M. Lee Davisson

NaCaCl relations in basinal fluids

Abstract A new mathematical transformation of Na, Ca, and Cl concentrations in numerous basinal fluids around the world produces a linear slope of unity between the mill iequivalencies of Na and Ca cations. The transformation entails a simple milliequivalent comparison between the excess Ca and the Na deficit relative to seawater reference ratios. The relevant parameters are: Ca excess = [ Ca means − ( Ca/Cl ) sw Cl means ] 2 40.08 , Na deficit = [( Na/Cl ) sw Cl means − Na means ] 1 22.99 , where the concentrations (in mg/L) of the ions measured (meas) in a sample are referred to those in seawater (sw), and the numerical constants convert the results to meq/L. For >800 samples from numerous fluid reservoirs, with Cl concentrations that range from approximately 1–300 g/L and host lithologies from carbonates to granites, a highly correlated regression termed the Basinal Fluid Line (BFL) is found: Caexcess = 0.967 (Nadeficit) + 140.3R = 0.981. The unit slope of the BFL indicates a net cation exchange ratio of 2 Na for 1 Ca. The excess-deficit parameters show no correlation to Mg or K. If a single predominating reaction is presumed to control the BFL, only albitization of plagioclase by 2 Na for 1 Ca exchange is plausible. The BFL offers no support for a predominating reaction involving the 1:1 exchange of Na for Ca that has also been proposed for albitization reactions, nor for the hypothesis that dolomitization produces the elevated Ca contents of basinal fluids. The BFL may incorporate the effects of other water-rock reactions provided that they involve a net exchange of 2 Na for 1 Ca in sedimentary basins. The small y-intercept of 140.3 of the BFL is generally consistent with an origination of the brines from seawater, which would plot at the origin of an excess-deficit graph. However, for regressions derived for fluids from individual basins, the y-intercepts increase with increasing salinity of their fluids, consistent with model predictions for dissolution of halite into either a seawater or freshwater parent, followed by 2 Na for 1 Ca exchange. Because the hydrosphere is dominated by seawater and the upper crust by feldspar minerals, the BFL arguably represents the overall product of cation exchange of high salinity fluids in deep continental environments.

ISOTOPE HYDROLOGY OF VOLUMINOUS COLD SPRINGS IN FRACTURED ROCK FROM AN ACTIVE VOLCANIC REGION, NORTHEASTERN CALIFORNIA

The more than 1550 km2 (600 mi2) Hat Creek Basin in northeastern California is host to several first magnitude cold springs that emanate from Quaternary basaltic rocks with individual discharge rates ranging from 1.7 to 8.5 m3 s−1 (60–300 ft3 s−1). Stable isotope (δ18O, δD, δ13C) and 14C measurements of surface and groundwater samples were used to identify recharge areas, and to evaluate aquifer residence times and flow paths. Recharge locations were constrained from the regional decrement in meteoric water δ18O values as a function of elevation, determined to be −0.23‰ per 100 m for small springs and creek waters collected along the western Cascade slope of this region. In general, the large-volume springs are lower in (δ18O than surrounding meteoric waters, and are inferred to originate in high-elevation, high-precipitation regions up to 50 km away from their discharge points. Large spring 14C abundances range from 99 to 41 % modern carbon (pmc), and most show evidence of interaction with three distinct carbon isotope reservoirs. These reservoirs are tentatively identified as (1) soil CO2 gas equilibrated under open system conditions with groundwater in the recharge zone [δ13CDIC ≈ −18‰, 14C > 100 pmc], (2) dissolved carbon equilibrated with atmospheric CO2 gas [δ13CDIC ≈ +1‰, 14C > 100 pmc], and (3) dissolved carbon derived from volcanic CO2 gas emissions [δ13CDIC≈0‰, 14C=0 pmc]. Many regional waters show a decrease in 14C abundance with increasing δ13C values, a pattern indicative of interaction with dead carbon originating from volcanic CO2 gas. Several lines of evidence suggest that actual groundwater residence times are too short (⩽ 200 years) to apply radiocarbon dating corrections. In particular, water temperatures measured at springs show that deep groundwater circulation does not occur, which implies an insufficient aquifer volume to account for both the high discharge rates and long residence times suggested by 14C apparent ages. The large springs also exhibit rapid decreases in flow during periods of drought that suggests a high level of aquifer interconnectivity to the recharge area. The estimated amount of volcanic CO2 dissolved in surface and groundwater originating from the Lassen highlands is consistent with the conversion of approximately 10% of the geothermal CO2 flux into dissolved inorganic carbon.

