Phenolics and Proteins Affecting Palatability of Spartina Leaves to the Gastropod Littoraria irrorata

Along the southeastern coast of the United States, the saltmarsh periwinkle Littoraria irrorata is a major consumer of Spartina alterniflora . It prefers to feed on dead rather than living plants. During senescence and early decay, S. alterniflora leaves become colonized by fungi, their phenolic content declines, and their lipid content increases. In this study, the food preferences of L. irrorata were assessed by offering intact leaves or leaf powder suspended in agar. Relative palatabilities were determined by measuring the weight loss of intact leaves, or by estimating the area of feeding marks left on the surface of leaf powder suspensions. Both techniques demonstrated a clear preference for standing dead rather than yellow-green (senescent) leaves. Yellow-green leaves contained methanol-soluble feeding deterrents. A comparable deterrent effect could be achieved by adding ferulic acid, a phenolic compound common in yellow-green S. alterniflora , to leaf powder. The deterrent effects of methanol extracts or ferulic acid could be neutralized by simultaneously adding fungal mycelium or BSA. Littoraria irrorata preferred leaves colonized by fungi or bacteria over sterile leaves. When offered a choice of sterile leaves colonized by different fungi, the results were variable. In one experiment, L. irrorata clearly preferred one of three leaffungus combinations. The same preference was shown after the food items were treated with methanol/chloroform to remove lipids. In a second experiment with four other fungal strains, there was only a clear preference for one leaf-fungus combination after removal of lipids. The results suggest that the saltmarsh periwinkle prefers S. alterniflora leaves with low concentrations of phenolic deterrents, most likely ferulic acid, and with sufficient fungal biomass. The food choice may be influenced to a smaller degree by fungal components, which, depending on the species or strain, may be lipids or other compounds.     

Sediment Nitrogen Fixation: a Call for Re-evaluating Coastal N Budgets

Coastal ocean primary productivity is often limited by nitrogen (N) availability, which is determined by the balance between N sources (e.g., N-fixation, groundwater, river inputs, etc.) and sinks (e.g., denitrification, sediment burial, etc.). Historically, heterotrophic N-fixation in sediments was excluded as a significant source of N in estuarine budgets, based on low, indirectly measured rates (e.g., acetylene reduction assay) and because it was unnecessary to achieve mass balance. Many recent studies using net N₂ flux measurements have shown that sediment N-fixation can equal or exceed N₂ loss. In an effort to quantify N₂ production and consumption simultaneously, we measured N-fixation and denitrification directly in sediment cores from a temperate estuary (Waquoit Bay, MA). N-fixation, dissimilatory nitrate reduction to ammonium, and denitrification occurred simultaneously, and the net N₂ flux shifted from uptake (N-fixation) to efflux (denitrification) over the 120-h incubation. Evidence for N-fixation included net ²⁸N₂ and ³⁰N₂ uptake, ¹⁵NH₄ ⁺ production from ³⁰N₂ additions, ¹⁵N_{organic matter} production, and nifH expression. N-fixation from ³⁰N₂ was up to eight times higher than potential denitrification. However, N-fixation calculated from ¹⁵NO₃ ^? was one half of the measured fixation from ³⁰N₂, indicating that ¹⁵NO₃-isotope labeling calculations may underestimate N-fixation. These results highlight the dynamic nature of sediment N cycling and suggest that quantifying individual processes allows a greater understanding of what net N₂ fluxes signify and how that balance varies over time.     

Regional studies of potential carbon monoxide sources based on space shuttle and aircraft measurements

Carbon monoxide measurements made from the space shuttle show maxima over South America, central Africa, the eastern Mediterranean, and China. The maxima appear to be associated with either concomitant or prior convection in the air masses which carries boundary layer air into the upper troposphere. Previous aircraft measurements of carbon monoxide and ozone over South America are shown to be consistent with this view. In the tropics the three regions of long-term mean rising motion, which form part of the Walker circulation, are associated with elevated carbon monoxide.     

H<Subscript>2</Subscript>-rich and Hydrocarbon Gas Recovered in a Deep Precambrian Well in Northeastern Kansas

