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.     

A comparison of early juvenile red drum densities among various habitat types in Galveston Bay, Texas

Seagrass meadows are often cited as important nursery areas for newly settled red drum even though many estuaries, such as Galveston Bay, Texas, support large numbers of red drum and have limited seagrass cover, suggesting the use of alternate nursery areas. We examined patterns of habitat use for newly settled red drum at six sampling areas in Galveston Bay; two areas had seagrass beds and four areas had no seagrass. We measured densities in different habitat types using epibenthic sleds and enclosure samplers. Peak recruitment of young red drum to the estuary occurred during September through December. Highest densities of new settlers were found in seagrass meadows (primarilyHalodule wrightii), but when seagrass was absent, the highest densities of red drum occurred along theSpartina alterniflora marsh edge interface. Densities were relatively low on nonvegetated bottom away from the marsh edge. We also examined density patterns in other habitat types at selected sampling areas and found no red drum within marsh vegetation away from the marsh edge interface (5 and 10 m into the marsh interior). Oyster reefCrassostrea virginica was sampled using lift nets, and we found no red drum using this habitat, although adjacent seagrass and marsh interface habitats were used. Even though red drum densities in marsh edge were low relative to seagrass, the large areal extent of marshes in the bay complex probably makes marsh edge the most important nursery habitat for red drum in Galveston Bay.     

Macrophyte detritus in the winter diet of the estuarine mysid,Neomysis americana

Neomysis americana, a common prey item in the diet of estuarine fish, is seasonally abundant in saltmarsh tidal creeks of North Inlet, South Carolina. Visual examination of mysids collected in winter revealed only diatom tests in their guts, with nearly all of the ingesta unidentifiable. Immunological diet analysis provided strong evidence that proteins fromSpartina alterniflora detritus were present in the guts of field-collected mysids. Laboratory determinations of weight-specific ingestion rates for male and female mysids fed particulateS. alterniflora were best described by a curvilinear quadratic function. Ingestion rates ranged from zero to 0.116 mg C ingested per mg C body weight per hr, or greater than 200% of body carbon per day if continuous feeding is assumed. These high ingestion rates may indicate low assimilation efficiency, but ifN. americana’s assimilation efficiency is similar to that of other mysid species, then this mysid may represent an efficient trophic link between saltmarsh macrophyte production and higher trophic levels. The occurrence ofSpartina detritus in the guts of winter mysids suggests that detritivory may be important during periods of scarce food.     

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.     

Formation of the Bencubbin polymict meteoritic breccia

The Bencubbin meteorite is a polymict breccia consisting of a host fraction of ~60% metal and ~40% ferromagnesian silicates and a selection of carbonaceous, ordinary and ‘enstatite’ chondritic clasts. Concentrations of 27 elements were determined by neutron activation in replicate samples of the host silicates and the ordinary and carbonaceous chondritic clasts; 12 elements were determined in the host metal. Compositional data for the ordinary chondrite clast indicate a classification of LL4 ± 1. Refractory element data for the carbonaceous chondrite clast indicate that it belongs to the CI-CM-CO clan; its volatile element abundances are intermediate between those of CM and CO chondrites. Abundances of nonvolatile elements in the silicate host are similar to those in the carbonaceous chondrite clast and in CM chondrites; the rare earths are unfractionated. We conclude that it is not achondritic as previously designated, but chondritic and that it is probably related to the CI-CM-CO clan; its volatile abundances are lower than those in CO chondrites. Oxygen isotope data are consistent with these classifications. Host metal in Bencubbin and in the closely related Weatherford meteorite has low abundances of moderately volatile siderophiles; among iron meteorite groups its nearest relative is group IIIF.We suggest that Bencubbin and Weatherford formed as a result of an impact event on a carbonaceous chondrite regolith. The impact generated an ‘instant magma’ that trapped and surrounded regolithic clasts to form the polymict breccia. The parent of this ‘magma’ was probably the regolith itself, perhaps mainly consisting of the so-called ‘enstatite’ chondrite materials. Accretion of such a variety of materials to a small parent body was probably only possible in the asteroid belt.     

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.     

Isotopic compositions of oxygen, iron, chromium, and nickel in cosmic spherules: Toward a better comprehension of atmospheric entry heating effects

