Response of suspended sediment particle size distributions to changes in water chemistry at an Andean mountain stream confluence receiving arsenic rich acid drainage

Acid drainage is an important water quality issue in Andean watersheds, affecting the sustainability of urban, agricultural, and industrial activities. Mixing zones receiving acid drainage are critical sites where changes in pH and chemical environment promote the formation and dissolution of iron and aluminum oxy/hydroxides. These particles can significantly change the speciation of toxic metals and metalloids throughout drainage networks via sorption, desorption, and settling processes. However, little is known about the behavior of particle size distributions (PSDs) in streams affected by acid drainage and their relationship to metal speciation. This work studied: (a) the PSDs for a wide range of mixing ratios found at a fluvial confluence affected by acid drainage, and (b) the response of PSDs and arsenic speciation to environmental changes found when the particles approach complete mixing conditions. The confluence between the Azufre River (pH ~ 2, high concentration of dissolved metals) and Caracarani River (pH = 8.6, low concentration of dissolved metals) was used as a representative model for study. Field measurements show a bimodal PSD with modal diameters of ~50 and 300 μm. At shorter distances from the junction, the smaller modes with smaller particle volumes were dominant across the stream cross‐sections. A systematic shift towards larger particle sizes and larger particle volumes occurred downstream. The analysis of laboratory PSDs for Azufre/Caracarani mixing ratios between 0.01 and 0.5 (pH from 6.2 to 2.3) showed a bimodal trend with ~15 and 50 μm characteristic diameters; larger particles formed at pH>4. When particle suspensions were transferred in laboratory experiments from very low pH to full mixing conditions (pH ~ 2.8 and mixing ratio ~ 0.25) particle sizes varied, and the dissolved arsenic concentration decreased. The observed reaction kinetics were slow compared to the time scale of advective transport, creating opportunities for engineered controls for arsenic. This work contributes to a better understanding of the chemical‐hydrodynamic interactions in watersheds affected by mining, and identifying opportunities to improve water quality at points of use.     

A GLUE‐based uncertainty assessment framework for tritium‐inferred transit time estimations under baseflow conditions

The last decade has seen major technical and scientific improvements in the study of water transfer time through catchments. Nevertheless, it has been argued that most of these developments used conservative tracers that may disregard the oldest component of water transfer, which often has transit times greater than 5 years. Indeed, although the analytical reproducibility of tracers limits the detection of the older flow components associated with the most dampened seasonal fluctuations, this is very rarely taken into account in modelling applications. Tritium is the only environmental tracer at hand to investigate transfer times in the 5‐ to 50‐year range in surface waters, as dissolved gases are not suitable due to the degassing process. Water dating with tritium has often been difficult because of the complex history of its atmospheric concentration, but its current stabilization together with recent analytical improvements open promising perspectives. In this context, the innovative contribution of this study lies in the development of a generalized likelihood uncertainty estimation‐based approach for analysing the uncertainties associated with the modelling of transit time due to both parameter identification and tracer analytical precision issues. A coupled resampling procedure allows assessment of the statistical significance of the transfer time differences found in diverse waters. This approach was developed for tritium and the exponential‐piston model but can be implemented for virtually any tracer and model. Stream baseflow, spring and shallow aquifer waters from the Vallcebre research catchments, analysed for tritium in different years with different analytical precisions, were investigated by using this approach and taking into account other sources of uncertainty. The results showed three groups of waters of different mean transit times, with all the stream baseflow and spring waters older than the 5‐year threshold needing tritium. Low sensitivity of the results to the model structure was also demonstrated. Dual solutions were found for the waters sampled in 2013, but these results may be disambiguated when additional analyses will be made in a few years. Copyright © 2016 John Wiley & Sons, Ltd.     

Using hydrogeochemical signatures of stream water to assess pathways for rainfall events: towards a predictive model

