Intercomparison of soil pore water extraction methods for stable isotope analysis and interpretation of hillslope runoff sources

Intercomparison of soil pore water extraction methods for stable isotope analysis has been a focus of recent studies in relation to plant source waters, which found a wide isotopic variance depending on the extraction method. Few studies have yet explored extraction effects for mobile pore waters that relate to hillslope runoff. This is because it is extremely difficult in natural systems to control the boundary conditions in order to assess and compare impacts of pore water extraction on resulting hillslope flow. With our new semicontrolled experiments on outdoor mini‐hillslopes, we studied mixing and runoff processes by means of stable isotopes of water and quantified relations between pore water extraction methods. We tested the null hypothesis that nondestructive and destructive pore water sampling methods sample the same soil water pool. Three hillslopes were mounted on load cells, filled with loamy sand textured soils from the Landscape Evolution Observatoryat Biosphere 2, equipped with soil moisture and temperature sensors, a bottom outflow, and a surface runoff gauge for isotope sampling. We followed the precipitation isotopic composition over and through the soil profile. One hillslope was instrumented with suction cups, on the second we installed sampling ports for in‐situ soil water vapour measurements, and the third hillslope was sampled destructively for applying the centrifugation and vapour equilibrium methods. All hillslopes were sampled at four depths (0–10, 10–20, 20–30, and 30–40 cm) at three different downslope positions. ²H and ¹⁸O analyses were performed via laser spectroscopy. We found no isotopic differences between rainfall, surface runoff, and bottom outflow. The in situ vapour ports' soil isotope data showed the widest spread over all hillslope positions and depths. Centrifugation's and suction cups' isotope results plotted closest to the local meteoric water line and within the range of hillslope runoff and bottom outflow data. Hillslope position did not influence the soil isotope results. These results suggest caution be used in the field when selecting an extraction technique for matching soil waters to runoff waters. Soil suction lysimeters and centrifugation appeared to be the most appropriate tools in this regard.     

Tree water deficit and dynamic source water partitioning

The stable isotopes of hydrogen and oxygen (δ²H and δ¹⁸O, respectively) have been widely used to investigate tree water source partitioning. These tracers have shed new light on patterns of tree water use in time and space. However, there are several limiting factors to this methodology (e.g., the difficult assessment of isotope fractionation in trees, and the labor-intensity associated with the collection of significant sample sizes) and the use of isotopes alone has not been enough to provide a mechanistic understanding of source water partitioning. Here, we combine isotope data in xylem and soil water with measurements of tree's physiological information including tree water deficit (TWD), fine root distribution, and soil matric potential, to investigate the mechanism driving tree water source partitioning. We used a 2 m³ lysimeter with willow trees (Salix viminalis) planted within, to conduct a high spatial–temporal resolution experiment. TWD provided an integrated response of plant water status to water supply and demand. The combined isotopic and TWD measurement showed that short-term variation (within days) in source water partitioning is determined mainly by plant hydraulic response to changes in soil matric potential. We observed changes in the relationship between soil matric potential and TWD that are matched by shifts in source water partitioning. Our results show that tree water use is a dynamic process on the time scale of days. These findings demonstrate tree's plasticity to water supply over days can be identified with high-resolution measurements of plant water status. Our results further support that root distribution alone is not an indicator of water uptake dynamics. Overall, we show that combining physiological measurements with traditional isotope tracing can reveal mechanistic insights into plant responses to changing environmental conditions.     

In situ record of sedimentary processes near the Rhône River mouth during winter events (Gulf of Lions,Mediterranean Sea)

The environment is impacted by natural and anthropogenic disturbances that occur at different spatial and temporal scales, and that lead to major changes and even disequilibria when exceeding the resiliency capacities of the ecosystem. With an annual mean flow of 1700 m³ s⁻¹, the Rhône River is the largest of the western Mediterranean basin. Its annual solid discharges vary between 2 and 20 Mt, with flood events responsible for more than 70% of these amounts.     

Sulfur isotope signatures in gypsiferous sediments of the Estancia and Tularosa Basins as indicators of sulfate sources, hydrological processes, and microbial activity

