From geometry to dynamics of microstructure: using boundary lengths to quantify boundary misorientations and anisotropy

The microstructure of a quartzite experimentally deformed and partially recrystallised at 900 °C, 1.2 GPa confining pressure and strain rate 10⁻⁶/s was investigated using orientation contrast and electron backscatter diffraction (EBSD). Boundaries between misoriented domains (grains or subgrains) were determined by image analysis of orientation contrast images. In each domain, EBSD measurements gave the complete quartz lattice orientation and enabled calculation of misorientation angles across every domain boundary. Results are analysed in terms of the boundary density, which for any range of misorientations is the boundary length for that range divided by image area. This allows a more direct comparison of misorientation statistics between different parts of a sample than does a treatment in terms of boundary number.The strain in the quartzite sample is heterogeneous. A 100×150 μm low-strain partially recrystallised subarea C was compared with a high-strain completely recrystallised subarea E. The density of high-angle (>10°) boundaries in E is roughly double that in C, reflecting the greater degree of recrystallisation. Low-angle boundaries in C and E are produced by subgrain rotation. In the low-angle range 0–10° boundary densities in both C and E show an exponential decrease with increasing misorientation. The densities scale with exp(−θ/λ) where λ is approximately 2° in C and 1° in E; in other words, E has a comparative dearth of boundaries in the 8–10° range. We explain this dearth in terms of mobile high-angle boundaries sweeping through and consuming low-angle boundaries as the latter increase misorientation through time. In E, the density of high-angle boundaries is larger than in C, so this sweeping would have been more efficient and could explain the relative paucity of 8–10° boundaries.The boundary density can be generalised to a directional property that gives the degree of anisotropy of the boundary network and its preferred orientation. Despite the imposed strain, the analysed samples show that boundaries are not, on average, strongly aligned. This is a function of the strong sinuosity of high-angle boundaries, caused by grain boundary migration. Low-angle boundaries might be expected, on average, to be aligned in relation to imposed strain but this is not found.Boundary densities and their generalisation in terms of directional properties provide objective measures of microstructure. In this study the patterns they show are interpreted in terms of combined subgrain rotation and migration recrystallisation, but it may be that other microstructural processes give distinctive patterns when analysed in this fashion.     

Multicomponent magnetization in western Dolpo (Tethyan Himalaya, Nepal): tectonic implications

A palaeomagnetic study has been carried out in the Tethyan Himalaya (TH; the northern margin of Greater India). Twenty-six palaeomagnetic sites have been sampled in Triassic low-grade metasediments of western Dolpo. Two remanent components have been identified. A pyrrhotite component, characterized by unblocking temperatures of 270–335 °C, yields an in situ mean direction of D=191.7°, I=−30.9° (k=29.5, α₉₅=5.7°, N=23 sites). The component fails the fold test at the 99% confidence level (k_{in situ}/k_bed=6.9) and is therefore of postfolding origin. For reason of the low metamorphic grade, this pyrrhotite magnetization is believed to be of thermo-chemical origin. Geochronological data and inclination matching indicate an acquisition age around 35 Ma. The second remanence component has higher unblocking temperatures (>400 °C and up to 500–580 °C range) and resides in magnetite. A positive fold test and comparison with expected Triassic palaeomagnetic directions suggest a primary origin.The postfolding character of the pyrrhotite component, and its interpreted age of remanence acquisition, implies that the main Himalayan folding is older than 35 Ma in the western Dolpo area. This study also suggests that the second metamorphic event (Neo-Himalayan) was more significant in the Dolpo area than the first (Eo-Himalayan) one.A clockwise rotation of 10–15° is inferred from the pyrrhotite component, which is compatible with oroclinal bending and/or rotational underthrusting models. This rotation is also supported by the magnetite component, indicating that no rotation of the Tethyan Himalaya relative to India took place before 35 Ma.     

