Chemical Oxidation Performance in High Temperature,Saline Groundwater Impacted With Hydrocarbons

A series of laboratory microcosm experiments and a field pilot test were performed to evaluate the potential for in situ chemical oxidation (ISCO) of aromatic hydrocarbons and methyl tertiary butyl ether (MTBE), a common oxygenate additive in gasoline, in saline, high temperature (more than 30 °C) groundwater. Groundwater samples from a site in Saudi Arabia were amended in the laboratory portion of the study with the chemical oxidants, sodium persulfate (Na₂S₂O₈) and sodium percarbonate (Na₂(CO₃)₂), to evaluate the changes in select hydrocarbon and MTBE concentrations with time. Almost complete degradation of the aromatic hydrocarbons, naphthalene and trimethylbenzenes (TMBs), was found in the groundwater sample amended with persulfate, whereas the percarbonate‐amended sample showed little to no degradation of the target hydrocarbon compounds in the laboratory. Isotopic analyses of the persulfate‐amended samples suggested that C‐isotope fractionation for xylenes occurred after approximately 30 percent reduction in concentration with a decline of about 1 percent in the δ¹³C values of xylenes. Based on the laboratory results, pilot‐scale testing at the Saudi Arabian field site was carried out to evaluate the effectiveness of chemical oxidation using nonactivated persulfate on a high temperature, saline petroleum hydrocarbon plume. Approximately 1,750 kg of Na₂S₂O₈ was delivered to the subsurface using a series of injection wells over three injection events. Results obtained from the pilot test indicated that all the target compounds decreased with removal percentages varying between 86 percent for naphthalene and more than 99 percent for the MTBE and TMBs. The benzene, toluene, ethylbenzene, and xylene compounds decreased to 98 percent on average. Examination of the microbial population upgradient and downgradient of the ISCO reactive zone suggested that a bacteria population was present following the ISCO injections with sulfate‐reducing bacteria (SRB) being the dominant bacteria present. Measurements of inorganic parameters during injection and postinjection indicated that the pH of the groundwater remained neutral following injections, whereas the oxidation–reduction potential remained anaerobic throughout the injection zone with time. Nitrate concentrations decreased within the injection zone, suggesting that the nitrate may have been consumed by denitrification reactions, whereas sulfate concentrations increased as expected within the reactive zone, suggesting that the persulfate produced sulfate. Overall, the injection of the oxidant persulfate was shown to be an effective approach to treat dissolved aromatic and associated hydrocarbons within the groundwater. In addition, the generation of sulfate as a byproduct was an added benefit, as the sulfate could be utilized by SRBs present within the subsurface to further biodegrade any remaining hydrocarbons. ©2015 Wiley Periodicals, Inc.     

The Southeastern Aerosol Research and Characterization Study,Part 3: Continuous Measurements of Fine Particulate Matter Mass and Composition

Abstract

Deployment of continuous analyzers in the Southeastern Aerosol Research and Characterization Study (SEARCH) network began in 1998 and continues today as new technologies are developed. Measurement of fine particulate matter (PM_2.5) mass is performed using a dried, 30 °C tapered element oscillating microbalance (TEOM). TEOM measurements are complemented by observations of light scattering by nephelometry. Measurements of major constituents include: (1) SO₄ ^2? via reduction to SO₂; (2) NH₄ ⁺ and NO₃ ^? via respective catalytic oxidation and reduction to NO, (3) black carbon (BC) by optical absorption, (4) total carbon by combustion to CO₂, and (5) organic carbon by difference between the latter two measurements. Several illustrative examples of continuous data from the SEARCH network are presented. A distinctive composite annual average diurnal pattern is observed for PM_2.5 mass, nitrate, and BC, likely indicating the influence of traffic-related emissions, growth, and break up of the boundary layer and formation of ammonium nitrate. Examination of PM_2.5 components indicates the need to better understand the continuous composition of the unmeasured “other” category, because it contributes a significant fraction to total mass during periods of high PM_2.5 loading. Selected episodes are presented to illustrate applications of SEARCH data. An SO₂ conversion rate of 0.2%/hr is derived from an observation of a plume from a coal-fired power plant during early spring, and the importance of local, rural sources of NH₃ to the formation of ammonium nitrate in particulate matter (PM) is demonstrated.     

Integrating Remediation and Reuse to Achieve Whole‐System Sustainability Benefits

This perspective article was prepared by members of the Sustainable Remediation Forum (SURF), a professional nonprofit organization seeking to advance the state of sustainable remediation within the broader context of sustainable site reuse. SURF recognizes that remediation and site reuse, including redevelopment activities, are intrinsically linked—even when remediation is subordinate to or sometimes a precursor of reuse. Although the end of the remediation life cycle has traditionally served as the beginning of the site's next life cycle, a disconnect between these two processes remains. SURF recommends a holistic approach that brings together remediation and reuse on a collaborative parallel path and seeks to achieve whole‐system sustainability benefits. This article explores the value of integrating remediation into the reuse process to fully exploit synergies and minimize the costs and environmental impacts associated with bringing land back into beneficial use. © 2013 Wiley Periodicals, Inc.     

