Reduction of pertechnetate [Tc(VII)] by aqueous Fe(II) and the nature of solid phase redox products

The subsurface behaviour of ⁹⁹Tc, a contaminant resulting from nuclear fuels reprocessing, is dependent on its valence (e.g., IV or VII). Abiotic reduction of soluble Tc(VII) by Fe(II)_(aq) in pH 6-8 solutions was investigated under strictly anoxic conditions using an oxygen trap (<7.5 × 10⁻⁹ atm O₂). The reduction kinetics were strongly pH dependent. Complete and rapid reduction of Tc(VII) to a precipitated Fe/Tc(IV) form was observed when 11 μmol/L of Tc(VII) was reacted with 0.4 mmol/L Fe(II) at pH 7.0 and 8.0, while no significant reduction was observed over 1 month at pH 6.0. Experiments conducted at pH 7.0 with Fe(II)_(aq) = 0.05-0.8 mmol/L further revealed that Tc(VII) reduction was a combination of homogeneous and heterogeneous reaction. Heterogeneous reduction predominated after approximately 0.01 mmol/L of Fe(II) was oxidized. The heterogeneous reaction was more rapid, and was catalyzed by Fe(II) that adsorbed to the Fe/Tc(IV) redox product. Wet chemical and Fe-X-ray absorption near edge spectroscopy measurements (XANES) showed that Fe(II) and Fe(III) were present in the Fe/Tc(IV) redox products after reaction termination. ⁵⁷Fe-Mössbauer, extended X-ray adsorption fine structure (EXAFS), and transmission electron microscopy (TEM) measurements revealed that the Fe/Tc(IV) solid phase was poorly ordered and dominated by Fe(II)-containing ferrihydrite with minor magnetite. Tc(IV) exhibited homogeneous spatial distribution within the precipitates. According to Tc-EXAFS measurements and structural modeling, its molecular environment was consistent with an octahedral Tc(IV) dimer bound in bidentate edge-sharing mode to octahedral Fe(III) associated with surface or vacancy sites in ferrihydrite. The precipitate maintained Tc(IV)_aq concentrations that were slightly below those in equilibrium with amorphous Tc(IV)O₂·nH₂O_(s). The oxidation rate of sorbed Tc(IV) in the Fe/Tc precipitate was considerably slower than Tc(IV)O₂·nH₂O_(s) as a result of its intraparticle/intragrain residence. Precipitates of this nature may form in anoxic sediments or groundwaters, and the intraparticle residence of sorbed/precipitated Tc(IV) may limit ⁹⁹Tc remobilization upon the return of oxidizing conditions.     

Evidence of the recent decade change in global fresh water discharge and evapotranspiration revealed by reanalysis and satellite observations

Variations of global evapotranspiration (ET) and fresh water discharge from land to oceans (D) are important components of global climate change, but have not been well monitored. In this study, we present an estimate of twenty years (1989 to 2008) variations of global D and ET derived from satellite remote-sensed measurements and recent reanalysis products, ERA-Interim and CFSR, by using a novel application of the water balance equations separately over land and over oceans. Time series of annual mean global D and ET from both satellite observations and reanalyses show clear positive and negative trends, respectively, as a result of modest increase of oceanic evaporation (E _o ). The inter-annual variations of D are similar to the in-situ-based observations, and the negative trend of ET supports the previous result that relative humidity has decreased while temperature has increased on land. The results suggest considerable sensitivity of the terrestrial hydrological cycles (e.g., D and ET) to small changes in precipitation and oceanic evaporation.     

Spectral filtering as a method of visualising and removing striped artefacts in digital elevation data

Spectral filtering was compared with traditional mean spatial filters to assess their ability to identify and remove striped artefacts in digital elevation data. The techniques were applied to two datasets: a 100 m contour derived digital elevation model (DEM) of southern Norway and a 2 m LiDAR DSM of the Lake District, UK. Both datasets contained diagonal data artefacts that were found to propagate into subsequent terrain analysis. Spectral filtering used fast Fourier transformation (FFT) frequency data to identify these data artefacts in both datasets. These were removed from the data by applying a cut filter, prior to the inverse transform. Spectral filtering showed considerable advantages over mean spatial filters, when both the absolute and spatial distribution of elevation changes made were examined. Elevation changes from the spectral filtering were restricted to frequencies removed by the cut filter, were small in magnitude and consequently avoided any global smoothing. Spectral filtering was found to avoid the smoothing of kernel based data editing, and provided a more informative measure of data artefacts present in the FFT frequency domain. Artefacts were found to be heterogeneous through the surfaces, a result of their strong correlations with spatially autocorrelated variables: landcover and landsurface geometry. Spectral filtering performed better on the 100 m DEM, where signal and artefact were clearly distinguishable in the frequency data. Spectrally filtered digital elevation datasets were found to provide a superior and more precise representation of the landsurface and be a more appropriate dataset for any subsequent geomorphological applications. Copyright © 2007 John Wiley & Sons, Ltd.     

