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Groundwater hydrology and chemistry of Jamestown Island, Virginia—Potential effects of tides, storm surges, and sea-level rise on archaeological, cultural, and ecological resources

As the site of the first permanent English settlement in North America in 1607, Jamestown Island, Colonial National Historical Park (COLO), Virginia, contains a rich archaeological record that extends from the Paleoindian period (15,000 to 8,000 years ago) through the 20th century. The island is located on the lower James River near the mouth of Chesapeake Bay. Jamestown Island vegetation is dominated by upland forests surrounded by tidal, freshwater-to-oligohaline marshes. Along the Virginia coast, relative sea-level rise was more than 2.5 times the global average during the 20th century. Consequently, the National Park Service (NPS) has identified COLO as one of the 25 national parks most threatened by climate change. Surface waters across the island are hydraulically connected to the laterally continuous Surficial aquifer. The land-surface altitude of the island is low, with two-thirds of the island less than 5 feet (ft) above the North American Vertical Datum of 1988 (NAVD 88). Consequently, sea-level rise, combined with tides and storm surges, threatens the island and its resources as surface-water and groundwater levels rise, saltwater enters the Surficial aquifer, and groundwater chemistry changes. The impact of sea-level rise on the island’s surface-water resources has been well studied, but groundwater effects have been largely ignored. Quantifying the effects of tides, storm surges, and sea-level rise on groundwater levels and chemistry is essential to developing an effective strategy for managing climate-induced changes. The first step in developing a response strategy includes a parkwide general risk assessment for archaeological sites on the island, so that sites can be prioritized for management actions. The U.S. Geological Survey and the NPS began a study in 2015 to develop a long-term groundwater-monitoring program to evaluate this risk and to develop an updated management strategy. The groundwater-monitoring program consists of 45 wells and piezometers in two individual clusters and three transects across the island in different hydrologic and chemical settings. Samples for water quality were collected from the wells and piezometers from October 2015 through September 2018 at variable time intervals. Results of the monitoring identified disparate hydrologic and chemical responses to saltwater intrusion across the island. Specific conductance (an indicator of salinity) of groundwater beneath several marshes responded differently to changes in James River salinity. Groundwater response to changes in James River specific conductance appeared to be controlled by land-surface altitude and slope, differences in lateral and vertical sediment characteristics, distance from surface waters, and the degree of surface water/groundwater connectivity between channels and the aquifer. Groundwater chemistry data from monitoring wells at Black Point, a low-altitude, upland setting, are in contrast with conditions observed in Island House observation wells, a high-altitude, upland setting. Specific conductance (less than 200 microsiemens per centimeter [μS/cm]) and pH (greater than 5.0) of groundwater beneath much of the uplands that characterize the Island House observation wells are typical of groundwater in noncarbonate sedimentary aquifers recharged by precipitation. At Black Point, specific conductance ranged from 2,490 to 15,200 μS/cm, and pH ranged from 3.1 to 6.6 standard units. At the Black Point observation wells, the most saline and dense water was at the water table rather than deeper in the aquifer, causing a density inversion that persisted throughout the study. The density inversion likely resulted from differences in permeability between the shallow clay and fine-grained sands and the deeper coarse-grained sand and gravel. Groundwater with the lowest pH was at the water table. As saline groundwater flows through organic sediment beneath the marshes, bacterial biodegradation of organic matter creates anoxic conditions. Continued biodegradation concomitantly reduces iron-oxide minerals in the sediment and sulfate in saline water. When oxygen is reintroduced into groundwater, iron and sulfur can reoxidize to form sulfuric acid, locally lowering the pH of the water. This report describes the groundwater monitoring network design, rationale for site selection, monitoring approach, and results of monitoring from October 2015 through September 2018. Maps of inundation at selected water-level altitudes are included to identify the risk to archaeological, cultural, and ecological resources. The monitoring results of the hydrology and chemistry data are interpreted, and the different hydrologic and chemical settings are described. The implications of the study results for management decisions are presented, and suggestions for improving the monitoring network are included.

