted using PHREEQC together with different thermodynamic databases. Applying calcite surface areas, which were previously acquired by N₂-BET or calculated based on grain diameters, respectively, to the rate laws according to Plummer et al. (Am J Sci 278:179–216, doi:10.2475/ajs.278.2.179, 1978) or Palandri and Kharaka (US Geol Surv Open file Rep 2004–1068:71, 2004) in the numerical simulations led to an overestimation of the calcite dissolution rate by up to three orders of magnitude compared to the results of the column experiments. Only reduction of the calcite surface area in the simulations as a fitting procedure allowed reproducing the experimental results. A reason may be that the diffusion boundary layer (DBL), which depends on the groundwater flow velocity and develops at the calcite grain surface separating it from the bulk of the solution, has to be regarded: The DBL leads to a decrease in the calcite dissolution rate under natural laminar flow conditions compared to turbulent mixing in traditional batch experiments. However, varying the rate constants by three orders of magnitudes in a field scale PHREEQC model simulating a CO₂ leakage produced minor variations in the pH buffering through calcite dissolution. This justifies the use of equilibrium models when calculating the calcite dissolution in CO₂ leakage scenarios for porous aquifers and slow or moderate groundwater flow velocities. However, the selection of the thermodynamic database has an impact on the dissolved calcium concentration, leading to an uncertainty in the simulation results. The resulting uncertainty, which applies also to the calculated propagation of an aquifer zone depleted in calcite through dissolution, seems negligible for shallow aquifers of approximately 60 m depth, but amounts to 35 % of the calcium concentration for aquifers at a depth of approximately 400 m.     

A geological database for parameterization in numerical modeling of subsurface storage in northern Germany

Underground land use can play a significant role in future concepts of energy and gas storage and requires an improved understanding of the parameters of potential storage formations (saline aquifers), for instance of porosity and permeability, and also of mineralogical and gas compositions. This study aims at providing data examples and calculating vertical spatial variations through variogram analyses of important North German geological reservoirs from Dogger, Rhaetian, Middle Buntsandstein, and Rotliegend (Sub)Groups and Formations, focusing on the western part of the North German Basin. Vertical correlation lengths of porosity and permeability data range between 0 and 30 m, while most results are calculated at approximately 2–4 m and do not show relevant differences among the evaluated formations. In the majority of the regarded formations, the Kozeny–Carman relationship between porosity and permeability is supported as long as low porosity and permeability values are excluded from the evaluation. Mineral percentages varied significantly among the evaluated sediments. Besides quartz, ankerite is the main compound in the Dogger Group, while feldspars and clay minerals were more frequent in the Rhaetian, Middle Buntsandstein, and Rotliegend sediments. Methane was the main gas compound in the reservoirs, followed by nitrogen, ethane, and carbon dioxide. This study serves as preparatory work to allow for the parameterization of geological models and a subsequent simulation of fluid transport to evaluate (long-term) safety and impacts of geothermal and gas storage projects.     

Homogeneous reprocessing of GPS,GLONASS and SLR observations

The International GNSS Service (IGS) provides operational products for the GPS and GLONASS constellation. Homogeneously processed time series of parameters from the IGS are only available for GPS. Reprocessed GLONASS series are provided only by individual Analysis Centers (i. e. CODE and ESA), making it difficult to fully include the GLONASS system into a rigorous GNSS analysis. In view of the increasing number of active GLONASS satellites and a steadily growing number of GPS+GLONASS-tracking stations available over the past few years, Technische Universität Dresden, Technische Universität München, Universität Bern and Eidgenössische Technische Hochschule Zürich performed a combined reprocessing of GPS and GLONASS observations. Also, SLR observations to GPS and GLONASS are included in this reprocessing effort. Here, we show only SLR results from a GNSS orbit validation. In total, 18 years of data (1994–2011) have been processed from altogether 340 GNSS and 70 SLR stations. The use of GLONASS observations in addition to GPS has no impact on the estimated linear terrestrial reference frame parameters. However, daily station positions show an RMS reduction of 0.3 mm on average for the height component when additional GLONASS observations can be used for the time series determination. Analyzing satellite orbit overlaps, the rigorous combination of GPS and GLONASS neither improves nor degrades the GPS orbit precision. For GLONASS, however, the quality of the microwave-derived GLONASS orbits improves due to the combination. These findings are confirmed using independent SLR observations for a GNSS orbit validation. In comparison to previous studies, mean SLR biases for satellites GPS-35 and GPS-36 could be reduced in magnitude from \(-35\) and \(-38\)  mm to \(-12\) and \(-13\)  mm, respectively. Our results show that remaining SLR biases depend on the satellite type and the use of coated or uncoated retro-reflectors. For Earth rotation parameters, the increasing number of GLONASS satellites and tracking stations over the past few years leads to differences between GPS-only and GPS+GLONASS combined solutions which are most pronounced in the pole rate estimates with maximum 0.2 mas/day in magnitude. At the same time, the difference between GLONASS-only and combined solutions decreases. Derived GNSS orbits are used to estimate combined GPS+GLONASS satellite clocks, with first results presented in this paper. Phase observation residuals from a precise point positioning are at the level of 2 mm and particularly reveal poorly modeled yaw maneuver periods.     

