The redox states of basic and silicic magmas: a reflection of their source regions?

At present the best estimates of the oxygen fugacity of spinel-lherzolites that could be the source material of basic magmas is about five log units below the Ni–NiO buffer to one above it. However partially glassy basic lavas, ranging from MORBs to minettes, all with olivine on their liquidus, cover a wider range, and may have oxygen fugacities that extend to four log units above NNO. Surprisingly the range of oxygen fugacities observed in silicic lavas and ashflows with quartz phenocrysts is smaller, despite a crustal dominated evolution. The peralkaline silicic lava type pantellerite is the most reduced, equivalent to MORBs, whereas the large volume ashflows with phenocrysts of hornblende and/or sphene are the most oxidised. As the concentration of water in the basic lavas is correlated with increase in their redox state, it would seem that water could be the agent of this increase. That this is unlikely is seen in the behavior of silicic ashflows and lavas, particularly those of Yellowstone. Here the silicic magmas of the last 2Ma contain about 2 wt% FeO_(total), and typically phenocrysts of fayalite, quartz and Fe–Ti oxides. Despite extensive exchange of the ¹⁸O of the magma with meteoric water after caldera collapse (Hildreth et al. 1984), there is no displacement of the redox equilibria. Thus the thermal dissociation of molecular H₂O to H₂, and its subsequent diffusive loss to cause oxidation must have been minimal. This could only be so if the activity of water was small, as it would be if H₂O reacted with the silicate liquid to form OH groups (Stolper 1982). The conclusion is that silicic magmas with small amounts of iron and large amounts of water do not have their redox states reset, which in turn presumably reflect their generation. By analogy basic magmas with large amounts of iron and far less water are even less likely to have their redox equilibria disturbed, so that their oxygen fugacities will also reflect their source regions. The effect of pressure on the ferric-ferrous equilibrium in basic magmas can be calculated from experimental measurements of the partial molar volumes of FeO and Fe₂O₃, and their pressure derivatives V/P, in silicate liquids. The effect of pressure is found to be about the same on the liquid as it is for various solid oxygen buffers. Accordingly there should be mantle source regions covering the same range of oxygen fugacity as that found in basic lavas, but so far samples of spinel-lherzolite of equivalent oxygen fugacity to minettes or other potassic lavas have not been found. Whether or not the redox state of phlogopite-pyroxenites is equivalent to these potassic lavas cannot be established without experiment.     

Quaternary minettes and associated volcanic rocks of Mascota,western Mexico: a consequence of plate extension above a subduction modified mantle wedge

 Pleistocene-Holocene volcanism in the Jalisco block of western Mexico is confined to two conspicuous grabens, where potassic eruptives range from absarokites (48–52% SiO₂) and minettes (49–54% SiO₂) through basaltic andesites (53–57% SiO₂), the most voluminous type, to andesites and their lamprophyric equivalent spessartite (58–62% SiO₂); there are no contemporary rhyolitic rocks. This suite has high concentrations of Mg, Cr (<550 ppm) and Ni (<450 ppm) accompanied by large concentrations of K, P, Ba (<4000 ppm) and Sr (<5000 ppm) and elements such as LREE and Zr (<600 ppm). No combination of crystal fractionation and/or crustal contamination can reproduce the compositional range of these magmas, which nevertheless are believed to be genetically related because of their proximity in time and space. Hydrous minerals in the lamprophyres and the typical absence of plagioclase phenocrysts in both basaltic andesites and andesites reflect the relatively high concentrations of water in the magmas, which suppressed the crystallisation of feldspar. Experimental verification of the minimal amounts of water required to reproduce the phenocryst assemblages in selected rocks range from 3.5 to 6%. During ascent in a volcanic conduit, andesitic magma may lose water and consequently precipitate plagioclase, or it may ascend more rapidly, retaining more of its initial water, which stabilises phenocrysts of hornblende at the expense of plagioclase. Our estimates of water concentrations, which are consistent with the various low pressure phenocryst assemblages, will be minimal for the magmas in their source regions, and the process of magmatic dewatering on ascent may be typical in well established volcanic conduits. In accord with the compositions of phenocrystic olivine in the basaltic andesites and the minettes, the values of FeO and Fe₂O₃ of the bulk lavas and scoriae are demonstrably pristine. As a consequence, there are two characteristic features of the Mascota suite: the high range of relative oxygen fugacities (ΔNNO=1–5) and the high Mg# (MgO/MgO+FeO) that ranges from 0.70 to 0.91 (with only one andesite as low as 0.66). From the evidence of phlogopite phenocrysts, a partial melt involving phlogopite would have a higher Mg# than one from olivine (Fo₉₀) and pyroxene alone. As the Mascota series shows a correlation between K₂O and Mg#, we conclude that it was generated by partial fusion of the mantle wedge, with a variable contribution of phlogopite and apatite from veins throughout the lherzolitic assemblage. In conformity with an origin by varying increments of partial fusion of a phlogopite-bearing mantle, all incompatible elements vary linearly with Ti (or K) as if phlogopite (+apatite) in the source dominated their contribution to the partial melts. Fluids from dehydration of the subducting slab presumably deposit hydrous and other minerals in veins in the mantle wedge and also increase its redox state. As the Mascota volcanism occurs in grabens closer to the trench than the main andesite arc, it is concluded that the eruption of these small volumes of hydrous magmas require the tectonically favored ascent paths offered by the extensional grabens to reach the surface from their mantle sources. Received: 24 January 1995 / Accepted: 21 February 1996     