Virginia

Methodology for estimating times of remediation associated with monitored natural attenuation

Natural attenuation processes combine to disperse, immobilize, and biologically transform anthropogenic contaminants, such as petroleum hydrocarbons and chlorinated ethenes, in ground-water systems. The time required for these processes to lower contaminant concentrations to levels protective of human health and the environment, however, varies widely between different hydrologic systems, different chemical contaminants, and varying amounts of contaminants. This report outlines a method for estimating timeframes required for natural attenuation processes, such as dispersion, sorption, and biodegradation, to lower contaminant concentrations and mass to predetermined regulatory goals in groundwater systems. The time-of-remediation (TOR) problem described in this report is formulated as three interactive components: (1) estimating the length of a contaminant plume once it has achieved a steady-state configuration from a source area of constant contaminant concentration, (2) estimating the time required for a plume to shrink to a smaller, regulatoryacceptable configuration when source-area contaminant concentrations are lowered by engineered methods, and (3) estimating the time needed for nonaqueous phase liquid (NAPL) contaminants to dissolve, disperse, and biodegrade below predetermined levels in contaminant source areas. This conceptualization was used to develop Natural Attenuation Software (NAS), an interactive computer aquifers. NAS was designed as a screening tool and requires the input of detailed site information about hydrogeology, redox conditions, and the distribution of contaminants. Because NAS is based on numerous simplifications of hydrologic, microbial, and geochemical processes, the program may introduce unacceptable errors for highly heterogeneous hydrologic systems. In such cases, application of the TOR framework outlined in this report may require more detailed, site-specific digital modeling. The NAS software may be downloaded from the Web site http://www.cee.vt.edu/NAS/ Application of NAS illustrates several general characteristics shared by all TOR problems. First, the distance of stabilization of a contaminant plume is strongly dependent on the natural attenuation capacity of particular ground-water systems. The time that it takes a plume to reach a steady-state configuration, however, is independent of natural attenuation capacity. Rather, the time of stabilization is most strongly affected by the sorptive capacity of the aquifer, which is dependent on the organic matter content of the aquifer sediments, as well as the sorptive properties of individual contaminants. As a general rule, a high sorptive capacity retards a plume.s growth or shrinkage, and increases the time of stabilization. Finally, the time of NAPL dissolution depends largely on NAPL mass, composition, geometry, and hydrologic factors, such as ground-water flow rates. An example TOR analysis for petroleum hydrocarbon NAPL was performed for the Laurel Bay site in South Carolina. About 500 to 1,000 pounds of gasoline leaked into the aquifer at this site in 1991, and the NAS simulations suggested that TOR would be on the order of 10 years for soluble and poorly sorbed compounds, such as benzene and methyl tertiary-butyl ether (MTBE). Conversely, TOR would be on the order of 40 years for less soluble, more strongly sorbed compounds, such as toluene, ethylbenzene, and xylenes (TEX). These TOR estimates are roughly consistent with contaminant concentrations observed over 10 years of monitoring at this site where benzene and MTBE concentrations were observed to decrease rapidly and are approaching regulatory maximum concentration limits, whereas toluene, ethylbenzene, and xylene concentrations decreased at a slower rate and have remained relatively high. An example TOR analysis for petroleum hydrocarbon NAPL was performed for the Laurel Bay site in South Carolina.

South Carolina

Processes affecting the trihalomethane concentrations associated with the third injection, storage, and recovery rest at Lancaster, Antelope Valley, California, March 1998 through April 1999