In late 2005 and early 2006, the WTW Operating, LLC (W.T.W. Oil Co., Inc.) #1 Wilson well (T.D. = 5772 ft; 1759.3 m) was drilled for 1826 ft (556.6 m) into Precambrian basement underlying the Forest City Basin in northeastern Kansas. Approximately 4500 of the 380,000 wells drilled in Kansas penetrate Precambrian basement. Except for two previous wells drilled into the arkoses and basalts of the 1.1-Ga Midcontinent Rift and another well drilled in 1929 in basement on the Nemaha Uplift east of the Midcontinent Rift, this well represents the deepest penetration into basement rocks in the state to date. Granite is the typical lithology observed in wells that penetrate the Precambrian in the northern Midcontinent. Although no cores were taken to definitively identify lithologies, well cuttings and petrophysical logs indicate that this well encountered basement metamorphic rocks consisting of schist, gneiss, and amphibolitic gneiss, all cut by aplite dikes. The well was cased and perforated in the Precambrian, and then acidized. After several days of swabbing operations, the well produced shows of low-Btu gas, dominated by the non-flammable component gases of nitrogen (20%), carbon dioxide (43%), and helium (1%). Combustible components include methane (26%), hydrogen (10%), and higher molecular-weight hydrocarbons (1%). Although Coveney and others [Am. Assoc. Petroleum Geologists Bull., v. 71, no, 1, p. 39–48, 1987] identified H₂-rich gas in two wells located close to the Midcontinent Rift in eastern Kansas, this study indicates that high levels of H₂ may be a more widespread phenomenon than previously thought. Unlike previous results, the gases in this study have a significant component of hydrocarbon gas, as well as H₂, N₂, and CO₂. Although redox reactions between iron-bearing minerals and groundwater are a possible source of H₂ in the Precambrian basement rocks, the hydrocarbon gas does not exhibit the characteristics typically associated with proposed abiogenic hydrocarbon gases from Precambrian Shield sites in Canada, Finland, and South Africa. Compositional and isotopic signatures for gas from the #1 Wilson well are consistent with a predominantly thermogenic origin, with possible mixing with a component of microbial gas. Given the geologic history of uplift and rifting this region, and the major fracture systems present in the basement, this hydrocarbon gas likely migrated from source rocks and reservoirs in the overlying Paleozoic sediments and is not evidence for abiogenic hydrocarbons generated in situ in the Precambrian basement.     

Stratospheric energetics and mass transport

Summary Two approaches are used to describe and distinguish between those regions of the atmosphere which most closely resemble heat engines and those which operate like refrigerators. Estimates of the conversion from eddy potential energy to mean zonal potential energy are presented as a function of height, latitude and season; the region of forced motion (or refrigerator) in the lower stratosphere appears to be closely related to the maximum westerly winds of the upper troposphere. A preliminary attempt is made to relate some values of mass transport derived from the observations of trace substances to the energy conversions.The research reported in this article was sponsored by the Atomic Energy Commission under Contract AT (30-1) 2241.     

Progress in Remediation of Groundwater at Petroleum Sites in California

Quantifying the overall progress in remediation of contaminated groundwater has been a significant challenge. We utilized the GeoTracker database to evaluate the progress in groundwater remediation from 2001 to 2011 at over 12,000 sites in California with contaminated groundwater. This paper presents an analysis of analytical results from over 2.1 million groundwater samples representing at least $100 million in laboratory analytical costs. Overall, the evaluation of monitoring data shows a large decrease in groundwater concentrations of gasoline constituents. For benzene, half of the sites showed a decrease in concentration of 85% or more. For methyl tert‐butyl ether (MTBE), this decrease was 96% and for TBE, 87%. At remediation sites in California, the median source attenuation rate was 0.18/year for benzene and 0.36/year for MTBE, corresponding to half‐lives of 3.9 and 1.9 years, respectively. Attenuation rates were positive (i.e., decreasing concentration) for benzene at 76% of sites and for MTBE at 85% of sites. An evaluation of sites with active remediation technologies suggests differences in technology effectiveness. The median attenuation rates for benzene and MTBE are higher at sites with soil vapor extraction or air sparging compared with sites without these technologies. In contrast, there was little difference in attenuation rates at sites with or without soil excavation, dual phase extraction, or in situ enhanced biodegradation. The evaluation of remediation technologies, however, did not evaluate whether specific systems were well designed or implemented and did not control for potential differences in other site factors, such as soil type.     

Field Investigation of Vapor‐Phase‐Based Groundwater Monitoring

The use of in‐field analysis of vapor‐phase samples to provide real‐time volatile organic compound (VOC) concentrations in groundwater has the potential to streamline monitoring by simplifying the sample collection and analysis process. A field validation program was completed to (1) evaluate methods for collection of vapor samples from monitoring wells and (2) evaluate the accuracy and precision of field‐portable instruments for the analysis of vapor‐phase samples. The field program evaluated three vapor‐phase sample collection methods: (1) headspace samples from two locations within the well, (2) passive vapor diffusion (PVD) samplers placed at the screened interval of the well, and (3) field vapor headspace analysis of groundwater samples. Two types of instruments were tested: a field‐portable gas chromatograph (GC) and a photoionization detector (PID). Field GC analysis of PVD samples showed no bias and good correlation to laboratory analysis of groundwater collected by low‐flow sampling (slope = 0.96, R² = 0.85) and laboratory analysis of passive water diffusion bag samples from the well screen (slope = 1.03; R² = 0.96). Field GC analysis of well headspace samples, either from the upper portion of the well or at the water‐vapor interface, resulted in higher variability and much poorer correlation (consistently biased low) relative to laboratory analysis of groundwater samples collected by low‐flow sample or passive diffusion bags (PDBs) (slope = 0.69 to 0.76; R² = 0.60 to 0.64). These results indicate that field analysis of vapor‐phase samples can be used to obtain accurate measurements of VOC concentrations in groundwater. However, vapor samples collected from the well headspace were not in equilibrium with water collected from the well screen. Instead, PVD samplers placed in the screened interval represent the most promising approach for field‐based measurement of groundwater concentrations using vapor monitoring techniques and will be the focus of further field testing.     

