Spatial patterns of groundwater‐lake exchange – implications for acid neutralization processes in an acid mine lake

Exchange of groundwater and lake water with typically quite different chemical composition is an important driver for biogeochemical processes at the groundwater‐lake interface, which can affect the water quality of lakes. This is of particular relevance in mine lakes where anoxic and slightly acidic groundwater mixes with oxic and acidic lake water (pH < 3). To identify links between groundwater‐lake exchange rates and acid neutralization processes in the sediments, exchange rates were quantified and related to pore‐water pH, sulfate and iron concentrations as well as sulfate reduction rates within the sediment. Seepage rates measured with seepage meters (?2.5 to 5.8 L m^‐2 d^‐1) were in reasonable agreement with rates inverted from modeled chloride profiles (?1.8 to 8.1 L m^‐2 d^‐1). Large‐scale exchange patterns were defined by the (hydro)geologic setting but superimposed by smaller scale variations caused by variability in sediment texture. Sites characterized by groundwater upwelling (flow into the lake) and sites where flow alternated between upwelling and downwelling were identified. Observed chloride profiles at the alternating sites reflected the transient flow regime. Seepage direction, as well as seepage rate, were found to influence pH, sulfate and iron profiles and the associated sulfate reduction rates. Under alternating conditions proton‐consuming processes, for example, sulfate reduction, were slowed. In the uppermost layer of the sediment (max. 5 cm), sulfate reduction rates were significantly higher at upwelling (>330 nmol g^‐1 d^‐1) compared to alternating sites (<220 nmol g^‐1 d^‐1). Although differences in sulfate reduction rates could not be explained solely by different flux rates, they were clearly related to the prevailing groundwater‐lake exchange patterns and the associated pH conditions. Our findings strongly suggest that groundwater‐lake exchange has significant effects on the biogeochemical processes that are coupled to sulfate reduction such as acidity retention and precipitation of iron sulfides. Copyright © 2012 John Wiley & Sons, Ltd.     

On the enhanced smoothing over topography in some mesometeorological models

An equation is derived for the components of the horizontal (turbulent) frictional force in the -coordinate system with special attention to mesometeorological flow models. The starting point is the horizontal equation of motion in its flux-form in the -system in which we replace (following Reynolds' procedure) the velocity components u,v and % MathType!MTEF!2!1!+- % feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGafq4WdmNbai % aaaaa!37B8! \[ \dot \sigma \] aswell as other relevant quantities by terms of the form u = + u,..., = ± + % MathType!MTEF!2!1!+- % feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGafq4WdmNbai % Gbauaaaaa!37C3! \[ \dot \sigma ' \] , etc. ( = time average of u; u = fluctuating part of u.) Next, the equation is averaged with respect to time and terms which we believe are small in mesometeorological flows, are neglected. On expressing by an appropriate expression that involves w, the result shows the appearance of two new terms which, have not been considered previously in the published literature. While the expression earlier used in the literature involved the -derivative of % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaWaa0aaaeaace% WG1bGbauaaceWG3bGbauaaaaaaaa!380B!\[\overline {u'w'} \] alone, the new terms add the -derivatives of % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaWaa0aaaeaace% WG1bGbauaadaahaaWcbeqaaiaaikdaaaaaaaaa!37EC!\[\overline {u'^2 } \] and % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaWaa0aaaeaace% WG1bGbauaaceWG2bGbauaaaaaaaa!380A!\[\overline {u'v'} \] for the x-component of the force, and the -derivatives of % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaWaa0aaaeaace% WG2bGbauaadaahaaWcbeqaaiaaikdaaaaaaaaa!37ED!\[\overline {v'^2 } \]} and % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaWaa0aaaeaace% WG1bGbauaaceWG2bGbauaaaaaaaa!380A!\[\overline {u'v'} \] for the y-component, where and are the slopes of the -surfaces in the x- and y-directions, respectively. Further, a few numerical simulations of the sea-breeze over topography are carried out with and without the correction terms. It is shown that when corrections terms are not included the effective smoothing is stronger above the sloping regions and may amount to as high as 50 percent of the convergence with slopes of ~.04. The ìnclusìon of the new terms does not lead to any special computational difficulties and for that reason there is no compelling reason to neglect them, all the more so because, as is shown, the addition of the new terms results in a consistent apportioning of the degree of horizontal diffusion.On leave from CIMMS, Norman, OK.Now visiting Dept. of Met., Helsinki, Finland.     

