A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions

This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing N(E) equilibrium reactions and a set of reactive transport equations of M-N(E) kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.     

Spatial and temporal patterns of dissolved nitrogen and phosphorus in surface waters of a multi-land use basin

Research on relationships between dissolved nutrients and land-use at the watershed scale is a high priority for protecting surface water quality. We measured dissolved nitrogen (DN) and ortho-phosphorus (P) along 130 km of the Calapooia River (Oregon, USA) and 44 of its sub-basins for 3 years to test for associations with land-use. Nutrient concentrations were analyzed for spatial and seasonal patterns and for relationships with land-use and stream discharge. Ortho-P and DN were higher in lower-elevation sub-basins dominated by poorly drained soils and agricultural production compared with higher-elevation sub-basins dominated by well-drained soils and forests. Eight lower basins had at least one sample period with nitrate-N?>?10 mg L^?1. The Calapooia River had lower concentrations of dissolved nutrients compared with lower sub-basins, often by an order of magnitude. Dissolved organic N represented a greater proportion of DN in the upper forested sub-basins. Seasonal nutrient concentrations had strong positive correlations to the percent of a sub-basin that was managed for agriculture in all seasons (p?values?≤?0.019) except summer. Results suggest that agricultural lands are contributing to stream nutrient concentrations. However, poorly drained soils in agricultural areas may also contribute to the strong relationships that we found between dissolved nutrients and agriculture.     

Hydrologic Landscape Classification to Estimate Bristol Bay,Alaska Watershed Hydrology

Hydrologic landscapes (HLs) have proven to be a useful tool for broad scale assessment and classification of landscapes across the United States as they help organize larger geographical areas into areas of similar hydrologic characteristics. We developed a HL classification for the Bristol Bay watershed of southwest Alaska that incorporates indices of annual climate and seasonality, terrain, geology, and the influences of large lakes and glaciers. A HL classification is particularly useful in this large watershed because of its hydrologic and landscape variability, important salmon fishery, variety of environmental and potential anthropogenic stressors, and lack of widespread hydrologic data. Following creation of Bristol Bay basin‐wide HL classes, we compared the HL distributions within watersheds grouped by two calculated runoff parameters derived from available long‐term streamflow records and found HL distributions within these groups provided predictive insight on hydrologic behavior. Using these developed runoff groups, we estimated expected hydrologic behavior in watersheds across the larger Bristol Bay watershed that lacked gauged streamflow records. The HL approach provides a scientific basis for estimating the first‐order hydrologic behavior of watersheds and landscapes that lack detailed hydrologic information.     

Climate-Smart Design for Ecosystem Management: A Test Application for Coral Reefs

Environmental Management - The interactive and cumulative impacts of climate change on natural resources such as coral reefs present numerous challenges for conservation planning and management....     

The legitimacy of leadership in international climate change negotiations

Leadeship is an essential ingredient in reaching international agreements and overcoming the collective action problems associated with responding to climate change. In this study, we aim at answering two questions that are crucial for understanding the legitimacy of leadership in international climate change negotiations. Based on the responses of the three consecutive surveys distributed at COPs 14-16, we seek first to chart which actors are actually recognized as leaders by climate change negotiation participants. Second, we aim to explain what motivates COP participants to support different actors as leaders. Both these questions are indeed crucial for understanding the role, importance, and legitimacy of leadership in the international climate change regime. Our results show that the leadership landscape in this issue area is fragmented, with no one clear-cut leader, and strongly suggest that it is imperative for any actor seeking recognition as climate change leader to be perceived as being devoted to promoting the common good.     

Application of an Adapted Version of MT3DMS for Modeling Back‐Diffusion Remediation Timeframes

Simulation of back‐diffusion remediation timeframe for thin silt/clay layers, or when contaminant degradation is occurring, typically requires the use of a numerical model. Given the centimeter‐scale vertical grid spacing required to represent diffusion‐dominated transport, simulation of back‐diffusion in a 3‐D model may be computationally prohibitive. Use of a local 1‐D model domain approach for simulating back‐diffusion is demonstrated to have advantages but is limited to only some applications. Incorporation of a local domain approach for simulating back‐diffusion in a new model, In Situ Remediation‐MT3DMS (ISR‐MT3DMS) is validated based on a benchmark with MT3DMS and comparisons with a highly discretized finite difference numerical model. The approach used to estimate the vertical hydrodynamic dispersion coefficient is shown to have a significant influence on the simulated flux into and out of silt/clay layers in early time periods. Previously documented back‐diffusion at a Florida site is modeled for the purpose of evaluating the sensitivity of the back‐diffusion controlled remediation timeframe to various site characteristics. A base case simulation with a clay lens having a thickness of 0.2 m and a length of 100 m indicates that even after 99.96 percent aqueous TCE removal from the clay lens, the down‐gradient concentrations still exceed the MCL in groundwater monitoring wells. This shows that partial mass reduction from a NAPL source zone via in situ treatment may have little benefit for the long‐term management of contaminated sites, given that back‐diffusion will sustain a groundwater plume for a long period of time. Back‐diffusion model input parameters that have the greatest influence on remediation timeframe and thus may warrant more attention during field investigations, include the thickness of silt/clay lenses, retardation coefficient representing sorbed mass in silt/clay, and the groundwater velocity in adjacent higher permeability zones. Therefore, pump‐and‐treat systems implemented for the purpose of providing containment may have an additional benefit of reducing back‐diffusion remediation timeframe due to enhanced transverse advective fluxes at the sand/clay interface. Remediation timeframes are also moderately sensitive to the length of the silt/clay layers and transverse vertical dispersivity, but are less sensitive to degradation rates within silt/clay, contaminant solubility, contact time, tortuosity coefficient, and monitoring well‐screen length for the scenarios examined. ©2015 Wiley Periodicals, Inc.     

A Tracer Study of Headspace Ventilation in a Collector Sewer

ABSTRACT

A field-scale tracer test was conducted to evaluate in-situ ventilation rates in a major collector sewer. The sewer under study was ~11 km long and ranged from 0.61 to 2.1 m in diameter. For the purposes of the tracer testing, the collector was divided into four reaches, each of which was tested individually. The tracer test involved injecting a measured volume of CO gas into a manhole over a short time period. CO concentrations were then measured in the collector headspace at selected manholes along the length of the reach.

The technique employed successfully measured average headspace velocities over extended lengths of the collector. In a section that had a relatively stagnant headspace, ~1.1 km of sewer could be evaluated, with substantial tracer loss attributed to losses to manholes. In a section of the sewer with elevated headspace velocities, a section ~7.0 km long was successfully tested with one injection of tracer gas. The velocities observed in the collector varied substantially with time and location in the collector. The lowest velocities measured were in the upstream sections, with a minimum observed value of 3.8 m/min. The highest velocities were observed in the downstream sections, with a maximum value of 31.5 m/min. The presence of a substantial drop structure appeared to reduce the headspace velocity in the upstream reach. In general, there was an increasing trend in gas-phase flows with distance along the length of the collector. Flows at the discharge end of the collector were almost 2 orders of magnitude greater than those at the beginning.