The formation and fate of trihalomethanes (THM) during the third injection, storage, and recovery test at Lancaster, Antelope Valley, California, were investigated as part of a program to assess the long-term feasibility of using injection, storage, and recovery as a water-supply method and as a way to reduce water-level declines and land-subsidence in the Antelope Valley. The program was conducted by the U.S. Geological Survey in cooperation with the Los Angeles County Department of Public Works and the Antelope Valley-East Kern Water Agency. The water used for injection, storage, and recovery must be disinfected before injection and thus contains THMs and other disinfection by-products. THMs (chloroform, CHCl3, bromodichloromethane, CHCl2Br, dibromochloromethane, CHClBr2, and bromoform, CHBr3) are formed by reaction between natural dissolved organic carbon that is present in water and chlorine that is added during the disinfection step of the drinking water treatment process. THMs are carcinogenic compounds, and their concentrations in drinking water are regulated by the U.S. Environmental Protection Agency. During previous cycles of the Lancaster program, extracted water still contained measurable concentrations of THMs long after continuous pumping had extracted a greater volume of water than had been injected. This raised concerns about the potential long-term effect of injection, storage, and recovery cycles on ground-water quality in Antelope Valley aquifers. The primary objectives of this investigation were to determine (1) what controlled continued THM formation in the aquifer after injection, (2) what caused of the persistence of THMs in the extracted water, even after long periods of pumping, (3) what controlled the decrease of THM concentrations during the extraction period, and (4) the potential for natural attenuation of THMs in the aquifer. Laboratory experiments on biodegradation of THMs in microcosms of aquifer materials indicate that aquifer bacteria did not degrade CHCl3 or CHBr3 under aerobic conditions, but did degrade CHBr3 under anaerobic conditions. However, the aquifer is naturally aerobic and CHCl3 is the dominant THM species; therefore, biodegradation is not considered an important attenuation mechanism for THMs in this aquifer. The alluvial-fan sediments comprising the aquifer have very low contents of organic matter; therefore, sorption is not considered to be an important attenuation mechanism for THMs in this aquifer. Laboratory experiments on formation of THMs in the injection water indicate that continued THM formation in the injection water after injection into the aquifer was limited by the amount of residual chlorine in the injection water at the time of injection. After accounting for THMs formed by reaction of this residual chlorine, THMs behaved as conservative constituents in the aquifer, and the only process affecting the concentration of THMs was mixing of the injection water and the ground water. The mixing process was quantified using mass balances of injected constituents, the sulfur hexafluoride (SF6) tracer that was added to the injected water, and a simple descriptive mathematical mixing model. Mass balance calculations show that only 67 percent of the injected THMs and chloride were recovered by the time that a volume of water equivalent to 132 percent of the injection water volume was extracted. Pumping 250 percent of the injection water volume only increased recovery of injected THMs to 80 percent. THM and SF6 concentrations in the extracted water decreased concomitantly during the extraction period, and THM concentrations predicted from SF6 concentrations closely matched the measured THM concentrations. Because SF6 is a conservative tracer that was initially only present in the injection water, parallel decreases in SF6 and THM concentrations in the extracted water must be due to dilution of injection water with ground water. The simple descriptive mixing mode

Water-Resources Investigations Report

Fate and Transport Modeling of Selected Chlorinated Organic Compounds at Hangar 1000, U.S. Naval Air Station, Jacksonville, Florida

The Jacksonville Naval Air Station occupies 3,800 acres adjacent to the St. Johns River in Jacksonville, Florida. Two underground storage tanks at Hangar 1000 contained solvents from the late 1960s until they were removed in 1994. Ground-water samples at one of the tank sites had levels of trichloroethene (TCE) and total dichloroethene (DCE) of 8,710 micrograms per liter (mg/L) and 4,280 mg/L, respectively. Vinyl chloride (VC) at the site is the result of the biodegradation of DCE. Ground water beneath Hangar 1000 flows toward a storm sewer. TCE and DCE plumes travel with the ground water and presumably have reached the storm sewer, which discharges to the St. Johns River. Simulation of solute transport indicates that the traveltime from the storage tank site to the storm sewer is 16, 14, and 12 years for TCE, DCE, and VC respectively. TCE has the longest traveltime because it has the highest retardation factor at 2.5, DCE takes less time with a retardation factor of 2.0, and VC has the quickest traveltime because it has the lowest retardation factor of 1.7. Based on modeling results, the release of contaminants in the aquifer occurred more than 16 years ago. Model-derived dispersivity values at Hangar 1000 were: longitudinal 1.5 feet (ft), transverse 0.27 ft, and vertical 0.27 ft. The model-derived first order decay rates for biodegradation of TCE, DCE, and VC were 0.0002 per day (d-1), 0.0002 d-1, and 0.06 d-1, respectively. These rates are equivalent to half-lives of 13.7 years for TCE and DCE and 17 days for VC. Source area reductions in contaminant concentrations of 50 and 100 percent were modeled to simulate remediation. As expected, reducing the source concentration by 50 percent resulted in eventual TCE, DCE, and VC concentrations that were half of the original concentrations. About 16 years were needed for new steady-state TCE concentrations to develop, about 14 years for DCE, and about 12 years for VC. Reducing the source area concentrations by 100 percent in the model eventually resulted in zero concentrations of TCE, DCE, and VC. The modeled period of time for the contaminants to be removed from the aquifer once the source was removed was about 17 years for TCE, 15 years for DCE, and 13 years for VC.

