Sulfur Concentration in Geochemical Reference Materials by Solution Inductively Coupled Plasma‐Mass Spectrometry

With implications for the origin of ore deposits, redox state of the atmosphere, and effects of volcanic outgassing, understanding the sulfur cycle is vital to our investigation of Earth processes. However, the paucity of sulfur concentration measurements in silicate rocks and the lack of well‐calibrated reference materials with concentrations relevant to the rocks of interest have hindered such investigations. To aid in this endeavour, this study details a new method to determine sulfur concentration via high mass resolution solution inductively coupled plasma‐mass spectrometry (ICP‐MS). The method is based on an aqua regia leach, involving relatively rapid sample preparation and analysis, and uses small test portion masses (< 50 mg). We utilised two independently prepared standard solutions to calibrate the analyses, resulting in 4% accuracy, and applied the method to eight geochemical reference materials. Measurements were reproducible to within ~ 10%. Sulfur concentrations and isotopes of six reference materials were measured additionally by elemental analyser‐combustion‐isotope ratio mass spectrometry to independently evaluate the accuracy of the ICP‐MS method. Reference materials that yielded reproducible measurements identical to published values from other laboratories (JGb‐1, JGb‐2 and MAG‐1) are considered useful materials for the measurement of sulfur. Reference materials that varied between studies but were reproducible for a given test portion perhaps suffer from sample heterogeneity and are not recommended as sulfur reference materials.     

A modification of freeze-core technology for collecting granular fluvial sediment samples

The presence of coarse-grained sediment can potentially reduce the effectiveness of conventional sampling methods in recovering fluvial sediments. A modification to freeze-core technology was used to collect fine to coarse sands, silts, and clays in fluvial deposits that contain significant amounts of gravels, cobbles, and boulders for the purpose of characterizing the extent of heavy metal contamination. This modification uses either a 2.5 or 2.9 cm diameter by 30-cm- long finned mechanical or hand-driven samplers. The sediment is frozen to the outside of the sampler by injecting liquid CO₂ into the sampler. The fins protect the sample from coarse material upon removal. Field testing and laboratory testing of the method were completed to establish a methodology and assess possible cross contamination of the sediment layers during the driving of the sampler. The results indicated that this method is effective for recovering non-cohesive sediment samples at depths up to 6 m for the purpose of characterizing the extent of heavy metal contamination.     

Deciphering petrogenic processes using Pb isotope ratios from time-series samples at Bezymianny and Klyuchevskoy volcanoes,Central Kamchatka Depression

The Klyuchevskoy group of volcanoes in the Kamchatka arc erupts compositionally diverse magmas (high-Mg basalts to dacites) over small spatial scales. New high-precision Pb isotope data from modern juvenile (1956–present) erupted products and hosted enclaves and xenoliths from Bezymianny volcano reveal that Bezymianny and Klyuchevskoy volcanoes, separated by only 9 km, undergo varying degrees of crustal processing through independent crustal columns. Lead isotope compositions of Klyuchevskoy basalts–basaltic andesites are more radiogenic than Bezymianny andesites (²⁰⁸Pb/²⁰⁴Pb = 37.850–37.903, ²⁰⁷Pb/²⁰⁴Pb = 15.468–15.480, and ²⁰⁶Pb/²⁰⁴Pb = 18.249–18.278 at Bezymianny; ²⁰⁸Pb/²⁰⁴Pb = 37.907–37.949, ²⁰⁷Pb/²⁰⁴Pb = 15.478–15.487, and ²⁰⁶Pb/²⁰⁴Pb = 18.289–18.305 at Klyuchevskoy). A mid-crustal xenolith with a crystallization pressure of 5.2 ± 0.6 kbars inferred from two-pyroxene geobarometry and basaltic andesite enclaves from Bezymianny record less radiogenic Pb isotope compositions than their host magmas. Hence, assimilation of such lithologies in the middle or lower crust can explain the Pb isotope data in Bezymianny andesites, although a component of magma mixing with less radiogenic mafic recharge magmas and possible mantle heterogeneity cannot be excluded. Lead isotope compositions for the Klyuchevskoy Group are less radiogenic than other arc segments (Karymsky—Eastern Volcanic Zone; Shiveluch—Northern Central Kamchatka Depression), which indicate increased lower-crustal assimilation beneath the Klyuchevskoy Group. Decadal timescale Pb isotope variations at Klyuchevskoy demonstrate rapid changes in the magnitude of assimilation at a volcanic center. Lead isotope data coupled with trace element data reflect the influence of crustal processes on magma compositions even in thin mafic volcanic arcs.     

