Understanding the mechanisms of formation of nanophase compounds from Stardust: Combined experimental and observational approach

Abstract– We have experimentally produced nanophase sulfide compounds and magnetite embedded in Si‐rich amorphous materials by flash‐cooling of a gas stream. Similar assemblages are ubiquitous, and often dominant components of samples of impact‐processed silica aerogel tiles and submicron grains from comet 81P/Wild 2 were retrieved by NASA’s Stardust mission. Although the texture and compositions of nanosulfide compounds have been reproduced experimentally, the mechanisms of formation of these minerals and their relationship with the surrounding amorphous materials have not been established. In this study, we present evidence that both of these materials may not only be produced through cooling of a superheated liquid but they may have also been formed simultaneously by flash‐cooling and subsequent deposition of a gas dominated by Fe‐S‐SiO‐O₂. In a dust generator at the Goddard Space Flight Center, samples are produced by direct gas‐phase condensation from gaseous precursors followed by deposition, which effectively isolates the effects of gas‐phase reactions from the effects of melting and condensation. High‐resolution transmission electron microscopy images and energy‐dispersive spectroscopy analysis show that these experiments replicate key features of materials from type B and type C Stardust tracks, including textures, distribution of inclusions, nanophase size, and compositional diversity. We argue that gas‐phase reactions may have played a significant role in the capture environment for nanophase materials. Our results are consistent with a potential progenitor assemblage of micron and submicron‐sized sulfides and submicron silica‐bearing phases, which are commonly observed in chondritic interplanetary dust particles and in the matrices of the most pristine chondritic meteorites.     

Thermal contraction crack polygons on Mars: A synthesis from HiRISE, Phoenix, and terrestrial analog studies

Thermal contraction crack polygons are complex landforms that have begun to be deciphered on Earth and Mars by the combined investigative efforts of geomorphology, environmental monitoring, physical models, paleoclimate reconstruction, and geochemistry. Thermal contraction crack polygons are excellent indicators of the current or past presence of ground ice, ranging in ice content from weakly cemented soils to debris-covered massive ice. Relative to larger topographic features, polygons may form rapidly, and reflect climate conditions at the time of formation—preserving climate information as relict landforms in the geological record. Polygon morphology and internal textural characteristics can be used to distinguish surfaces modified by the seasonal presence of a wet active layer or dry active layer, and to delimit subsurface ice conditions. Analysis of martian polygon morphology and distribution indicates that geologically-recent thermal contraction crack polygons on Mars form predominantly in an ice-rich latitude-dependent mantle, more likely composed of massive ice deposited by precipitation than by cyclical vapor diffusion into regolith. Regional and local heterogeneities in polygon morphology can be used to distinguish variations in ice content, deposition and modification history, and to assess microclimate variation on timescales of ka to Ma. Analyses of martian polygon morphology, guided by investigations of terrestrial analog thermal contraction crack polygons, strongly suggest the importance of excess ice in the formation and development of many martian thermal contraction crack polygons—implying the presence of an ice-rich substrate that was fractured during and subsequent to obliquity-driven depositional periods and continually modified by ongoing vapor equilibration processes.     

A nutrient loading budget for Biscayne Bay, Florida

The water quality in Biscayne Bay has been significantly affected by past and continuing coastal and watershed development. The nutrient concentrations in the Bay have been dramatically changed by the conversion of natural creeks and sheet flow freshwater inputs to rapid and episodic canal inputs from the large and rapidly expanding Miami metropolitan area. This study is an evaluation of nutrient loadings to Biscayne Bay for 1994-2002 from canal, atmospheric, and groundwater sources. Dissolved inorganic nitrogen (DIN, as nitrate, nitrite, and ammonium) and total phosphorus (TP) loadings by the canals were influenced by their geographic locations relative to discharge amount, watershed land use, stormwater runoff, and proximity to landfills. Annual budgets showed that canals contributed the bulk of N loading to the bay as 1687.2 metric ton N yr(-1) (88% total load). Direct atmospheric DIN load for Biscayne Bay was only 231.7 ton N yr(-1), based on surface area. Of the canal DIN load, nitrate+nitrite (NO(x)(-)) loading (1294.5 ton N yr(-1)) made up a much greater proportion than that of ammonium (NH(4)(+), 392.6 ton N yr(-1)). In the urbanized north and central Bay, canal DIN load was evenly split between NO(x)(-) and NH(4)(+). However, in the south, 95% of the DIN load was in the form of NO(x)(-), reflecting the more agricultural land use. Contrary to N, canals contributed the only 66% of P load to the bay (27.5 ton P yr(-1)). Atmospheric TP load was 14 ton Pyr(-1). In the north, canal P load dominated the budget while in the south, atmospheric load was almost double canal load. Groundwater inputs, estimated only for the south Bay, represented an important source of N and P in this zone. Groundwater input of N (141 ton N yr(-1)) was about equal to atmospheric load, while P load (5.9 ton P yr(-1)) was about equal to canal load.     