In order to reconstruct paleo-environmental conditions for the saline playa lakes of the Rio Grande Rift, we investigated sediment sulfate sources using sulfur isotope compositions of dissolved ions in modern surface water, groundwater, and precipitated in the form of gypsum sediments deposited during the Pleistocene and Holocene in the Tularosa and Estancia Basins. The major sulfate sources are Lower and Middle Permian marine evaporites (δ³⁴S of 10.9-14.4‰), but the diverse physiography of the Tularosa Basin led to a complex drainage system which contributed sulfates from various sources depending on the climate at the time of sedimentation. As inferred from sulfur isotope mass balance constraints, weathering of sulfides of magmatic/hydrothermal and sedimentary origin associated with climate oscillations during Last Glacial Maximum contributed about 35-50% of the sulfates and led to deposition of gypsum with δ³⁴S values of −1.2‰ to 2.2‰ which are substantially lower than Permian evaporates. In the Estancia Basin, microbial sulfate reduction appears to overprint sulfur isotopic signatures that might elucidate past groundwater flows. A Rayleigh distillation model indicates that about 3-18% of sulfates from an inorganic groundwater pool (δ³⁴S of 12.6-13.8‰) have been metabolized by bacteria and preserved as partially to fully reduced sulfur-bearing minerals species (elemental sulfur, monosulfides, disulfides) with distinctly negative δ³⁴S values (−42.3‰ to −20.3‰) compared to co-existing gypsum (−3.8‰ to 22.4‰). For the Tularosa Basin microbial sulfate reduction had negligible effect on δ³⁴S value of the gypsiferous sediments most likely because of higher annual temperatures (15-33 °C) and lower organic carbon content (median 0.09%) in those sediments leading to more efficient oxidation of H₂S and/or smaller rates of sulfate reduction compared to the saline playas of the Estancia Basin (5-28 °C; median 0.46% of organic carbon).The White Sands region of the Tularosa Basin is frequently posited as a hydrothermal analogue for Mars. High temperatures of groundwater (33.3 °C) and high δ¹⁸O(H₂O) values (1.1‰) in White Sands, however, are controlled predominantly by seasonal evaporation rather than the modern influx of hydrothermal fluids. Nevertheless, it is possible that some of the geochemical processes in White Sands, such as sulfide weathering during climate oscillations and upwelling of highly mineralized waters, might be considered as valid terrestrial analogues for the sulfate cycle in places such as Meridiani Planum on Mars.     

Oxygen isotope evidence for sorption of molecular oxygen to pyrite surface sites and incorporation into sulfate in oxidation experiments

Experiments were conducted to investigate (i) the rate of O-isotope exchange between SO₄ and water molecules at low pH and surface temperatures typical for conditions of acid mine drainage (AMD) and (ii) the O- and S-isotope composition of sulfates produced by pyrite oxidation under closed and open conditions (limited and free access of atmospheric O₂) to identify the O source/s in sulfide oxidation (water or atmospheric molecular O₂) and to better understand the pyrite oxidation pathway. An O-isotope exchange between SO₄ and water was observed over a pH range of 0–2 only at 50 °C, whereas no exchange occurred at lower temperatures over a period of 8 a. The calculated half-time of the exchange rate for 50 °C (pH = 0 and 1) is in good agreement with former experimental data for higher and lower temperatures and excludes the possibility of isotope exchange for typical AMD conditions (T  25 °C, pH  3) for decades.Pyrite oxidation experiments revealed two dependencies of the O-isotope composition of dissolved sulfates: O-isotope values decreased with longer duration of experiments and increasing grain size of pyrite. Both changes are interpreted as evidence for chemisorption of molecular O₂ to pyrite surface sites. The sorption of molecular O₂ is important at initial oxidation stages and more abundant in finer grained pyrite fractions and leads to its incorporation in the produced SO₄. The calculated bulk contribution of atmospheric O₂ in the dissolved SO₄ reached up to 50% during initial oxidation stages (first 5 days, pH 2, fine-grained pyrite fraction) and decreased to less than 20% after about 100 days. Based on the direct incorporation of molecular O₂ in the early-formed sulfates, chemisorption and electron transfer of molecular O₂ on S sites of the pyrite surface are proposed, in addition to chemisorption on Fe sites. After about 10 days, the O of all newly-formed sulfates originates only from water, indicating direct interaction of hydroxyls from water with S at the anodic S pyrite surface site. Then, the role of molecular O₂ is as proposed in previous studies: acting as electron acceptor only at the cathodic Fe pyrite surface site for oxidation of Fe(II) to Fe(III).     

Composition and origin of stromatactis‐bearing mud‐mounds (Upper Devonian,Frasnian), southern Rocky Mountains,western Canada