Water source dynamics of high Arctic river basins

Arctic river basins are amongst the most vulnerable to climate change. However, there is currently limited knowledge of the hydrological processes that govern flow dynamics in Arctic river basins. We address this research gap using natural hydrochemical and isotopic tracers to identify water sources that contributed to runoff in river basins spanning a gradient of glacierization (0–61%) in Svalbard during summer 2010 and 2011. Spatially distinct hydrological processes operating over diurnal, weekly and seasonal timescales were characterized by river hydrochemistry and isotopic composition. Two conceptual water sources (‘meltwater’ and ‘groundwater’) were identified and used as a basis for end‐member mixing analyses to assess seasonal and year‐to‐year variability in water source dynamics. In glacier‐fed rivers, meltwater dominated flows at all sites (typically >80%) with the highest contributions observed at the beginning of each study period in early July when snow cover was most extensive. Rivers in non‐glacierized basins were sourced initially from snowmelt but became increasingly dependent on groundwater inputs (up to 100% of total flow volume) by late summer. These hydrological changes were attributed to the depletion of snowpacks and enhanced soil water storage capacity as the active layer expanded throughout each melt season. These findings provide insight into the processes that underpin water source dynamics in Arctic river systems and potential future changes in Arctic hydrology that might be expected under a changing climate. Copyright © 2013 John Wiley & Sons, Ltd.     

Long‐term streamflow trends in Hawai'i and implications for native stream fauna

Climate change has fundamentally altered the water cycle in tropical islands, which is a critical driver of freshwater ecosystems. To examine how changes in streamflow regime have impacted habitat quality for native migratory aquatic species, we present a 50‐year (1967–2016) analysis of hydrologic records in 23 unregulated streams across the five largest Hawaiian Islands. For each stream, flow was separated into direct run‐off and baseflow and high‐ and low‐flow statistics (i.e., Q10 and Q90) with ecologically important hydrologic indices (e.g., frequency of flooding and low flow duration) derived. Using Mann–Kendall tests with a running trend analysis, we determined the persistence of streamflow trends through time. We analysed native stream fauna from ~400 sites, sampled from 1992 to 2007, to assess species richness among islands and streams. Declines in streamflow metrics indicated a general drying across the islands. In particular, significant declines in low flow conditions (baseflows), were experienced in 57% of streams, compared with a significant decline in storm flow conditions for 22% of streams. The running trend analysis indicated that many of the significant downward trends were not persistent through time but were only significant if recent decades (1987–2016) were included, with an average decline in baseflow and run‐off of 10.90% and 8.28% per decade, respectively. Streams that supported higher native species diversity were associated with moderate discharge and baseflow index, short duration of low flows, and negligible downward trends in flow. A significant decline in dry season flows (May–October) has led to an increase in the number of no‐flow days in drier areas, indicating that more streams may become intermittent, which has important implications for mauka to makai (mountain to ocean) hydrological connectivity and management of Hawai'i's native migratory freshwater fauna.     