Organic geochemistry and pore water chemistry of sediments from Mangrove Lake,Bermuda

Mangrove Lake, Bermuda, is a small coastal, brackish-water lake that has accumulated 14 m of banded, gelatinous, sapropelic sediments in less than 10⁴ yr. Stratigraphic evidence indicates that Mangrove Lake's sedimentary environment has undergone three major depositional changes (peat, freshwater gel, brackish-water gel) as a result of sea level changes. The deposits were examined geochemically in an effort to delineate sedimentological and diagenetic changes. Gas and pore water studies include measurements of sulfides, ammonia, methane, nitrogen gas, calcium, magnesium, chloride, alkalinity, and pH. Results indicate that sulfate reduction is complete, and some evidence is presented for bacterial denitrification and metal sulfide precipitation. The organic-rich sapropel is predominantly algal in origin, composed mostly of carbohydrates and insoluble macromolecular organic matter called humin with minor amounts of proteins, lipids, and humic acids. Carbohydrates and proteins undergo hydrolysis with depth in the marine sapropel but tend to be preserved in the freshwater sapropel. The humin, which has a predominantly aliphatic structure, increases linearly with depth and composes the greatest fraction of the organic matter. Humic acids are minor components and are more like polysaccharides than typical marine humic acids. Fatty acid distributions reveal that the lipids are of an algal and/or terrestrial plant source. Normal alkanes with a total concentration of 75 ppm exhibit two distribution maxima. One is centered about n-C₂₂ with no odd/even predominance, suggestive of a degraded algal source. The other is centered at n-C₃₁ with a distinct odd/even predominance indicative of a vascular plant origin. Stratigraphic changes in the sediment correlate to observed changes in the gas and pore water chemistry and the organic geochemistry.     

Dissolution of secondary copper sulphides using complex-forming agents (EDTA,EDA). Part II: Chalcocite dissolution in EDTA and EDA

This work is immediate continuation of Part I, using an identical method and evaluation for kinetic studies. The systems chalcocite-ethylene diamine tetra-acetic acid and chalcocite-ethylene diamine were studied. It was necessary to refine the geometrical model method for chalcocite in order to establish dissolution kinetics of polydispersions. This work confirms that chalcocite leaching proceeds through covellite even in the medium of complex-forming agents and kinetic equations for both leaching stages were evaluated with an attempt at physical interpretation.     

Derivation Of Refractive Index And Temperature Gradients From Optical Scintillometry To Correct Atmospherically Induced Errors For Highly Precise Geodetic Measurements

Refraction effects of optical beams are generally caused by an inhomogeneous propagation medium and are a major source of systematic errors in the precise optical determination of angles and distances in the atmospheric surface layer. In this contribution a method for deriving vertical temperature and refractive index gradients from optical scintillation is presented. Knowledge of these gradients is required for the compensation of atmospherically induced errors for highly precise terrestrial geodetic measurements, like direct transfer and levelling. The advantage of the present optical method is, that temperature and refractive index gradients can be derived as line-averaged values over the propagation path, which is not possible by meteorological point measurements. Field observations have been carried out with a displaced-beam scintillometer over flat terrain and under different atmospheric conditions in order to verify this method. The experiments show, that this method allows to derive accurate correction values for precise terrestrial geodetic measurements.     

The Skien lavas, Oslo Rift: petrological disequilibrium and geochemical evolution

The Skien lavas, which form the earliest phase of basaltic magmatism within the Permo-Carboniferous Oslo Rift, contain multiple generations of clinopyroxene which exhibit strong petrological and geochemical disequilibrium. Three principal core compositions have been identified: (1) low-jadeite, high-Mg, Cr-diopside cores (CrMgDi) with strongly depleted trace-element signatures, which are believed to be xenocrystic in origin; (2) Mg-rich, Cr-poor diopside cores (MgDi) with moderately depleted trace-element signatures which probably represent early cognate growth; and (3) more dominant, low-Mg, phenocrystic diopside cores (PhenDi). Several samples contain CrMgDi or MgDi cores which have been subjected to resorption and partial re-equilibration with their host melts, indicative of extensive disequilibrium and magma mixing. These three core types are overgrown by trace-element-enriched Ti-augite, which also forms megacrysts and late-stage lava groundmass. Calculated Ti-augite/melt partition coefficients show clinopyroxene compatibility of the M-HREE, Zr, Hf and Y. The LILE, Sr, and Nb remain incompatible. )Sr₃₀₀ and )Nd₃₀₀ of Ti-augite overgrowths, phenocrystic diopside, and MgDi diopside cores show that intrasample isotopic disequilibrium existed when the host basalts were erupted. All epsilon values lie within the range of data previously published for the Skien lavas. Detailed examination of the chemical, isotopic and textural disequilibrium features seen in these lavas has enabled us to place constraints upon the magmatic evolution of this basalt suite, ranging from xenocryst incorporation to cognate multistage pyroxene growth, as well as identifying clear evidence of magma mixing and possible crustal contamination.     

