Distribution and sources of pre-anthropogenic lead isotopes in deep ocean water from FeMn crusts

The lead isotope composition of ocean water is not well constrained due to contamination by anthropogenic lead. Here the global distribution of lead isotopes in deep ocean water is presented as derived from dated (ca. 100 ka) surface layers of hydrogenetic Fe-Mn crusts. The results indicate that the radiogenic lead in North Atlantic deep water is probably supplied from the continents by river particulates, and that lead in Pacific deep water is similar to that characteristic of island and continental volcanic arcs. Despite a short residence time in deep water (80–100 a), the isotopes of lead appear to be exceedingly well mixed in the Pacific basin. There is no evidence for the import of North Atlantic deep water-derived lead into the Pacific ocean, nor into the North Indian Ocean. This implies that the short residence time of lead in deep water prohibits advection over such long distances. Consequently, any climate-induced changes in deep-water flow are not expected to result in major changes in the seawater Pb-isotope record of the Pacific Ocean.     

The identifiability of parameters in a water quality model of the Biebrza River, Poland

The identifiability of model parameters of a steady state water quality model of the Biebrza River and the resulting variation in model results was examined by applying the Monte Carlo method which combines calibration, identifiability analysis, uncertainty analysis, and sensitivity analysis. The water quality model simulates the steady state concentration profiles of chloride, phosphate, ammonium, and nitrate as a function of distance along a river. The water quality model with the best combination of parameter values simulates the observed concentrations very well. However, the range of possible modelled concentrations obtained for other more or less equally eligible combinations of parameter values is rather wide. This range in model outcomes reflects possible errors in the model parameters. Discrepancies between the range in model outcomes and the validation data set are only caused by errors in model structure, or (measurement) errors in boundary conditions or input variables. In this sense the validation procedure is a test of model capability, where the effects of calibration errors are filtered out. It is concluded that, despite some slight deviations between model outcome and observations, the model is successful in simulating the spatial pattern of nutrient concentrations in the Biebrza River.     

Crustal thickening in an extensional regime: application to the mid-Norwegian Vøring margin

The structure of the mid-Norwegian volcanic Vøring margin at the onset of the Maastrichtian–Paleocene extension phase reflects the cumulative effect of earlier consecutive rifting events. Lateral structural differences present on the margin at that time are a consequence of migration of the location of maximum extension in time between Norway and Greenland. The most important imprints (Moho depth, thermal structure) of these events on the lithosphere are incorporated in a numerical simulation of the final extension phase. We focus on a possible mechanism of formation of the Vøring Marginal High and address the relationship between spatial and temporal evolution of crustal thinning and thickening, uplift of the surface and strength of the lithosphere.It is found that the Vøring Basin formed the strongest part of the margin which explains why the Maastrichtian–Paleocene rift axis was not located here but instead jumped westward with respect to the earlier rift axes locations. The modeling study predicts that local crustal thickening during extension can be expected when large lateral thermal variations are present in the lithosphere at the onset of extension. Negative buoyancy induced by lateral temperature differences increases downwelling adjacent to the rifting zone; convergence of material at the particular part of the margin is mainly taken up by the lower crust. The model shows that during the final phase of extension, the crust in the Vøring Marginal High area was thickened and the surface uplifted. It is likely that this dynamic process and the effects of magmatic intrusions both acted in concert to form the Marginal High.     

The influence of particle composition on thorium scavenging in the NE Atlantic ocean (POMME experiment)

²³⁰Th, ²³²Th and ²³⁴Th were analyzed in sinking particles collected by moored and drifting sediment traps in the NE Atlantic Ocean (POMME experiment) in order to constrain the phase(s) carrying Th isotopes in the water column. It reveals a contrasted behaviour between ²³⁴Th and ²³⁰Th. ²³⁴Th is correlated to the particulate organic carbon suggesting that it is primarily scavenged by organic compounds in the surface waters. ²³⁰Th_xs is correlated with Mn, Ba and the lithogenic fraction that are enriched in small suspended particles and incorporated in the sinking particulate flux throughout the water column. The lack of correlation between ²³⁰Th_xs and CaCO₃ or biogenic silica (bSi) indicates that CaCO₃ and bSi are not responsible for ²³⁰Th scavenging in the deep waters of this oceanic region. ²³⁰Th is generally correlated with the lithogenic content of the trapped material but this correlation disappears in winter during strong atmospheric dust inputs suggesting that lithogenic matter is not directly responsible for ²³⁰Th scavenging in the deep waters or that sufficient time is required to achieve particle–solution equilibration. MnO₂ could be the prevalent ²³⁰Th_xs-bearing phase. The narrow range of K_{d_MnO2}^Th obtained for very contrasted oceanic environments supports a global control of ²³⁰Th_xs scavenging by MnO₂ and raises the possibility that the ²³⁰Th–²³¹Pa fractionation is controlled by the amount of colloidal MnO₂ in seawater.     

