Alkalinity titration in seawater: How accurately can the data be fitted by an equilibrium model?

Displaying “calculated minus observed” data for precise titrations of seawater with strong acid permits direct evaluation of important parameters and detection of systematic errors.At least two data sets from the GEOSECS (Geochemical Ocean Sections) program fit an equilibrium model (which includes carbonate, borate, sulfate, silicate, fluoride, and phosphate) within the most stringent experimental error, less than 2 μmol kg⁻¹. The effect of various parameters on the fit of calculated to observed values depends strongly on pH. Although standard potential E₀, total alkalinity A_t, total carbonate C_t, and first acidity constant of carbon dioxide pK₁ are nearly independent, and can be determined for each data set, other parameters are strongly correlated. Within such groups, all but one parameter must be determined from data other than the titration curve.Adding an acid-base pair to the theoretical model (e.g. C_x=20 μmol kg⁻¹, pK_x=6.2) produces a deviation approaching 20 μmol kg⁻¹ at constant C_t; however, adjustment of C_t by about −18 μmol kg⁻¹ to produce a good fit leaves only ± 1.5 μmol kg⁻¹ residual deviation from the reference values. Thus, at current standards of precision, an unidentified weak acid cannot be distinguished from carbonate purely on the basis of the titration curve shape.There are few full sets of numerical data published, and most show larger systematic errors (3–12 μmol l⁻¹) than the above; one well-defined source is experiments performed in unsealed vessels. Total carbonate can be explicitly obtained as a function of pH by a rearrangement of the titration curve equation; this can reveal a systematic decrease in C_t in the pH range 5–6, as a result of CO₂ gas loss from the titration vessel. Attempts to compensate for this by adjustment of A_t, C_t, or pK₁ produce deviations which mimic those produced by an additional acid-base pair.Changing from the free H⁺ scale (for which [HSO₄⁻] and [HF] are explicit terms in the alkalinity) to the seawater scale (SWS) (where those terms are part of a constant factor multiplying [H⁺]) requires modification of the titration curve equation as well as adjustment of acidity constants. Even with this change, however, omission of pH-dependent terms in [HSO₄⁻] and [HF] produces small systematic errors at low pH.Shifts in liquid junction potential also introduce small systematic errors, but are significant only at pH <3. High-pH errors due to response of the glass electrode to Na⁺ as well as H⁺ can be adequately compensated to pH 9.5 by a linear selectivity expression.     

Inherent Limitations of Hydraulic Tomography

We offer a cautionary note in response to an increasing level of enthusiasm regarding high-resolution aquifer characterization with hydraulic tomography. We use synthetic examples based on two recent field experiments to demonstrate that a high degree of nonuniqueness remains in estimates of hydraulic parameter fields even when those estimates are based on simultaneous analysis of a number of carefully controlled hydraulic tests. We must, therefore, be careful not to oversell the technique to the community of practicing hydrogeologists, promising a degree of accuracy and resolution that, in many settings, will remain unattainable, regardless of the amount of effort invested in the field investigation. No practically feasible amount of hydraulic tomography data will ever remove the need to regularize or bias the inverse problem in some fashion in order to obtain a unique solution. Thus, along with improving the resolution of hydraulic tomography techniques, we must also strive to couple those techniques with procedures for experimental design and uncertainty assessment and with other more cost-effective field methods, such as geophysical surveying and, in unconsolidated formations, direct-push profiling, in order to develop methods for subsurface characterization with the resolution and accuracy needed for practical field applications.     

Depositional processes across the Sinú Accretionary Prism,offshore Colombia

The Pliocene to Recent of the Sinú Accretionary Prism, offshore Colombia, features gravity current dominated basins characterised primarily by channel- and sheet-like architectures and those with dominantly hemipelagic fills. The prism is fed by rivers that drain from uplifted older basins and volcanic Andean terranes to the south and east which source large volumes of sediment to the Colombian Shelf into the Colombian Basin. Some basin fills show evidence of both localised fold-induced sediment failure and regional-scale shelf collapse, both related to the generation and destruction of oversteepened slopes. Large scale collapses can create new sediment routing pathways and/or local depocentres into which sediment subsequently accumulates. In the Colombian Basin, even relatively distal basins show evidence of channel activity related primarily to the creation of new sediment distribution pathways through breaches in the substrate barriers between basins. These channels are often orientated parallel to the regional drainage trend, suggesting that regional sediment transport trends can assert themselves relatively early in a basin filling history regardless of the local bathymetric grain. While, at a regional scale, sediment dispersal fairways reflect drainage from the continental shelf to the basin floor, intraslope basins form local bathymetric obstructions that can drive local spatial variations in sediment distribution. Thus, both local and regional length scales of bathymetric control are evident within the intraslope basins of the Sinú Accretionary Prism. Although regional dispersal patterns generally become more important in time, individual intraslope basins exhibit more complex filling histories because events such as sill or shelf collapse may serve to disrupt established distribution pathways, initiating repeated episodes of adjustment.     

Late stage differential exhumation of crustal blocks in the central Eastern Alps: evidence from fission track and (U–Th)/He thermochronology

Thermal history modelling based on zircon‐ and apatite fission track and apatite (U–Th)/He data constrain and refine the near‐surface exhumation of the south‐eastern Tauern Window (Penninic units) and neighbouring Austroalpine basement units in the Eastern Alps. Fast exhumation on both sides of the Penninic/Austroalpine boundary coincides with a period of lateral extrusion and tectonic denudation of the Penninic units in Miocene time (22–12 Ma). The jump to older ages occurs within the Austroalpine unit along the Polinik fault, which therefore defines the boundary between the tectonically denuded units and the hangingwall at that time. According to the different (U–Th)/He ages between the Penninic Hochalm‐ and Sonnblick Domes we demonstrate a differential cooling history of these two domes in the latest Miocene and early Pliocene.     