The Herschel PACS photometer calibration

We present a flux calibration scheme for the PACS chopped point-source photometry observing mode based on the photometry of five stellar standard sources. This mode was used for science observations only early in the mission. Later, it was only used for pointing and flux calibration measurements. Its calibration turns this type of observation into fully validated data products in the Herschel Science Archive. Systematic differences in calibration with regard to the principal photometer observation mode, the scan map, are derived and amount to 5 ? 6 %. An empirical method to calibrate out an apparent response drift during the first 300 Operational Days is presented. The relative photometric calibration accuracy (repeatability) is as good as 1 % in the blue and green band and up to 5 % in the red band. Like for the scan map mode, inconsistencies among the stellar calibration models become visible and amount to 2 % for the five standard stars used. The absolute calibration accuracy is therefore mainly limited by the model uncertainty, which is 5 % for all three bands.     

Barnacle fouling in the Mediterranean sponges Axinella polypoides and Axinella verrucosa

Secondary metabolites protect many marine sponges (Phylum: Porifera) from settlement by fouling organisms. Previous studies on the subtidal demosponge Axinella verrucosa collected in the Western Mediterranean led to the isolation of compounds that inhibited the settlement of cyprids larvae of the intertidal barnacle Balanus amphitrite, and the enzyme chitinase, which plays a key role in the molting cycle of crustaceans. However, in a field survey conducted at three locations in Israel, Eastern Mediterranean Sea, we observed that A. verrucosa is fouled by the subtidal barnacle Balanus trigonus, a previously unknown association. Settlement inhibition assays using B. amphitrite with chemical extracts from Israeli A. verrucosa and Axinella polypoides, a sympatric, congeneric sponge that seems not to be fouled by B. trigonus, showed that cyprid larvae of B. amphitrite were inhibited by the extracts of both sponges from settlement at concentrations several magnitudes lower than natural volumetric extract concentration in the sponges. These results indicate that, unlike the intertidal barnacle B. amphitrite, the subtidal B. trigonus is unaffected by the compounds from A. verrucosa, stressing and underlining the importance of using suitable target organisms (i.e. from the same habitat) to test for ecologically relevant antifouling activities.     

Spatio-temporal variability in debris-flow activity: a tree-ring study at Geisstriftbach (Swiss Alps) extending back to AD 1736

Past debris-flow activity on the forested cone of the Geisstriftbach torrent (St. Niklaus, Valais, Swiss Alps) was assessed from growth disturbances in old conifer trees, providing a much improved record of past events. The study of 633 tree-ring sequences sampled from 252 European larch (Larix decidua Mill.), Norway spruce (Picea abies (L.) Karst.) and Silver birch (Betula pendula Roth.) trees allowed reconstruction of 53 debris-flow events since AD 1736. The spatial analysis of trees affected during particular events on the geomorphic map allowed for a spatial representation of individual events and a reconstruction of four flow patterns. Based on our results and Siegfried maps, we believe that before the formation of a dogleg near the cone apex in the late 1890s, debris flows preferentially used the channels located in the west-southwestern part of the Geisstriftbach cone. This study contributes to our understanding of debris-flow processes on cones and provides an example of how dendrogeomorphic techniques may help in the reconstruction and understanding of debris flows in Alpine areas.     

