Analysis of munitions constituents in groundwater using a field-portable GC-MS

The use of munitions constituents (MCs) at military installations can produce soil and groundwater contamination that requires periodic monitoring even after training or manufacturing activities have ceased. Traditional groundwater monitoring methods require large volumes of aqueous samples (e.g., 2-4 L) to be shipped under chain of custody, to fixed laboratories for analysis. The samples must also be packed on ice and shielded from light to minimize degradation that may occur during transport and storage. The laboratory’s turn-around time for sample analysis and reporting can be as long as 45 d. This process hinders the reporting of data to customers in a timely manner; yields data that are not necessarily representative of current site conditions owing to the lag time between sample collection and reporting; and incurs significant shipping costs for samples.The current work compares a field portable Gas Chromatograph-Mass Spectrometer (GC-MS) for analysis of MCs on-site with traditional laboratory-based analysis using High Performance Liquid Chromatography with UV absorption detection. The field method provides near real-time (within ∼1 h of sampling) concentrations of MCs in groundwater samples. Mass spectrometry provides reliable confirmation of MCs and a means to identify unknown compounds that are potential false positives for methods with UV and other non-selective detectors.     

Developing a translational discourse to communicate uncertainty in flood risk between science and the practitioner

The language and tools of risk and uncertainty estimation in flood risk management (FRM) are rarely optimized for the extant communication challenge. This paper develops the rationale for a pragmatic semiotics of risk communication between scientists developing flood models and forecasts and those professional groups who are the receptors for flood risk estimates and warnings in the UK. The current barriers to effective communication and the constraints involved in the formation of a communication language are explored, focusing on the role of the professional's agenda or "mission" in creating or reducing those constraints. The tools available for the development of this discourse, for both flood warnings in real time and generalized FRM communications, are outlined. It is argued that the contested ownership of the articulation of uncertainties embedded in flood risk communications could be reduced by the development of a formally structured translational discourse between science and professionals in FRM, through which process "codes of practice" for uncertainty estimation in different application areas can be developed. Ways in which this might take place in an institutional context are considered.     

Modeling dispersion from toxic gas released after a train collision in Graniteville, SC

The Savannah River National Laboratory (SRNL) Weather Information and Display System was used to provide meteorological and atmospheric modeling/consequence assessment support to state and local agencies after the collision of two Norfolk Southern freight trains on the morning of January 6, 2005. This collision resulted in the release of several toxic chemicals to the environment, including chlorine. The dense and highly toxic cloud of chlorine gas that formed in the vicinity of the accident was responsible for 9 fatalities and caused injuries to more than 500 others. Transport model results depicting the forecast path of the ongoing release were made available to emergency managers in the county's Unified Command Center shortly after SRNL received a request for assistance. Support continued over the ensuing 2 days of the active response. The SRNL also provided weather briefings and transport/consequence assessment model results to responders from the South Carolina Department of Health and Environmental Control, the Savannah River Site (SRS) Emergency Operations Center, Department of Energy headquarters, and hazard material teams dispatched from the SRS. Operational model-generated forecast winds used in consequence assessments conducted during the incident were provided at 2-km horizontal grid spacing during the accident response. High-resolution Regional Atmospheric Modeling System (RAMS, version 4.3.0) simulation was later performed to examine potential influences of local topography on plume migration in greater detail. The detailed RAMS simulation was used to determine meteorology using multiple grids with an innermost grid spacing of 125 m. Results from the two simulations are shown to generally agree with meteorological observations at the time; consequently, local topography did not significantly affect wind in the area. Use of a dense gas dispersion model to simulate localized plume behavior using the higher-resolution winds indicated agreement with fatalities in the immediate area and visible damage to vegetation.     

New insights into the benefits of flood warnings: Results from a household survey in England and Wales

The flood defence agency in England and Wales has been pursuing a programme of flood warning system enhancement, engaging householders at risk in improving their warning responses. The immediate aim of this paper is to test and revise a model of economic benefits of warnings, but the survey data also generate insights into the constraints acting upon flood warning responses. Damage saving is less than previously anticipated: warning reliability and householder availability problems limit savings. Warnings are less likely to be received by those in lower social grades, and flood warning lead time is a factor in avoiding damage. The survey data indicate the complexities involved in improving flood warning response, and provide policy pointers.     