Development of large‐scale seismites in Upper Cretaceous fluvial sandstones in a fault‐proximal setting

Large‐scale soft‐sediment deformation structures occur within fluvial sandstone bodies of the Upper Cretaceous Wahweap Formation in the Kaiparowits basin, southern Utah, USA. These structures represent an exceptional example of metre‐scale fault‐proximal, seismogenic load structures in nearly homogenous sandstones. The load structures consist of two types: large‐scale load casts and wedge‐shaped load structures. Large‐scale load casts penetrate up to 4·5 m into the underlying sandstone bed. Wedge‐shaped load structures include metre‐scale, parallel, sub‐vertical features and decimetre‐scale features along the periphery of the large‐scale load casts or other wedge‐shaped load structures. Wedge‐shaped load structures contain well‐developed, medial cataclastic shear deformation bands. All load structures contain pervasive well‐defined millimetre‐thick to centimetre‐thick internal laminae, oriented parallel to the outside form of the load structures and asymptotic to deformation bands. Both types of load structures formed because of an inverted density profile, earthquake‐triggered liquefaction and growth of irregularities (a Rayleigh–Taylor instability) on the sandstone–sandstone erosional contact. The internal laminae and deformation bands formed during deformation and clearly demonstrate polyphase deformation, recording a transition from liquefied to hydroplastic to brittle modes of deformation. Decimetre‐scale wedge‐shaped load structures on the edge of the large‐scale load casts probably formed towards the end of a seismic event after the sediment dewatered and increased the frictional contact of grains enough to impart strength to the sands. Metre‐scale wedge‐shaped load structures were created as the tips of downward foundering sediments were driven into fractures, which widened incrementally with seismic pulsation. With each widening of the fracture, gravity and a suction effect would draw additional sediment into the fracture. Superimposed laminae indicate a secondary syndeformational origin for internal laminae, probably by flow‐generated shearing and vibrofluidization mechanisms. Large‐scale and wedge‐shaped load structures, polyphase deformation and secondary laminae may characterize soft‐sediment deformation in certain fault‐proximal settings.     

Policy options to streamline the carbon market for agricultural nitrous oxide emissions

The majority of emissions of nitrous oxide – a potent greenhouse gas (GHG) – are from agricultural sources, particularly nitrogen fertilizer applications. A growing focus on these emission sources has led to the development in the United States of GHG offset protocols that could enable payment to farmers for reducing fertilizer use or implementing other nitrogen management strategies. Despite the development of several protocols, the current regional scope is narrow, adoption by farmers is low, and policy implementation of protocols has a significant time lag. Here we utilize existing research and policy structures to propose an ‘umbrella’ approach for nitrogen management GHG emissions protocols that has the potential to streamline the policy implementation and acceptance of such protocols. We suggest that the umbrella protocol could set forth standard definitions common across multiple protocol options, and then modules could be further developed as scientific evidence advances. Modules could be developed for specific crops, regions, and practices. We identify a policy process that could facilitate this development in concert with emerging scientific research and conclude by acknowledging potential benefits and limitations of the approach.

Key policy insights

• Agricultural greenhouse gas market options are growing, but are still underutilized

• Streamlining protocol development through an umbrella process could enable quicker development of protocols across new crops, regions, and practices

• Effective protocol development must not compromise best available science and should follow a rigorous pathway to ensure appropriate implementation

     

Molecular distribution, 13C‐isotope,and enantiomeric compositions of carbonaceous chondrite monocarboxylic acids