Seasonal and interannual behaviour of groundwater catchment boundaries in a Chalk aquifer

Groundwater catchment boundaries and their associated groundwater catchment areas are typically assumed to be fixed on a seasonal basis. We investigated whether this was true for a highly permeable carbonate aquifer in England, the Berkshire and Marlborough Downs Chalk aquifer, using both borehole hydrograph data and a physics‐based distributed regional groundwater model. Borehole hydrograph data time series were used to construct a monthly interpolated water table surface, from which was then derived a monthly groundwater catchment boundary. Results from field data showed that the mean annual variation in groundwater catchment area was about 20% of the mean groundwater catchment area, but interannual variation can be very large, with the largest estimated catchment size being approximately 80% greater than the smallest. The flow in the river was also dependent on the groundwater catchment area. Model results corroborated those based on field data. These findings have significant implications for issues such as definition of source protection zones, recharge estimates based on water balance calculations and integrated conceptual modelling of surface water and groundwater systems. Copyright © 2015 John Wiley & Sons, Ltd.     

A rapid method for hydraulic profiling in unconsolidated formations

Information on vertical variations in hydraulic conductivity ( K ) can often shed much light on how a contaminant will move in the subsurface. The direct-push injection logger has been developed to rapidly obtain such information in shallow unconsolidated settings. This small-diameter tool consists of a short screen located just behind a drive point. The tool is advanced into the subsurface while water is injected through the screen to keep it clear. Upon reaching a depth at which information about K is desired, advancement ceases and the injection rate and pressure are measured on the land surface. The rate and pressure values are used in a ratio that serves as a proxy for K . A vertical profile of this ratio can be transformed into a K profile through regressions with K estimates determined using other techniques. The viability of the approach was assessed at an extensively studied field site in eastern Germany. The assessment demonstrated that this tool can rapidly identify zones that may serve as conduits for or barriers to contaminant movement.     

Interpretation of Water Level Changes in the High Plains Aquifer in Western Kansas

Water level changes in wells provide a direct measure of the impact of groundwater development at a scale of relevance for management activities. Important information about aquifer dynamics and an aquifer's future is thus often embedded in hydrographs from continuously monitored wells. Interpretation of those hydrographs using methods developed for pumping‐test analyses can provide insights that are difficult to obtain via other means. These insights are demonstrated at two sites in the High Plains aquifer in western Kansas. One site has thin unconfined and confined intervals separated by a thick aquitard. Pumping‐induced responses in the unconfined interval indicate a closed (surrounded by units of relatively low permeability) system that is vulnerable to rapid depletion with continued development. Responses in the confined interval indicate that withdrawals are largely supported by leakage. Given the potential for rapid depletion of the unconfined interval, the probable source of that leakage, it is likely that large‐scale irrigation withdrawals will not be sustainable in the confined interval beyond a decade. A second site has a relatively thick unconfined aquifer with responses that again indicate a closed system. However, unlike the first site, previously unrecognized vertical inflow can be discerned in data from the recovery periods. In years of relatively low withdrawals, this inflow can produce year‐on‐year increases in water levels, an unexpected occurrence in western Kansas. The prevalence of bounded‐aquifer responses at both sites has important ramifications for modeling studies; transmissivity values from pumping tests, for example, must be used cautiously in regional models of such systems.     

The Kwakshua Watersheds Observatory,central coast of British Columbia,Canada

The Kwakshua Watersheds Observatory (KWO) is an integrative watersheds observatory on the coastal margin of a rain-dominated bog-forest landscape in British Columbia (BC), Canada. Established in 2013, the goal of the KWO is to understand and model the flux of terrestrial materials from land to sea – the origins, pathways, processes and ecosystem consequences – in the context of long-term environmental change. The KWO consists of seven gauged watersheds and a network of observation sites spanning from land to sea and along drainage gradients within catchments. Time-series datasets include year-round measurements of weather, soil hydrology, streamflow, aquatic biogeochemistry, microbial ecology and nearshore oceanographic conditions. Sensor measurements are recorded every 5 min and water samples are collected approximately monthly. Additional observations are made during high-flow conditions. We used remote sensing to map watershed terrain, drainage networks, soils and terrestrial ecosystems. The watersheds range in size from 3.2 to 12.8 km², with varying catchment characteristics that influence hydrological and biogeochemical responses. Despite local variation, the overall study area is a global hotspot for yields of dissolved organic carbon, dissolved organic nitrogen and dissolved iron at the coastal margin. This observatory helps fill an important gap in the global network of observatories, in terms of spatial location (central coast of BC), climate (temperate oceanic), hydrology (very high runoff, pluvial regime), geology (igneous intrusive, glacially scoured), vegetation (bog rainforest) and soils (large stores of organic carbon).     

Has the amount of tar on the open ocean changed in the past decade?

Quantitative surveys of beach tar on Bermuda during 1978–1979 are compared with similar surveys in 1971–1972. A 15% increase in the mean, while not significantly different from previously observed levels, is significantly higher than the reported 27% decrease due to improvements in tanker operations.