Using chloride and other ions to trace sewage and road salt in the Illinois Waterway

Chloride concentrations in waterways of northern USA are increasing at alarming rates and road salt is commonly assumed to be the cause. However, there are additional sources of Cl⁻ in metropolitan areas, such as treated wastewater (TWW) and water conditioning salts, which may be contributing to Cl⁻ loads entering surface waters. In this study, the potential sources of Cl⁻ and Cl⁻ loads in the Illinois River Basin from the Chicago area to the Illinois River’s confluence with the Mississippi River were investigated using halide data in stream samples and published Cl⁻ and river discharge data. The investigation showed that road salt runoff and TWW from the Chicago region dominate Cl⁻ loads in the Illinois Waterway, defined as the navigable sections of the Illinois River and two major tributaries in the Chicago region. Treated wastewater discharges at a relatively constant rate throughout the year and is the primary source of Cl⁻ and other elements such as F⁻ and B. Chloride loads are highest in the winter and early spring as a result of road salt runoff which can increase Cl⁻ concentrations by up to several hundred mg/L. Chloride concentrations decrease downstream in the Illinois Waterway due to dilution, but are always elevated relative to tributaries downriver from Chicago. The TWW component is especially noticeable downstream under low discharge conditions during summer and early autumn when surface drainage is at a minimum and agricultural drain tiles are not flowing.     

中国东部富钾埃达克岩成因的实验约束

Adakite在地球化学上具明显特征的火山岩和深成花岗岩类岩石，见于洋内岛孤环境和大陆孤，如安底斯孤。在洋内岛孤，由热的消减的大洋岩石圈熔融形成（叫做“板片熔融”），而在大陆孤，熔融曾发生在构造或岩浆加厚的下地壳底（叫做“下地壳熔融”）。在这两种产状环境中，adakite的鲜明地球化学特征被认为是起因子，一种不同程度含水的变质基性原岩在足够深度上的部分熔融，这里的足够深度是指可使石榴子石在残余结晶组合（即石榴角闪石和/或榴辉石的残余）中保持稳定的深度。“原始”或“母”adakite熔体一旦形成，便可能在其向上运移和侵位上地壳期间受到同化作用（或是地幔，或是大陆物质）和结晶分异作用的改造。中国东部晚中生代（早中白垩世，160-110Ma）的adakite,与见于同一地区和其它地方的钠质adakite相比，通常富含钾(K2O)和其它大离子亲石元素（如Ba,Th,U），有较低的Na2O/K2O比值（-1.0-1.1）,类似于玄武岩在石榴角闪岩-榴辉岩相含水熔融实验中所产生adakite熔体，要么是由洋壳板片熔融所形成，要么是由不同成分的玄武质下地壳原岩部分熔融所形成。尽管有些成分差异，它们的总体化学特征仍然可将中国东部的富钾花岗岩类岩石定均adakite。我们把这些富钾的adakite的独特化学行特征，归因于成分来源的特殊性，或adakite母岩浆遭受了同化混染和结晶分异(AFC)作用的改造。虽然中国东部与消减带环境明显不同这一点表明，那里的adakite可由板块底部侵位的（岩浆加厚的）镁铁质下地壳部分熔融所形成，但燕山运动期间中国东部存在“平坦”俯冲的地球动力学环境是可能被排除的。     

500-yr. precipitation variability in Southern Taihang Mountains,China, and its linkages to ENSO and PDO

An annually resolved and absolutely dated ring-width chronology spanning 657 yrs. is constructed with Whitebark pine (Pinus bungeana Zucc.) samples from the southern Taihang Mountains, Eastern China. On the basis of a significant correlation between the tree-ring width index and observed instrumental data, precipitation in current May is reconstructed for the region since AD 1510, with predictor variables accounting for 37.9 % of the variance in precipitation data. In agreement with other drought reconstructions, notable dry spells occur in the 1630s–1650s, 1680s–1700s, and 1770s–1800s, whereas wet periods prevail in the 1530s–1570s, 1840s–1870s, and 1950s-present. Wavelet analysis reveals clear 2–8, 20–40, and 80–130 yrs cycles at the 95 % confidence level for the reconstructed series over the past 500 yrs, suggesting possible linkages with the El Niño-Southern Oscillation (ENSO) and the Pacific Decadal Oscillation (PDO). Correlation analysis between the tree-ring series, ENSO, and PDO index further demonstrates that precipitation is negatively correlated with PDO and ENSO in the long term.