The water‐soluble organic compounds in carbonaceous chondrite meteorites constitute a record of the synthetic reactions occurring at the birth of the solar system and those taking place during parent body alteration and may have been important for the later origins and development of life on Earth. In this present work, we have developed a novel methodology for the simultaneous analysis of the molecular distribution, compound‐specific δ¹³C, and enantiomeric compositions of aliphatic monocarboxylic acids (MCA) extracted from the hot‐water extracts of 16 carbonaceous chondrites from CM, CR, CO, CV, and CK groups. We observed high concentrations of meteoritic MCAs, with total carbon weight percentages which in some cases approached those of carbonates and insoluble organic matter. Moreover, we found that the concentration of MCAs in CR chondrites is higher than in the other meteorite groups, with acetic acid exhibiting the highest concentration in all samples. The abundance of MCAs decreased with increasing molecular weight and with increasing aqueous and/or thermal alteration experienced by the meteorite sample. The δ¹³C isotopic values of MCAs ranged from ?52 to +27‰, and aside from an inverse relationship between δ¹³C value and carbon straight‐chain length for C₃–C₆ MCAs in Murchison, the ¹³C‐isotopic values did not correlate with the number of carbon atoms per molecule. We also observed racemic compositions of 2‐methylbutanoic acid in CM and CR chondrites. We used this novel analytical protocol and collective data to shed new light on the prebiotic origins of chondritic MCAs.     

Effect of polychromatic X‐ray microtomography imaging on the amino acid content of the Murchison CM chondrite

X‐ray microcomputed tomography (μCT) is a useful means of characterizing cosmochemical samples such as meteorites or robotically returned samples. However, there are occasional concerns that the use of μCT may be detrimental to the organic components of a chondrite. Small organic compounds such as amino acids comprise up to ~10% of the total solvent extractable carbon in CM carbonaceous chondrites. We irradiated three samples of the Murchison CM carbonaceous chondrite under conditions akin to and harsher than those typically used during typical benchtop X‐ray μCT imaging experiments to determine if detectable changes in the amino acid abundance and distribution relative to a nonexposed Murchison control sample occurred. After subjecting three meteorite samples to ionizing radiation dosages between ~300 Gray (Gy) and 3 kGy with bremstrahlung X‐rays, we analyzed the amino acid content of each sample. Within sampling and analytical errors, we cannot discern differences in the amino acid abundances and amino acid enantiomeric ratios when comparing the control samples (nonexposed Murchison) and the irradiated samples. We conclude that a polychromatic X‐ray μCT experiment does not alter the abundances of amino acids to a degree greater than how well those abundances are measured with our techniques and therefore any damage to amino acids is minimal.     

Cartograms for Use in Forecasting Weather-Driven Natural Hazards

This paper evaluates the potential of using cartograms for visualizing and interpreting forecasts of weather-driven natural hazards in the context of global weather forecasting and early warning systems. The use of cartograms is intended to supplement traditional cartographic representations of the hazards in order to highlight the severity of an upcoming event. Cartogrammetric transformations are applied to forecasts of floods, heatwaves, windstorms and snowstorms taken from the European Centre for Medium-range Weather Forecasts (ECMWF) forecast archive. Key cartogram design principles in standard weather forecast visualization are tested. Optimal cartogram transformation is found to be dependent on geographical features (such as coastlines) and forecast features (such as snowstorm intensity). For highly spatially autocorrelated weather variables used in analysing several upcoming natural hazards such as 2m temperature anomaly, the visualization of the distortion provides a promising addition to standard forecast visualizations for highlighting upcoming weather-driven natural hazards.     

The spawning and early life-history of a New Zealand endemic amphidromous eleotrid,bluegill bully (Gobiomorphus hubbsi)

The larval stage of fishes is critical in determining their dispersal, survival and recruitment, but little is known of the larval behaviours and tolerances of amphidromous fishes, particularly in New Zealand. We report the results of a series of observational and experimental studies on bluegill bully (Gobiomorphus hubbsi), including spawning sites and behaviours, larval characteristics at hatch, phototactic responses of larvae, and larval survival at different salinity levels. Spawning primarily occurred in the lower reaches of the river, and larvae from different nests exhibited marked differences in, and trade-offs between, larval characteristics at hatch, potentially affecting larval success. Larvae were positively phototactic to intense light, an unexpected result based on diel drift patterns and international research. Finally, larvae exhibited markedly higher survival rates when reared at intermediate salinities compared to freshwater or seawater, suggesting estuaries may play an important role as nursery grounds for bluegill bully and other amphidromous fish.