The influence of a season of extreme wet weather events on exposure of the World Heritage Area Great Barrier Reef to pesticides

The 2010-2011 wet season was one of extreme weather for the State of Queensland, Australia. Major rivers adjacent to the Great Barrier Reef (GBR) were discharging at rates 1.5 to >3 times higher than their long term median. Exposure to photosystem II herbicides has been routinely monitored over a period of up to 5 years at 12 inshore GBR sites. The influence of this wet season on exposure to photosystem II herbicides was examined in the context of this long-term monitoring record and during flood plume events in specific regions. Median exposures expressed as diuron equivalent concentration were an average factor of 2.3 times higher but mostly not significantly different (p<0.05) to the median for the long-term monitoring record. The herbicides metolachlor and tebuthiuron were frequently detected in flood plume waters at concentrations that reached or exceeded relevant water quality guidelines (by up to 4.5 times).     

Tile drainage causes flashy streamflow response in Ohio watersheds

Artificial subsurface (tile) drainage is used to increase trafficability and crop yield in much of the Midwest due to soils with naturally poor drainage. Tile drainage has been researched extensively at the field scale, but knowledge gaps remain on how tile drainage influences the streamflow response at the watershed scale. The purpose of this study is to analyse the effect of tile drainage on the streamflow response for 59 Ohio watersheds with varying percentages of tile drainage and explore patterns between the Western Lake Erie Bloom Severity Index to streamflow response in heavily tile-drained watersheds. Daily streamflow was downloaded from 2010 to 2019 and used to calculated mean annual peak daily runoff, mean annual runoff ratio, the percent of observations in which daily runoff exceeded mean annual runoff (T_Qmean), baseflow versus stormflow percentages, and the streamflow recession constant. Heavily-drained watersheds (>40% of watershed area) consistently reported flashier streamflow behaviour compared to watersheds with low percentages of tile drainage (<15% of watershed area) as indicated by significantly lower baseflow percentages, T_Qmean, and streamflow recession constants. The mean baseflow percent for watersheds with high percentages of tile drainage was 20.9% compared to 40.3% for watersheds with low percentages of tile drainage. These results are in contrast to similar research regionally indicating greater baseflow proportions and less flashy hydrographs (higher T_Qmean) for heavily-drained watersheds. Stormflow runoff metrics in heavily-drained watersheds were significantly positively correlated to western Lake Erie algal bloom severity. Given the recent trend in more frequent large rain events and warmer temperatures in the Midwest, increased harmful algal bloom severity will continue to be an ecological and economic problem for the region if management efforts are not addressed at the source. Management practices that reduce the streamflow response time to storm events, such as buffer strips, wetland restoration, or drainage water management, are likely to improve the aquatic health conditions of downstream communities by limiting the transport of nutrients following storm events.     

Recommended Sampling Intervals for Arsenic in Private Wells

Geogenic arsenic in drinking water is a worldwide problem. For private well owners, testing (e.g., private or government laboratory) is the main method to determine arsenic concentration. However, the temporal variability of arsenic concentrations is not well characterized and it is not clear how often private wells should be tested. To answer this question, three datasets, two new and one publicly available, with temporal arsenic data were utilized: 6370 private wells from New Jersey tested at least twice since 2002, 2174 wells from the USGS NAWQA database, and 391 private wells sampled 14 years apart from Bangladesh. Two arsenic drinking water standards are used for the analysis: 10 µg/L, the WHO guideline and EPA standard or maximum contaminant level (MCL) and 5 µg/L, the New Jersey MCL. A rate of change was determined for each well and these rates were used to predict the temporal change in arsenic for a range of initial arsenic concentrations below an MCL. For each MCL and initial concentration, the probability of exceeding an MCL over time was predicted. Results show that to limit a person to below a 5% chance of drinking water above an MCL, wells that are ½ an MCL and above should be tested every year and wells below ½ an MCL should be tested every 5 years. These results indicate that one test result below an MCL is inadequate to ensure long-term compliance. Future recommendations should account for temporal variability when creating drinking water standards and guidance for private well owners.     