Thanks to its simple division into agricultural and forestry land use, the Corbeira catchment (Galicia, Spain) is used as a case study to build a predictive model using hydrogeochemical signatures. Stream data acquired under recessional flow conditions over a one year period were obtained from a sampling station near the downstream end of the catchment, and using principal component analysis, it is shown that some of the analytical parameters are covariant, and some are negatively correlated. These findings support inferences about the pathways of rainfall in the catchment. Specific signatures may be associated with the dominant hydrological source, either surface runoff or subsurface waters: additionally, the dominant land use in that part of the catchment, where the flow originated, can also be predicted. The dominant runoff shows a strong covariance between suspended solids (SS) and particulate phosphorus (PP), with a clear negative correlation with pH. Dissolved organic carbon (DOC) data are associated with this covariant set when these compounds are available in the soils in question. Dissolved phosphorus, total organic nitrogen and dissolved nitrates are also associated with the same covariant set when the runoff flows through areas of extensive agricultural use. The SS ? PP covariance is less significant at lower flows. Typical base flow regimes show a significant covariance between salinity and pH, with a marked negative correlation with SS ? PP set, confirming the dominance of subsurface waters in the baseflow, as expected. Seasonally divergent DOC ? SS behaviour proves to be a useful tracer for rainfall regimes. The DOC trend shows a sinusoidal annual variation in amplitude, determined by the rainfall regime. As a result, flow from the catchment is dominated by surface water whenever there is synchronicity between the peaks of DOC and SS. Copyright © 2013 John Wiley & Sons, Ltd.     

Bismuth‐melt trails trapped in cassiterite–quartz veins

Native bismuth in the form of metallic melt has been considered instrumental to the formation of some metallic ore deposits via a mechanism dubbed the “Liquid Bismuth Collector Model.” Here, we provide petrographical documentation of trail‐forming, μm‐sized blebs of native bismuth in cassiterite–quartz veins from the Santa Bárbara greisen Sn deposit in the Rondônia tin province of northern Brazil. These inclusions suggest the trapping of a Bi melt that took place during vein formation, in a mechanism similar to the entrapment of fluid inclusions.     

Metals discharged during different flow conditions from a mixed agricultural‐forest catchment (NW Spain)

Metal loads were determined from water samples collected under different streamflow conditions (baseflow and storm events) in a rural catchment (NW Spain) during 4 years. A study at annual, seasonal and storm‐event scales was carried out. In all analysed scales, the export order was Fe > Al > Mn > Zn > Cu. A high inter‐annual, seasonal and storm‐event scale variability of metal load was observed. The total metal loads in stream were higher during baseflow conditions than during storm events, which only represented 4% of the duration of the study period and 25% of streamflow. During storm events, both Al and Fe loads accounted 45% of the total load of the study period, whereas Mn, Cu and Zn loads represented 42%, 33% and 24%, respectively. This highlights the role of high flows on metal export. Only four big events exported around 30% of load of each metal transported in events. At all time scales, a prevalence of export of particulate metals over dissolved metals was observed, more pronounced for Al, Fe and Mn than for Cu and Zn. The export of metals in the Corbeira catchment is influenced by runoff and, to a lesser extent, by the rainfall amount. Copyright © 2014 John Wiley & Sons, Ltd.     

Exploring lava‐flow hazards at Pico Island,Azores Archipelago (Portugal)

Pico, the youngest island of the Azores Archipelago (Portugal), is characterized by a central volcano and a 30‐km‐long fissure zone. Its eruption rate is the highest of the Azores islands, with more than 35 eruptions in the last 2000 years. Here, we estimate the lava‐flow hazard for Pico Island by combining the vent opening probability derived from the spatial distribution of eruptive fissures, the classes of expected eruptions inferred from the physical and chemical characteristics of historical eruptions, and the lava‐flow paths simulated by the MAGFLOW model. The most likely area to host new eruptions is along a WNW–ESE trend centred on the central volcano, with the highest hazard affecting the two main residential zones of Lajes do Pico and Madalena. Our analysis is the first attempt to assess the lava‐flow hazard for Pico Island, and may have important implications for decision‐making in territorial management and future land‐use planning.     

Detecting the stepwise propagation of the Eastern Sicily thrust belt (Italy): insight from thermal and thermochronological constraints

An extensive dataset of vitrinite reflectance, FTIR parameters on organic matter, illite content in mixed layers illite‐smectite, apatite fission tracks and U‐Th/He dating has been used to reconstruct the stepwise propagation of the Eastern Sicily fold‐and‐thrust belt during Late Palaeogene and Neogene times. The results indicate that the fold‐and‐thrust belt is divisible into two levels of thermal maturity. These levels consist of a less evolved level of thermal maturity that records limited sedimentary burial and minor heating, and a more evolved level of thermal maturity that indicates tectonic burial and exhumation at different times. Deformation and exhumation of shallowly buried units are linked to wedge forward propagation by low‐angle thrusts, whereas the evolution of deeply buried units is associated with tectonic imbrications by duplex formation and steep thrusts. The two tectonic styles alternate during evolution of the fold‐and‐thrust belt under low erosion rates.