An experimental determination of chlorine isotope fractionation in acid systems and applications to volcanic fumaroles

The δ³⁷Cl values of volcanic fumarole gases and bubbling springs were measured from the Central American and the Kurile arcs. Low temperature gas samples from the Central American arc have δ³⁷Cl values generally between −2 and 2‰, whereas high-temperature fumaroles (>100 °C) range from 4 to 12‰, with several outliers. This is in contrast to the high-temperature fumaroles from the Kurile island Kudryavy which have slightly positive δ³⁷Cl values, averaging 0.8‰ (±0.6, 1σ), and from our previous work on Izu and Mariana arc samples in which the δ³⁷Cl values of fumarole and ash samples are similar to each other and negative. Assuming that the source for the high-T Central American fumaroles has typical subduction δ³⁷Cl values (−2.5 to 1‰), then there must be a large Cl isotope fractionation in the near-surface fumarolic system. The most likely fractionation mechanism for the high δ³⁷Cl values is between Cl⁻_aq − HCl(g), but published theoretical fractionation for this pair is only ∼1.5‰, insufficient to explain the large range of values observed in the fumaroles. Three experiments were undertaken in order to identify a process that could cause the wide range of δ³⁷Cl values observed in the high-temperature fumaroles. Results are the following: (1) A sub-boiling equilibration experiment between aqueous chloride and HCl gas had , in agreement with the theoretical calculations. (2) Evaporation of HCl(g) from hydrochloric acid at room temperature had fractionation in the opposite sense, with a . (3) A ‘synthetic fumarole’ gave large positive fractionations up to 9‰, with ³⁷Cl strongly partitioned into the vapor phase. The ‘fumarole’ experiments were made by bubbling dry air through boiling hydrochloric acid in an Erlenmeyer flask, and collecting the evolved HCl(g) in a second ‘downstream’ flask filled with distilled water. This extreme enrichment is likely due to a distillation process in which ³⁷Cl-enriched HCl(g) is stripped from the hydrochloric acid followed by a significant fraction of the light HCl(g) redissolving into the constantly condensing water vapor on the walls of the first flask. This distillation experiment creates a Cl isotope fractionation that is the same order of magnitude as observed in the high-temperature fumaroles in Central America. These results suggest that there must be a H₂O liquid-vapor region in the sub-surface fumarole conduit where light Cl is stripped from the HCl gas as it passes through the fumarole. Similar ³⁷Cl enrichments are expected in fossil epithermal boiling systems.     

Time-window-based filtering method for near-surface detection of leakage from geologic carbon sequestration sites

We use process-based modeling techniques to characterize the temporal features of natural biologically controlled surface CO₂ fluxes and the relationships between the assimilation and respiration fluxes. Based on these analyses, we develop a signal-enhancing technique that combines a novel time-window splitting scheme, a simple median filtering, and an appropriate scaling method to detect potential signals of leakage of CO₂ from geologic carbon sequestration sites from within datasets of net near-surface CO₂ flux measurements. The technique can be directly applied to measured data and does not require subjective gap filling or data-smoothing preprocessing. Preliminary application of the new method to flux measurements from a CO₂ shallow-release experiment appears promising for detecting a leakage signal relative to background variability. The leakage index of ±2 was found to span the range of biological variability for various ecosystems as determined by observing CO₂ flux data at various control sites for a number of years.     

Airborne remote sensing of cloud radiative smoothing during the Baltex Bridge Cloud campaign

Based on airborne observations during the Baltex Bridge Cloud (BBC) campaign in September 2001, the impact of two layer cloud systems, gas absorption and surface albedo on cloud radiative smoothing is investigated. Multispectral nadir radiance measurements have been conducted which cover the visible and near infrared wavelength range. The observed radiances are transformed into Fourier space where ranges of scale-invariance are identified. Associated slopes and scale breaks are determined and used to characterize the impacts on cloud radiative smoothing. The results reveal that an increase of gas absorption reduces the small scale slope and the scale break due to a decreasing likelihood of horizontal photon transport. Another impact is that the increasing gas absorption reduces the cloud surface interaction, which is indicated by an increase of the large scale slope. An increasing surface albedo results in large scale cloud radiative smoothing and is associated with a decrease of the large scale slope. This effect depends on the cloud height and the cloud morphology. Two layer cloud systems exhibit a similar behaviour in Fourier space as large surface albedos beneath a single cloud deck. It is argued that the impact of two layer cloud systems on large scale cloud radiative smoothing may not be typical for two layer clouds.     

How well can we simulate complex hydro‐geomorphic process chains? The 2012 multi‐lake outburst flood in the Santa Cruz Valley (Cordillera Blanca,Perú)

Changing high‐mountain environments are characterized by destabilizing ice, rock or debris slopes connected to evolving glacial lakes. Such configurations may lead to potentially devastating sequences of mass movements (process chains or cascades). Computer simulations are supposed to assist in anticipating the possible consequences of such phenomena in order to reduce the losses. The present study explores the potential of the novel computational tool r.avaflow for simulating complex process chains. r.avaflow employs an enhanced version of the Pudasaini ( 2012 ) general two‐phase mass flow model, allowing consideration of the interactions between solid and fluid components of the flow. We back‐calculate an event that occurred in 2012 when a landslide from a moraine slope triggered a multi‐lake outburst flood in the Artizón and Santa Cruz valleys, Cordillera Blanca, Peru, involving four lakes and a substantial amount of entrained debris along the path. The documented and reconstructed flow patterns are reproduced in a largely satisfactory way in the sense of empirical adequacy. However, small variations in the uncertain parameters can fundamentally influence the behaviour of the process chain through threshold effects and positive feedbacks. Forward simulations of possible future cascading events will rely on more comprehensive case and parameter studies, but particularly on the development of appropriate strategies for decision‐making based on uncertain simulation results. © 2017 The Authors. Earth Surface Processes and Landforms published by John Wiley & Sons Ltd.