Structure of Palaeogene sediments in east Ellesmere Island: Constraints on Eurekan tectonic evolution and implications for the Nares Strait problem

The “Nares Strait problem” represents a debate about the existence and magnitude of left-lateral movements along the proposed Wegener Fault within this seaway. Study of Palaeogene Eurekan tectonics at its shorelines could shed light on the kinematics of this fault. Palaeogene (Late Paleocene to Early Eocene) sediments are exposed at the northeastern coast of Ellesmere Island in the Judge Daly Promontory. They are preserved as elongate SW–NE striking fault-bounded basins cutting folded Early Paleozoic strata. The structures of the Palaeogene exposures are characterized by broad open synclines cut and displaced by steeply dipping strike-slip faults. Their fold axes strike NE–SW at an acute angle to the border faults indicating left-lateral transpression. Weak deformation in the interior of the outliers contrasts with intense shearing and fracturing adjacent to border faults. The degree of deformation of the Palaeogene strata varies markedly between the northwestern and southeastern border faults with the first being more intense. Structural geometry, orientation of subordinate folds and faults, the kinematics of faults, and fault-slip data suggest a multiple stage structural evolution during the Palaeogene Eurekan deformation: (1) The fault pattern on Judge Daly Promontory is result of left-lateral strike-slip faulting starting in Mid to Late Paleocene times. The Palaeogene Judge Daly basin formed in transtensional segments by pull-apart mechanism. Transpression during progressive strike-slip shearing gave rise to open folding of the Palaeogene deposits. (2) The faults were reactivated during SE-directed thrust tectonics in Mid Eocene times (chron 21). A strike-slip component during thrusting on the reactivated faults depends on the steepness of the fault segments and on their obliquity to the regional stress axes.Strike-slip displacement was partitioned to a number of sub-parallel faults on-shore and off-shore. Hence, large-scale lateral movements in the sum of 80–100 km or more could have been accommodated by a set of faults, each with displacements in the order of 10–30 km. The Wegener Fault as discrete plate boundary in Nares Strait is replaced by a bundle of faults located mainly onshore on the Judge Daly Promontory.     

Arsenic mobility in the ambient sulfidic environment: Sorption of arsenic(V) and arsenic(III) onto disordered mackinawite

Arsenate, As(V), sorption onto synthetic iron(II) monosulfide, disordered mackinawite (FeS), is fast. As(V) sorption decreases above the point of zero surface charge of FeS and follows the pH-dependent concentration of positively charged surface species. No redox reaction is observed between the As(V) ions and the mineral surface over the time span of the experiments. This observation shows that As(V) dominantly forms an outer-sphere complex at the surface of mackinawite. Arsenite, As(III), sorption is not strongly pH-dependent and can be expressed by a Freundlich isotherm. Sorption is fast, although slower than that of As(V). As(III) also forms an outer-sphere complex at the surface of mackinawite. In agreement with previous spectroscopic studies, complexation at low As(V) and As(III) concentration occurs preferentially at the mono-coordinated sulfide edge sites. The K_d (L g⁻¹) values obtained from linear fits to the isotherm data are ∼9 for As(V) and ∼2 for As(III). Stronger sorption of As(V) than As(III), and thus a higher As(III) mobility, may be reflected in natural anoxic sulfidic waters when disordered mackinawite controls arsenic mobility.     

Characterisation of hydroclimatological trends and variability in the Lake Naivasha basin,Kenya

Recent hydro‐climatological trends and variability characteristics were investigated for the Lake Naivasha basin with the aim of understanding the changes in water balance components and their evolution over the past 50 years. Using a Bayesian change point analysis and modified Mann–Kendall tests, time series of annual mean, maximum, minimum, and seasonal precipitation and flow, as well as annual mean lake volumes, were analysed for the period 1960–2010 to uncover possible abrupt shifts and gradual trends. Double cumulative curve analysis was used to investigate the changes in hydrological response attributable to either human influence or climatic variability. The results indicate a significant decline in lake volumes at a mean rate of 9.35 × 10⁶ m³ year^?1. Most of the river gauging stations showed no evidence of trends in the annual mean and maximum flows as well as seasonal flows. Annual minimum flows, however, showed abrupt shifts and significant (upward/downward) trends at the main outlet stations. Precipitation in the basin showed no evidence of abrupt shifts, but a few stations showed gradual decline. The observed changes in precipitation could not explain the decline in both minimum flows and lake volumes. The findings show no evidence of any impact of climate change for the Lake Naivasha basin over the past 50 years. This implies that other factors, such as changes in land cover and infrastructure development, have been responsible for the observed changes in streamflow and lake volumes. Copyright © 2015 John Wiley & Sons, Ltd.     

Spatiotemporal variability in hydrochemistry of shallow groundwater in a small pre‐alpine catchment: The importance of landscape elements

Topography and landscape characteristics affect the storage and release of water and, thus, groundwater dynamics and chemistry. Quantification of catchment scale variability in groundwater chemistry and groundwater dynamics may therefore help to delineate different groundwater types and improve our understanding of which parts of the catchment contribute to streamflow. We sampled shallow groundwater from 34 to 47 wells and streamflow at seven locations in a 20‐ha steep mountainous catchment in the Swiss pre‐Alps, during nine baseflow snapshot campaigns. The spatial variability in electrical conductivity, stable water isotopic composition, and major and trace ion concentrations was large and for almost all parameters larger than the temporal variability. Concentrations of copper, zinc, and lead were highest at sites that were relatively dry, whereas concentrations of manganese and iron were highest at sites that had persistent shallow groundwater levels. The major cation and anion concentrations were only weakly correlated to individual topographic or hydrodynamic characteristics. However, we could distinguish four shallow groundwater types based on differences from the catchment average concentrations: riparian zone‐like groundwater, hillslopes and areas with small upslope contributing areas, deeper groundwater, and sites characterized by high magnesium and sulfate concentrations that likely reflect different bedrock material. Baseflow was not an equal mixture of the different groundwater types. For the majority of the campaigns, baseflow chemistry most strongly resembled riparian‐like groundwater for all but one subcatchment. However, the similarity to the hillslope‐type groundwater was larger shortly after snowmelt, reflecting differences in hydrologic connectivity. We expect that similar groundwater types can be found in other catchments with steep hillslopes and wet areas with shallow groundwater levels and recommend sampling of groundwater from all landscape elements to understand groundwater chemistry and groundwater contributions to streamflow.