Water-Resources Investigations Report

Assessment of intrinsic bioremediation of gasoline contamination in the shallow aquifer, Laurel Bay Exchange, Marine Corps Air Station Beaufort, South Carolina

Laboratory, field, and digital solute-transport- modeling studies demonstrate that microorganisms indigenous to the shallow ground-water system at Laurel Bay Exchange, Marine Corps Air Station Beaufort, South Carolina, can degrade petroleum hydrocarbons in gasoline released at the site. Microorganisms in aquifer sediments incubated in the laboratory under aerobic and anaerobic conditions mineralized radiolabeled carbon 14-toluene to 14 C-carbon dioxide with first-order rate constants of K bio = -0.640 per day and K bio = -0.003 per day, respectively. Digital solute- transport modeling using the numerical code SUTRA revealed that anaerobic biodegradation of benzene occurs with a first-order rate constant near K bio = -0.00025 per day. Sandy aquifer material beneath Laurel Bay Exchange is characterized by relatively high hydraulic conductivities (K aq = 8.9 to 17.3 feet per day), average ground-water flow rate of about 60 feet per year, and a relatively uniform hydraulic gradient of 0.004 feet per foot. The sandy aquifer material also has low adsorptive potentials for toluene and benzene (both about K ad = 2.0 x 10 -9 cubic feet per milligram), because of the lack of natural organic matter in the aquifer. The combination of this ground-water-flow rate and absence of significant adsorptive capacity in the aquifer permits toluene and benzene concentrations to be detected downgradient from the source area in monitoring wells, even though biodegradation of these compounds has been demonstrated. Solute-transport simulations, however, indicate that toluene and benzene will not reach the Broad River, the nearest point of contact with wildlife or human populations, about 3,600 feet west of the site boundary. These simulations also show that contamination will not be transported to the nearest Marine Corps property line about 2,400 feet south of the site. This is primarily because the source of contaminants has essentially been removed, and the low adsorptive capacity of the aquifer sediments has prevented the occurrence of an adsorbed, continuous source of petroleum hydrocarbons. Therefore, digital simulations of toluene and benzene transport at Laurel Bay Exchange indicate that intrinsic bioremediation could be a successful remediation alternative for prohibiting transport of dissolved toluene and benzene to the Broad River.

South Carolina

Geology, hydrogeology, and potential of intrinsic bioremediation at the National Park Service Dockside II site and adjacent areas, Charleston, South Carolina, 1993-94

A long history of industrial and commercial use of the National Park Service property and adjacent properties located in downtown Charleston, South Carolina, has caused extensive contamination of the shallow subsurface soils and water-table aquifer. The National Park Service property is located adjacent to a former manufactured-gas plant site, which is the major source of the contamination. Contamination of this shallow water-table aquifer is of concern because shallow ground water discharges to the Cooper River and contains contaminants, which may affect adjacent wildlife or human populations. The geology of the National Park Service property above the Ashley Formation of the Cooper Group consists of two Quaternary lithostratigraphic marine units, the Wando Formation and Holocene deposits, overlain by artificial fill. The Wando Formation overlies the Ashley Formation, a sandy calcareous clay, and consists of soft, organic clay overlain by gray sand. The Holocene deposits are composed of clayey to silty sand and soft organic-rich clay. The artificial fill, which was placed at the site to create dry land where salt marsh existed previously, is composed of sand, silt, and various scrap materials. The shallow hydrogeology of the National Park Service property overlying the Ashley Formation can be subdivided into two sandy aquifers separated by a leaky, black, organic-rich clay. The unconfined upper surficial aquifer is primarily artificial fill. The lower surficial aquifer consists of the Wando sand unit and is confined by the leaky organic-rich clay. Aquifer tests performed on the wells screened in these aquifers resulted in hydraulic conductivities from 0.1 to 10 feet per day for the upper surficial aquifer, and 16 feet per day for the lower surficial aquifer. Vertical hydraulic gradients at the site are typically low. A downward gradient from the upper surficial aquifer to the lower surficial aquifer occurs throughout most of the year. A brick-lined storm-water-drainage archway located in the study area is a conduit for the overflow of seawater into the surficial aquifer during exceptionally high tides. The efficiency of intrinsic bioremediation to reduce contaminant migration in the upper surficial aquifer at the National Park Service site was assessed to determine if, and at what concentrations, contaminants are being transported to the Cooper River. This assessment required incorporating hydrologic, geochemical, microbiologic, and demographic information into a predictive solute-transport model to determine rates of contaminant transport to the Cooper River. The transport of toluene and naphthalene was modeled as a surrogate for the transport of aromatic and other hydrocarbon compounds at the study area. Laboratory estimates of the adsorption coefficients for sediments of the upper surficial aquifer suggest preferential adsorption of naphthalene over toluene. The adsorption coefficient of naphthalene is at least two orders of magnitude greater than that determined for toluene. Laboratory microbial-biodegradation experiments indicate that microorganisms present in the shallow aquifer have the potential to degrade toluene under anaerobic and aerobic conditions, and naphthalene primarily under aerobic conditions. Rates of microbial biodegradation are similar for both compounds under aerobic conditions. Flow-model calibration to the January 1994 water-table surface of the upper surficial aquifer was achieved by specifying appropriate hydrogeologic boundary conditions and using hydraulic conductivity values determined in the field. The brick-lined storm-water drainage archway located in the study area was modeled to account for ground-water discharge through this drain. An exploratory modeling approach was used to evaluate the range of possible solutions that approximate the transport of contaminants to the observed distributions. Approximate toluene solute-transport conditions for January 1994 were estimated using velocity dist

