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.     

A reconstruction of the palaeohydrological conditions of a flood‐plain: a multi‐proxy study from the Grabia River valley mire,central Poland

This study investigated the Grabia River valley mire in central Poland to reconstruct its palaeoenvironmental conditions from the Younger Dryas to the present. We analysed sedimentological, biological and geochemical data from the palaeo‐oxbow lake and valley mire to identify the principal hydrological trends, especially episodes of high water level. During the Lateglacial and Holocene, the Grabia River had a meandering channel, and its hydraulic parameters and the channel dimensions changed in response to climatic oscillations and vegetation development. We identified phases of high flood intensity and high groundwater level that correlate with regional and supraregional climatic events. The frequency and timing of palaeohydroclimatic oscillations show strong similarities to records from other sites in Poland and the rest of Europe. We show that various analytical methods, namely, pollen, plant macrofossils, Cladocera, Chironomidae, sedimentological, geochemical and radiocarbon data, can be effective tools for reconstructing past hydroclimatic changes in palaeo‐oxbow lakes and investigating the effects of past climate changes on river environments. The high sensitivity of the biota, especially Cladocera, to changes in water level permits the reconstruction of palaeoecological changes, especially flood episodes that occurred in the river valley. In particular, the increase in the proportion of sediment‐associated Cladocera and pelagic taxa was closely correlated with floods. Through comparisons with the palaeobiological data, geochemical data allowed the identification of humid phases within the fen associated with a rising groundwater table, direct fluvial activity (floods) and alluvial deposition. We also discuss the limitations of palaeohydrological reconstructions based on these proxies, especially on fossil aquatic invertebrates.     

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.     

Root‐related rhodochrosite and concretionary siderite formation in oxygen‐deficient conditions induced by a ground‐water table rise

Sedimentological, mineralogical, stable carbon and oxygen isotope determinations and biomarker analyses were performed on siderite concretions occurring in terrestrial silts to understand their formation and to characterize the sedimentary and diagenetic conditions favouring their growth. High δ¹³C values (6·4‰ on average) indicate that siderite precipitated in an anoxic environment where bacterial methanogenesis operated. The development of anoxic conditions during shallow burial was induced by a change in sedimentary environment from flood plain to swamp, related to a rise of the ground‐water table. Large amounts of decaying plant debris led to efficient oxygen consumption within the pore‐water in the peat. Oxygen depletion, in combination with a decrease in sedimentation rate, promoted anoxic diagenetic conditions under the swamp and favoured abundant siderite precipitation. This shows how a change in sedimentary conditions can have a profound impact on the early‐diagenetic environment and carbonate authigenesis. The concretions contain numerous rhizoliths; they are cemented with calcium‐rhodochrosite, a feature which has not been reported before. The rhodochrosite cement has negative δ¹³C values (?16·5‰ on average) and precipitated in suboxic conditions due to microbial degradation of roots coupled to manganese reduction. The exceptional preservation of the epidermis/exodermis and xylem vessels of former root tissues indicates that the rhodochrosite formed shortly after the death of a root in water‐logged sediments. Rhodochrosite precipitated during the initial stages of concretionary growth in suboxic microenvironments within roots, while siderite cementation occurred simultaneously around them in anoxic conditions. These suboxic microenvironments developed because oxygen was transported from the overlying oxygenated soil into sediments saturated with anoxic water via roots acting as permeable conduits. This model explains how separate generations of carbonate cements having different mineralogy and isotopic compositions, which would conventionally be regarded as cements precipitated sequentially in different diagenetic zones during gradual burial, can form simultaneously in shallow burial settings where strong redox gradients exist around vertically oriented permeable root structures.     

In situ high-temperature X-ray diffraction and spectroscopic study of fibroferrite,FeOH(SO<Subscript>4</Subscript>)·5H<Subscript>2</Subscript>O

The thermal dehydration process of fibroferrite, FeOH(SO₄)·5H₂O, a secondary iron-bearing hydrous sulfate, was investigated by in situ high-temperature synchrotron X-ray powder diffraction (HT-XRPD), in situ high-temperature Fourier transform infrared spectroscopy (HT-FTIR) and thermal analysis (TGA-DTA) combined with evolved gas mass spectrometry. The data analysis allowed the determination of the stability fields and the reaction paths for this mineral as well as characterization of its high-temperature products. Five main endothermic peaks are observed in the DTA curve collected from room T up to 800 °C. Mass spectrometry of gases evolved during thermogravimetric analysis confirms that the first four mass loss steps are due to water emission, while the fifth is due to a dehydroxylation process; the final step is due to the decomposition of the remaining sulfate ion. The temperature behavior of the different phases occurring during the heating process was analyzed, and the induced structural changes are discussed. In particular, the crystal structure of a new phase, FeOH(SO₄)·4H₂O, appearing at about 80 °C due to release of one interstitial H₂O molecule, was solved by ab initio real-space and reciprocal-space methods. This study contributes to further understanding of the dehydration mechanism and thermal stability of secondary sulfate minerals.