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An extensive suite of isotopic and geochemical tracers in groundwater has been used to provide hydrologic assessments of the hierarchy of flow systems in aquifers underlying the central Great Plains (southeastern Colorado and western Kansas) of the United States and to determine the late Pleistocene and Holocene paleotemperature and paleorecharge record. Hydrogeologic and geochemical tracer data permit classification of the samples into late Holocene, late Pleistocene-early Holocene, and much older Pleistocene groups. Paleorecharge rates calculated from the Cl concentration in the samples show that recharge rates were at least twice the late Holocene rate during late Pleistocene-early Holocene time, which is consistent with their relative depletion in 16O and D. Noble gas (Ne, Ar, Kr, Xe) temperature calculations confirm that these older samples represent a recharge environment approximately 5°C cooler than late Holocene values. These results are consistent with the global climate models that show a trend toward a warmer, more arid climate during the Holocene. (C) 2000 University of Washington.

A suite of chemical and isotope tracers (dissolved noble gases, stable isotopes of water, radiocarbon, and CI) have been analyzed along a flow path in the Dakota aquifer system to determine likely recharge sources, ground water residence times, and the extent of mixing between local and intermediate flow systems, presumably caused by large well screens. Three water types were distinguished with the tracers, each having a very different history. Two of the water types were found in south-eastern Colorado where the Dakota is poorly confined. The tracer data suggest that the first group recharged locally during the last few thousand years and the second group was composed of ground water that recharged earlier during a cooler climate, presumably during the last glacial period (LGP) and mixed aged water. The paleotemperature record archived in this groundwater system indicates that south-eastern Colorado was about 5°C cooler during the LGP than during the late Holocene. Similar temperature changes derived from dissolved noble gases in other aquifer systems have been reported earlier for the south-western United States. The third water type was located down gradient of the first two in the confined Dakota in western and central Kansas. Groundwater residence time of this water mass is on the order of 104-105 yrs and its recharge location is near the Colorado and Kansas border down gradient of the other water types. The study shows the importance of using multiple tracers when investigating ground water systems.

Hydrated secondary mineralization readily forms on the surface of UO 2 particles exposed to humidity in an oxidizing environment. The oxygen stable isotope composition of the secondary uranium oxide may reflect that of the water vapor, as well as the hydrogen and oxygen stable isotopic composition of the mineral hydration water. The geospatial organization of δ 2 H and δ 18 O values of atmospheric humidity and precipitation is increasingly well understood, which suggests that the hydrogen and oxygen stable isotopes in secondary mineral hydration water may yield information on the environment in which the mineralization formed. UO 2 powders were exposed to air with constant 30%, 61%, and 91% relative humidity, and constant H and O stable isotope composition. Aliquots were sampled from the UO 2 materials at intervals of 1-10 days through the total humidity exposure duration of 180 days. Scanning electron microscopy, transmission electron microscopy, and x-ray diffraction analysis of the humidity-exposed UO 2 indicates that schoepite/metaschoepite [(UO 3 )•2H 2 O] secondary phases had formed on the underlying UO 2 . The δ 2 H and δ 18 O values of mineral hydration waters were determined by thermogravimetry-enabled isotope ratio infrared spectroscopy (TGA-IRIS). Results indicate that hydrogen in the surface sorbed and mineral hydration waters is exchangeable and thus their δ 2 H values are difficult to interpret. However, oxygen in these waters is less exchangeable, and thus the oxygen stable isotope composition of the schoepite/metaschoepite hydration water is likely to be related to that of the exposure water vapor. After formation of schoepite/metaschoepite, the δ 18 O values of the hydration water in schoepite/metaschoepite does not change in response to changes in exposure vapor δ 18 O values, which suggests that the δ 18 O values of the hydration water is relatively durable. These findings suggest that information about the origin and storage history of a UO 2 sample may be discernable from δ 18 O values of schoepite/metaschoepite hydration water., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Rationale: Water vapor exposure experiments have applications for studying water physisorption and chemisorption hydration and hydroxylation reactions on a wide variety of material surfaces. The stable isotopes of hydrogen and oxygen in the water molecule are useful tracers of water exchange mechanisms and/or rates in such vapor exposure experiments., Methods: We designed and built a humidity chamber system that uses membrane-mediated liquid-vapor exchange of water followed by mixing with dry air to control the relative humidity of air and its δ 2 H and δ 18 O isotopic composition. We tested the stability and precision of the humidity and its isotopic composition on hourly to 90-day timescales., Results: The humidity chamber design reported here is capable of providing relative humidity control to within ±1%, and consistent δ 2 H and δ 18 O values of the water vapor that are similar to our cavity ringdown spectroscopy (CRDS) measurement precision (δ 2 H vap  ± 0.7‰ and δ 18 O vap  ± 0.24‰). We quantify the isotopic enrichment effects of Rayleigh distillation in the system and provide information on water reservoir sizes large enough to buffer isotopic enrichment effects to within measurement precision., Conclusions: The humidity chamber design reported here provides a means to create constant δ 2 H and δ 18 O values over the course of an exposure experiment. The design has applications to a wide range of studies of water sorption on material surfaces from foods and pharmaceuticals to geological materials., (© 2018 John Wiley & Sons, Ltd.)

