Geochemical characterization of the organic matter, pore water constituents and shallow methane gas in the eastern part of the Ulleung Basin, East Sea (Japan Sea)

Abstract Geochemical analyses of sediments, pore water and headspace gas of the piston cores taken from the eastern part of Ulleung Basin of the East Sea (Japan Sea) were carried out to assess the origin of the sedimentary organic matter and interstitial fluid. Several tephra layers within the core are identified as the Ulleung‐Oki (10.1 ka), the Aira‐Tanzawa (23 ka) and the Ulleung‐Yamato (30.9 ka) tephras. With the exception of these volcanic layers, the cores consist predominantly of muddy sediments that contain >0.5% total organic carbon. Atomic C/N ratios and δ¹³C_org values suggest that the organic matter originated from marine algae rather than from land vascular plants, whereas Rock‐Eval pyrolysis suggests that the organic matter is thermally immature and comes from a land vascular plant (Type III). These conflicting results seem to be caused by the heavy oxidization of the marine organic matter. Sulphate concentration profiles of pore waters show strongly linear depletion (r² > 0.97) with sediment depth. The estimated sulphate–methane interface (SMI) depth using the sulphate concentration gradient was nearly 3.5 m below seafloor (mbsf) in the southern part of the study area, and deeper than 6 mbsf in the northern part of the area. The difference in SMI depths is likely associated with the amount of the methane flux. The methane concentration below the SMI in the two southern cores increases rapidly, implying the occurrence of methanogenesis and anaerobic methane oxidation (AMO). In contrast, the two northern cores have a low methane concentration below the SMI. values measured from all cores were in the range of −83.5 to −69.5‰, which suggests that the methane derives from a methanogenic microbe. values become decreased toward SMI, but increased below SMI; therefore, has eventually the minimum value near the SMI. The values are also decreased when the methane concentration is increased. These phenomena support the typical occurrence of AMO in the study area.     

Mobility Enhancement of Mn Oxide during Permanganate Oxidation of TCE

Manganese (Mn) oxide precipitation during in situ permanganate oxidation of organic compounds can cause pore clogging, reduce permeability, and increase resistance to mass transfer. Stability of Mn oxide is required to enhance oxidation effectiveness. Batch tests were conducted at eight polyphosphate (PP) to permanganate () mass ratios (0 to 8) at three MnO₄⁻¹ concentrations (500, 1000, or 2000 mg/L) for identifying mass ratios to maximize stability of Mn oxide produced in the presence of trichloroethylene (TCE). In general, stability of Mn oxide was the maximum at mass ratio of approximately 4. Three column tests were designed to investigate the impact of PP on overall removal of 4.6 or 7.0 g TCE emplaced as nonaqueous phase liquid within the column porous media. Water flush, chemical flush using alone (1000 mg/L), and chemical flush using (1000 mg/L) and PP (4000 mg/L) were conducted. Mass removal of TCE and changes in media permeability were estimated over a period of 78 to 312 h (12 to 49 pore volumes [PVs]). Column tests demonstrated enhanced removal (~90%) of TCE during chemical flush with and PP in 12 PVs as compared with approximately 64% during -only flush and approximately 26% during water flush. Pressure drop changes across the column captured change in media permeability and revealed that water flush and PP and flush caused significantly lower flow resistance as compared with -only flush. These results indicate that PP was capable of mobilizing Mn oxide away from the reaction zones, thereby reducing pore clogging and enabling better and long-term contact between TCE and the aqueous phase.     

From an initial transient-state to a steady-state in metamorphic reactions: An experimental approach in the system dolomite-quartz-H2O

