13C/12C composition, a novel parameter to study the downward migration of paper sludge in soils?

δ ¹³C values of crop and forest soils were measured 8 years after disposal of paper sewage sludge. The carbon transfer from paper sludge downward to the first humic layer is evidenced by a ¹³C-enrichnient of up to + 5.6‰ due to the input of ¹³C-enriched sludge carbonates. ¹³C/¹²C composition is thus a novel, sensitive parameter to follow the downward transfer of paper sludge carbon.     

Rare earth elements in the water column of Lake Vanda, McMurdo Dry Valleys, Antarctica

We present data on the composition of water from Lake Vanda, Antarctica. Vanda and other lakes in the McMurdo Dry Valleys of Antarctica are characterized by closed basins, permanent ice covers, and deep saline waters. The meromictic lakes provide model systems for the study of trace metal cycling owing to their pristine nature and the relative simplicity of their biogeochemical systems. Lake Vanda, in the Wright Valley, is supplied by a single input, the Onyx River, and has no output. Water input to the lake is balanced by sublimation of the nearly permanent ice cap that is broken only near the shoreline during the austral summer. The water column is characterized by an inverse thermal stratification of anoxic warm hypersaline water underlying cold oxic freshwater.Water collected under trace-element clean conditions was analyzed for its dissolved and total rare earth element (REE) concentrations by inductively coupled plasma mass spectrometry. Depth profiles are characterized by low dissolved REE concentrations (La, Ce, <15 pM) in surface waters that increase slightly (La, 70 pM; Ce, 20 pM) with increasing depth to ∼55 m, the limit of the fresh oxic waters. Below this depth, a sharp increase in the concentrations of strictly trivalent REE (e.g., La, 5 nM) is observed, and a submaximum in redox sensitive Ce (2.6 nM) is found at 60- to 62-m depth. At a slightly deeper depth, a sharper Ce maximum is observed with concentrations exceeding 11 nM at a 67-m depth, immediately above the anoxic zone. The aquatic concentrations of REE reported here are ∼50-fold higher than previously reported for marine oxic/anoxic boundaries and are, to our knowledge, the highest ever observed at natural oxic/anoxic interfaces. REE maxima occur within stable and warm saline waters. All REE concentrations decrease sharply in the sulfidic bottom waters. The redox-cline in Lake Vanda is dominated by diffusional processes and vertical transport of dissolved species driven by concentration gradients. Furthermore, because the ultraoligotrophic nature of the lake limits the potential for organic phases to act as metal carriers, metal oxide coatings and sulfide phases appear to largely govern the distribution of trace elements. We discuss REE cycling in relation to the roles of redox reactions and competitive scavenging onto Mn- and Fe-oxides coatings on clay sized particles in the upper oxic water column and their release by reductive dissolution near the anoxic/oxic interface.     

Holocene loess deposition and soil formation as competing processes, Matanuska Valley, southern Alaska

Although loess–paleosol sequences are among the most important records of Quaternary climate change and past dust deposition cycles, few modern examples of such sedimentation systems have been studied. Stratigraphic studies and 22 new accelerator mass spectrometry radiocarbon ages from the Matanuska Valley in southern Alaska show that loess deposition there began sometime after 6500 ¹⁴C yr B.P. and has continued to the present. The silts are produced through grinding by the Matanuska and Knik glaciers, deposited as outwash, entrained by strong winds, and redeposited as loess. Over a downwind distance of 40 km, loess thickness, sand content, and sand-plus-coarse-silt content decrease, whereas fine-silt content increases. Loess deposition was episodic, as shown by the presence of paleosols, at distances >10 km from the outwash plain loess source. Stratigraphic complexity is at a maximum (i.e., the greatest number of loesses and paleosols) at intermediate (10–25 km) distances from the loess source. Surface soils increase in degree of development with distance downwind from the source, where sedimentation rates are lower. Proximal soils are Entisols or Inceptisols, whereas distal soils are Spodosols. Ratios of mobile CaO, K₂O, and Fe₂O₃ to immobile TiO₂ show decreases in surface horizons with distance from the source. Thus, as in China, where loess deposition also takes place today, eolian sedimentation and soil formation are competing processes. Study of loess and paleosols in southern Alaska shows that particle size can vary over short distances, loess deposition can be episodic over limited time intervals, and soils developed in stabilized loess can show considerable variability under the same vegetation.     