Identification of ore extraction and metal working in ancient times: a case study of Sagalassos (SW Turkey)

The extensive territory of the ancient (Hellenistic to Byzantine) city of Sagalassos (SW Turkey) offered a rich variety in natural mineral resources. The frequent occurrence of iron slag in the excavations at the site proved the local working of metal. A geochemical prospection campaign was done in the territory of the ancient city in order to identify or discard the city and its territory as a self-sustaining metallurgical centre. Secondly, the geochemical impact of ancient metallurgy was investigated. Geochemical anomalies identified in stream sediments are explained by the presence of mineralised deposits and ancient metal working. Mg, Cr, Co and Ni anomalies point to chromite and chrysotile-magnetite deposits related to the basic rocks of the Lycian nappes in the area. Fe, V and Ti anomalies indicate the presence of iron mineralisations, which have been worked for iron production in ancient times. Finally, the association of P, Cu, Pb, Mn, As and Ag anomalies are an indicator of human activity at archaeological sites. Within the framework of this geochemical prospection, a metal working site apart from the city of Sagalassos was identified. Here, ore was both extracted and processed to workable iron.     

Ion microprobe measurements of O/O ratios of phosphate minerals in the Martian meteorites ALH84001 and Los Angeles

Oxygen isotope ratios of merrillite and chlorapatite in the Martian meteorites ALH84001 and Los Angeles have been measured by ion microprobe in multicollector mode. δ¹⁸O values of phosphate minerals measured in situ range from ∼3 to 6‰, and are similar to Martian meteorite whole-rock values, as well as the δ¹⁸O of igneous phosphate on Earth. These results suggest that the primary, abiotic, igneous phosphate reservoir on Mars is similar in oxygen isotopic composition to the basaltic phosphate reservoir on Earth. This is an important first step in the characterization of Martian phosphate reservoirs for the use of δ¹⁸O of phosphate minerals as a biomarker for life on Mars. Cumulative textural, major-element, and isotopic evidence presented here suggest a primary, igneous origin for the phosphates in Los Angeles and ALH84001; textural and chemical evidence suggests that phosphates in ALH84001 were subsequently shock-melted in a later event.     

Desorption kinetics of radiocesium from subsurface sediments at Hanford Site, USA

The desorption of ¹³⁷Cs⁺ was investigated on sediments from the United States Hanford site. Pristine sediments and ones that were contaminated by the accidental release of alkaline ¹³⁷Cs⁺-containing high level nuclear wastes (HLW, 2 × 10⁶ to 6 × 10⁷ pCi ¹³⁷Cs⁺/g) were studied. The desorption of ¹³⁷Cs⁺ was measured in Na⁺, K⁺, Rb⁺, and NH₄⁺electrolytes of variable concentration and pH, and in presence of a strong Cs⁺-specific sorbent (self-assembled monolayer on a mesoporous support, SAMMS). ¹³⁷Cs⁺ desorption from the HLW-contaminated Hanford sediments exhibited two distinct phases: an initial instantaneous release followed by a slow kinetic process. The extent of ¹³⁷Cs⁺ desorption increased with increasing electrolyte concentration and followed a trend of Rb⁺ ≥ K⁺ > Na⁺ at circumneutral pH. This trend followed the respective selectivities of these cations for the sediment. The extent and rate of ¹³⁷Cs⁺ desorption was influenced by surface armoring, intraparticle diffusion, and the collapse of edge-interlayer sites in solutions containing K⁺, Rb⁺, or NH₄⁺. Scanning electron microscopic analysis revealed HLW-induced precipitation of secondary aluminosilicates on the edges and basal planes of micaceous minerals that were primary Cs⁺ sorbents. The removal of these precipitates by acidified ammonium oxalate extraction significantly increased the long-term desorption rate and extent. X-ray microprobe analyses of Cs⁺-sorbed micas showed that the ¹³⁷Cs⁺ distributed not only on mica edges, but also within internal channels parallel to the basal plane, implying intraparticle diffusive migration of ¹³⁷Cs⁺. Controlled desorption experiments using Cs⁺-spiked pristine sediment indicated that the ¹³⁷Cs⁺ diffusion rate was fast in Na⁺-electrolyte, but much slower in the presence of K⁺ or Rb⁺, suggesting an effect of edge-interlayer collapse. An intraparticle diffusion model coupled with a two-site cation exchange model was used to interpret the experimental results. Model simulations suggested that about 40% of total sorbed ¹³⁷Cs⁺ was exchangeable, including equilibrium and kinetic desorbable pools. At pH 3, this ratio increased to 60-80%. The remainder of the sorbed ¹³⁷Cs⁺ was fixed or desorbed at much slower rate than our experiments could detect.     