Abstract We carried out hydrothermal experiments in the system dolomite‐quartz‐H₂O to track the temporal change in reaction rates of simultaneous reactions during the development of reaction zones. Two types of configurations for the starting materials were prepared: dolomite single crystals + quartz powder + water and quartz single crystals + dolomite powder + water, both sealed separately in gold capsules. Runs at 0.1GPa and 600°C with cold seal pressure vessels gave the following results. (i) In short duration (45–71 h) runs metastable layer sequences involving wollastonite and talc occur in the reaction zone, whereas they disappear in longer duration (168–336 h) runs. (ii) The layer sequence of the reaction zones in short duration runs differs from place to place on the dolomite crystal even in the same run. (iii) The diversity of layer sequences in the short duration runs merges into a unique layer sequence in the longer duration runs. (iv) The reaction zone develops locally on the dolomite crystal, but no reaction zone was observed on the quartz crystal in any of the runs. The lines of evidence (i)–(iii) show that the system evolves from an initial transient‐ to a steady‐state and that the kinetic effect is important in the development of reaction zones. A steady diffusion model for the unique layer sequence Qtz/Di/Fo + Cal/Dol + Cal/Dol shows that the Dol + Cal layer cannot be formed by diffusion‐controlled process and that the stability of the layer sequence Qtz/Di/Fo + Cal/Dol depends not only on L‐ratios (a = /L_CaOCaO and b = /L_MgOMgO) but also on the relative rate P = (−2ξ₁ − ξ₂)/(–ξ₁ − 2ξ₂) of competing reactions: Dol + 2Qtz = Di + 2CO₂ (ξ₁) and 2Dol + Qtz = Fo + 2Cal + 2CO₂ (ξ₂). For smaller P the stability field will shift to higher values of a and b. The steady diffusion model also shows that the apparent‐non‐reactivity on the quartz surface can be attributed to void formation in a large volume fraction in the diopside layer.     

Accuracy of kinematic wave and diffusion wave approximations for time-independent flows

Errors in the kinematic wave and diffusion wave approximations for time-independent (or steady-state) cases of channel flow were derived for three types of boundary conditions: zero flow at the upstream end, and critical flow depth and zero depth gradient at the downstream end. The diffusion wave approximation was found to be in excellent agreement with the dynamic wave approximation, with errors in the range 1–2% for values of KF (? 7.5), where K is the kinematic wave number and F₀ is the Froude number. Even for small values of KF (e.g. KF²₀ = 0.75), the errors were typically less than 15%. The accuracy of the diffusion wave approximation was greatly influenced by the downstream boundary condition. The error of the kinematic wave approximation was found to be less than 13% in the region 0.1 ? x ? 0.95 for KF = 7.5 and was greater than 30% for smaller values of KF (? 0.75). This error increased with strong downstream boundary control.     

Effect of SO on 1,1,1‐Trichloroethane Degradation by Fe0 in Aqueous Solution

Sulfate in groundwater has been previously shown to change the reactivity of Fe⁰ in permeable reactive barriers for reducing chlorinated organics. To better understand the effect and mechanism of SO, the degradation of 1,1,1‐trichloroethane (TCA) by Fe⁰ in unbuffered aqueous solutions with and without SO was investigated. In a Fe⁰‐TCA‐H₂O system with initial pH of 2.0 to 10.0, the maximum removal rate of TCA was achieved at the initial pH 6.0 with pseudo‐first‐order constant K_obs 9.0 × 10^?3/min. But in a Fe⁰‐TCA‐Na₂SO₄‐H₂O system, the removal rate of TCA decreased remarkably with a reduction in K_obs to 1.0 × 10^?3/min, and the pH varied from 6.0 to 9.6, indicating an inhibition of TCA dehydrochlorination by SO. Sulfate remarkably inhibited TCA degradation via changing the route of Fe⁰ dissolution. It accelerated the dissolution of Fe⁰ and transformed the intermediate form Fe(OH)_ads to Fe₂(SO₄)_ads, which weakened the affinity between Fe and TCA, and thus depressed the degradation of TCA by Fe⁰.     