An alternative approach to reconstructing organic matter accumulation with contrasting watershed disturbance histories from lake sediments

A number of proxies, including carbon to nitrogen ratio (C:N) and stable isotopes (delta(13)C and delta(15)N), have been used to reconstruct organic matter (OM) profiles from lake sediments and these proxies individually or in combination cannot clearly discriminate different sources. Here we present an alternative approach to elucidate this problem from lake sediments as a function of watershed scale land use changes. Stable isotope signatures of defined OM sources from the study watersheds, Shawnigan Lake (SHL) and Elk Lake (ELL), were compared with sedimentary proxy records. Results from this study reveal that terrestrial inputs and catchment soil coinciding with the watershed disturbances histories probably contributed in recent trophic enrichment in SHL. In contrast, cultural eutrophication in ELL was partially a result of input from catchment soil (agricultural activities) with significant input from lake primary production as well. Results were consistent in both IsoSource (IsoSource version 1.2 is a Visual Basic program used for source separation, (http://www.epa.gov/wed/pages/models/isosource/isosource.htm) and discriminant analysis (statistical classification technique).     

Pesticide concentrations in water and sediment and associated invertebrate toxicity in Del Puerto and Orestimba Creeks, California, 2007�C2008

The California??s San Joaquin River and its tributaries including Orestimba (ORC) and Del Puerto (DPC) Creeks are listed on the 2006 US EPA Clean Water Act §303(d) list for pesticide impairment. From December 2007 through June 2008, water and sediment samples were collected from both creeks in Stanislaus County to determine concentrations of organophosphorus (OP) and pyrethroid insecticides and to identify toxicity to Ceriodaphnia dubia and Hyalella azteca. OPs were detected in almost half (10 of 21) of the water samples, at concentrations from 0.005 to 0.912 ??g L^???1. Diazinon was the most frequently detected OP, followed by chlorpyrifos and dimethoate. Two water samples were toxic to C. dubia; based on median lethal concentrations (LC₅₀), chlorpyrifos was likely the cause of this toxicity. Pyrethroids were detected more frequently in sediment samples (18 detections) than in water samples (three detections). Pyrethroid concentrations in water samples ranged from 0.005 to 0.021 ??g L^???1. These concentrations were well below reported C. dubia LC₅₀s, and toxicity was not observed in laboratory bioassays. Cyfluthrin, bifenthrin, esfenvalerate, and ??-cyhalothrin were detected in sediment samples at concentrations ranging from 1.0 to 74.4 ng g^???1, dry weight. At DPC, all but one sediment sample caused 100% toxicity to H. azteca. Based on estimated toxicity units (TUs), bifenthrin was likely responsible for this toxicity and ??-cyhalothrin also contributed. At ORC, survival of H. azteca was significantly reduced in four of the 11 sediment samples. However, pyrethroids were detected in only two of these samples. Based on TUs, bifenthrin and ??-cyhalothrin likely contributed to the toxicity.     

Iron‐mediated abiotic degradation of RDX in a contaminated aquifer

The influence of aqueous‐ and mineral‐phase iron on royal demolition explosive (RDX) destruction has been previously investigated in theoretical settings and bench‐scale tests by various practitioners. The feasible use of in situ redox manipulation to create reactive Fe(II) is contingent upon the aquifer containing enough iron oxides and iron‐bearing clay minerals for the treated zone to remain effective. The following is a summary of a bench‐scale assessment of this relationship using aquifer material from an ongoing groundwater remediation effort at the Iowa Army Ammunition Plant (IAAP). A bench‐scale study was designed to determine the relative contributions of the biotic and iron‐mediated abiotic degradation processes to the net decrease in RDX observed at the site using saturated aquifer samples collected from within the RDX plume. Sterilized samples with a sufficient stoichiometric excess of both soluble and mineral‐phase iron reduced concentrations of RDX in both the soil and water fractions to the same extent as the samples containing native biota. These results indicate that in situ, abiotic degradation of RDX is feasible in areas unsuitable to biotic degradation processes, yielding an additional alternative for in situ RDX remediation. © 2012 Wiley Periodicals, Inc.     

Incorporating Recreational Users into Marine Protected Area Planning: A Study of Recreational Boating in British Columbia, Canada

Marine protected areas (MPAs) and zoning plans require an understanding of stakeholders if they are to be successful at achieving social and biological objectives. This study examines recreational boaters in a proposed MPA in British Columbia, Canada, using the recreation opportunity spectrum (ROS) and models of recreation conflict as a basis for investigation. Boaters (n = 543) visiting the region during the summer completed face-to-face surveys. Results show variability in boater setting preferences, supporting an ROS-based approach to MPA planning and zoning. While boaters as a whole placed the greatest importance on natural settings, sailboat operators expressed stronger preferences for natural and quiet settings relative to motorboats, and motorboat operators expressed stronger preferences for settings characterized by built facilities and extractive activities relative to sailboats. Several marine activities emerged as sources of perceived conflict for boaters, including personal watercraft, commercial whale watching vessels, and shellfish aquaculture. Our analysis indicates that while some of these may be addressed through zoning, others are better addressed through education and communication. Recommendations for both MPA management and future research are made.     

Life-history traits and the fate of translocated populations

Attempts to identify predictors and mechanisms of invasion success have been weakened by poor data quality, mostly because monitoring does not begin immediately after introduction events. To overcome this issue, we used data from conservation translocations of threatened bird species. We analyzed information on >1200 translocation events of >150 bird species to investigate how life-history traits affect population establishment measured based on rates of survival and reproduction. Species position along the slow–fast life-history continuum was a key predictor of translocation success. Species with fast-paced life histories were less likely to survive (over both short- and mid-term) and more likely to breed successfully than species with slow life histories. The temporal partitioning of reproductive effort (number of clutches per year) also affected the probability of successful reproduction. Our results illustrate how conservation-motivated reintroduction programs can provide proxies for the initial stages of the invasion process, enabling empirical tests of predictions from life-history theory and informing management.