Contrasting geochemical signatures on land from the Middle and Late Permian extinction events

The end of the Palaeozoic is marked by two mass‐extinction events during the Middle Permian (Capitanian) and the Late Permian (Changhsingian). Given similarities between the two events in geochemical signatures, such as large magnitude negative δ¹³C anomalies, sedimentological signatures such as claystone breccias, and the approximate contemporaneous emplacement of large igneous provinces, many authors have sought a common causal mechanism. Here, a new high‐resolution continental record of the Capitanian event from Portal Mountain, Antarctica, is compared with previously published Changhsingian records of geochemical signatures of weathering intensity and palaeoclimatic change. Geochemical means of discriminating sedimentary provenance (Ti/Al, U/Th and La/Ce ratios) all indicate a common provenance for the Portal Mountain sediments and associated palaeosols, so changes spanning the Capitanian extinction represent changes in weathering intensity rather than sediment source. Proxies for weathering intensity chemical index of alteration, ?W and rare earth element accumulation all decline across the Capitanian extinction event at Portal Mountain, which is in contrast to the increased weathering recorded globally at the Late Permian extinction. Furthermore, palaeoclimatic proxies are consistent with unchanging or cooler climatic conditions throughout the Capitanian event, which contrasts with Changhsingian records that all indicate a significant syn‐extinction and post‐extinction series of greenhouse warming events. Although both the Capitanian and Changhsingian event records indicate significant redox shifts, palaeosol geochemistry of the Changhsingian event indicates more reducing conditions, whereas the new Capitanian record of reduced trace metal abundances (Cr, Cu, Ni and Ce) indicates more oxidizing conditions. Taken together, the differences in weathering intensity, redox and the lack of evidence for significant climatic change in the new record suggest that the Capitanian mass extinction was not triggered by dyke injection of coal‐beds, as in the Changhsingian extinction, and may instead have been triggered directly by the Emeishan large igneous province or by the interaction of Emeishan basalts with platform carbonates.     

Scales and causes of heterogeneity in bars in a large multi‐channel river: Río Paraná, Argentina

To date, published studies of alluvial bar architecture in large rivers have been restricted mostly to case studies of individual bars and single locations. Relatively little is known about how the depositional processes and sedimentary architecture of kilometre‐scale bars vary within a multi‐kilometre reach or over several hundreds of kilometres downstream. This study presents Ground Penetrating Radar and core data from 11, kilometre‐scale bars from the Río Paraná, Argentina. The investigated bars are located between 30 km upstream and 540 km downstream of the Río Paraná – Río Paraguay confluence, where a significant volume of fine‐grained suspended sediment is introduced into the network. Bar‐scale cross‐stratified sets, with lengths and widths up to 600 m and thicknesses up to 12 m, enable the distinction of large river deposits from stacked deposits of smaller rivers, but are only present in half the surface area of the bars. Up to 90% of bar‐scale sets are found on top of finer‐grained ripple‐laminated bar‐trough deposits. Bar‐scale sets make up as much as 58% of the volume of the deposits in small, incipient mid‐channel bars, but this proportion decreases significantly with increasing age and size of the bars. Contrary to what might be expected, a significant proportion of the sedimentary structures found in the Río Paraná is similar in scale to those found in much smaller rivers. In other words, large river deposits are not always characterized by big structures that allow a simple interpretation of river scale. However, the large scale of the depositional units in big rivers causes small‐scale structures, such as ripple sets, to be grouped into thicker cosets, which indicate river scale even when no obvious large‐scale sets are present. The results also show that the composition of bars differs between the studied reaches upstream and downstream of the confluence with the Río Paraguay. Relative to other controls on downstream fining, the tributary input of fine‐grained suspended material from the Río Paraguay causes a marked change in the composition of the bar deposits. Compared to the upstream reaches, the sedimentary architecture of the downstream reaches in the top ca 5 m of mid‐channel bars shows: (i) an increase in the abundance and thickness (up to metre‐scale) of laterally extensive (hundreds of metres) fine‐grained layers; (ii) an increase in the percentage of deposits comprised of ripple sets (to >40% in the upper bar deposits); and (iii) an increase in bar‐trough deposits and a corresponding decrease in bar‐scale cross‐strata (<10%). The thalweg deposits of the Río Paraná are composed of dune sets, even directly downstream from the Río Paraguay where the upper channel deposits are dominantly fine‐grained. Thus, the change in sedimentary facies due to a tributary point‐source of fine‐grained sediment is primarily expressed in the composition of the upper bar deposits.     