The hindguts of lower termites harbor highly diverse, endemic communities of symbiotic protists, bacteria, and archaea essential to the termite's ability to digest wood. Despite over a century of experimental studies, ecological roles of many of these microbes are unknown, partly because almost none can be cultivated. Many of the protists associate with bacterial symbionts, but hypotheses for their respective roles in nutrient exchange are based on genomes of only two such bacteria. To show how the ecological roles of protists and nutrient transfer with symbiotic bacteria can be elucidated by direct imaging, we combined stable isotope labeling (13C-cellulose) of live termites with analysis of fixed hindgut microbes using correlated scanning electron microscopy, focused ion beam-scanning electron microscopy (FIB-SEM), transmission electron microscopy, and high resolution imaging mass spectrometry (NanoSIMS). We developed methods to prepare whole labeled cells on solid substrates, whole labeled cells milled with a FIB-SEM instrument to reveal cell interiors, and ultramicrotome sections of labeled cells for NanoSIMS imaging of 13C enrichment in protists and associated bacteria. Our results show these methods have the potential to provide direct evidence for nutrient flow and suggest the oxymonad protist Oxymonas dimorpha phagocytoses and enzymatically degrades ingested wood fragments, and may transfer carbon derived from this to its surface bacterial symbionts.

We observed that a naturally occurring mouse strain developed age-related retinal degeneration (arrd2). These mice had normal fundi, electroretinograms (ERGs) and retinal histology at 6 months of age; vessel attenuation, RPE atrophy and pigmentary abnormalities at 14 months, which progressed to complete loss of photoreceptors and extinguished ERG by 22 months. Genetic analysis revealed that the retinal degeneration in arrd2 segregates in an autosomal recessive manner and the disease gene localizes to mouse chromosome 10. A positional candidate cloning approach detected a nonsense mutation in the mouse double minute-1 gene (Mdm1), which results in the truncation of the putative protein from 718 amino acids to 398. We have identified a novel transcript of the Mdm1 gene, which is the predominant transcript in the retina. The Mdm1 transcript is localized to the nuclear layers of neural retina. Expression of Mdm1 in the retina increases steadily from post-natal day 30 to 1 year, and a high level of Mdm1 are subsequently maintained. The Mdm1 transcript was found to be significantly depleted in the retina of arrd2 mice and the transcript was observed to degrade by nonsense-mediated decay. These results indicate that the depletion of the Mdm1 transcript may underlie the mechanism leading to late-onset progressive retinal degeneration in arrd2 mice. Analysis of a cohort of patients with age-related macular degeneration (AMD) wherein the susceptibility locus maps to chromosome 12q, a region bearing the human ortholog to MDM1, did not reveal association between human MDM1 and AMD.

Laboratory experiments were conducted to determine environmental variables that affect the affinities and persistence of the nerve agent O-ethyl S-(2-diisopropylaminoethyl) methylphosphonothiolate (VX) at dilute concentrations in environmental matrices. Quantitative analyses of VX and its degradation products were performed using LC-MS. Batch hydrolysis experiments demonstrated an increasing hydrolysis rate as pH increased, as shown in previous studies, but also indicated that dissolved aqueous constituents can cause significant differences in the absolute hydrolysis rate. Adsorption isotherms from batch aqueous experiments revealed that VX has a high affinity for hydrophobic organics, a moderate affinity for montmorillonite clay, and a very low affinity for an iron-oxyhydroxide soil mineral, goethite. The adsorption on goethite was increased with the presence of dissolved organic matter in solution. VX degraded rapidly when dried onto goethite, when specific adsorption was forced. No enhanced degradation occurred with goethite in small amounts of water. These results suggest that aqueous conditions have important controls on VX adsorption and degradation in the environment and a more mechanistic understanding of these controls is needed in order to enable accurate predictions of its long-term fate and persistence.