Oceanographic influences on the dive behavior of juvenile loggerhead turtles (Caretta caretta) in the North Pacific Ocean

Satellite telemetry data from 17 juvenile loggerhead turtles (43.5–66.5 cm straight carapace length) were used in conjunction with oceanographic data to analyze the influence of regional and seasonal oceanography on dive behavior in the North Pacific Ocean. Combined dive behavior for all individuals showed that turtles spent more than 80% of their time at depths <5 m, and more than 90% of their time at depths <15 m. Multivariate classifications of dive data revealed four major dive types, three representing deeper, longer dives, and one representing shallower dives shorter in duration. Turtles exhibited variability in these dive types across oceanographic regions, with deeper, longer dives in the Hawaii longline swordfish fishing grounds during the first quarter of the year, as well as in the Kuroshio Extension Bifurcation Region and the region near the Baja California Peninsula, Mexico. Turtles in the Kuroshio Extension Bifurcation Region also exhibited dive variability associated with mesoscale eddy features, with turtles making deeper, longer dives while associated with the strongest total kinetic energy. Turtles in the central North Pacific exhibited seasonality in dive behavior that appeared to reflect synchronous latitudinal movements with the North Pacific Subtropical Front and the associated seasonal, large-scale oceanography. Turtles made deeper, longer dives during the first quarter of the year within this region, the reported time and area where the highest loggerhead bycatch occurs by the longline fishery. These results represent the first comprehensive study of dive data for this species in this region. The increased understanding of juvenile loggerhead dive behavior and the influences of oceanography on dive variability should provide further insight into why interactions with longline fisheries occur and suggest methods for reducing the bycatch of this threatened species.     

The UN climate change negotiations and the role of the United States: assessing American leadership from Copenhagen to Paris

The role of American leadership in the UN climate negotiations that produced the 2015 Paris Agreement is examined. First, United States (US) climate goals are identified. Then, utilizing unique survey data collected at eight UN climate summits between 2008 and 2015, the extent to which the US was recognized as a leader by potential followers is investigated. Finally, the extent to which US goals are reflected in negotiation outcomes is evaluated. Recognition of the US as a leader varied over time, peaking at the UN climate meetings in Copenhagen and Paris, reflecting US leadership in shaping the outcomes of both meetings. Although the results reveal a divided leadership landscape in which the US must compete for leadership with other actors, such as the European Union and China, US leadership was crucial to the successful adoption of the Paris Agreement.     

Long-term ground penetrating radar monitoring of a small volume DNAPL release in a natural groundwater flow field

An earlier field experiment at Canadian Forces Base Borden by Brewster and Annan [Geophysics 59 (1994) 1211] clearly demonstrated the capability of ground penetrating radar (GPR) reflection profiling to detect and monitor the formation of DNAPL layers in the subsurface. Their experiment involved a large volume release (770 L) of tetrachloroethylene into a portion of the sand aquifer that was hydraulically isolated from groundwater flow by sheet pile walls. In this study, we evaluated the ability of GPR profiling to detect and monitor much smaller volume releases (50 L). No subsurface confining structure was used in this experiment; hence, the DNAPL impacted zone was subjected to the natural groundwater flow regime. This condition allowed us to geophysically monitor the DNAPL mass loss over a 66 month period. Reflectivity variations on the GPR profiles were used to infer the presence and evolution of the solvent layers. GPR imaging found significant reflectivity increases due to solvent layer formation during the two week period immediately after the release. These results demonstrated the capacity of GPR profiling for the detection and monitoring of lesser volume DNAPL releases that are more representative of small-scale industrial spills. The GPR imaged solvent layers subsequently reduced in both areal extent and reflectivity after 29 months and almost completely disappeared by the end of the 66 month monitoring period. Total DNAPL mass estimates based on GPR profiling data indicated that the solvent mass was reduced to 34%-36% of its maximum value after 29 months; only 4%-9% of the solvent mass remained in the study area after 66 months. These results are consistent with independent hydrogeological estimates of remaining DNAPL mass based on the downgradient monitoring of the dissolved solvent phase. Hence, we have concluded that the long-term GPR reflectivity changes of the DNAPL layers are likely the result from the dissolution of chlorinated solvents residing in those layers. The long-term monitoring results demonstrated that GPR profiling is a promising non-invasive method for use at DNAPL contaminated sites in sandy aquifers where temporal information about immiscible contaminant mass depletion due to either natural flow or remediation is needed. However, our results also indicated that the GPR signature of older DNAPL impacted zones may not differ greatly from the uncontaminated background if significant mass reduction due to dissolution has occurred.     

