Optimization of the Sampling Technique for the Determination of Dissolved Hydrogen in Groundwater

In this study a field‐sampling technique for dissolved hydrogen (H₂) in groundwater will be presented which allows the transport of gaseous samples into the laboratory for further analysis. The method consists of transferring the headspace trapped in a gas‐sampling bulb which is continuously purged by groundwater into previously evacuated vials using a gas‐tight syringe. Three transfer steps with preceding evacuation of the vial led to a H₂‐recovery of 100 % in laboratory experiments. The method has been applied to determine H₂ concentrations in an aquifer contaminated with chlorinated solvents. Tests concerning the effect of different pumping techniques on H₂ concentrations revealed that most reliable values were obtained with a bladder pump, while an electrically driven submersible pump generated considerable amounts of hydrogen due to electrochemical interactions with the sampled water. Concentrations of dissolved hydrogen in field and laboratory samples were about two orders of magnitude higher when sampling was performed with the electrically driven submersible pump compared to sampling with the bladder pump and a peristaltic pump. Lab experiments with a Plexiglas reservoir to produce H₂‐enriched water were used to study the effect of two tubing materials (PVC, polyamide) on H₂ losses. PVC tubing turned out to allow transfer of H₂‐enriched water over 25 m without significant losses, while PA‐tubing was not suitable for sampling of H₂.     

The Geysers - Cobb Mountain Magma System, California (Part 1): U-Pb zircon ages of volcanic rocks, conditions of zircon crystallization and magma residence times

Combined U-Pb zircon and ⁴⁰Ar/³⁹Ar sanidine data from volcanic rocks within or adjacent to the Geysers geothermal reservoir constrain the timing of episodic eruption events and the pre-eruptive magma history. Zircon U-Pb concordia intercept model ages (corrected for initial ²³⁰Th disequilibrium) decrease as predicted from stratigraphic and regional geological relationships (1σ analytical error): 2.47 ± 0.04 Ma (rhyolite of Pine Mountain), 1.38 ± 0.01 Ma (rhyolite of Alder Creek), 1.33 ± 0.04 Ma (rhyodacite of Cobb Mountain), 1.27 ± 0.03 Ma (dacite of Cobb Valley), and 0.94 ± 0.01 Ma (dacite of Tyler Valley). A significant (∼0.2-0.3 Ma) difference between these ages and sanidine ⁴⁰Ar/³⁹Ar ages measured for the same samples demonstrates that zircon crystallized well before eruption. Zircons U-Pb ages from the underlying main-phase Geysers Plutonic Complex (GPC) are indistinguishable from those of the Cobb Mountain volcanics. While this is in line with compositional evidence that the GPC fed the Cobb Mountain eruptions, the volcanic units conspicuously lack older (∼1.8 Ma) zircons from the shallowest part of the GPC. Discontinuous zircon age populations and compositional relationships in the volcanic and plutonic samples are incompatible with zircon residing in a single long-lived upper crustal magma chamber. Instead we favor a model in which zircons were recycled by remelting of just-solidified rocks during episodic injection of more mafic magmas. This is consistent with thermochronologic evidence that the GPC cooled below 350° C at the time the Cobb Mountain volcanics were erupted.     

Quartz and feldspar zoning in the eastern Erzgebirge volcano-plutonic complex (Germany, Czech Republic): evidence of multiple magma mixing

Zoned quartz and feldspar phenocrysts of the Upper Carboniferous eastern Erzgebirge volcano-plutonic complex were studied by cathodoluminescence and minor and trace element profiling. The results verify the suitability of quartz and feldspar phenocrysts as recorders of differentiation trends, magma mixing and recharge events, and suggest that much heterogeneity in plutonic systems may be overlooked on a whole-rock scale. Multiple resorption surfaces and zones, element concentration steps in zoned quartz (Ti) and feldspar phenocrysts (anorthite content, Ba, Sr), and plagioclase-mantled K-feldspars etc. indicate mixing of silicic magma with a more mafic magma for several magmatic phases of the eastern Erzgebirge volcano-plutonic complex. Generally, feldspar appears to be sensitive to the physicochemical changes of the melt, whereas quartz phenocrysts are more stable and can survive a longer period of evolution and final effusion of silicic magmas. The regional distribution of mixing-compatible textures suggests that magma mingling and mixing was a major process in the evolution of these late-Variscan granites and associated volcanic rocks.

