Microbial degradation of chloroethenes in groundwater systems

The chloroethenes, tetrachloroethene (PCE) and trichloroethene (TCE) are among the most common contaminants detected in groundwater systems. As recently as 1980, the consensus was that chloroethene compounds were not significantly biodegradable in groundwater. Consequently, efforts to remediate chloroethene-contaminated groundwater were limited to largely unsuccessful pump-and-treat attempts. Subsequent investigation revealed that under reducing conditions, aquifer microorganisms can reductively dechlorinate PCE and TCE to the less chlorinated daughter products dichloroethene (DCE) and vinyl chloride (VC). Although recent laboratory studies conducted with halorespiring microorganisms suggest that complete reduction to ethene is possible, in the majority of groundwater systems reductive dechlorination apparently stops at DCE or VC. However, recent investigations conducted with aquifer and stream-bed sediments have demonstrated that microbial oxidation of these reduced daughter products can be significant under anaerobic redox conditions. The combination of reductive dechlorination of PCE and TCE under anaerobic conditions followed by anaerobic microbial oxidation of DCE and VC provides a possible microbial pathway for complete degradation of chloroethene contaminants in groundwater systems. Résumé Les chloroéthanes, tétrachloroéthane (PCE) et trichloroéthane (TCE) sont parmi les polluants les plus communs trouvés dans les aquifères. Depuis les années 1980, on considère que les chloroéthanes ne sont pas significativement biodégradables dans les aquifères. Par conséquent, les efforts pour dépolluer les nappes contaminées par des chloroéthanes se sont limités à des tentatives de pompage-traitement globalement sans succès. Des travaux ultérieurs ont montré que dans des conditions réductrices, des micro-organismes présents dans les aquifères peuvent, par réduction, dégrader les PCE et TCE en composés moins chlorés, comme le dichloréthane (DCE) et le chlorure de vinyl (VC). Bien que des études de laboratoire réalisées avec des micro-organismes adaptés aux composés halogénés montrent que la réduction complète en éthane est possible, dans la plupart des nappes la réaction de déchloration par réduction s'arrête apparemment au DCE et au VC. Cependant, des recherches récentes menées sur des sédiments d'un aquifère et d'alluvions ont démontré que l'oxydation microbienne de ces descendants réduits peut se produire de manière significative dans des conditions de redox anérobies. La déchloration par réduction de PCE et de TCE dans des conditions anérobies suivie par une oxydation microbienne anérobie des DCE et VC fournit une piste microbienne possible pour obtenir une dégradation complète des chloroéthanes polluants dans les aquifères. Resumen Los cloroetanos (tetracloroetano PCE y tricloroetano TCE) son contaminantes muy habituales en los acuíferos. Hasta 1980 se consideraba que los cloroetanos no eran biodegradables y, por tanto, los métodos de rehabilitación en acuíferos contaminados con cloroetanos se limitaban al pump-and-treat, generalmente con poco éxito. Posteriormente se vio que, en condiciones reductoras, algunos microorganismos pueden reducir PCE y TCE a unos subproductos menos clorados, como el dicloroetano (DCE) y el cloruro de vinilo (VC). Aunque estudios de laboratorio recientes sugieren que la reducción completa a etano es posible, en la mayoría de los sistemas acuíferos la decloración suele detenerse en los DCE o VC. Sin embargo, investigaciones más recientes en acuíferos y sedimentos fluviales demuestran que la oxidación microbiana de estos subproductos puede ser importante bajo condiciones redox anaerobias. La combinación de la reducción de PCE y TCE en condiciones anaerobias seguida de la oxidación microbiana anaerobia de DCE y VC proporciona un método potencial para la degradación total de los cloroetanos en los sistemas acuíferos.     

Continuous field estimation of dissolved organic carbon concentration and biochemical oxygen demand using dual‐wavelength fluorescence,turbidity and temperature