Experimental constraints on Fe isotope fractionation during magnetite and Fe carbonate formation coupled to dissimilatory hydrous ferric oxide reduction

Iron isotope fractionation between aqueous Fe(II) and biogenic magnetite and Fe carbonates produced during reduction of hydrous ferric oxide (HFO) by Shewanella putrefaciens, Shewanella algae, and Geobacter sulfurreducens in laboratory experiments is a function of Fe(III) reduction rates and pathways by which biogenic minerals are formed. High Fe(III) reduction rates produced ⁵⁶Fe/⁵⁴Fe ratios for Fe(II)_aq that are 2-3‰ lower than the HFO substrate, reflecting a kinetic isotope fractionation that was associated with rapid sorption of Fe(II) to HFO. In long-term experiments at low Fe(III) reduction rates, the Fe(II)_aq-magnetite fractionation is −1.3‰, and this is interpreted to be the equilibrium fractionation factor at 22°C in the biologic reduction systems studied here. In experiments where Fe carbonate was the major ferrous product of HFO reduction, the estimated equilibrium Fe(II)_aq-Fe carbonate fractionations were ca. 0.0‰ for siderite (FeCO₃) and ca. +0.9‰ for Ca-substituted siderite (Ca_0.15Fe_0.85CO₃) at 22°C. Formation of precursor phases such as amorphous nonmagnetic, noncarbonate Fe(II) solids are important in the pathways to formation of biogenic magnetite or siderite, particularly at high Fe(III) reduction rates, and these solids may have ⁵⁶Fe/⁵⁴Fe ratios that are up to 1‰ lower than Fe(II)_aq. Under low Fe(III) reduction rates, where equilibrium is likely to be attained, it appears that both sorbed Fe(II) and amorphous Fe(II)(s) components have isotopic compositions that are similar to those of Fe(II)_aq.The relative order of δ⁵⁶Fe values for these biogenic minerals and aqueous Fe(II) is: magnetite > siderite ≈ Fe(II)_aq > Ca-bearing Fe carbonate, and this is similar to that observed for minerals from natural samples such as Banded Iron Formations (BIFs). Where magnetite from BIFs has δ⁵⁶Fe >0‰, the calculated δ⁵⁶Fe value for aqueous Fe(II) suggests a source from midocean ridge (MOR) hydrothermal fluids. In contrast, magnetite from BIFs that has δ⁵⁶Fe ≤0‰ apparently requires formation from aqueous Fe(II) that had very low δ⁵⁶Fe values. Based on this experimental study, formation of low-δ⁵⁶Fe Fe(II)_aq in nonsulfidic systems seems most likely to have been produced by dissimilatory reduction of ferric oxides by Fe(III)-reducing bacteria.     

Fluid and Solute Transport from a Conduit to the Matrix in a Carbonate Aquifer System

Within carbonate systems, the working hypothesis suggests that when a conduit is flooded fluid and solute migrate from the conduit into the matrix. This flux of fluid and solute into the matrix creates a reservoir that can be slowly released once the flooding recedes. Although hypothesized, these fluxes have never been measured. To quantify the distance that a fluid and solute would move into a matrix, the fluxes of fluid and solute from a conduit into a matrix were simulated for nine different carbonate aquifer systems. Two independent numerical approaches were used to simulate (1) fluid flux into the matrix and (2) solute flux into the matrix during a flooding event. When flooding occurs within the conduit, the volume of water transported into and stored in the matrix with a high porosity and high hydraulic conductivity (Floridan Aquifer) was less than 0.34 m³ along a 1 m length of conduit, resulting in a penetration depth of 7.2×10⁻² m into the matrix. In a low porosity and low hydraulic conductivity matrix (Ozark Plateau), the volume of water transported into and stored in the matrix was less than 6.85×10⁻⁵ m³ along a 1 m length of conduit, resulting in a penetration depth of 2.0×10⁻⁴ m into the matrix. Simulated solute flow shows that less than 0.1% of the solute moves in to the matrix. The two approaches demonstrate that during high flow conditions fluid and solute are forced through the conduits, with very little moving into the carbonate matrix. Once the fluid and solute enter a conduit and are moving, they will remain in the conduit until they are discharged at an outlet. Thus, a carbonate matrix does not become a reservoir for solute and fluid during a high-flow event.     

The southeastern border of the Upper Rhine Graben: a 3D geological model and its importance for tectonics and groundwater flow

A 3D geological model of the area east of Basel on the southeastern border of the Upper Rhine Graben, consisting of 47 faults and six stratigraphic horizons relevant for groundwater flow, was developed using borehole data, geological maps, geological cross sections, and outcrop data. This model provides new insight into the discussions about the kinematics of the area between the southeastern border of the Upper Rhine Graben and the Tabular Jura east of Basel. A 3D analysis showed that both thin-skinned and thick-skinned tectonic elements occur in the modeled area and that the Anticline and a series of narrow graben structures developed simultaneously during an extensional stress-field varying from E–W to SSE–NNW, which lasted from the Middle Eocene to Late Oligocene. In a new approach the faults and horizons of the 3D geological model were transferred into discrete elements with distributed hydrogeological properties in order to simulate the 3D groundwater flow regime within the modeled aquifers. A three-layer approach with a horizontal regularly spaced grid combined with an irregular property distribution of transmissivity in depth permitted the piezometric head of the steady-state model to be automatically calibrated to corresponding measurements using more than 200 piezometers. Groundwater modeling results demonstrated that large-scale industrial pumping affected the groundwater flow field in the Upper Muschelkalk aquifer at distances of up to 2 km to the south. The results of this research will act as the basis for further model developments, including salt dissolution and solute transport in the area, and may ultimately help to provide predictions for widespread land subsidence risks.     