Quartz phenocrysts from 14 magmatic phases of the eastern Erzgebirge volcano-plutonic complex provide information on the relative timing of different mixing processes, storage and recharge, allowing a model for the distribution of magma reservoirs in space and time. At least two levels of magma storage are envisioned: deep reservoirs between 24 and 17 km (the crystallisation level of quartz phenocrysts) and subvolcanic reservoirs between 13 and 6 km. Deflation of the shallow reservoirs during the extrusion of the Teplice rhyolites triggered the formation of the Altenberg-Teplice caldera above the eastern Erzgebirge volcano-plutonic complex. The deep magma reservoir of the Teplice rhyolite also has a genetic relationship to the younger mineralised A-type granites, as indicated by quartz phenocryst populations. The pre-caldera biotite granites and the rhyodacitic Schönfeld volcanic rocks represent temporally and spatially separate magma sources. However, the deep magma reservoir of both is assumed to have been at a depth of 24–17 km. The drastic chemical contrast between the pre-caldera Schönfeld (Westfalian B–C) and the syn-caldera Teplice (Westfalian C–D) volcanic rocks is related to the change from late-orogenic geotectonic environment to post-orogenic faulting, and is considered an important chronostratigraphic marker.     

Luminescence dating of ice‐marginal deposits in northern Germany: evidence for repeated glaciations during the Middle Pleistocene (MIS 12 to MIS 6)

The exact number, extent and chronology of the Middle Pleistocene Elsterian and Saalian glaciations in northern Central Europe are still controversial. This study presents new luminescence data from Middle Pleistocene ice‐marginal deposits in northern Germany, giving evidence for repeated glaciations during the Middle Pleistocene (MIS 12 to MIS 6). The study area is located in the Leine valley south of the North German Lowlands. The data set includes digital elevation models, high‐resolution shear wave seismic profiles, outcrop and borehole data integrated into a 3D subsurface model to reconstruct the bedrock relief surface. For numerical age determination, we performed luminescence dating on 12 ice‐marginal and two fluvial samples. Luminescence ages of ice‐marginal deposits point to at least two ice advances during MIS 12 and MIS 10 with ages ranging from 461±34 to 421±25 ka and from 376±27 to 337±21 ka. The bedrock relief model and different generations of striations indicate that the older ice advance came from the north and the younger one from the northeast. During rapid ice‐margin retreat, subglacial overdeepenings were filled with glaciolacustrine deposits, partly rich in re‐worked Tertiary lignite and amber. During MIS 8 and MIS 6, the study area may have been affected by two ice advances. Luminescence ages of glaciolacustrine delta deposits point to a deposition during MIS 8 or early MIS 6, and late MIS 6 (250±20 to 161±10 ka). The maximum extent of both the Elsterian (MIS 12 and MIS 10) and Saalian glaciations (MIS 8? and MIS 6) approximately reached the same position in the Leine valley and was probably controlled by the formation of deep proglacial lakes in front of the ice sheets, preventing a further southward advance.     

Landscape controls on long‐term runoff in subhumid heterogeneous Boreal Plains catchments

We compared median runoff (R) and precipitation (P) relationships over 25 years from 20 mesoscale (50 to 5,000 km²) catchments on the Boreal Plains, Alberta, Canada, to understand controls on water sink and source dynamics in water‐limited, low‐relief northern environments. Long‐term catchment R and runoff efficiency (RP^?1) were low and varied spatially by over an order of magnitude (3 to 119 mm/year, 1 to 27%). Intercatchment differences were not associated with small variations in climate. The partitioning of P into evapotranspiration (ET) and R instead reflected the interplay between underlying glacial deposit texture, overlying soil‐vegetation land cover, and regional slope. Correlation and principal component analyses results show that peatland‐swamp wetlands were the major source areas of water. The lowest estimates of median annual catchment ET (321 to 395 mm) and greatest R (60 to 119 mm, 13 to 27% of P) were observed in low‐relief, peatland‐swamp dominated catchments, within both fine‐textured clay‐plain and coarse‐textured glacial deposits. In contrast, open‐water wetlands and deciduous‐mixedwood forest land covers acted as water sinks, and less catchment R was observed with increases in proportional coverage of these land covers. In catchments dominated by hummocky moraines, long‐term runoff was restricted to 10 mm/year, or 2% of P. This reflects the poor surface‐drainage networks and slightly greater regional slope of the fine‐textured glacial deposit, coupled with the large soil‐water and depression storage and higher actual ET of associated shallow open‐water marsh wetland and deciduous‐forest land covers. This intercatchment study enhances current conceptual frameworks for predicting water yield in the Boreal Plains based on the sink and source functions of glacial landforms and soil‐vegetation land covers. It offers the capability within this hydro‐geoclimatic region to design reclaimed catchments with desired hydrological functionality and associated tolerances to climate or land‐use changes and inform land management decisions based on effective catchment‐scale conceptual understanding.     