Dissolved organic matter (DOM) quality and quantity is not measured routinely in‐situ limiting our ability to quantify DOM process dynamics. This is problematic given legislative obligations to determine event based variability; however, recent advances in field deployable optical sensing technology provide the opportunity to address this problem. In this paper, we outline a new approach for in‐situ quantification of DOM quantity (Dissolved Organic Carbon: DOC) and a component of quality (Biochemical Oxygen Demand: BOD) using a multi‐wavelength, through‐flow fluorescence sensor. The sensor measured tryptophan‐like (Peak T) and humic‐like (Peak C) fluorescence, alongside water temperature and turbidity. Laboratory derived coefficients were developed to compensate for thermal quenching and turbidity interference (i.e., light attenuation and scattering). Field tests were undertaken on an urban river with ageing wastewater and stormwater infrastructure (Bourn Brook; Birmingham, UK). Sensor output was validated against laboratory determinations of DOC and BOD collected by discrete grab sampling during baseflow and stormflow conditions. Data driven regression models were then compared to laboratory correction methods. A combination of temperature and turbidity compensated Peak T and Peak C was found to be a good predictor of DOC concentration (R² = 0.92). Conversely, using temperature and turbidity correction coefficients provided low predictive power for BOD (R² = 0.46 and R² = 0.51, for Peak C and T, respectively). For this study system, turbidity appeared to be a reasonable proxy for BOD, R² = 0.86. However, a linear mixed effect model with temperature compensated Peak T and turbidity provided a robust BOD prediction (R² = 0.95). These findings indicate that with careful initial calibration, multi‐wavelength fluorescence, coupled with turbidity, and temperature provides a feasible proxy for continuous, in‐situ measurement of DOC concentration and BOD. This approach represents a cost effective monitoring solution, particularly when compared to UV – absorbance sensors and DOC analysers, and could be readily adopted for research and industrial applications.     

Quantifying annual groundwater recharge and storage in the central Sierra Nevada using naturally occurring 35S

Identifying aquifer vulnerability to climate change is of vital importance in the Sierra Nevada and other snow‐dominated basins where groundwater systems are essential to water supply and ecosystem health. Quantifying the component of new (current year's) snowmelt in groundwater and surface water is useful in evaluating aquifer vulnerability because significant annual recharge may indicate that streamflow will respond rapidly to annual variability in precipitation, followed by more gradual decreases in recharge as recharge declines over decades. Hydrologic models and field‐based studies have indicated that young (<1 year) water is an important component of streamflow. The goal of this study was to utilize the short‐lived, naturally occurring cosmogenic isotope sulfur‐35 (³⁵S) to quantify new snowmelt contribution to groundwater and surface waters in Sagehen Creek Basin (SCB) and Martis Valley Groundwater Basin (MVGB) located within the Tertiary volcanics of the central Sierra Nevada, CA. Activities of ³⁵S were measured in dissolved sulfate (³⁵SO₄^2?) in SCB and MVGB snowpack, groundwater, springs, and streamflow. The percent of new snowmelt (PNS) in SCB streamflow ranged from 0.2 ± 6.6% during baseflow conditions to 14.0 ± 3.4% during high‐flow periods of snowmelt. Similar to SCB, the PNS in MVGB groundwater and streamflow was typically <30% with the largest fractions occurring in late spring or early summer following peak streamflow. The consistently low PNS suggests that a significant fraction of annual snowmelt in SCB and MVGB recharges groundwater, and groundwater contributions to streamflow in these systems have the potential to mitigate climate change impacts on runoff.     

Locating cryptotephra in lake sediments using fluid imaging technology

We report a new approach to locate and quantify cryptotephra in sedimentary archives using a continuously-imaging Flow Cytometer and Microscope (FlowCAM^®). The FlowCAM rapidly photographs particles flowing in suspension past a microscope lens and performs semi-automated analysis of particle images. It has had primarily biological applications, although the potential sedimentological applications are numerous. Here we test the ability of this instrument to image irregularly shaped, vesicular glass shards and to screen sediment samples for the presence of cryptotephra. First, reference samples of basalt and rhyolite tephra (sieved <63 μm) were analyzed with the FlowCAM, demonstrating the ability of the instrument to photograph individual tephra shards. The highest-quality images were used to create a reference library of tephra particles, against which other particle morphologies could be automatically compared. Lake sediment samples with known concentrations of tephra were then analyzed. The tephra image library was used to perform pattern recognition calculations, automatically distinguishing tephra-like images from other particles in the sediment samples. The number of tephra shards identified by the FlowCAM technique was compared to manual counting using a polarizing light microscope, demonstrating that this rapid approach is capable of determining the relative concentrations of tephra in a given sediment sample. However, the FlowCAM systematically underestimates tephra concentrations relative to manual counts. We conclude that with a well-developed image library, the FlowCAM can be an effective tool for cryptotephra and sedimentological applications, but it may be inappropriate for large volume samples or if particle morphologies are outside the range of the image library.     