Rayleigh wave tomography in the North Atlantic: high resolution images of the Iceland, Azores and Eifel mantle plumes

Presented in this paper is a high resolution S_v-wave velocity and azimuthal anisotropy model for the upper mantle beneath the North Atlantic and surrounding region derived from the analysis of about 9000 fundamental and higher-mode Rayleigh waveforms. Much of the dataset comes from global and national digital seismic networks, but to improve the path coverage a number of instruments at coastal sites in northwest Europe, Iceland and eastern Greenland was deployed by us and a number of collaborators. The dense path coverage, the wide azimuthal distribution and the substantial higher-mode content of the dataset, as well as the relatively short path-lengths in the dataset have enabled us to build an upper mantle model with a horizontal resolution of a few hundred kilometers extending to 400 km depth. Low upper mantle velocities exist beneath three major hotspots: Iceland, the Azores and Eifel. The best depth resolution in the model occurs in NW Europe and in this area low S_v-velocities in the vicinity of the Eifel hotspot extend to about 400 km depth. Major negative velocity anomalies exist in the North Atlantic upper mantle beneath both Iceland and the Azores hotspots. Both anomalies are, above 200 km depth, 4–7% slow with respect to PREM and elongated along the mid-Atlantic Ridge. Low velocities extend to the south of Iceland beneath the Reykjanes Ridge where other geophysical and geochemical observations indicate the presence of hot plume material. The low velocities also extend beneath the Kolbeinsey Ridge north of Iceland, where there is also supporting geochemical evidence for the presence of hot plume material. The low-velocity upper mantle beneath the Kolbeinsey Ridge may also be associated with a plume beneath Jan Mayen. The anomaly associated with the Azores extends from about 25°N to 45°N along the ridge axis, which is in agreement with the area influenced by the Azores Plume, predicted from geophysical and geochemical observations. Compared to the anomaly associated with Iceland, the Azores anomaly is elongated further along the ridge, is shallower and decays more rapidly with depth. The fast propagation direction of horizontally propagating S_v-waves in the Atlantic south of Iceland correlates well with the east–west ridge-spreading direction at all depths and changes to a direction close to NS in the vicinity of Iceland.     

Lowland Canterbury landscapes in the making

Abstract: This article explores environmental imaginaries of colonization in lowland Canterbury. In 1844 Edward Shortland observed that his Māori companions had an exceptionally detailed geographical knowledge of the area and its resources, yet a few years later European settlers were viewing it as an empty stage on which to envision newly‐constructed landscapes. The terrain was contested, but colonial ‘improvement’, through the creation of spaces of modernity, took no cognizance of this. The legacies of that transformation are a simplified, orderly landscape, and fractured but persistent memories of indigenous ecosystems that are now being revived.     

Geomorphic controls on contaminant distribution along an ephemeral stream

Sediment‐borne contamination in a watershed can be highly variable as a result of ?uvial processes operating over a range of time scales. This study presents a detailed analysis of the distribution of one contaminant along an ephemeral stream after 55 years of sediment transport, deposition, and exchange by ?ash ?oods. Wastewater containing plutonium was discharged into the Pueblo Canyon watershed from 1945 until 1964, and plutonium concentrations in ?uvial deposits vary over ?ve orders of magnitude. These variations can be attributed to three primary factors: time since contaminant releases, particle‐size sorting, and mixing of sediment from different sources. The highest concentrations occur in ?ne‐grained sediment deposits near the source that date to the period of ef?uent releases, and concentrations are lower in younger deposits, in coarser‐grained deposits, and in deposits farther downstream. The spatial distribution of plutonium is strongly affected by longitudinal variations in the size of sediment deposits of different age. A major aggradation–degradation cycle in the lower canyon overlapped with the period of active ef?uent releases, and a signi?cant portion of the total plutonium inventory is contained within large coarse‐grained deposits below ?ll terraces that post‐date 1945. The spatial pattern of contamination is thus determined by the speci?c geomorphic history of the watershed, in addition to processes of mixing and sorting during transport that occur in all ?uvial systems. Copyright © 2004 John Wiley & Sons, Ltd.     

An intercomparison between finite difference and finite element (TELEMAC) approaches to modelling west coast of Britain tides

A finite element model (namely TELEMAC) with a range of mesh refinements and assumptions of coastal water depths is used to determine an optimal mesh for computing the M ₂ tide in a region of significant geographical extent. The region adopted is the west coast of Britain covering the Irish and Celtic Seas. The nature of the spatially varying topography and tidal distribution, together with a comprehensive set of measurements and existing accurate finite difference model makes it ideal for such a study. Calculations show that a water-depth dependent criterion for determining element size gives an optimal distribution over the majority of the region. However, local refinements in narrow channels such as the North Channel and Bristol Channel are required. Although the specification of a zero coastal water depth, leads to a fine near coastal grid, this does not yield the most accurate solution. In addition the computational cost is high. In practice in a large area model the use of a non-zero coastal water depth yields optimum accuracy at minimal computational cost. However, calculations show that accuracy is critically dependent upon nearshore water depths. Comparison with the finite difference model shows that the bias in elevation amplitude in the finite difference solution is removed in the finite element calculation.