Three-dimensional density-dependent flow and multicomponent reactive transport modeling of chlorinated solvent oxidation by potassium permanganate

A popular method for the treatment of aquifers contaminated with chlorinated solvents is chemical oxidation based on the injection of potassium permanganate (KMnO₄). Both the high density (1025 gL^− 1) and reactivity of the treatment solution influence the fate of permanganate (MnO₄) in the subsurface and affect the degree of contaminant treatment. The MIN3P multicomponent reactive transport code was enhanced to simulate permanganate-based remediation, to evaluate the pathways of MnO₄ utilization, and to assess the role of density contrasts for the delivery of the treatment solution. The modified code (MIN3P-D) provides a direct coupling between density-dependent fluid flow, solute transport, contaminant treatment, and geochemical reactions. The model is used to simulate a field trial of TCE oxidation in a sandy aquifer that is underlain by an aquitard. Three-dimensional simulations are conducted for a coupled reactive system comprised of ten aqueous components, two mineral phases, TCE (dissolved, adsorbed, and NAPL), reactive organic matter, and including ion exchange reactions. Model parameters are constrained by literature data and a detailed data set from the field site under investigation. The general spatial and transient evolution in observed concentrations of the oxidant, dissolved TCE, and reaction products are adequately reproduced by the simulations. The model elucidates the important role of density-induced flow and transport on the distribution of the treatment solution into NAPL containing regions located at the aquifer–aquitard interface. Model results further suggest that reactions that do not directly affect the stability of MnO₄ have a negligible effect on solution density and MnO₄ delivery.     

Changes in the leachability of metals from dredged canal sediments during drying and oxidation

The behaviour of metals in canal sediments after their disposal to land has important implications for the environmental management of canal dredgings. The leaching behaviour of trace metals was investigated in a laboratory-based experiment using sediment from a canal in the UK (139 mg Zn kg-1dry sediment, 1.1 mg Cd, kg-1dry sediment 31.5 mg Cr kg-1dry sediment, 20.6 mg Cu kg-1dry sediment 48.4 mg Ni kg-1dry sediment, 43.4 mg Pb kg-1dry sediment and 7.6 mg As kg-1dry sediment). The sediment was allowed to dry. Cores (10 cm long) of the drying canal sediment were taken over a period of 12 weeks. A simple water extraction procedure was used to investigate changes in metal leachability at varying depths through the cores. Metal leachability increased over the first five weeks of drying and then subsequently decreased between weeks five and twelve, (e.g. Cd increased from approximately 0.006 to 0.018 mg/kgsediment then decreased to approximately 0.006 mg/kgsediment, Zn increased from approximately 1.5 to 3 mg/kgsediment and then decreased to approximately 1.5 mg/kgsediment). These results were combined with sulphide/sulphate ratios, which showed a decrease as the sediment dried (e.g. at 2-4 cm depth from approximately 1 to 0.49), and BCR sequential extraction data. Most metals (except Cd and As) showed a redistribution from the residual phase into more mobile phases as the sediment dried and oxidised. Metal leachability was strongly correlated with the sulphide/sulphate ratio with leachability normally increasing with decreasing sulphide/sulphate ratio. The combined results were used to infer the likely behaviour of dredged material upon disposal to land.