The impact of salt on the late Messinian to recent tectonostratigraphic evolution of the Cyprus subduction zone

Messinian evaporites of locally more than 3‐km thickness occupy the subduction zone between Cyprus and Eratosthenes Seamount. Based on a dense grid of seismic reflection profiles, we report on compressional salt tectonics and its impact on the Late Miocene to Quaternary structural evolution of the Cyprus subduction zone. Results show that evaporites have experienced significant post‐Messinian shortening along the plate boundary. Shortening has initiated allochthonous salt advance between Cyprus and Eratosthenes Seamount, representing an excellent example of salt which efficiently escapes subduction and accretion. Further east, between Eratosthenes Seamount and the Hecataeus Rise, evaporites were compressionally inflated without having advanced across post‐Messinian strata. Such differences in the magnitude of salt tectonic shortening may reflect a predominately north–south oriented post‐Messinian convergence direction, raising the possibility of a later coupling between the motion of Cyprus and Anatolia than previously thought. Along the area bordered by Cyprus and Eratosthenes Seamount a prominent step in the seafloor represents the northern boundary of a controversially debated semi‐circular depression. Coinciding with the southern edge of the salt sheet, this bathymetric feature is suggested to have formed as a consequence of compressional salt inflation and seamount‐directed salt advance. Topographic lows on top of highly deformed evaporites are locally filled by up to 700 m of late Messinian sediments. The uppermost 200 m of these sediments were drilled in the course of ODP Leg 160 and interpreted to represent Lago Mare‐type deposits (Robertson, Tectonophysics, 1998d, 298 , 63‐82). Lago Mare deposits are spatially restricted to the western part of the subduction zone, pinching out towards the east whereas presumably continuing into the Herodotus Basin further west. We suggest a sea level control on late Messinian Lago Mare sedimentation, facilitating sediment delivery into basinal areas whereas inhibiting Lago Mare deposition into the desiccated Levant Basin. Locally, early salt deformation is believed to have provided additional accommodation space for Lago Mare sedimentation, resulting in the presently observed minibasin‐like geometry.     

In situ LA-ICPMS Isotopic and Geochronological Studies on Carbonatites and Phoscorites from the Guli Massif,Maymecha-Kotuy,Polar Siberia

In this study we present a fresh isotopic data, as well as U–Pb ages from different REE-minerals in carbonatites and phoscorites of Guli massif using in situ LA-ICPMS technique. The analyses were conducted on apatites and perovskites from calcio-carbonatite and phoscorite units, as well as on pyrochlores and baddeleyites from the carbonatites. The ⁸⁷Sr/⁸⁶Sr ratios obtained from apatites and perovskites from the phoscorites are 0.70308–0.70314 and 0.70306–0.70313, respectively; and 0.70310–0.70325 and 0.70314–0.70327, for the pyrochlores and apatites from the carbonatites, respectively.Furthermore, the in situ laser ablation analyses of apatites and perovskites from the phoscorite yield εNd from 3.6 (±1) to 5.1 (±0.5) and from 3.8 (±0.5) to 4.9 (±0.5), respectively; εNd of apatites, perovskites and pyrochlores from carbonatite ranges from 3.2 (±0.7) to 4.9 (±0.9), 3.9 (±0.6) to 4.5 (±0.8) and 3.2 (±0.4) to 4.4 (±0.8), respectively. Laser ablation analyses of baddeleyites yielded an eHf(t)d of +8.5 (± 0.18); prior to this study Hf isotopic characteristic of Guli massif was not known. Our new in situ εNd, ⁸⁷Sr/⁸⁶Sr and eHf data on minerals in the Guli carbonatites imply a depleted source with a long time integrated high Lu/Hf, Sm/Nd, Sr/Rb ratios.In situ U–Pb age determination was performed on perovskites from the carbonatites and phoscorites and also on pyrochlores and baddeleyites from carbonatites. The co-existing pyrochlores, perovskites and baddeleyites in carbonatites yielded ages of 252.3 ± 1.9, 252.5 ± 1.5 and 250.8 ± 1.4 Ma, respectively. The perovskites from the phoscorites yielded an age of 253.8 ± 1.9 Ma. The obtained age for Guli carbonatites and phoscorites lies within the range of ages previously reported for the Siberian Flood Basalts and suggest essentially synchronous emplacement with the Permian-Triassic boundary.