Cassini between Earth and asteroid belt: first in-situ charge measurements of interplanetary grains

Dust particles in interplanetary space are expected to charge up to an electrostatic potential of about +5 V mostly by the solar UV (Horányi, 1996, Annu. Rev. Astrophys. 34, 383). Since the dynamics of charged grains may be quite different from neutral particles, the knowledge of the grain charge Q_d is highly desirable. In the last two decades, several detectors on spacecraft were flown to measure the dust charge in-situ, but the instrumentation was not capable of determining the dust charge unambiguously. The Cosmic Dust Analyser (CDA) on the Cassini spacecraft includes a charge sensitive entrance grid system (QP detector). While entering the instrument, sufficiently charged particles induce a characteristic charge feature onto the grid system, which allows a reliable determination of Q_d as well as of the impact speed v_d. Here we report the first successful in-situ measurement of charged interplanetary dust grains by CDA. Amongst 37 impacts by interplanetary grains registered between November 1999 and January 2000, we identified 6 impacts whose QP signals show a clear feature caused by charged grains, corresponding to Q_d between 1.3 and 5.4 fC. Knowledge of Q_d also allows us to estimate the grain mass m_d. Assuming a potential of φ_d≈+5 V and spheroidal grain morphologies with ratios of the maximum size to the minimum size of less than 2 the masses derived from Q_d were found to be in excess of 10⁻¹³ kg. The dynamics of such particles are dominated by the Sun's gravity. In the framework of the micro-meteoroid models of the Solar System these grains belong to the core population of interplanetary grains (Divine, 1993, J. Geophys. Res. 98, 17029). Furthermore, a rate of 6 impacts of grains with m_d?10⁻¹³ kg during 107 days is in good agreement with the predictions of the interplanetary dust environment model by Staubach et al. (1997, Adv. Space Res. 19, 301). This result demonstrates that charge detectors as the CDA QP system offer a reliable in-situ technique for determining simultaneously both the mass and velocity of big interplanetary grains. The primary CDA subsystem to determine m_d and v_d, however, is an impact ionisation detector. The majority of the 37 recorded dust impacts produced impact charges are well outside the calibrated range. Moreover, these impacts were usually characterised by impact ionisation signals which differ significantly from signals taken in calibration experiments. In this paper we took advantage of the fact that the measurement of Q_d is not affected by the subsequent impact of the grain with the detector. By relating m_d and v_d derived from Q_d of the 6 QP impactors to their corresponding ionisation signals we show that in many cases even for energetic impacts outside the calibrated range meaningful values for the dust mass can be obtained. The observed deviations of the ionisation signals from the calibration measurements are likely due to the large amount of plasma generated by such impacts. We discuss the implications of these findings on a meaningful reduction of impact ionisation signals caused by big particle impacts. A new scheme to identify and to evaluate such signals is presented. These finding are of great importance for future Cassini measurements in the saturnian system.     

A simple fiber-optic microprobe for high resolution light measurements: application in marine sediment

A fiber-optic microphobe is described which is inexpensive and simple to build and use. It consists of an 80-micrometers optical fiber which at the end is tapered down to a rounded sensing tip of 20-30-micrometers diameter. The detector is a hybrid photodiode/amplifier. The probe has a sensitivity of 0.01 microEinst m-2 s-1 and a spectral range of 300-1,100 nm. Spectral light gradients were measured in fine-grained San Francisco Bay sediment that had an undisturbed diatom coating on the surface. The photic zone of the mud was only 0.4 mm deep. Measured in situ spectra showed extinction maxima at 430-520, 620-630, 670, and 825-850 nm due to absorption by chlorophyll a, carotenoids, phycocyanin, and bacterio-chlorophyll a. Maximum light penetration in the visible range was found in both the violet and the red < or = 400 and > or = 700 nm.     

Aerogel keystones: Extraction of complete hypervelocity impact events from aerogel collectors

Abstract— In January 2006, the Stardust mission will return the first samples from a solid solar system body beyond the Moon and the first samples of contemporary interstellar dust ever collected. Although sophisticated laboratory instruments exist for the analysis of Stardust samples, techniques for the recovery of particles and particle residues from aerogel collectors remain primitive. Here, we describe our recent progress in developing techniques for extracting small volumes of aerogel, which we have called “keystones,” which completely contain particle impacts but minimize the damage to the surrounding aerogel collector. These keystones can be fixed to custom‐designed micromachined silicon fixtures (so called “microforklifts”). In this configuration, the samples are self‐supporting, which can be advantageous in situations where interference from a supporting substrate is undesirable. The keystones may also be extracted and placed onto a substrate without a fixture. We have also demonstrated the capability of homologously crushing these unmounted keystones for analysis techniques that demand flat samples.