Pullout Response of Uniaxial Geogrid in Tire Shred–Sand Mixtures

Use of tire shred–soil mixtures as backfill materials in mechanically stabilized earth walls has several advantages over other backfill materials: (1) good drainage, (2) high shear strength, and (3) low compacted unit weight. This paper presents the results of laboratory pullout tests performed on uniaxial geogrid embedded in tire shred–sand mixtures. The effects of tire shred size, tire shred–sand mixing ratio and confining pressure on the interaction between the geogrid and tire shred–sand mixtures are evaluated. Three sizes of tire shreds are considered: tire chips (with 9.5 mm nominal size), tire shreds 50-to-100 mm long and tire shreds 100-to-200 mm in length, with mixing ratios of 0, 12, 25 and 100 % of tire shreds in the mixtures (by weight). Based on compaction testing of a number of mixtures, the optimal mixing proportion of tire shreds and sand was found to lie between 25/75 and 30/70 (by weight of tire shred and sand); this is equivalent to approximately 40/60 and 50/50, respectively, by volume of tire shreds and sand. The pullout resistance of a geogrid embedded in tire shred–sand mixtures is significantly higher than that of the same geogrid embedded in tire shreds only. The size of the tire shreds has negligible effect on the pullout resistance of a geogrid embedded in mixtures prepared with either low (12/88 mix) or high (100/0 mix) tire shred content. However, when the 25/75 mixture is used, greater geogrid pullout resistance was obtained for the geogrid embedded in tire chip–sand mixtures than in tire shred–sand mixtures.     

Mineral inclusions in fibrous diamonds: constraints on cratonic mantle refertilization and diamond formation

We analyzed mineral microinclusions in fibrous diamonds from the Wawa metaconglomerate (Superior craton) and Diavik kimberlites (Slave craton) and compared them with published compositions of large mineral inclusions in non-fibrous diamonds from these localities. The comparison, together with similar datasets available for Ekati and Koffiefontein kimberlites, suggest a general pattern of metasomatic alteration imposed on the ambient mantle by formation of fibrous diamond. Calcium and Fe enrichment of peridotitic garnet and pyroxenes and Fe enrichment of olivine associated with fibrous diamond-forming fluids contributes to refertilization of the cratonic mantle. Saline—carbonatitic—silicic fluid trapped by fibrous diamonds may represent one of the elusive agents of mantle refertilization. Calcium enrichment of peridotitic garnet and pyroxenes is expected in local mantle segments during fibrous diamond production, as Ca in the carbonatitic fluids is deposited into the surrounding mantle when oxidized carbon is reduced to diamond. Harzburgitic garnet evolves towards Ca-rich compositions even when it interacts with Ca-poor saline fluids. An unusual trend of Mg enrichment to Fo_95–98 is observed in some olivine inclusions in Wawa fibrous diamonds. The trend may result from the carbonatitic composition of the fluid that promotes crystallization of magnesian olivine and preferentially oxidizes the fayalite component. We propose a generic model of fibrous and non-fibrous diamond formation from carbonatitic fluids that explains enrichment of the mantle in mafic magmaphile and incompatible elements and accounts for locally metasomatized compositions of diamond inclusions.     

Graded-Density Reservoirs for Accessing High Stress Low Temperature Material States

In recently developed laser-driven shockless compression experiments an ablatively driven shock in a primary target is transformed into a ramp compression wave in a secondary target via unloading followed by stagnation across an intermediate vacuum gap. Current limitations on the achievable peak longitudinal stresses are limited by the ability of shaping the temporal profile of the ramp compression pulse. We report on new techniques using graded density reservoirs for shaping the loading profile and extending these techniques to high peak pressures.