Seismic anisotropy of shales

Shales are a major component of sedimentary basins, and they play a decisive role in fluid flow and seismic‐wave propagation because of their low permeability and anisotropic microstructure. Shale anisotropy needs to be quantified to obtain reliable information on reservoir fluid, lithology and pore pressure from seismic data, and to understand time‐to‐depth conversion errors and non‐hyperbolic moveout. A single anisotropy parameter, Thomsen's δ parameter, is sufficient to explain the difference between the small‐offset normal‐moveout velocity and vertical velocity, and to interpret the small‐offset AVO response. The sign of this parameter is poorly understood, with both positive and negative values having been reported in the literature. δ is sensitive to the compliance of the contact regions between clay particles and to the degree of disorder in the orientation of clay particles. If the ratio of the normal to shear compliance of the contact regions exceeds a critical value, the presence of these regions acts to increase δ, and a change in the sign of δ, from the negative values characteristic of clay minerals to the positive values commonly reported for shales, may occur. Misalignment of the clay particles can also lead to a positive value of δ. For transverse isotropy, the elastic anisotropy parameters can be written in terms of the coefficients W₂₀₀ and W₄₀₀ in an expansion of the clay‐particle orientation distribution function in generalized Legendre functions. For a given value of W₂₀₀, decreasing W₄₀₀ leads to an increase in δ, while for fixed W₄₀₀, δ increases with increasing W₂₀₀. Perfect alignment of clay particles with normals along the symmetry axis corresponds to the maximum values of W₂₀₀ and W₄₀₀, given by and . A comparison of the predictions of the theory with laboratory measurements shows that most shales lie in a region of the (W₂₀₀, W₄₀₀)‐plane defined by W₄₀₀/W₂₀₀≤W^max₄₀₀/W^max₂₀₀ .     

VSP traveltime inversion for anisotropy in a buried layer

We present a method for calculating the anisotropy parameter of a buried layer by inverting the total traveltimes of direct arrivals travelling from a surface source to a well‐bore receiver in a vertical seismic profiling (VSP) geometry. The method assumes two‐dimensional media. The medium above the layer of interest (and separated from it by a horizontal interface) can exhibit both anisotropy and inhomogeneity. Both the depth of the interface as well as the velocity field of the overburden are assumed to be known. We assume the layer of interest to be homogeneous and elliptically anisotropic, with the anisotropy described by a single parameter χ. We solve the function describing the traveltime between source and receiver explicitly for χ. The solution is expressed in terms of known quantities, such as the source and receiver locations, and in terms of quantities expressed as functions of the single argument x_r, which is the horizontal coordinate of the refraction point on the interface. In view of Fermat's principle, the measured traveltime T possesses a stationary value or, considering direct arrivals, a minimum value, . This gives rise to a key result ‐‐ the condition that the actual anisotropy parameter . Owing to the explicit expression , this result allows a direct calculation of in the layer of interest. We perform an error analysis and show this inverse method to be stable. In particular, for horizontally layered media, a traveltime error of one millisecond results in a typical error of about 20% in the anisotropy parameter. This is almost one order of magnitude less than the error inherent in the slowness method, which uses a similar set of experimental data. We conclude by detailing possible extensions to non‐elliptical anisotropy and a non‐planar interface.     

3D angle-domain common-image gathers for migration velocity analysis

Angle‐domain common‐image gathers (ADCIGs) are an essential tool for migration velocity analysis (MVA). We present a method for computing ADCIGs in 3D from the results of wavefield‐continuation migration. The proposed methodology can be applied before or after the imaging step in a migration procedure. When computed before imaging, 3D ADCIGs are functions of the offset ray parameters (p, p) ; we derive the geometric relationship that links the offset ray parameters to the aperture angle γ and the reflection azimuth φ. When computed after imaging, 3D ADCIGs are directly produced as functions of γ and φ. The mapping of the offset ray parameters (p, p) into the angles (γ, φ) depends on both the local dips and the local interval velocity; therefore, the transformation of ADCIGs computed before imaging into ADCIGs that are functions of the actual angles is difficult in complex structure. By contrast, the computation of ADCIGs after imaging is efficient and accurate even in the presence of complex structure and a heterogeneous velocity function. On the other hand, the estimation of the offset ray parameters (p, p) is less sensitive to velocity errors than the estimation of the angles (γ, φ). When ADCIGs that are functions of the offset ray parameters (p, p) are adequate for the application of interest (e.g. ray‐based tomography), the computation of ADCIGs before imaging might be preferable. Errors in the migration velocity cause the image point in the angle domain to shift along the normal to the apparent geological dip. By assuming stationary rays (i.e. small velocity errors), we derive a quantitative relationship between this normal shift and the traveltime perturbation caused by velocity errors. This relationship can be directly used in an MVA procedure to invert depth errors measured from ADCIGs into migration velocity updates. In this paper, we use it to derive an approximate 3D residual moveout (RMO) function for measuring inconsistencies between the migrated images at different γ and φ. We tested the accuracy of our kinematic analysis on a 3D synthetic data set with steeply dipping reflectors and a vertically varying propagation velocity. The tests confirm the accuracy of our analysis and illustrate the limitations of the straight‐ray approximation underlying our derivation of the 3D RMO function.     

