Spatiotemporal variation of stable isotopic composition in precipitation: Post‐condensational effects in a humid area

In the present study, a 2‐year dataset on δ¹⁸O and δ²H in precipitation is used to investigate hydrometeorologic controls on the isotopic compositions in a temperate maritime climate. Data was collected in Denmark along a transect of Six sampling stations across a landscape with a small topographic gradient and predominant westerly winds. Data showed the local meteoric water line for this region is expressed by the equation δ²H = 7.4δ¹⁸O + 5.4‰. A significant trend correlating enriched isotopic values to humidities around 70% during dry season and more depleted isotopic values to humidities around 90% during wet season was derived from the dataset. Temperature was found to only influence the isotopic composition in a secondary way, whereas no significant relationship was obtained for precipitation amount and evapotranspiration. It is suggested that subcloud post‐condensation exchange strongly influences the isotopic composition at the study site. A simple model of evaporation on falling rain was applied with the aim to reproduce observational data and show the potential influence of changing humidity conditions on precipitation compositions. The rather simple model approach did not fully explain the observational data, but it highlights the drastic isotopic changes from a falling raindrop that potentially can occur due to its release into a dryer atmosphere. This study shows that regional conditions and especially humidity can alter the isotopic composition in precipitation substantially even in regions without major topographic and hydrometeorologic gradients.     

Deep-rooted piercement structures in deep sedimentary basins — Manifestations of supercritical water generation at depth?

Deep-rooted enigmatic piercement structures in sedimentary basins, including ‘mud volcanoes’, ‘shale diapirs’, ‘salt diapirs’, and ‘asphalt volcanoes’, range in size from less than 1 km², surface area, up to 64 km², and have often an unknown depth of penetration due to incomplete imaging. We propose that they form a family associated with fluid flow. Our argument is based partly on their inferred location (above deep faults) and on the chemical analysis of emitted products, which includes liquid clays, brines and other substances from salt diapirs, and asphalt and light oils from the asphalt volcanoes. We explain these compositions by chemical alteration caused partly by supercritical water, a phase of water existent at high pressure and temperature, locally and temporarily achieved at depths generally beyond 10 km below surface, i.e., at the sediment–crust boundary. Our hypothesis overcomes some of the problems with interpreting fluid flow products, which are otherwise very difficult to explain. In case this hypothesis can be further verified, the family could perhaps be called ‘hydrothermally associated piercement structures’.     

Clay minerals in the late Quaternary sediment of Tulare Lake,California: Implications for climate change,weathering, and erosion processes

The clay mineralogy of Tulare Lake sediment was examined to investigate hydroclimatic and environmental changes in the southern Sierra Nevada Mountains (SNM) since the most recent glacial maximum. Evolution of clay mineral assemblages elucidates significant changes in weathering, erosion, and hydroclimatic condition in the catchment. During the last glacial period (24.4–15.1 cal ka BP), low illite content implies less physical erosion of the granitic batholith rocks and a cold and arid environment in the southern SNM. Abrupt increases of illite content at 21.8–20.8 and 17.6 cal ka BP resulted from the glacier advances to the ablation zone and illite-rich glacier flour was transported down to the lake. The gradual increase of smectite induced by progressive depletion of illite-rich glacier flour from 17.6 cal ka BP toward the end of this period indicates climate was beginning to get warm and wet. From 11.9 to 5.3 cal ka BP, two warm and wet periods (10.7–9.4 and 8.2–5.2 cal ka BP) were characterized by high smectite/illite content ratios and low illite crystallinity values, suggesting intensive rainfall precipitation and more physical erosion in the highland and lowland catchment as well as more smectite formation in the terrace soils. Since the last glacial period, physical erosion, in comparison to the chemical weathering, was the dominant process responding to the hydroclimatic change in the Tulare Lake catchment. Moderate to weak chemical weathering was signified by the mostly low illite chemical weathering index of the core sediments. Such results suggest that vegetation cover in the southern SNM was low and limited.     