South Carolina

Arsenic in petroleum-contaminated groundwater near Bemidji, Minnesota is predicted to persist for centuries

We used a reactive transport model to investigate the cycling of geogenic arsenic (As) in a petroleum-contaminated aquifer. We simulated As mobilization and sequestration using surface complexation reactions with Fe(OH) 3 during petroleum biodegradation coupled with Fe-reduction. Model results predict that dissolved As in the plume will exceed the U.S. and EU 10 µg/L drinking water standard for ~400 years. Non-volatile dissolved organic carbon (NVDOC) in the model promotes As mobilization by exerting oxygen demand, which maintains anoxic conditions in the aquifer. After NVDOC degrades, As re-associates with Fe(OH) 3 as oxygenated conditions are re-established. Over the 400-year simulation, As transport resembles a “roll front” in which: (1) arsenic sorbed to Fe(OH) 3 is released during Fe-reduction coupled to petroleum biodegradation; (2) dissolved As resorbs to Fe(OH) 3 at the plume’s leading edge; and (3) over time, the plume expands, and resorbed As is re-released into groundwater. This “roll front” behavior underscores the transience of sorption as an As attenuation mechanism. Over the plume’s lifespan, simulations suggest that As will contaminate more groundwater than benzene from the oil spill. At its maximum, the model simulates that ~5.7× more groundwater will be contaminated by As than benzene, suggesting that As could pose a greater long-term water quality threat than benzene in this petroleum-contaminated aquifer.

Minnesota

Alkylcyclohexanes in environmental geochemistry

Two case studies of oil spills that demonstrate the changing distribution patterns resulting from long-term anaerobic microbial degradation were presented. These spills were the 1979 crude-oil spill in Bemidji, MN, and a chronic diesel-fuel spillage from 1953-1991 at Mandan, ND. The alkylcyclohexanes in both spilled oil products were affected by similar biodegradative processes in which the compounds underwent a consistent pattern of loss from the high molecular weight end of the homolog distribution. Degradation resulted in a measurable increase in the concentrations of the homologs in the lower molecular weight range, a gradual lowering in carbon number of the homolog maximum, and a gradual decrease of the total homolog range from the high molecular weight end. The Mandan diesel fuel spill showed that the progressive enhancement of the low-molecular-mass n-alkane and n-alkylcyclohexane homologs reflected an absolute increase in their concentrations as the high-molecular-mass homologs were diminishing. These degradation patterns were different from those observed in aerobic or physically weathered systems, where loss of n-alkenes and other aliphatic homologs occurred from the low molecular weight end of the distributions. Spilled diesel and other mid-cut refinery fuels were defined by the range and distribution of the n-alkylcyclohexanes. If the biodegradation has progressed well into or beyond n-alkane loss and to the stage of low-molecular-mass n-alkylcyclohexane enhancement and high-molecular-mass loss, the hydrocarbon pattern could be erroneously attributed to other lower-range middle distillate fuels or admixtures of fuels. This is an abstract presented at the 25th Arctic and Marine OilSpill Program Technical Seminar (Calgary, Alberta, 6/11-13/2002).