The origin of organic matter in the solar system: evidence from the interplanetary dust particles

The detailed examination of meteorites and interplanetary dust particles provides an opportunity to infer the origin of the organic matter found in primitive Solar System materials. If this organic matter were produced by aqueous alteration of elemental (graphitic or amorphous) carbon on an asteroid, then we would expect to see the organic matter occurring preferentially in interplanetary materials that exhibit evidence of aqueous activity, such as the presence of hydrated silicates. On the other hand, if the organic matter were produced either during the nebula phase of Solar System evolution or in the interstellar medium, we might expect this organic matter to be incorporated into the dust as it formed. In that case pre-biotic organic matter would be present in both the anhydrous and the hydrated interplanetary materials. We have performed carbon X-ray absorption near-edge structure spectroscopy and infrared spectroscopy on primitive anhydrous and hydrated interplanetary dust particles (IDPs) collected by NASA from the Earth's stratosphere. We find that organic matter is present in similar types and abundances in both the anhydrous and the hydrated IDPs, and, in the anhydrous IDPs some of this organic matter is the “glue” that holds grains together. These measurements provide the first direct, experimental evidence from the comparison of extraterrestrial samples that the bulk of the pre-biotic organic matter occurs in similar types and abundances in both hydrated and anhydrous samples. This indicates that the bulk of the pre-biotic organic matter in the Solar System did not form by aqueous processing, but, instead, had already formed at the time that primitive, anhydrous dust was being assembled. Thus, the bulk of the pre-biotic organic matter in the Solar System was formed by non-aqueous processing, occurring in either the Solar nebula or in an interstellar environment. Aqueous processing on asteroids may have altered this pre-existing organic matter, but such processing did not affect in any substantial way the C=O content of the organic matter, the aliphatic C-H abundance, or the mean aliphatic chain length.     

Determination of food web support and trophic position of the mummichog,Fundulus heteroclitus, in New Jersey smooth cordgrass (Spartina alterniflora), common reed (Phragmites australis), and restored salt marshes

The invasion ofPhragmites australis into tidal marshes formerly dominated bySpartina alterniflora has resulted in considerable interest in the consequences of this invasion for the ecological functions of marsh habitat. We examined the provision of trophic support for a resident marsh fish,Fundulus heteroclitus, in marshes dominated byP. australis, byS. alterniflora, and in restored marshes, using multiple stable isotope analysis. We first evaluated our ability to distinguish among potential primary producers using the multiple stable isotope approach. Within a tidal creek system we found significant marsh and elevation effects on microalgal isotope values, and sufficient variability and overlap in primary producer isotope values to create some difficulty in identifying unique end members. The food webs supportingF. heteroclitus production were examined using dual isotope plots. At both sites, the δ¹³C values ofF. heteroclitus were clustered over values for benthic microalgae (BMI) and approximately midway between δ¹³C values ofSpartina andPhragmites. Based on comparisons of fish and primary producer δ¹³C, δ¹⁵N, and δ³⁴S values, and consideration ofF. heteroclitus feeding habits, we conclude that BMI were a significant component of the food web supportingF. heteroclitus in these brackish marshes, especially recently-hatched fish occupying pools on the marsh surface. A 2‰ difference in δ¹³C betweenFundulus occupying nearly adjacentSpartina andPhragmites marshes may be indicative of relatively less reliance on BMI and greater reliance onPhragmites production inPhragmites-dominated marshes, a conclusion consistent with the reduced BMI biomass found inPhragmites marshes. The mean δ¹³C value ofF. heteroclitus from restored marshes was intermediate between values of fish from naturally occurringSpartina marshes and areas invaded byPhragmites. We also examined the isotopic evidence for ontogenetic changes in the trophic position of larval and juvenileF. heteroclitus. We found significant positive relationships betweenF. heteroclitus δ¹⁵N values and total length, reflective of an increase in trophic position as fish grow.F. heteroclitus δ¹⁵N values indicate that these fish are feeding approximately two trophic levels above primary producers.     