Pore pressure profiles in fractured and compliant rocks1

Fluid permeability in fractured rocks is sensitive to pore-pressure changes. This dependence can have large effects on the flow of fluids through rocks. We define the permeability compliance γ= 1/k(k/δp_p)_pc, which is the sensitivity of the permeability k to the pore pressure p_p at a constant confining pressure p_c, and solve the specific problems of constant pressure at the boundary of a half-space, a cylindrical cavity and a spherical cavity. The results show that when the magnitude of permeability compliance is large relative to other compliances, diffusion is masked by a piston-like pressure profile. We expect this phenomenon to occur in highly fractured and compliant rock systems where γ may be large. The pressure profile moves rapidly when fluids are pumped into the rock and very slowly when fluids are pumped out. Consequently, fluid pressure, its history and distribution around injection and production wells may be significantly different from pressures predicted by the linear diffusion equation. The propagation speed of the pressure profile, marked by the point where δp_p/δx is a maximum, decreases with time approximately as and the amplitude of the profile also dissipates with time (or distance). The effect of permeability compliance can be important for fluid injection into and withdrawal from reservoirs. For example, excessive drawdown could cause near-wellbore flow suffocation. Also, estimates of the storage capacity of reservoirs may be greatly modified when γ is large. The large near-wellbore pressure gradients caused during withdrawal by large γ can cause sanding and wellbore collapse due to excessive production rates.     

Theoretical investigation of the time variation of drainage density

A theoretical equation was developed to express the time variation of drainage density in a basin or geomorphic surface: D_i(t, T) is the drainage density at time T on the i-th basin or geomorphic surface, which was formed at time t; β(τ) is a factor related to the erosional force causing the development of the rivers of the basin or surface at time τ; δ_i is the maximum drainage density; and D_i is the initial drainage density on the i-th geomorphic surface or basin. The equation is based on the assumption that the drainage density increases with time until it reaches a specific upper limit δ_i(t)), the maximum drainage density, which is related to certain physical properties of the basin. The equations for various dated basins or geomorphic surfaces can be combined into one modified equation if the same relative erosional forces have acted on those basins or surfaces (β(t) = β(t) and if the basins or surfaces have the same physical properties δ_i(t) = δ_i(t), (D_i = D₀). The application of this equation to coastal terraces and glacial tills shows that the model is compatible with observed drainage densities on various dated basins or surfaces.     

PERFORMANCE OF 2000 AND 6000 PSI AIR GUNS: THEORY AND EXPERIMENT*

Air guns have been used in various applications for a number of years. They were first used in coal-mining operations and were operated at up to 16000 psi charge pressures. Later, single air guns, operated at 2000 psi, found application as an oceanographic survey tool. Air gun arrays were first used in offshore seismic exploration in the mid-1960's. These early arrays were several hundred cubic inches in total volume and were operated at 2000 psi; they were either tuned arrays or several large guns of the same size with wave-shape kits. Today's arrays have total volumes greater than 5000 cu in. and are typically operated at 2000 psi. Recently, higher-pressure, lower-volume arrays operated at 4000–5000 psi have been introduced; guns used in these arrays are descendants of the coal-mining gun. On first thought one would equate increased gun pressure linearly with the amplitude of the initial pulse. This is approximately true for the signature radiated by a “free-bubble” (no confining vessel) and recorded broadband. The exact relation depends on the depth at which the gun is operated; from solution of the free-bubble oscillation equation, the relation is If P_c,1= 6014.7 psia, P_c,2= 2014.7 psia and P_{O, 1}=P_{O, 2}= 25.8 psia (corresponding to absolute pressure at 25 ft water depth), then Experiments were conducted offshore California in deep water to determine the performance of several models of air guns at pressures ranging from 2000 to 6000 psi and gun volumes ranging from 5 to 300 cu in. At a given gun pressure, the initial acoustic pulse P_a correlated with gun volume V_c according to the classical relation For 1 ms sampled data the ratio varied between 4.5 and 5.5 dB depending on gun model. Pulse width of the 2000 psi signatures indicated they are compatible with 2 ms sample-rate recording while pulse width of the 6000 psi signatures was greater, indicating they are less compatible with 2 ms sample-rate recording. Conclusions reached were that 2000 psi air guns are more efficient than higher pressure guns and are more compatible with 2 ms sample-rate requirements.     