Large, correlated, mass-dependent enrichments in the heavier isotopes of O, Cr, Fe, and Ni are observed in type-I (metal/metal oxide) cosmic spherules collected from the deep sea. Limited intraparticle variability of oxygen isotope abundances, typically <5‰ in δ¹⁸O, indicates good mixing of the melts and supports the application of the Rayleigh equation for the calculation of fractional evaporative losses during atmospheric entry. Fractional losses for oxygen evaporation from wüstite, assuming a starting isotopic composition equal to that of air (δ¹⁸O = 23.5‰; δ¹⁷O = 11.8‰), are in the range 55%-77%, and are systematically smaller than evaporative losses calculated for Fe (69%-85%), Cr (81%-95%), and especially Ni (45%-99%). However, as δ¹⁸O values increase, fractional losses for oxygen approach those of Fe, Cr, and Ni indicating a shift in the evaporating species from metallic to oxidized forms as the spherules are progressively oxidized during entry heating. The observed unequal fractional losses of O and Fe can be reconciled by allowing for a kinetic isotope mass-dependent fractionation of atmospheric oxygen during the oxidation process and/or that some metallic Fe may have undergone Rayleigh evaporation before oxidation began.In situ measurements of oxygen isotopic abundances were also performed in 14 type-S (silicate) cosmic spherules, 13 from the Antarctic ice and one from the deep sea. Additional bulk Fe and Cr isotopic abundances were determined for two type-S deep-sea spherules. The isotopic fractionation of Cr isotopes suggest appreciable evaporative loss of Cr, perhaps as a sulfide. The oxygen isotopic compositions for the type-S spherules range from δ¹⁸O = −2‰ to + 27‰. The intraspherule isotopic variations are typically small, ∼5% relative, except for the less-heated porphyritic spherules which have preserved large isotopic heterogeneities in at least one case. A plot of δ¹⁷O vs. δ¹⁸O values for these spherules defines a broad parallelogram bounded at higher values of δ¹⁷O by the terrestrial fractionation line, and at lower values of δ¹⁷O by a line parallel to it and anchored near the isotopic composition of δ¹⁸O = −2.5‰ and δ¹⁷O = −5‰. Lack of independent evidence for substantial evaporative losses suggests that much of this variation reflects the starting isotopic composition of the precursor materials, which likely resembled CO, CM, or CI chondrites. However, the enrichments in heavy isotopes indicate that some mixing with atmospheric oxygen was probably involved during atmospheric entry for some of the spherules. Isotopic fractionation due to evaporation of incoming grain is not required to explain most of the oxygen isotopic data for type-S spherules. However spherules with barred olivine textures that are thought to have experienced a more intense heating than the porphyritic ones might have undergone some distillation. Two cosmic spherules, one classified as a radial pyroxene type and the other showing a glassy texture, show unfractionated oxygen isotopic abundances. They are probably chondrule fragments that survived atmospheric entry unmelted.Possible reasons type-I spherules show larger degrees of isotopic fractionation than type-S spherules include: a) the short duration of the heating pulse associated with the high volatile content of the type-S spherule precursors compared to type-I spherules; b) higher evaporation temperatures for at least a refractory portion of the silicates compared to that of iron metal or oxide; c) lower duration of heating of type-S spherules compared to type-I spherules as a consequence of their lower densities.     

Identification of Uranyl Minerals Using Oxygen K‐Edge X‐Ray Absorption Spectroscopy

Although most of the world's uranium exists as pitchblende or uraninite, this mineral can be weathered to a great variety of secondary uranium minerals, most containing the uranyl cation. Anthropogenic uranium compounds can also react in the environment, leading to spatial–chemical alterations that could be useful for nuclear forensics analyses. Soft X‐ray absorption spectroscopy (XAS) has the advantages of being non‐destructive, element‐specific and sensitive to electronic and physical structure. The soft X‐ray probe can also be focused to a spot size on the order of tens of nanometres, providing chemical information with high spatial resolution. However, before XAS can be applied at high spatial resolution, it is necessary to find spectroscopic signatures for a variety of uranium compounds in the soft X‐ray spectral region. To that end, we collected the near edge X‐ray absorption fine structure (NEXAFS) spectra of a variety of common uranyl‐bearing minerals, including uranyl carbonates, oxyhydroxides, phosphates and silicates. We find that uranyl compounds can be distinguished by class (carbonate, oxyhydroxide, phosphate or silicate) based on their oxygen K‐edge absorption spectra. This work establishes a database of reference spectra for future spatially resolved analyses. We proceed to show scanning X‐ray transmission microscopy (STXM) data from a schoepite particle in the presence of an unknown contaminant.     

Dating megafaunal extinction on the Pleistocene Darling Downs,eastern Australia: the promise and pitfalls of dating as a test of extinction hypotheses

A key to understanding Late Pleistocene megafaunal extinction dynamics is knowledge of megafaunal ecological response(s) to long-term environmental perturbations. Strategically, that requires targeting fossil deposits that accumulated during glacial and interglacial intervals both before and after human arrival, with subsequent palaeoecological models underpinned by robust and reliable chronologies. Late Pleistocene vertebrate fossil localities from the Darling Downs, eastern Australia, provide stratigraphically-intact, abundant megafaunal sequences, which allows for testing of anthropogenic versus climate change megafauna extinction hypotheses. Each stratigraphic unit at site QML796, Kings Creek Catchment, was previously shown to have had similar sampling potential, and the basal units contain both small-sized taxa (e.g., land snails, frogs, bandicoots, rodents) and megafauna. Importantly, sequential faunal horizons show stepwise decrease in taxonomic diversity with the loss of some, but not all, megafauna in the geographically-small palaeocatchment. The purpose of this paper is to present the results of our intensive, multidisciplinary dating study of the deposits (>40 dates). Dating by means of accelerator mass spectrometry (AMS) ¹⁴C (targeting bone, freshwater molluscs, and charcoal) and thermal ionisation mass spectrometry U/Th (targeting teeth and freshwater molluscs) do not agree with each other and, in the case of AMS ¹⁴C dating, lack internal consistency. Scanning electron microscopy and rare earth element analyses demonstrate that the dated molluscs are diagenetically altered and contain aragonite cements that incorporated secondary young C, suggesting that such dates should be regarded as minimum ages. AMS ¹⁴C dated charcoals provide ages that occur out of stratigraphic order, and cluster in the upper chronological limits of the technique (～40–48 ka). Again, we suggest that such results should be regarded as suspicious and only minimum ages. Subsequent OSL and U/Th (teeth) dating provide complimentary results and demonstrate that the faunal sequences actually span ～120–83 ka, thus occurring beyond the AMS ¹⁴C dating window. Importantly, the dates suggest that the local decline in biological diversity was initiated ～75,000 years before the colonisation of humans on the continent. Collectively, the data are most parsimoniously consistent with a pre-human climate change model for local habitat change and megafauna extinction, but not with a nearly simultaneous extinction of megafauna as required by the human-induced blitzkrieg extinction hypothesis. This study demonstrates the problems inherent in dating deposits that lie near the chronological limits of the radiocarbon dating technique, and highlights the need to cross-check previously-dated archaeological and megafauna deposits within the timeframe of earliest human colonisation and latest megafaunal survival.