Deconvolving the δO seawater component from subseasonal coral δO and Sr/Ca at Rarotonga in the southwestern subtropical Pacific for the period 1726 to 1997

To reconstruct oceanographic variations in the subtropical South Pacific, 271-year long subseasonal time series of Sr/Ca and δ¹⁸O were generated from a coral growing at Rarotonga (21.5°S, 159.5°W). In this case, coral Sr/Ca appears to be an excellent proxy for sea surface temperature (SST) and coral δ¹⁸O is a function of both SST and seawater δ¹⁸O composition (δ¹⁸O_sw). Here, we focus on extracting the δ¹⁸O_sw signal from these proxy records. A method is presented assuming that coral Sr/Ca is solely a function of SST and that coral δ¹⁸O is a function of both SST and δ¹⁸O_sw. This method separates the effects of δ¹⁸O_sw from SST by breaking the instantaneous changes of coral δ¹⁸O into separate contributions by instantaneous SST and δ¹⁸O_sw changes, respectively. The results show that on average δ¹⁸O_sw at Rarotonga explains ∼39% of the variance in δ¹⁸O and that variations in SST explains the remaining ∼61% of δ¹⁸O variance. Reconstructed δ¹⁸O_sw shows systematic increases in summer months (December-February) consistent with the regional pattern of variations in precipitation and evaporation. The δ¹⁸O_sw also shows a positive linear correlation with satellite-derived estimated salinity for the period 1980 to 1997 (r = 0.72). This linear correlation between reconstructed δ¹⁸O_sw and salinity makes it possible to use the reconstructed δ¹⁸O_sw to estimate the past interannual and decadal salinity changes in this region. Comparisons of coral δ¹⁸O and δ¹⁸O_sw at Rarotonga with the Pacific decadal oscillation index suggest that the decadal and interdecadal salinity and SST variability at Rarotonga appears to be related to basin-scale decadal variability in the Pacific.     

A method for precise measurement of argon 40/36 and krypton/argon ratios in trapped air in polar ice with applications to past firn thickness and abrupt climate change in Greenland and at Siple Dome, Antarctica

We describe a method for measuring the ⁴⁰Ar/³⁶Ar ratio and the ⁸⁴Kr/³⁶Ar ratio in air from bubbles trapped in ice cores. These ratios can provide constraints on the past thickness of the firn layer at the ice core site and on the magnitude of past rapid temperature variations when combined with measured ¹⁵N/¹⁴N. Both variables contribute to paleoclimatic studies and ultimately to the understanding of the controls on Earth’s climate. The overall precision of the ⁴⁰Ar/³⁶Ar method (1 standard error of the mean) is 0.012‰ for a sample analyzed in duplicate, corresponding to ±0.6 m in reconstructed firn thickness. We use conventional dynamic isotope ratio mass spectrometry with minor modifications and special gas handling techniques designed to avoid fractionation. About 100 g of ice is used for a duplicate pair of analyses. An example of the technique applied to the GISP2 ice core yields an estimate of 11 ± 3K of abrupt warming at the end of the last glacial period 15,000 years ago. The krypton/argon ratio can provide a diagnostic of argon leakage out of the bubbles, which may happen (naturally) during bubble close-off or (artifactually) if samples are warmed near the freezing point during core retrieval or storage. Argon leakage may fractionate the remaining ⁴⁰Ar/³⁶Ar ratio by +0.007‰ per ‰ change in ⁸⁴Kr/³⁶Ar, introducing a possible bias in reconstructed firn thickness of about +2 m if thermal diffusion is not accounted for or +6 m if thermal diffusion effects are quantified with measured ¹⁵N/¹⁴N. Reproducibility of ⁸⁴Kr/³⁶Ar measured in air is about ±0.2‰ (1 standard error of the mean) but is about ±1‰ for ice core samples. Ice core samples are systematically enriched in ⁸⁴Kr/³⁶Ar relative to atmosphere by ∼5‰, probably reflecting preferential size-dependent exclusion of the smaller argon atom during bubble entrapment. Recent results from the Siple Dome ice core reveal two climate events during the last deglaciation, including an 18-m reduction in firn thickness associated with an abrupt warming at sometime between 18 and 22 kyr BP and a partial or total removal of the firn during an ablation event at 15.3 kyr BP.