Organic Geochemical Microanalysis by Time‐of‐Flight Secondary Ion Mass Spectrometry (ToF‐SIMS)

Time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) is a powerful method for the chemical analysis of solid surfaces. In this paper, the capabilities and limitations of this technique and the potential for its use in geochemical research are outlined. Using ToF‐SIMS, the chemical composition of sample structures down to 10–100 μm can be determined, without the need for pre‐selection or labelling of the analysed substances. In addition, the lateral distribution of organic and inorganic compounds can be mapped in geochemical samples at a resolution in the micrometre range. The capabilities of the technique in geochemistry are illustrated by two examples. In the first example, it is shown that ToF‐SIMS can be used to detect biomarkers in oil samples, making it a promising method for the analysis of biomarkers in fluid inclusions. In the second example, a number of specific lipid biomarkers were identified and mapped on the surface of a microbial mat cryosection surface. Post‐measurement optical microscopy correlated the localisation of the lipids with the presence of methanotrophic archaea in the microbial mat.     

SPM response to tide and river flow in the hyper-turbid Ems River

In this paper, we analyse the behaviour of fine sediments in the hyper-turbid Lower Ems River, with focus on the river’s upper reaches, a stretch of about 25 km up-estuary of Terborg. Our analysis is based on long records of suspended particulate matter (SPM) from optical backscatter (OBS) measurements close to the bed at seven stations along the river, records of salinity and water level measurements at these stations, acoustic measurements on the vertical mud structure just up-estuary of Terborg and oxygen profiles in the lower 3 m of the water column close to Leerort and Terborg. Further, we use cross-sectionally averaged velocities computed with a calibrated numerical model. Distinction is made between four timescales, i.e. the semi-diurnal tidal timescale, the spring–neap tidal timescale, a timescale around an isolated peak in river flow (i.e. about 3 weeks) and a seasonal timescale. The data suggest that a pool of fluid/soft mud is present in these upper reaches, from up-estuary of Papenburg to a bit down-estuary of Terborg. Between Terborg and Gandersum, SPM values drop rapidly but remain high at a few gram per litre. The pool of fluid/soft mud is entrained/mobilized at the onset of flood, yielding SPM values of many tens gram per litre. This suspension is transported up-estuary with the flood. Around high water slack, part of the suspension settles, being remixed during ebb, while migrating down-estuary, but likely not much further than Terborg. Around low water slack, a large fraction of the sediment settles, reforming the pool of fluid mud. The rapid entrainment from the fluid mud layer after low water slack is only possible when the peak flood velocity exceeds a critical value of around 1 m/s, i.e. when the stratified water column seems to become internally supercritical. If the peak flood velocity does not reach this critical value, f.i. during neap tide, fluid mud is not entrained up to the OBS sensors. Thus, it is not classical tidal asymmetry, but the peak flood velocity itself which governs the hyper-turbid state in the Lower Ems River. The crucial role of river flow and river floods is in reducing these peak flood velocities. During elongated periods of high river flow, in e.g. wintertime, SPM concentrations reduce, and the soft mud deposits consolidate and possibly become locally armoured as well by sand washed in from the river. We have no observations that sediments are washed out of the hyper-turbid zone. Down-estuary of Terborg, where SPM values do not reach hyper-turbid conditions, the SPM dynamics are governed by classical tidal asymmetry and estuarine circulation. Hence, nowhere in the river, sediments are flushed from the upper reaches of the river into the Ems-Dollard estuary during high river flow events. However, exchange of sediment between river and estuary should occur because of tide-induced dispersion.     

Temporal trends in δ18O composition of precipitation in Germany: insights from time series modelling and trend analysis