Spatial average aquifer recharge through atmospheric chloride mass balance and its uncertainty in continental Spain

The atmospheric chloride mass balance (CMB) method allows spatial evaluations of the average diffuse aquifer recharge by rainfall () in large and varied territories when long‐term steady conditions can be assumed. Often, the distributed average CMB variables necessary to calculate have to be estimated from the available variable‐length data series, which may be of suboptimal quality and spatial coverage. This paper explains the use of these data and the reliability of the results in continental Spain, chosen as a large and varied territory. The CMB variables have been regionalized by ordinary kriging at the same 4976 nodes of a 10 km × 10 km grid. Nodal values vary from 14 to 810 mm year^–1, 90% ranging from 30 to 300 mm year^–1. The recharge‐to‐precipitation ratios vary from 0.03 in low‐permeability formations and semiarid areas to 0.65 in some carbonate massifs. Integrated average results for the whole of continental Spain yield a potential aquifer recharge of 64 km³ year^?1, the net recharge over permeable formations (40% of the territory) being 32 km³ year^?1. Two main sources of uncertainty affecting (given by the coefficient of variation, CV), induced by the inherent natural variability of the variables (CV_R) and from mapping (), have been segregated. The average CV_R is 0.13 and could be improved with longer data series. The average is 0.07 and may be decreased with better data coverage. The estimates were compared with other regional and local recharge estimates, being 4% and 1% higher, respectively. Copyright © 2012 John Wiley & Sons, Ltd.     

TRAITEMENT AUTOMATIQUE DES SONDAGES ELECTRIQUES AUTOMATIC PROCESSING OF ELECTRICAL SOUNDINGS*

I. Introduction In this section the problem is stated, its physical and mathematical difficulties are indicated, and the way the authors try to overcome them are briefly outlined. Made up of a few measurements of limited accuracy, an electrical sounding does not define a unique solution for the variation of the earth resistivities, even in the case of an isotropic horizontal layering. Interpretation (i.e. the determination of the true resistivities and thicknesses of the ground-layers) requires, therefore, additional information drawn from various more or less reliable geological or other geophysical sources. The introduction of such information into an automatic processing is rather difficult; hence the authors developped a two-stage procedure:

• a) the field measurements are automatically processed, without loss of information, into more easily usable data;
• b) some additional information is then introduced, permitting the determination of several geologically conceivable solutions.