Evolving metasomatic agent in the Northern Andean subduction zone, deduced from magma composition of the long-lived Pichincha volcanic complex (Ecuador)

Geochemical studies of long-lived volcanic complexes are crucial for the understanding of the nature and composition of the subduction component of arc magmatism. The Pichincha Volcanic Complex (Northern Andean Volcanic Zone) consists of: (1) an old, highly eroded edifice, the Rucu Pichincha, whose lavas are mostly andesites, erupted from 1,100 to 150 ka; and (2) a younger, essentially dacitic, Guagua Pichincha composite edifice, with three main construction phases (Basal Guagua Pichincha, Toaza, and Cristal) which developed over the last 60 ka. This structural evolution was accompanied by a progressive increase of most incompatible trace element abundances and ratios, as well as by a sharp decrease of fluid-mobile to fluid-immobile element ratios. Geochemical data indicate that fractional crystallization of an amphibole-rich cumulate may account for the evolution from the Guagua Pichincha andesites to dacites. However, in order to explain the transition between the Rucu Pichincha andesites and Guagua Pichincha dacites, the mineralogical and geochemical data indicate the predominance of magma mixing processes between a mafic, trace-element depleted, mantle-derived end-member, and a siliceous, trace-element enriched, adakitic end-member. The systematic variation of trace element abundances and ratios in primitive samples leads us to propose that the Rucu Pichincha magmas came from a hydrous-fluid metasomatized mantle wedge, whereas Guagua Pichincha magmas are related to partial melting of a siliceous-melt metasomatized mantle. This temporal evolution implies a change from dehydration to partial melting of the slab, which may be associated with an increase in the geothermal gradient along the slab due to the presence of the subducted Carnegie Ridge at the subduction system. This work emphasizes the importance of studying arc-magma systems over long periods of time (of at least 1 million of years), in order to evaluate the potential variations of the slab contribution into the mantle source of the arc magmatism.     

Meteoric Be in soil profiles - A global meta-analysis

In order to assess current understanding of meteoric ¹⁰Be dynamics and distribution in terrestrial soils, we assembled a database of all published meteoric ¹⁰Be soil depth profiles, including 104 profiles from 27 studies in globally diverse locations, collectively containing 679 individual measurements. This allows for the systematic comparison of meteoric ¹⁰Be concentration to other soil characteristics and the comparison of profile depth distributions between geologic settings. Percent clay, ⁹Be, and dithionite-citrate extracted Al positively correlate to meteoric ¹⁰Be in more than half of the soils where they were measured, but the lack of significant correlation in other soils suggests that no one soil factor controls meteoric ¹⁰Be distribution with depth. Dithionite-citrate extracted Fe and cation exchange capacity are only weakly correlated to meteoric ¹⁰Be. Percent organic carbon and pH are not significantly related to meteoric ¹⁰Be concentration when all data are complied.The compilation shows that meteoric ¹⁰Be concentration is seldom uniform with depth in a soil profile. In young or rapidly eroding soils, maximum meteoric ¹⁰Be concentrations are typically found in the uppermost 20 cm. In older, more slowly eroding soils, the highest meteoric ¹⁰Be concentrations are found at depth, usually between 50 and 200 cm. We find that the highest measured meteoric ¹⁰Be concentration in a soil profile is an important metric, as both the value and the depth of the maximum meteoric ¹⁰Be concentration correlate with the total measured meteoric ¹⁰Be inventory of the soil profile.In order to refine the use of meteoric ¹⁰Be as an estimator of soil erosion rate, we compare near-surface meteoric ¹⁰Be concentrations to total meteoric ¹⁰Be soil inventories. These trends are used to calibrate models of meteoric ¹⁰Be loss by soil erosion. Erosion rates calculated using this method vary based on the assumed depth and timing of erosional events and on the reference data selected.     