Characterization and origin of polar dissolved organic matter from the Great Salt Lake

Polar dissolved organic matter (DOM) was isolated from a surface-water sample from the Great Salt Lake by separating it from colloidal organic matter by membrane dialysis, from less-polar DOM fractions by resin sorbents, and from inorganic salts by a combination of sodium cation exchange followed by precipitation of sodium salts by acetic acid during evaporative concentration. Polar DOM was the most abundant DOM fraction, accounting for 56% of the isolated DOM. Colloidal organic matter was 14C-age dated to be about 100% modern carbon and all of the DOM fractions were 14C-age dated to be between 94 and 95% modern carbon. Average structural models of each DOM fraction were derived that incorporated quantitative elemental and infrared, 13C-NMR, and electrospray/mass spectrometric data. The polar DOM model consisted of open-chain N-acetyl hydroxy carboxylic acids likely derived from N-acetyl heteropolysaccharides that constituted the colloidal organic matter. The less polar DOM fraction models consisted of aliphatic alicyclic ring structures substituted with carboxyl, hydroxyl, ether, ester, and methyl groups. These ring structures had characteristics similar to terpenoid precursors. All DOM fractions in the Great Salt Lake are derived from algae and bacteria that dominate DOM inputs in this lake.

Modeling Iso-octane HCCI Using CFD with Multi-Zone Detailed Chemistry; Comparison to Detailed Speciation Data Over a Range of Lean Equivalence Ratios

Multi-zone CFD simulations with detailed kinetics were used to model iso-octane HCCI experiments performed on a single-cylinder research engine. The modeling goals were to validate the method (multi-zone combustion modeling) and the reaction mechanism (LLNL 857 species iso-octane) by comparing model results to detailed exhaust speciation data, which was obtained with gas chromatography. The model is compared to experiments run at 1200 RPM and 1.35 bar boost pressure over an equivalence ratio range from 0.08 to 0.28. Fuel was introduced far upstream to ensure fuel and air homogeneity prior to entering the 13.8:1 compression ratio, shallow-bowl combustion chamber of this 4-stroke engine. The CFD grid incorporated a very detailed representation of the crevices, including the top-land ring crevice and headgasket crevice. The ring crevice is resolved all the way into the ring pocket volume. The detailed grid was required to capture regions where emission species are formed and retained. Results show that combustion is well characterized, as demonstrated by good agreement between calculated and measured pressure traces. In addition, excellent quantitative agreement between the model and experiment is achieved for specific exhaust species components, such as unburned fuel, formaldehyde, and many other intermediate hydrocarbon species. Some calculated trace intermediate hydrocarbon species do not agree as well with measurements, highlighting areas needing further investigation for understanding fundamental chemistry processes in HCCI engines.

Correlated SEM, FIB-SEM, TEM, and NanoSIMS imaging of microbes from the hindgut of a lower termite: methods for in situ functional and ecological studies of uncultivable microbes.

The hindguts of lower termites harbor highly diverse, endemic communities of symbiotic protists, bacteria, and archaea essential to the termites 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.