The final interpretation remains with the geophysicist who has to adjust the results of the processing to all the specific conditions of his actual problem. II. Principles of the procedure In this section the fundamental idea of the procedure is given as well as an outline of its successive stages. Since the early thirties, geophysicists have been working on direct methods of interpreting E.S. related to a tabular ground (sequence of parallel, homogeneous, isotropic layers of thicknesses h_i and resistivities ρ_i). They generally started by calculating the Stefanesco (or a similar) kernel function, from the integral equation of the apparent resistivity: where r is the distance between the current source and the observation point, S₀ the Stefanesco function, ρ(z) the resistivity as a function of the depth z, J₁ the Bessel function of order 1 and λ the integration variable. Thicknesses and resistivities had then to be deduced from S₀ step by step. Unfortunately, it is difficult to perform automatically this type of procedure due to the rapid accumulation of the errors which originate in the experimental data that may lead to physically impossible results (e.g. negative thicknesses or resistivities) (II. 1). The authors start from a different integral representation of the apparent resistivity: where K₁ is the modified Bessel function of order I. Using dimensionless variables t = r/2h₀ and y(t)=ζ (r)/ρ₁ and subdividing the earth into layers of equal thicknesses h₀ (highest common factor of the thicknesses h_i), ø becomes an even periodic function (period 2π) and the integral takes the form: The advantage of this representation is due to the fact that its kernel ø (function of the resistivities of the layers), if positive or null, always yields a sequence of positive resistivities for all values of θ and thus a solution which is surely convenient physically, if not geologically (II.3). Besides, it can be proved that ø(θ) is the Fourier transform of the sequence of the electric images of the current source in the successive interfaces (II.4). Thus, the main steps of the procedure are: a) determination of a non-negative periodic, even function ø(θ) which satisfies in the best way the integral equation of apparent resistivity for the points where measurements were made; b) a Fourier transform gives the electric images from which, c) the resistivities are obtained. This sequence of resistivities is called the “comprehensive solution”; it includes all the information contained in the original E.S. diagram, even if its too great detail has no practical significance. Simplification of the comprehensive solution leads to geologically conceivable distributions (h, ρ) called “particular solutions”. The smoothing is carried out through the Dar-Zarrouk curve (Maillet 1947) which shows the variations of parameters (transverse resistance R_i= h_i.ρ_i–as function of the longitudinal conductance C_i=h_i/ρ_i) well suited to reflect the laws of electrical prospecting (principles of equivalence and suppression). Comprehensive and particular solutions help the geophysicist in making the final interpretation (II.5). III. Computing methods In this section the mathematical operations involved in processing the data are outlined. The function ø(θ) is given by an integral equation; but taking into account the small number and the limited accuracy of the measurements, the determination of ø(θ) is performed by minimising the mean square of the weighted relative differences between the measured and the calculated apparent resistivities: minimum with inequalities as constraints: where t_l are the values of t for the sequence of measured resistivities and p_l are the weights chosen according to their estimated accuracy. When the integral in the above expression is conveniently replaced by a finite sum, the problem of minimization becomes one known as quadratic programming. Moreover, the geophysicist may, if it is considered to be necessary, impose that the automatic solution keep close to a given distribution (h, ρ) (resulting for instance from a preliminary interpretation). If φ(θ) is the ø-function corresponding to the fixed distribution, the quantity to minimize takes the form: where: The images are then calculated by Fourier transformation (III.2) and the resistivities are derived from the images through an algorithm almost identical to a procedure used in seismic prospecting (determination of the transmission coefficients) (III.3). As for the presentation of the results, resorting to the Dar-Zarrouk curve permits: a) to get a diagram somewhat similar to the E.S. curve (bilogarithmic scales coordinates: cumulative R and C) that is an already “smoothed” diagram where deeper layers show up less than superficial ones and b) to simplify the comprehensive solution. In fact, in arithmetic scales (R versus C) the Dar-Zarrouk curve consists of a many-sided polygonal contour which múst be replaced by an “equivalent” contour having a smaller number of sides. Though manually possible, this operation is automatically performed and additional constraints (e.g. geological information concerning thicknesses and resistivities) can be introduced at this stage. At present, the constraint used is the number of layers (III.4). Each solution (comprehensive and particular) is checked against the original data by calculating the E.S. diagrams corresponding to the distributions (thickness, resistivity) proposed. If the discrepancies are too large, the process is resumed (III.5). IV. Examples Several examples illustrate the procedure (IV). The first ones concern calculated E.S. diagrams, i.e. curves devoid of experimental errors and corresponding to a known distribution of resistivities and thicknesses (IV. 1). Example I shows how an E.S. curve is sampled. Several distributions (thickness, resistivity) were found: one is similar to, others differ from, the original one, although all E.S. diagrams are alike and characteristic parameters (transverse resistance of resistive layers and longitudinal conductance of conductive layers) are well determined. Additional informations must be introduced by the interpreter to remove the indeterminacy (IV.1.1). Examples 2 and 3 illustrate the principles of equivalence and suppression and give an idea of the sensitivity of the process, which seems accurate enough to make a correct distinction between calculated E.S. whose difference is less than what might be considered as significant in field curves (IV. 1.2 and IV. 1.3). The following example (number 4) concerns a multy-layer case which cannot be correctly approximated by a much smaller number of layers. It indicates that the result of the processing reflects correctly the trend of the changes in resistivity with depth but that, without additional information, several equally satisfactory solutions can be obtained (IV. 1.4). A second series of examples illustrates how the process behaves in presence of different kinds of errors on the original data (IV.2). A few anomalous points inserted into a series of accurate values of resistivities cause no problem, since the automatic processing practically replaces the wrong values (example 5) by what they should be had the E.S. diagram not been wilfully disturbed (IV.2.1). However, the procedure becomes less able to make a correct distinction, as the number of erroneous points increases. Weights must then be introduced, in order to determine the tolerance acceptable at each point as a function of its supposed accuracy. Example 6 shows how the weighting system used works (IV.2.2). The foregoing examples concern E.S. which include anomalous points that might have been caused by erroneous measurements. Geological effects (dipping layers for instance) while continuing to give smooth curves might introduce anomalous curvatures in an E.S. Example 7 indicates that in such a case the automatic processing gives distributions (thicknesses, resistivities) whose E.S. diagrams differ from the original curve only where curvatures exceed the limit corresponding to a horizontal stratification (IV.2.3). Numerous field diagrams have been processed (IV. 3). A first case (example 8) illustrates the various stages of the operation, chiefly the sampling of the E.S. (choice of the left cross, the weights and the resistivity of the substratum) and the selection of a solution, adapted from the automatic results (IV.3.1). The following examples (Nrs 9 and 10) show that electrical prospecting for deep seated layers can be usefully guided by the automatic processing of the E.S., even when difficult field conditions give original curves of low accuracy. A bore-hole proved the automatic solution proposed for E.S. no 10, slightly modified by the interpreter, to be correct.     