Glyphosate persistence in seawater

Glyphosate is one of the most widely applied herbicides globally but its persistence in seawater has not been reported. Here we quantify the biodegradation of glyphosate using standard “simulation” flask tests with native bacterial populations and coastal seawater from the Great Barrier Reef. The half-life for glyphosate at 25 °C in low-light was 47 days, extending to 267 days in the dark at 25 °C and 315 days in the dark at 31 °C, which is the longest persistence reported for this herbicide. AMPA, the microbial transformation product of glyphosate, was detected under all conditions, confirming that degradation was mediated by the native microbial community. This study demonstrates glyphosate is moderately persistent in the marine water under low light conditions and is highly persistent in the dark. Little degradation would be expected during flood plumes in the tropics, which could potentially deliver dissolved and sediment-bound glyphosate far from shore.     

Evaluation of temporal concentration profiles for ungauged rivers following pollution incidents

Abstract

In order to predict the impact of pollution incidents on rivers, it is necessary to predict the dispersion coefficient and the flow velocity corresponding to the discharge in the river of interest. This paper explores methods for doing this, particularly with a view to applications on ungauged rivers, i.e. those for which little hydraulic or morphometric data are available. An approach based on neural networks, trained on a wide-ranging database of optimized parameter values from tracer experiments and corresponding physical variables assembled for American and European rivers, is proposed. Tests using independent cases showed that the neural networks generally gave more reliable parameter estimates than a second-order polynomial regression approach. The quality of predictions of temporal concentration profiles was heavily influenced by the accuracy of the velocity prediction.

Citation Piotrowski, A. P., Napiorkowski, J. J., Rowinski, P. M. & Wallis, S. G. (2011) Evaluation of temporal concentration profiles for ungauged rivers following pollution incidents. Hydrol. Sci. J. 56(5), 883–894.     

Hydrothermal alteration of kimberlite by convective flows of external water

Kimberlite volcanism involves the emplacement of olivine-rich volcaniclastic deposits into volcanic vents or pipes. Kimberlite deposits are typically pervasively serpentinised as a result of the reaction of olivine and water within a temperature range of 130–400 °C or less. We present a model for the influx of ground water into hot kimberlite deposits coupled with progressive cooling and serpentisation. Large-pressure gradients cause influx and heating of water within the pipe with horizontal convergent flow in the host rock and along pipe margins, and upward flow within the pipe centre. Complete serpentisation is predicted for wide ranges of permeability of the host rocks and kimberlite deposits. For typical pipe dimensions, cooling times are centuries to a few millennia. Excess volume of serpentine results in filling of pore spaces, eventually inhibiting fluid flow. Fresh olivine is preserved in lithofacies with initial low porosity, and at the base of the pipe where deeper-level host rocks have low permeability, and the pipe is narrower leading to faster cooling. These predictions are consistent with fresh olivine and serpentine distribution in the Diavik A418 kimberlite pipe, (NWT, Canada) and with features of kimberlites of the Yakutian province in Russia affected by influx of ground water brines. Fast reactions and increases in the volume of solid products compared to the reactants result in self-sealing and low water–rock ratios (estimated at <0.2). Such low water–rock ratios result in only small changes in stable isotope compositions; for example, δO¹⁸ is predicted only to change slightly from mantle values. The model supports alteration of kimberlites predominantly by interactions with external non-magmatic fluids.     

Dissolved and particulate organic carbon in the North Inlet estuary,South Carolina: What controls their concentrations?

Water samples have been taken daily at 1030 EST from three locations within North Inlet (South Carolina) since June of 1980 in order to evaluate the tidal, seasonal, and eventually annual variability in carbon concentrations within this system and generate hypotheses explaining the observed trends. Dissolved organic carbon (DOC) concentrations within North Inlet (South Carolina) vary inversely with salinity (r²=0.65), suggesting the main source of DOC in North Inlet is freshwater entering from the adjacent forested watershed. This assertion is supported by an observed decrease of tidal water salinity with the onset of streamflow. DOC variability is also associated with (1) groundwater advection and/or runoff and seepage from the marsh surface; (2) removal from tidal water via either physical sorption or biological uptake; (3) sampling location; and (4) origin of water mass. Particulate organic carbon (POC) concentrations vary seasonally, higher values found during the summer. POC variability is controlled by a series of physical and biological factors. Evidence suggests that in the smaller tidal creeks, POC concentrations are associated with (1) rain events scouring the marsh surface, (2) phytoplankton concentrations varying as a function of tidal stage, and (3) removal of particulate material from the marsh surface on the ebb tide. In the larger tidal creeks tidal water velocity appears to be the main factor influencing POC values.