Holocene paleoenvironmental changes inferred from diatom assemblages in sediments of Kusawa Lake, Yukon Territory, Canada

The southwest Yukon Territory, Canada, is an important region for recovering sensitive records of Holocene paleoclimatic change. More information is needed, however, to constrain the timing of the major Holocene climatic transitions, and to understand associated impacts on different ecosystems. For example, paleolimnological studies have focused on small lakes and ponds, but the history of large lakes has received little study. We analyzed diatom assemblages, species richness, valve concentrations, and biogenic silica, in the sediments of Kusawa Lake (60°16.5'N; 136°10.9'W; 671 m a.s.l.) to reconstruct the responses of this large (surface area = 142 km²), deep (Z_max = 135 m) freshwater ecosystem to Holocene climatic transitions. Diatoms colonized the lake soon after ice retreat, around 11,000 cal yr BP; assemblages throughout the record were dominated by planktonic types. Diatom concentrations and biogenic silica were high during the Holocene Thermal Maximum between 10,700 and 7300 cal yr BP, then began to decrease in response to cooling associated with orbitally driven reductions in insolation. Diatom assemblages shifted towards taxa with lower surface water temperature optima after 8300 cal yr BP, perhaps in response to abrupt and progressive cooling. Our study confirms that diatom assemblages in large lakes are sensitive to regional-scale paleoclimatic changes.     

Rapid growth of an Archean continent by arc magmatism

The voluminous Meso- to Neoarchean rocks exposed in the Beartooth Mountains of the northern Wyoming Province of western North America comprise the Long Lake Magmatic Complex (LLMC), a variably metamorphosed and deformed association of igneous and meta-igneous plutonic rocks with SiO₂ ranging from at least 52 to 78 wt%. Within this compositional range, rock types include lineated amphibolites to hornblende-bearing gneisses of intermediate composition and multiple generations of foliated to unfoliated granitoids. Emplacement ages range between approximately 2.79 and 2.83 Ga, based on U–Pb zircon geochronology (SHRIMP). Field relations, elemental compositions, and geochronology indicate that these rocks do not represent a single fractional crystallization sequence, but rather, the LLMC was constructed by injection of numerous, discrete magmas as sill-like bodies over an ∼40 Ma period. Although there is a continuum of compositions in the LLMC, trace element abundances can be used to distinguish distinct sources and petrogenetic processes that can be broadly extrapolated to at least 3 compositional groupings: (1) trondhjemitic to granitic intrusive rocks with SiO₂ >70 wt%, (2) variably metamorphosed granodioritic orthogneisses with SiO₂ between 63 and 70 wt%, and (3) amphibole-bearing mafic to intermediate gneisses with SiO₂ between 52 and 63 wt%. Despite the range of SiO₂ contents, maximum LREE abundances are similar across the compositional range and, consequently, exhibit a wide range of (La/Yb)_n ratios (∼20–130). All LLMC rocks share a relative depletion in HFSE abundances similar to modern convergent margin magmas. Initial Sr and Nd isotopic compositions across the compositional range are consistently offset from typical bulk silicate earth (BSE) values and preclude unaltered derivation from primitive or depleted mantle. Common Pb isotopic data define a single array that lies above model crustal growth curves and, along with the Nd and Sr data, suggest relatively uniform interaction with, or derivation from, older lithosphere. The combined isotopic and elemental data suggest the LLMC resulted from simultaneous, rapid, and voluminous production of diverse magmas that represent melting of isotopically similar, but compositionally distinct, crustal and mantle sources. Dynamically, Meso- to Neo-archean crustal growth in the northern Wyoming Province appears to require an environment similar to a modern ocean–continent convergent margin with a comparable rate of crustal production and diversity of magma series. The resultant crust and associated mantle lithosphere (keel) appear to have suffered little-to-no modification prior to Laramide (Cretaceous) uplift and exposure.     