Testing the Established Hydrogeologic Model of Source Water to the Amargosa River Basin, Inyo and San Bernardino Counties, California

The current conceptual hydrogeologic model established for source water to the Amargosa River was tested in order to help inform management decisions regarding the Amargosa Rivers Federal designation as Wild and Scenic through an Act of Congress. The limited availability of water in this region results in the critical need for effective management in the basin to maintain its Wild and Scenic attributes inclusive of habitat for several endangered and threatened species. The use of forensic tools and integration of multiple lines of geologic, hydrogeologic, geochemical, and stable isotopic evidence suggest that the simple historical model for primary groundwater transport through this region is incorrect and that a large supply of regional baseflow does not provide the hydrogeological foundation of the Amargosa River basin. Data collected is consistent with an alternative model requiring complex source mixing and shallow alluvial groundwater that supports river flow. This conclusion also suggests Wild and Scenic conditions in this basin are more precarious than previously understood.

Recharge and Flow in the Medicine Lake Volcano–Fall River Springs Groundwater Basin, California

Isotopic measurements of the 34 m3/s discharge from the Fall River Springs of northern California indicate recharge from 50 km upgradient in high elevation regions of Medicine Lake Volcano. Age determinations suggest less than 20-year travel time. Data demonstrate Klamath Basin further north cannot be a recharge source. Mass balance calculations support that annual precipitation on the volcano supplies observed spring discharge, requiring 50%–75% recharge rates. Radiocarbon and δ13C of dissolved inorganic carbon indicate 30%–40% is derived from magmatic CO2. Measured excess 3He is also consistent with the presence of magmatic gas derived from the Quaternary Age Medicine Lake Volcano.

Water Vapor Exposure Chamber for Constant Humidity and Hydrogen and Oxygen Stable Isotope Composition

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 δ2 H and δ18 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 δ2 H and δ18 O values of the water vapor that are similar to our cavity ringdown spectroscopy (CRDS) measurement precision (δ2 Hvap  ± 0.7‰ and δ18 Ovap  ± 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 δ2 H and δ18 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.

Understanding the source of water for selected springs within Mojave Trails National Monument, California

ABSTRACT While water sources that sustain many of the springs in the Mojave Desert have been poorly understood, the desert ecosystem can be highly dependent on such resources. This evaluation updates the water resource forensics of Bonanza Spring, the largest spring in the southeastern Mojave Desert. The source of spring flow at Bonanza Spring was evaluated through an integration of published geologic maps, measured groundwater levels, water quality chemistry, and isotope data compiled from both published sources and new samples collected for water chemistry and isotopic composition. The results indicate that Bonanza Spring has a regional water source, in hydraulic communication with basin fill aquifer systems. Neighboring Lower Bonanza Spring appears to primarily be a downstream manifestation of surfacing water originally discharged from the Bonanza Spring source. Whereas other springs in the area, Hummingbird, Chuckwalla, and Teresa Springs, each appear to be locally sourced as “perched” springs. These conclusions have important implications for managing activities that have the potential to impact the desert ecosystem.

Low-Level Analytical Method for Selected Volatile Organic Compounds

of PCB sources is eventually reduced to a comparison of congener patterns derived from ambient samples, to a library of known or suspected source patterns (e.g., Aroclor compositions). In complex environmental systems, however, source identification is confounded by complexities such as dechlorination and differential volatilization of PCB congeners. Successful modeling and inference of sources requires sensitivity to and understanding of these processes. In this paper, we expand on the work of Chiarenzelli et al. (1997) and Quensen et al. (1990), who reported results of a series of laboratory volatilization and dechlorination experiments for each of four Aroclors, respectively. The patterns observed in both the volatile and residual fractions vary dramatically from the original Aroclor compositions. Herein, we present the congener patterns resulting from these processes and discuss the implications this has on quantitative source apportionment methods, in particular in the use of linear mixing models. We further present source receptor modeling results from an investigation of PCBs in sediments of Lake Hartwell, South Carolina. Polytopic vector analysis (PVA) was used to resolve contributing PCB patterns, and their relative contributions. The “source” profiles resolved by PVA did not match unaltered Aroclors. Rather, accurate interpretation required sensitivity to alteration process as well as source. These results suggest that the patterns from such experiments reasonably reflect processes at work in the environment, and highlight the importance of such experimental reference data in interpretation of source apportionment modeling results.