Spatial and temporal characterization of nutrient net uptake in a vegetated urban stream: Stream bank features leading to net uptake hotspots

Urban stream features can be used to promote nutrient retention; however, their interactions with different hydrological regimes impact nutrient cycling, decrease their retention capacity, and inhibit stream ecosystem functioning. This study analysed the temporal and spatial dynamics of the uptake of three nutrients (nitrate, ammonium, and phosphorus) in an urban drainage stream during high flows. In particular, we studied variations in net uptake along the right margin (with native vegetation and a roots mat) comparatively to the left margin (a non‐rooted grassy bank). Applying the spiralling approach within each subreach on either side, we determined nutrient subreach (sr) retention metrics: uptake rate coefficients , mass transfer rates , and areal uptake rates . Our results showed nitrate (NO₃) and ammonium (NH₄) net uptakes on the right side were higher and more frequent along subreaches where the root mat was more abundant ( [μg m^?2 s^?1] = 22.80 ± 1.13 for NO₃ and 10.50 ± 0.81 for NH₄), whereas on the left side both nutrients showed patchy and inconsistent net uptake patterns despite the homogeneous grass distribution. Net uptake for filtered reactive phosphorus (FRP) was not observed on either side at any flow rate. The impact of hydrological factors such as discharge, travel time, water depth, and concentration, on uptake metrics was studied. Despite increases in travel time as the flow decreased, there was a reduction in net uptake rates, and , on either side. This was attributed to a reduction in water level with declining flows, which decreased hydrologic connectivity with the stream banks, combined with a decrease in water velocity and a reduction in nutrient concentrations. We concluded the rooted bank acted as an effective retention area by systematically promoting net uptake resulting in a twofold increased dissolved inorganic nitrogen (DIN) retention relative to the non‐rooted side where net uptake was spatially localized and highly dynamic. Overall, this work emphasized the importance of strategically sampling close to biologically active surfaces to more accurately determine areas where gross uptake surpasses release process.     

Geochemistry of meteoric diagenesis in carbonate islands of the northern Bahamas: 1. Evidence from field studies

Processes driving carbonate diagenesis in islands of the northern Bahamas are investigated using major ion, dissolved oxygen and dissolved organic carbon analyses of water samples from surface and ground waters, and measurements of soil gas P. Meteoric waters equilibrate with aragonite, but reactions are water controlled rather than mineral‐controlled and drive dissolution rather than concurrent precipitation of calcite. Surface runoff waters equilibrate with atmospheric P and rapidly recharge the vadose zone, limiting subaerial bedrock dissolution to only 6·6–15 mg l^?1 Ca. P of soil gas measured in the summer wet season ((7·4 ± 3·7) × 10^?3 atm) is elevated compared with that of the atmosphere, despite the thin skeletal organic nature of the soil and the discontinuous soil cover. Soil waters retained in surface pockets are equilibrated with respect to aragonite and have dissolved 51 ± 19 mg l^?1 Ca. This is substantially less than the 93 ± 18 mg l^?1 Ca in samples from pumping boreholes that sample meteoric waters from the freshwater lens. The high P of the freshwater lens ((16 ± 8·3) × 10^?3 atm for pumping boreholes) suggests that significant additional CO₂ may be derived by oxidation of soil‐ and surface‐derived organic carbon within the lens. The suboxic nature of the majority of the freshwater lens and the observed depletion in sulphate support this suggestion, and indicate that both aerobic and anaerobic oxidation may take place. Shallow lens samples from observation boreholes are calcite supersaturated and have a lower P than deeper lens waters, indicating that CO₂ degasses from the water table, driving precipitation of calcite cements. We suggest that the geochemical evolution of waters in the vadose zone and upper part of the freshwater lens may be determined by the presence of a body of ground air with P controlled by production in the freshwater lens and soil and by degassing to the atmosphere. Copyright © 2007 John Wiley & Sons, Ltd.     