Conference Paper

Ground-water microbiology and geochemistry

Up-to-date coverage and a unique, multidisciplinary approach The ongoing effort to protect our valuable ground-water resources necessarily involves scientists and engineers from many disciplines. Ground-Water Microbiology and Geochemistry, Second Edition is designed to bridge the historical lack of communication among these disciplines by detailing-in language that cuts across specialties-the impact of microorganisms and microbial processes on ground-water systems. Carefully revised to reflect the many recent discoveries that have been made in the field, the Second Edition begins with an overview of microbiology, ideal for hydrologists and others who may lack formal training in the field. These initial chapters systematically cover the kinds of microorganisms found in subsurface environments, focusing on their growth, metabolism, genetics, and ecology. The second part of the book offers a hydrologic perspective on how microbial processes affect ground-water geochemistry in pristine systems. It also introduces the different classes of ground-water systems, and gives an overview of techniques for sampling subsurface environments. Readers gain an understanding of biogeochemical cycling in ground-water systems-in coverage unique to this book-and how ground-water chemistry can be used to study microbial processes in aquifer systems. The final section of the book deals with the biodegradation of human-introduced contaminants in ground-water systems, with an up-to-date review of the physiology, biochemistry, and redox conditions that favor biodegradation processes. Ground-Water Microbiology and Geochemistry, Second Edition is important reading for geoscientists, hydrologists, and environmental engineers, as well as for water planners and lawyers involved in environmental issues. It also serves as a compelling text for upper-level undergraduate and graduate courses in ground-water chemistry.

Book

Reactive transport modeling of geochemical controls on secondary water quality impacts at a crude oil spill site near Bemidji, MN

Anaerobic biodegradation of organic amendments and contaminants in aquifers can trigger secondary water quality impacts that impair groundwater resources. Reactive transport models help elucidate how diverse geochemical reactions control the spatiotemporal evolution of these impacts. Using extensive monitoring data from a crude oil spill site near Bemidji, Minnesota (USA), we implemented a comprehensive model that simulates secondary plumes of depleted dissolved O 2 and elevated concentrations of Mn 2+ , Fe 2+ , CH 4 , and Ca 2+ over a two-dimensional cross section for 30 years following the spill. The model produces observed changes by representing multiple oil constituents and coupled carbonate and hydroxide chemistry. The model includes reactions with carbonates and Fe and Mn mineral phases, outgassing of CH 4 and CO 2 gas phases, and sorption of Fe, Mn, and H + . Model results demonstrate that most of the carbon loss from the oil (70%) occurs through direct outgassing from the oil source zone, greatly limiting the amount of CH 4 cycled down-gradient. The vast majority of reduced Fe is strongly attenuated on sediments, with most (91%) in the sorbed form in the model. Ferrous carbonates constitute a small fraction of the reduced Fe in simulations, but may be important for furthering the reduction of ferric oxides. The combined effect of concomitant redox reactions, sorption, and dissolved CO 2 inputs from source-zone degradation successfully reproduced observed pH. The model demonstrates that secondary water quality impacts may depend strongly on organic carbon properties, and impacts may decrease due to sorption and direct outgassing from the source zone.

Minnesota

Field-scale observations of a transient geobattery resulting from natural attenuation of a crude oil spill

We present evidence of a geobattery associated with microbial degradation of a mature crude oil spill. Self-potential measurements were collected using a vertical array of nonpolarizing electrodes, starting at the land surface and passing through the smear zone where seasonal water table fluctuations have resulted in the coating of hydrocarbons on the aquifer solids. These passive electrical potential measurements exhibit a dipolar pattern associated with a current source. The anodic and cathodic reactions of this natural battery occur below and above the smear zone, respectively. The smear zone is characterized by high magnetic susceptibility values associated with the precipitation of semiconductive magnetic iron phase minerals as a by-product of biodegradation, facilitating electron transfer between the anode and the cathode. This geobattery response appears to have a transient nature, changing on a monthly scale, probably resulting from chemical and physical changes in subsurface conditions such as water table fluctuations.