Critical for the management of artificial recharge operations is detailed knowledge of ground water dynamics near spreading areas. Geochemical tracer techniques including stable isotopes of water, tritium/helium-3 (T/3He) dating, and deliberate gas tracer experiments are ideally suited for these investigations. These tracers were used to evaluate flow near an artificial recharge site in northern Orange County, California, where approximately 2.5 x 10(8) m3 (200,000 acre-feet) of water are recharged annually. T/3He ages show that most of the relatively shallow ground water within 3 km of the recharge facilities have apparent ages < 2 years; further downgradient apparent ages increase, reaching > 20 years at approximately 6 km. Gas tracer experiments using sulfur hexafluoride and xenon isotopes were conducted from the Santa Ana River and two spreading basins. These tracers were followed in the ground water for more than two years, allowing subsurface flow patterns and flow times to be quantified. Results demonstrate that mean horizontal ground water velocities range from < 1 to > 4 km/year. The leading edges of the tracer patch moved at velocities about twice as fast as the center of mass. Leading edge velocities are important when considering the potential transport of microbes and other "time sensitive" contaminants and cannot be determined easily with other methods. T/3He apparent ages and tracer travel times agreed within the analytical uncertainty at 16 of 19 narrow screened monitoring wells. By combining these techniques, ground water flow was imaged with time scales on the order of weeks to decades.

The nature and chlorine reactivity of organic constituents in reclaimed water (tertiary-treated municipal wastewater) before, during, and after recharge into groundwater at the Montebello Forebay in Los Angeles County, CA, was the focus of this study. Dissolved organic matter (DOM) in reclaimed water from this site is primarily a mixture of aromatic sulfonates from anionic surfactant degradation, N-acetyl amino sugars and proteins from bacterial activity, and natural fulvic acid, whereas DOM from native groundwaters in the aquifer to which reclaimed water was recharged consists of natural fulvic acids. The hydrophilic neutral N-acetyl amino sugars that constitute 40% of the DOM in reclaimed water are removed during the first 3 m of vertical infiltration in the recharge basin. Groundwater age dating with 3H and 3He isotopes, and determinations of organic and inorganic C isotopes, enabled clear differentiation of recent recharged water from older native groundwater. Phenol structures in natural fulvic acids in DOM isolated from groundwater produced significant trihalomethanes (THM) and total organic halogen (TOX) yields upon chlorination, and these structures also were responsible for the enhanced SUVA and specific fluorescence characteristics relative to DOM in reclaimed water. Aromatic sulfonates and fulvic acids in reclaimed water DOM produced minimal THM and TOX yields.

Background: Glaucoma is a blinding disease usually associated with high intraocular pressure (IOP). In some families, abnormal anterior segment development contributes to glaucoma. The genes causing anterior segment dysgenesis and glaucoma in most of these families are not identified and the affected developmental processes are poorly understood. Bone morphogenetic proteins (BMPs) participate in various developmental processes. We tested the importance of Bmp4 gene dosage for ocular development and developmental glaucoma., Results: Bmp4+/- mice have anterior segment abnormalities including malformed, absent or blocked trabecular meshwork and Schlemm's canal drainage structures. Mice with severe drainage structure abnormalities, over 80% or more of their angle's extent, have elevated IOP. The penetrance and severity of abnormalities is strongly influenced by genetic background, being most severe on the C57BL/6J background and absent on some other backgrounds. On the C57BL/6J background there is also persistence of the hyaloid vasculature, diminished numbers of inner retinal cells, and absence of the optic nerve., Conclusions: We demonstrate that heterozygous deficiency of BMP4 results in anterior segment dysgenesis and elevated IOP. The abnormalities are similar to those in human patients with developmental glaucoma. Thus, BMP4 is a strong candidate to contribute to Axenfeld-Rieger anomaly and other developmental conditions associated with human glaucoma. BMP4 also participates in posterior segment development and wild-type levels are usually critical for optic nerve development on the C57BL/6J background. Bmp4+/- mice are useful for studying various components of ocular development, and may allow identification of strain specific modifiers affecting a variety of ocular phenotypes.