Processing and quality control of flux data during LITFASS-2003

Different aspects of the quality assurance and quality control (QA/QC) of micrometeorological measurements were combined to create a comprehensive algorithm which was then applied to experimental data from LITFASS-2003 (Lindenberg Inhomogeneous Terrain—Fluxes between Atmosphere and Surface: a long term Study). Eddy-covariance measurements of the latent heat flux were the main focus of the QA/QC efforts. The results of a turbulence sensor intercomparison experiment showed deviations between the different eddy-covariance systems on the order of 15%, or less than 30 W m⁻², for the latent heat flux and 5%, or less than 10 W m⁻², for the sensible heat flux. In order to avoid uncertainties due to the post-processing of turbulence data, a comprehensive software package was used for the analysis of experimental data from LITFASS-2003, including all necessary procedures for corrections and quality control. An overview of the quality test results shows that for most of the days more than 80% of the available latent heat flux data are of high quality so long as there are no instrumental problems. The representativeness of a flux value for the target land-use type was analysed using a stochastic footprint model. Different methods to calculate soil heat fluxes at the surface are discussed and a sensitivity analysis is conducted to select the most robust method for LITFASS-2003. The lack of energy balance closure, which was found for LITFASS-2003, can probably be attributed to the presence of low-frequency flux contributions that cannot be resolved with an averaging time of 30 min. Though the QA/QC system has been developed for the requirements of LITFASS-2003, it can also be applied to other experiments dealing with similar objectives.     

The effect of mountainous topography on moisture exchange between the “surface” and the free atmosphere

Typical numerical weather and climate prediction models apply parameterizations to describe the subgrid-scale exchange of moisture, heat and momentum between the surface and the free atmosphere. To a large degree, the underlying assumptions are based on empirical knowledge obtained from measurements in the atmospheric boundary layer over flat and homogeneous topography. It is, however, still unclear what happens if the topography is complex and steep. Not only is the applicability of classical turbulence schemes questionable in principle over such terrain, but mountains additionally induce vertical fluxes on the meso-γ scale. Examples are thermally or mechanically driven valley winds, which are neither resolved nor parameterized by climate models but nevertheless contribute to vertical exchange. Attempts to quantify these processes and to evaluate their impact on climate simulations have so far been scarce. Here, results from a case study in the Riviera Valley in southern Switzerland are presented. In previous work, measurements from the MAP-Riviera field campaign have been used to evaluate and configure a high-resolution large-eddy simulation code (ARPS). This model is here applied with a horizontal grid spacing of 350 m to detect and quantify the relevant exchange processes between the valley atmosphere (i.e. the ground “surface” in a coarse model) and the free atmosphere aloft. As an example, vertical export of moisture is evaluated for three fair-weather summer days. The simulations show that moisture exchange with the free atmosphere is indeed no longer governed by turbulent motions alone. Other mechanisms become important, such as mass export due to topographic narrowing or the interaction of thermally driven cross-valley circulations. Under certain atmospheric conditions, these topographical-related mechanisms exceed the “classical” turbulent contributions a coarse model would see by several times. The study shows that conventional subgrid-scale parameterizations can indeed be far off from reality if applied over complex topography, and that large-eddy simulations could provide a helpful tool for their improvement.     

Determination of the distribution of size of irregularly shaped particles from laser diffractometer measurements

The formal stereological transformation equation for particle sieve size distribution from measurements in lower dimensional spaces is applied to laser diffractometer measurements. The transformation function for iron ore particles is measured experimentally, and modeled. The solution is tested against the measured transformation function data as well as synthetic composite distributions of the original sample. The natural size distribution of a sample taken from a grinding circuit stream was measured by a combination of standard sieving and cyclosizer, and the result is compared to the transformed size distribution calculated from laser diffractometer measurements. The stereological transformation technique performed well in all cases.