Journal of Geophysical Research G: Biogeosciences

Blueprints for riverine cod nest boxes draw from multiple design considerations

Designing aquatic nest boxes is rarely afforded detailed scientific account. Here we provide some historical context for nest boxes used in production of large-bodied fishes of the Australian freshwater cod genus Maccullochella . Our experience with eastern freshwater cod is used as a case study to: (a) convey aspects of the complexity of the nest box design process and to (b) demonstrate the importance of visual literacy in project communication across the variety of contributors to the eco-design process. Specifically, we describe a new, two-variant, triangular nest box design for application in rivers and modifications to a standard stainless steel nest box for hatchery-pond-based spawning of eastern freshwater cod M. ikei . We designed the boxes to test adult preference for single versus double entrance/exits to cavities in hatchery and field environments. An important consideration specific to hatchery production is harvesting demersal, adhesive eggs prior to hatching to minimise fungal infection of eggs and physical loss of larvae, in addition to providing critical first feeding of larvae. In contrast, field nest box design incorporated multiple factors and associated trade-offs related to both internal and external design, ranging from manufacturer capability, material types, cost, transportability, hydrological performance, biodegradability, retrievability, as well as biological and ecological function. Only preliminary findings from field nest box deployments are provided here, and we focus primarily on elements of visual language in the form of conceptual drawings, sketches and final schematics which have been central to our process. We emphasise the benefit of harnessing input from multiple fields of expertise and documenting and testing designs of nest boxes for cavity nesting fishes, under both controlled hatchery and more complex field conditions.

Aquaculture, Fish and Fisheries

Estimating cleanup times for groundwater contamination remediation strategies

This article presents the Natural Attenuation Software (NAS), available as a free download from Virginia Polytechnic University, which can help remedial project managers and their contractors estimate the time of groundwater remediation through consideration of such natural attenuation processes as advection, dispersion, sorption, source zone depletion, and biodegradation. NAS consists of a combination of computational tools implemented in three main interactive modules. The article discusses testing and evaluation of NAS along with expected benefits of the software tool.

Journal - American Water Works Association

Optical properties of dissolved organic matter (DOM): Effects of biological and photolytic degradation

Advances in spectroscopic techniques have led to an increase in the use of optical properties (absorbance and fluorescence) to assess dissolved organic matter (DOM) composition and infer sources and processing. However, little information is available to assess the impact of biological and photolytic processing on the optical properties of original DOM source materials. We measured changes in commonly used optical properties and indices in DOM leached from peat soil, plants, and algae following biological and photochemical degradation to determine whether they provide unique signatures that can be linked to original DOM source. Changes in individual optical parameters varied by source material and process, with biodegradation and photodegradation often causing values to shift in opposite directions. Although values for different source materials overlapped at the end of the 111-day lab experiment, multivariate statistical analyses showed that unique optical signatures could be linked to original DOM source material even after degradation, with 17 optical properties determined by discriminant analysis to be significant (p<0.05) in distinguishing between DOM source and environmental processing. These results demonstrate that inferring the source material from optical properties is possible when parameters are evaluated in combination even after extensive biological and photochemical alteration.

Limnology and Oceanography

Stable isotope analyses of oxygen (18O:17O:16O) and chlorine (37Cl:35Cl) in perchlorate: reference materials, calibrations, methods, and interferences

Rationale Perchlorate (ClO 4 − ) is a common trace constituent of water, soils, and plants; it has both natural and synthetic sources and is subject to biodegradation. The stable isotope ratios of Cl and O provide three independent quantities for ClO 4 − source attribution and natural attenuation studies: δ 37 Cl, δ 18 O, and δ 17 O (or Δ 17 O or 17 Δ) values. Documented reference materials, calibration schemes, methods, and interferences will improve the reliability of such studies. Methods Three large batches of KClO 4 with contrasting isotopic compositions were synthesized and analyzed against VSMOW-SLAP, atmospheric O 2 , and international nitrate and chloride reference materials. Three analytical methods were tested for O isotopes: conversion of ClO 4 − to CO for continuous-flow IRMS (CO-CFIRMS), decomposition to O 2 for dual-inlet IRMS (O2-DIIRMS), and decomposition to O 2 with molecular-sieve trap (O2-DIIRMS+T). For Cl isotopes, KCl produced by thermal decomposition of KClO 4 was reprecipitated as AgCl and converted into CH 3 Cl for DIIRMS. Results KClO 4 isotopic reference materials (USGS37, USGS38, USGS39) represent a wide range of Cl and O isotopic compositions, including non-mass-dependent O isotopic variation. Isotopic fractionation and exchange can affect O isotope analyses of ClO 4 − depending on the decomposition method. Routine analyses can be adjusted for such effects by normalization, using reference materials prepared and analyzed as samples. Analytical errors caused by SO 4 2 − , NO 3 − , ReO 4 2 − , and C-bearing contaminants include isotope mixing and fractionation effects on CO and O 2 , plus direct interference from CO 2 in the mass spectrometer. The results highlight the importance of effective purification of ClO 4 − from environmental samples. Conclusions KClO 4 reference materials are available for testing methods and calibrating isotopic data for ClO 4 − and other substances with widely varying Cl or O isotopic compositions. Current ClO 4 − extraction, purification, and analysis techniques provide relative isotope-ratio measurements with uncertainties much smaller than the range of values in environmental ClO 4 − , permitting isotopic evaluation of environmental ClO 4 − sources and natural attenuation.