Zur Bestimmung des gesamten anorganischen Kohlenstoffes in natürlichen Gewässern durch Titration mit Salzsäure

The knowledge of total inorganic carbon concentration (c) is important for characterizing natural waters. It is usually measured by the titration alkalinity (“m-value”) and pH which depend on temperature and ionic strength. This paper demonstrates that Ca (and Mg) can influence the calculation of from titration alkalinity, too. Errors result from neglecting this influence. In such cases the share of ion pair CaCO amounts to more than 50 % of . General relationships among the influencing factors are given by tables calculated with the help of a BASIC computer programme for calculation from titration alkalinity, pH and Ca concentration.     

FAST HANKEL TRANSFORMS*

Inspired by the linear filter method introduced by D. P. Ghosh in 1970 we have developed a general theory for numerical evaluation of integrals of the Hankel type: Replacing the usual sine interpolating function by sinsh (x) =a· sin (ρx)/sinh (aρx), where the smoothness parameter a is chosen to be “small”, we obtain explicit series expansions for the sinsh-response or filter function H*. If the input function f(λ exp (iω)) is known to be analytic in the region o < λ < ∞, |ω|≤ω₀ of the complex plane, we can show that the absolute error on the output function is less than (K(ω₀)/r) · exp (?ρω₀/Δ), Δ being the logarthmic sampling distance. Due to the explicit expansions of H* the tails of the infinite summation ((m?n)Δ) can be handled analytically. Since the only restriction on the order is ν > ? 1, the Fourier transform is a special case of the theory, ν=± 1/2 giving the sine- and cosine transform, respectively. In theoretical model calculations the present method is considerably more efficient than the Fast Fourier Transform (FFT).     

Chemical dynamics of N-containing ionic species in a boreal forest snowcover during the spring melt period

A study of the changes in the ionic loads of NO, NH, SO and H⁺ in a boreal forest snowpack at Lake Laflamme, Québec was carried out using hydrological and chemical data from field lysimeters. The results showed that depletion of the N-containing species occurs periodically in the snowpack during meltwater discharge. Rain-on-snow events led to in-pack losses of NO and NH at a rate of 130 μeq m^?2 day^?1 and 101·3 μeq m^?2day^?1 respectively. On dry days, however, dry deposition and deposition of organic debris from the canopy resulted in increases of 183·3 μeq m^?2day^?1 for NO and 4·5 μeq m^?2day^?1 for NH in the pack. In contrast, SO₄^2? showed continual in-pack increases due to deposition of 5·0 μeq m^?2day^?1 for wet days and 92·6 μeq m^?2day^?1 for dry days. The depletion of NO and NH is due to microbiological uptake of these nutrients during periods when the free water content of the pack is high. Controlled melts in a laboratory snowmelt simulator containing snow and organic matter from the forest canopy at Lake Laflamme showed losses of NO and NH similar to those observed in the field. As the microbiological uptake proceeds at a rate comparable to that of ionic load increases in the pack by dry deposition, models of the chemical dynamics of snowmelt should take the former into account in any system where organic content of the snowpack is appreciable.     

M computed from strong motion accelerograms recorded in Yugoslavia

It is shown that the new definition¹ of strong motion local magnitude M leads to stable estimates of magnitudes for earthquakes in Yugoslavia, with epicentral distances R <100 km and for 2.5 < M < 6.5. Tables with magnitudes computed using this new procedure are presented for all earthquakes contributing to the strong motion accelerogram files in EQINFOS for Yugoslavia.² The similarity of our findings with the analogous analyses for California suggests new possibilities for relative calibration between various local magnitude scales, which are used in southeastern Europe, and M_L in California.