Temporal and spatial variations of stable oxygen (¹⁸O) and hydrogen (²H) isotope measurements in precipitation act as important proxies for changing hydro‐meteorological and regional and global climate patterns. Temporal trends in time series of the stable isotope composition in precipitation were rarely observed, and they are poorly understood. These might be a result of a lack of proper trend detection tools and effort for exploring trend processes. Here, we investigate temporal trends of δ¹⁸O in precipitation at 17 observation stations in Germany between 1978 and 2009. We test if significant trends in the isotope time series from different models can be observed. Mann–Kendall trend tests are applied on the isotope series, using general multiplicative seasonal autoregressive integrate moving average (ARIMA) models, which account for first and higher order serial correlations. Effects of temperature, precipitation, and geographic parameters on isotope trends are also investigated in the proposed models. To benchmark our proposed approach, the ARIMA results are compared with a trend‐free pre‐whitening procedure, the state of the art method for removing the first order autocorrelation in environmental trend studies. Moreover, we further explore whether higher order serial correlations in isotope series affects our trend results. Overall, three out of the 17 stations show significant changes when higher order autocorrelation are adjusted, and four show a significant trend when temperature and precipitation effects are considered. The significant trends in the isotope time series generally occur only at low elevation stations. Higher order autoregressive processes are shown to be important in the isotope time series analysis. Results suggest that the widely used trend analysis with only the first order autocorrelation adjustment may not adequately take account of the high order autocorrelated processes in the stable isotope series. The investigated time series analysis method including higher autocorrelation and external climate variable adjustments is shown to be a better alternative. Copyright © 2014 John Wiley & Sons, Ltd.     

Implementing a Method of Screening One-Well Hydraulic Barrier Design Alternatives

This article provides details of applying the method developed by the authors ( Rubin et al. 2008b ) for screening one-well hydraulic barrier design alternatives. The present article with its supporting information (manual and electronic spreadsheets with a case history example) provides the reader complete details and examples of solving the set of nonlinear equations developed by Rubin et al. (2008b) . It allows proper use of the analytical solutions and also depicting the various charts given by Rubin et al. (2008b) . The final outputs of the calculations are the required position and the discharge of the pumping well. If the contaminant source is nonaqueous phase liquid (NAPL) entrapped within the aquifer, then the method provides an estimate of the aquifer remediation progress (which is a by-product) due to operating the hydraulic barrier.     

On Northern Hemisphere Wave Patterns Associated with Winter Rainfall Events in China

During extended winter(November–April),43% of the intraseasonal rainfall variability in China is explained by three spatial patterns of temporally coherent rainfall.These patterns were identified with empirical orthogonal teleconnection(EOT) analysis of observed 1982–2007 pentad rainfall anomalies and connected to midlatitude disturbances.However,examination of individual strong EOT events shows that there is substantial inter-event variability in their dynamical evolution,which implies that precursor patterns found in regressions cannot serve as useful predictors.To understand the physical nature and origins of the extratropical precursors,the EOT technique is applied to six simulations of the Met Office Unified Model at horizontal resolutions of 200–40 km,with and without air–sea coupling.All simulations reproduce the observed precursor patterns in regressions,indicating robust underlying dynamical processes.Further investigation into the dynamics associated with observed patterns shows that Rossby wave dynamics can explain the large inter-event variability.The results suggest that the apparently slowly evolving or quasi-stationary waves in regression analysis are a statistical amalgamation of more rapidly propagating waves with a variety of origins and properties.     

Constraining a Flow Model with Field Measurements to Assess Water Transit Time Through a Vadose Zone

The modeling of thick vadose zones is particularly challenging because of difficulties in collecting a variety of measured sediment properties, which are required for parameterizing the model. Some models rely on synthetic data, whereas others are simplified by running as homogeneous sediment domains and relying on a single set of sediment properties. Few studies have simulated flow processes through a thick vadose zone using real and comprehensive data sets comprising multiple measurements. Here, we develop a flow model for a 7-m-thick vadose zone. This model, combining the numerical codes CTRAN/W with SEEP/W, includes the measured sediment hydraulic properties of the investigated vadose zone and incorporates the actual climate and subsurface conditions of the study site (precipitations, water-table elevations, and stable isotope data). The model is calibrated by fitting the simulated and measured vertical profiles of water content. Our flow model calculates a transit time of 1 year for the travel of water through the 7-m vadose zone; this estimate matches stable isotope-based results obtained previously for this site. A homogeneous sediment domain flow model, which considers only a single set of sediment properties, produces a transit time that is approximately half the duration of that of the heterogeneous flow model. This difference highlights the importance of assuming heterogeneous material within models of thick vadose zones and testifies to the advantage gained when using real sediment hydraulic properties to parametrize a flow model.