Aquifer Storage Recovery (ASR) of chlorinated municipal drinking water in a confined aquifer

About 1.02 × 10⁶ m³ of chlorinated municipal drinking water was injected into a confined aquifer, 94–137 m below Roseville, California, between December 2005 and April 2006. The water was stored in the aquifer for 438 days, and 2.64 × 10⁶ m³ of water were extracted between July 2007 and February 2008. On the basis of Cl⁻ data, 35% of the injected water was recovered and 65% of the injected water and associated disinfection by-products (DBPs) remained in the aquifer at the end of extraction. About 46.3 kg of total trihalomethanes (TTHM) entered the aquifer with the injected water and 37.6 kg of TTHM were extracted. As much as 44 kg of TTHMs remained in the aquifer at the end of extraction because of incomplete recovery of injected water and formation of THMs within the aquifer by reactions with free-chlorine in the injected water. Well-bore velocity log data collected from the Aquifer Storage Recovery (ASR) well show as much as 60% of the injected water entered the aquifer through a 9 m thick, high-permeability layer within the confined aquifer near the top of the screened interval. Model simulations of ground-water flow near the ASR well indicate that (1) aquifer heterogeneity allowed injected water to move rapidly through the aquifer to nearby monitoring wells, (2) aquifer heterogeneity caused injected water to move further than expected assuming uniform aquifer properties, and (3) physical clogging of high-permeability layers is the probable cause for the observed change in the distribution of borehole flow. Aquifer heterogeneity also enhanced mixing of native anoxic ground water with oxic injected water, promoting removal of THMs primarily through sorption. A 3 to 4-fold reduction in TTHM concentrations was observed in the furthest monitoring well 427 m downgradient from the ASR well, and similar magnitude reductions were observed in depth-dependent water samples collected from the upper part of the screened interval in the ASR well near the end of the extraction phase. Haloacetic acids (HAAs) were completely sorbed or degraded within 10 months of injection.     

Geochemical and mineralogical evidence for Sahara and Sahel dust additions to Quaternary soils on Lanzarote,eastern Canary Islands,Spain

Africa is the most important source of dust in the world today, and dust storms are frequent on the nearby Canary Islands. Previous workers have inferred that the Sahara is the most important source of dust to Canary Islands soils, with little contribution from the Sahel region. Soils overlying a late Quaternary basalt flow on Lanzarote, Canary Islands, contain, in addition to volcanic minerals, quartz and mica, exotic to the island’s bedrock. Kaolinite in the soils also likely has an exotic origin. Trace‐element geochemistry shows that the soils are derived from varying proportions of locally derived basalt and African dust. Major‐element geochemistry, clay mineralogy and interpretation of satellite imagery suggest that dust additions to the Canary Islands come not only from the Sahara Desert, but also from the Sahel region.     

Postaudit evaluation of conceptual model uncertainty for a glacial aquifer groundwater flow and contaminant transport model

Numerical groundwater flow and contaminant transport modeling incorporating three alternative conceptual models was conducted in 2005 to assess remedial actions and predict contaminant concentrations in an unconfined glacial aquifer located in Milford, Michigan, USA. Three alternative conceptual models were constructed and independently calibrated to evaluate uncertainty in the geometry of an aquitard underlying the aquifer and the extent to which infiltration from two manmade surface water bodies influenced the groundwater flow field. Contaminant transport for benzene, cis-DCE, and MTBE was modeled for a 5-year period that included a 2-year history match from July 2003 to May 2005 and predictions for a 3-year period ending in July 2008. A postaudit of model performance indicates that predictions for pumping wells, which integrated the transport signal across multiple model layers, were reliable but unable to differentiate between alternative conceptual model responses. In contrast, predictions for individual monitoring wells with limited screened intervals were less consistent, but held promise for evaluating alternative hydrogeologic models. Results of this study suggest that model conceptualization can have important practical implications for the delineation of contaminant transport pathways using monitoring wells, but may exert less influence on integrated predictions for pumping wells screened over multiple numerical model layers.