Stromatactis‐bearing mud‐mounds remain an enigmatic reef type despite being common in Palaeozoic ramp settings. Two well preserved Upper Devonian (Frasnian) mud‐mounds in the Mount Hawk Formation crop out side by side in the southern Rocky Mountains of west‐central Alberta and provide an opportunity to develop a new case study that can be compared with the other coeval examples, such as those well‐known ones in southern Belgium, as well as evaluate competing hypotheses for mud‐mound formation. The southern mud‐mound is 46·2 m thick and 38·6 m wide at the base, whilst the northern one is 53·3 m thick and 72·2 m wide at the base, and they exhibit three or four growth stages indicated by interfingering and onlapping geometries with flanking strata. The biota is diverse, but fossils only occupy 10·7% by volume, among which sponge spicules, echinoderms, ostracods, brachiopods and calcimicrobes belonging to Girvanella and Rothpletzella are the most common. Five microfacies are discriminated in the mud‐mounds: biomicrite, clotted micrite, spiculite, stromatolite and laminite, with clotted micrite comprising the largest proportion. There is no internal vertical or lateral palaeoecological zonation, and the presence of calcimicrobes and calcareous algae throughout indicates accretion entirely within the photic zone, in a deeper ramp setting seaward of a large carbonate platform to the east. Stromatactis is abundant and the cavities were mostly due to excavation by currents rather than physical collapse of spiculate siliceous sponges. Formation of lime mud involved a combination of multiple organisms, mechanisms and processes. Cyanobacteria were integral to mud‐mound frame‐building and accretion because they stabilized the surface, often permineralized to form Girvanella and provided organic matter that was decomposed by bacteria. This induced precipitation of micrite, forming early indurated rigid masses, evidenced by the presence of intraclasts, stromatactis cavities, isopachous marine cements, absence of bioturbation and rare synsedimentary brittle deformation. The same microbial components, invertebrate biota and clotted micrite occur in underlying strata, suggesting that there was a protracted period of potential mud‐mound initiation before the exact conditions arose to trigger it. The ramp setting, antecedent sea floor topography and relative sea‐level likely contributed together to control this. This study indicates that mud‐mound formation was controlled by a combination of processes, but they are essentially a microbial buildup.     

Gibbsite solubility and thermodynamic properties of hydroxy-aluminum ions in aqueous solution at 25°C

Solubility curves were determined for a synthetic gibbsite and a natural gibbsite (Minas Gerais, Brazil) from pH 4 to 9, in 0.2% gibbsite suspensions in 0.01 M NaNO₃ that were buffered by low concentrations of non-complexing buffer agents. Equilibrium solubility was approached from oversaturation (in suspensions spiked with Al(NO₃)₃ solution), and also from undersaturation in some synthetic gibbsite suspensions. Mononuclear Al ion concentrations and pH values were periodically determined. Within 1 month or less, data from over-and undersaturated suspensions of synthetic gibbsite converged to describe an equilibrium solubility curve. A downward shift of the solubility curve, beginning at pH 6.7, indicates that a phase more stable than gibbsite controls Al solubility in alkaline systems. Extrapolation of the initial portion of the high-pH side of the synthetic gibbsite solubility curve provides the first unified equilibrium experimental model of Al ion speciation in waters from pH 4 to 9.The significant mononuclear ion species at equilibrium with gibbsite are Al³⁺, AlOH²⁺, Al(OH)⁺₂ and Al(OH)^?₄, and their ion activity products are $\text{1K}{}_{50}\text{= 1.29 × 10}{}^8$, $\text{1K}{}_{\mathrm{s1}}\text{= 1.33 × 10}{}^3$, $\text{1K}{}_{\mathrm{s2}}\text{= 9.49 × 10}{}^{\mathrm{?3}}$ and $\text{1K}{}_{\mathrm{s4}}\text{= 8.94 × 10}{}^{\mathrm{?15}}$. The calculated standard Gibbs free energies of formation (ΔG°_f) for the synthetic gibbsite and the A1OH²⁺, Al(OH)⁺₂ and Al(OH)^?₄ ions are ?276.0, ?166.9, ?216.5 and ?313.5 kcal mol^?1, respectively. These ΔG°_f values are based on the recently revised ΔG°_f value for Al³⁺ (?117.0 ± 0.3 kcal mol_?1) and carry the same uncertainty. The ΔG°_f of the natural gibbsite is ?275.1 ± 0.4 kcal mol^?, which suggests that a range of ΔG°_f values can exist even for relatively simple natural minerals.     

Regional landslide risk to the Cairns community

A GIS-based regional reconnaissance-level assessment of landslide risk to the Cairns community has been carried out to provide information to the Cairns City Council for planning and emergency management purposes. Magnitude recurrence relations were tentatively established for the two main slope processes: landslides on the hill slopes; and large debris flows extending out from the gully systems on to the plains. From the recurrence relations, landslide hazard (H) was estimated as the annual probability of a point being impacted by a landslide. The nature, number (E) and geographic distribution of the elements at risk were obtained by interrogating the GIS, and their vulnerabilities (V) to destruction by the two main landslide slope processes were assessed. From this information, specific risk (= H × V) and total risk (= H × V× E) maps were produced.Although total landslide risk is relatively low at present, it will increase as development extends further into the hill slopes, unless adequate mitigation measures are taken. Large debris flows, while considerably less frequent than landslides on cut slopes, could impact on subdivisions at the base of the slopes. Blockage by landslides of roads and railways providing access to Cairns can cause isolation of the community. Flash flooding in Freshwater Creek, or debris flows, have the potential to disrupt the Cairns water supply by blocking the intake or destroying sections of the pipeline.