Rapid Communications in Mass Spectrometry

Anaerobic aquifer transformations of 2,4-Dinitrophenol under different terminal electron accepting conditions

We evaluated the susceptibility of 2,4-dinitrophenol (2,4-DNP) and 2,4-diaminophenol to anaerobic biodegradation in aquifer slurries. Aquifer microorganisms depleted 2,4-DNP at rates of 25, 9 and 0.4 μM/day under methanogenic, sulfate-reducing and nitrate-reducing conditions, respectively. Rates of abiotic, 2,4-DNP loss in autoclaved control incubations were 7.2, 6.2 and 0.95 μM/day respectively. Abiotic, 2,4-DNP reduction was especially important as the first step in its transformation. 2-Amino-4-nitrophenol was produced by this process, but this compound was further metabolized in methanogenic and sulfate-reducing aquifer slurries. This partially reduced compound persisted in autoclaved controls and in the nitrate-reducing aquifer slurries. Aquifer slurries incubated with either 2,4-DNP or 2,4-diaminophenol produced methane when incubated with no other electron acceptor suggesting that mineralization had occurred under these conditions. In parallel experiments, aquifer slurries amended with 2,6-dinitrophenol or picric acid did not produce methane at levels above the substrate unamended controls.

Anaerobe

Microbial mineralization of VC and DCE under different terminal electron accepting conditions

Production of 14CO2 from [1,2-14C] dichloroethene (DCE) or [1,2-14C] vinyl chloride (VC) was quantified in aquifer and stream-bed sediment microcosms to evaluate the potential for microbial mineralization as a pathway for DCE and VC biodegradation under aerobic, Fe(III)-reducing, SO4-reducing, and methanogenic conditions. Mineralization of [1,2-14C] DCE and [1,2-14C] VC to 14CO2 decreased under increasingly reducing conditions, but significant mineralization was observed for both sediments even under anaerobic conditions. VC mineralization decreased in the order of aerobic > Fe(III)-reducing > SO4-reducing > methanogenic conditions. For both sediments, VC mineralization was greater than DCE mineralization under all electron-accepting conditions examined. For both sediments, DCE mineralization was at least two times greater under aerobic conditions than under anaerobic conditions. Although significant microbial mineralization of DCE was observed under anaerobic conditions, recovery of 14CO2 did not differ substantially between anaerobic treatments.

Anaerobe

Techniques for restoration of disturbed coastal wetlands of the Great Lakes

A long history of human-induced degradation of Great Lakes wetlands has made restoration a necessity, but the practice of wetland restoration is relatively new, especially in large lake systems. Therefore, we compiled tested methods and developed additional potential methods based on scientific understanding of Great Lakes wetland ecosytems to providc an overview of approaches for restoration. We addressed this challenge by focusing on four general fields of science: hydrology, sedimentology, chemistry, and biology. Hydrologic remediation methods include restoring hydrologic connections between diked and hydrologically altered wetlands and the lakes, restoring water tables lowered by ditching, and restoring natural variation in lake levels of regulated lakes Superior and Ontario. Sedimentological remediation methods include management of sediment input from uplands, removal or proper management of dams on tributary rivers, and restoration of protective barrier beaches and sand spits. Chemical remediation methods include reducing or eliminating inputs of contaminants from point and non-pont sources, natural sediment remediation by biodegradation and chemical degradation, and active sediment remediation by removal or by in situ treatment Biological remediation methods include control of non-target organisms, enhancing populations of target organisms, and enhancing habitat for target organisms. Some of these method were used in three major restoration projects (Metzger Marsh on Lake Erie and Cootes Paradise and Oshawa Second Marsh on Lake Ontario), which are described as case studies to show practical applications of wetland restoration in the Great Lakes. Successful restoration techniques that do not require continued manipulation must be founded in the basic tenets of ecology and should mimic natural processes. Success is demonstrated by the sustainability, productivity, nutrient-retention ability, invasibility, and biotic interactions within a restored wetland.

Wetlands