Characterization and Source History Modeling Using Low‐k Zone Profiles at Two Source Areas

Like tree rings, high‐resolution soil sampling of low‐permeability (low‐k) zones can be used to evaluate the style of source history at contaminated sites (i.e., historical pattern of concentration and composition vs. time since releases occurred at the interface with the low‐k zone). This is valuable for the development of conceptual site model (CSM) and can serve as an important line of evidence supporting monitored natural attenuation (MNA) as a long‐term remedy. Source histories were successfully reconstructed at two sites at Naval Air Station Jacksonville using a simple one‐dimensional (1D) model. The plume arrival time and historical composition were reconstructed from the time initial releases that were suspected to occur decades earlier. At the first site (Building 106), the source reconstructions showed relatively constant source concentrations, but significant attenuation over time in the downgradient plume in the transmissive zone, suggesting MNA may not be an appropriate remedy if source control is a requirement, but attenuation processes are clearly helping to maintain plume stability and reduce risk. At the second site (Building 780), source concentrations in the transmissive zone showed an approximately a one order of magnitude over time, but apparently less attenuation in the downgradient plume. The source reconstruction method appeared to reflect site remediation efforts (excavation, soil vapor extraction) implemented in the 1990s. Finally, a detailed analysis using molecular biological tools, carbon isotopes, and by‐products suggests that most degradation activity is associated with high‐k zones but not with low‐k zones at these source areas. Overall, the source reconstruction methodology provided insight into historical concentration trends not obtainable otherwise given the limited long‐term monitoring data.     

Time vs. Money: A Quantitative Evaluation of Monitoring Frequency vs. Monitoring Duration

The National Research Council has estimated that over 126,000 contaminated groundwater sites are unlikely to achieve low ug/L clean‐up goals in the foreseeable future. At these sites, cost‐effective, long‐term monitoring schemes are needed in order to understand the long‐term changes in contaminant concentrations. Current monitoring optimization schemes rely on site‐specific evaluations to optimize groundwater monitoring frequency. However, when using linear regression to estimate the long‐term zero‐order or first‐order contaminant attenuation rate, the effect of monitoring frequency and monitoring duration on the accuracy and confidence for the estimated attenuation rate is not site‐specific. For a fixed number of monitoring events, doubling the time between monitoring events (e.g., changing from quarterly monitoring to semi‐annual monitoring) will double the accuracy of estimated attenuation rate. For a fixed monitoring frequency (e.g., semi‐annual monitoring), increasing the number of monitoring events by 60% will double the accuracy of the estimated attenuation rate. Combining these two factors, doubling the time between monitoring events (e.g., quarterly monitoring to semi‐annual monitoring) while decreasing the total number of monitoring events by 38% will result in no change in the accuracy of the estimated attenuation rate. However, the time required to collect this dataset will increase by 25%. Understanding that the trade‐off between monitoring frequency and monitoring duration is not site‐specific should simplify the process of optimizing groundwater monitoring frequency at contaminated groundwater sites.     

Transport and retention in an upwelling region: The role of across-shelf structure

The paradox of upwelling is the relationship between strong wind forcing, nutrient enrichment, and shelf productivity. Here we investigate how across-shelf structure in velocity and hydrography plays a role in the retention (inshore) and export (offshore) of particles such as nutrients, plankton and larvae. We examine the spatial structure of the coastal currents during wind-driven upwelling and relaxation on the northern Californian Shelf. The field work was conducted as part of the Wind Events and Shelf Transport (WEST) project, a 5-year NSF/CoOP-funded study of the role of wind-driven transport in shelf productivity off Bodega Bay (northern California) from 2000 to 2003. We combine shipboard velocity profiles (ADCP) and water properties from hydrographic surveys during the upwelling season to examine the mean across-shelf structure of the hydrography and velocity fields during three contrasting upwelling seasons, and throughout the upwelling-relaxation cycle. We also present results from two winter seasons that serve as contrast to the upwelling seasons.During all three upwelling seasons clear spatial structure is evident in velocity and hydrography across the shelf, exemplified by current reversals inshore and the presence of a persistent upwelling jet at the shelf break. This jet feature changes in structure and distance from the coast under different wind forcing regimes. The jet also changes from the north of our region, where it is a single narrow jet, adjacent to the coast, and to the south of our region, where it broadens and at times two jets become evident. We present observations of the California Under Current, which was observed at the outer edge of our domain during all three upwelling seasons. The observed across-shelf structure could aid both in the retention of plankton inshore during periods of upwelling followed by relaxation and in the export of plankton offshore in the upwelling jet.