ISCO for Groundwater Remediation: Analysis of Field Applications and Performance

A critical analysis of in situ chemical oxidation (ISCO) projects was performed to characterize situations in which ISCO is being implemented, how design and operating parameters are typically employed, and to determine the performance results being achieved. This research involved design of a database, acquisition and review of ISCO project information, population of the database, and analyses of the database using statistical methods. Based on 242 ISCO projects included in the database, ISCO has been used to treat a variety of contaminants; however, chlorinated solvents are by far the most common. ISCO has been implemented at sites with varied subsurface conditions with vertical injection wells and direct push probes being the most common delivery methods. ISCO has met and maintained concentrations below maximum contaminant levels (MCLs), although not at any sites where dense nonaqueous phase liquids (DNAPL) were presumed to be present. Alternative cleanup levels and mass reduction goals have also been attempted, and these less stringent goals are met with greater frequency than MCLs. The use of pilot testing is beneficial in heterogeneous geologic media, but not so in homogeneous media. ISCO projects cost $220,000 on average, and cost on average $94/yd³ of target treatment zone. ISCO costs vary widely based on the size of the treatment zone, the presence of DNAPL, and the oxidant delivery method. No case studies were encountered in which ISCO resulted in permanent reductions to microbial populations or sustained increases in metal concentrations in groundwater at the ISCO-treated site.     

Inter-annual variability of wet season freshwater plume extent into the Great Barrier Reef lagoon based on satellite coastal ocean colour observations

Riverine freshwater plumes are the major transport mechanism for nutrients, sediments and pollutants into the Great Barrier Reef (GBR) lagoon and connect the land with the receiving coastal and marine waters. Knowledge of the variability of the freshwater extent into the GBR lagoon is relevant for marine park management to develop strategies for improving ecosystem health and risk assessments. In this study, freshwater extent has been estimated for the entire GBR lagoon area from daily satellite observations of the Moderate Resolution Imaging Spectroradiometer (MODIS) between 2002 and 2010. To enable a reliable mapping of freshwater plumes we applied a physics-based coastal ocean colour algorithm, that simultaneously retrieves chlorophyll-a, non-algal particulate matter and coloured dissolved organic matter (CDOM), from which we used CDOM as a surrogate for salinity (S) for mapping the freshwater extent.     

The influence of a season of extreme wet weather events on exposure of the World Heritage Area Great Barrier Reef to pesticides

The 2010-2011 wet season was one of extreme weather for the State of Queensland, Australia. Major rivers adjacent to the Great Barrier Reef (GBR) were discharging at rates 1.5 to >3 times higher than their long term median. Exposure to photosystem II herbicides has been routinely monitored over a period of up to 5 years at 12 inshore GBR sites. The influence of this wet season on exposure to photosystem II herbicides was examined in the context of this long-term monitoring record and during flood plume events in specific regions. Median exposures expressed as diuron equivalent concentration were an average factor of 2.3 times higher but mostly not significantly different (p<0.05) to the median for the long-term monitoring record. The herbicides metolachlor and tebuthiuron were frequently detected in flood plume waters at concentrations that reached or exceeded relevant water quality guidelines (by up to 4.5 times).     

Geochemical effects on metals following permanganate oxidation of DNAPLs

The application of in situ chemical oxidation for dense, nonaqueous phase liquid (DNAPL) remediation requires delivery of substantial levels of oxidant chemicals into the subsurface to degrade target DNAPLs and to satisfy natural oxidant demand. This practice can raise questions regarding changes in subsurface conditions, yet information regarding potential effects, especially at the field scale, has been lacking. This paper describes an evaluation of the effects on metals associated with in situ chemical oxidation using potassium permanganate at Launch Complex 34 (LC34), Cape Canaveral Air Station, Florida. At LC34, high concentrations of permanganate (1 to 2 wt%) were injected into the subsurface as part of a demonstration of DNAPL remediation technologies. In a companion experimental effort at the Colorado School of Mines, field samples were characterized and laboratory batch and mini-column studies were completed to assess effects of permanganate oxidation on metals in the subsurface one year after completion of the field demonstration. Results indicated there was potential for long-term immobilization of a portion of introduced manganese and no treatment-induced loss in subsurface permeability due to deposition of manganese oxides particles, which are a product of the oxidation reactions. Permanganate treatment did cause elevated manganese, chromium, and nickel concentrations in site ground water within the treated region. Some of these metals effects can be attenuated during downgradient flow through uncontaminated and untreated aquifer sediments.     

An early Paleogene sponge fauna,Chatham Island,New Zealand

A late Paleocene‐early Eocene (c. 60–53 Ma) poriferan fauna, comprising hexactinellids (Class Hexactinellida), astrophorids (Class Demospongiae: Family Astrophorida), and lithistids ("lithistid” Demospongiae) has been identified from the Tutuiri Greensand outcropping on the north coast of Chatham Island, New Zealand. Most of the fossils are hexactinellids, comprising extremely delicate siliceous networks embedded in friable sandstone. The sediment matrix within and around these skeletons contains numerous siliceous demosponge spicules, many of which are exceptionally well preserved. The soft friable matrix of the Tutuiri Greensand has made extraction a relatively simple process, making taxonomic identification of the material, and comparison with adjacent Recent and other New Zealand Eocene faunas possible. These sponge body fossils and spicule microfossils indicate a fauna that was once dominated by hexactinellids, lithistid, and astrophorid demosponges. A qualitative comparison of the abundance and diversity of the Tutuiri Greensand sponge fauna with the present‐day Chatham Rise sponge fauna indicates that the late Paleocene‐early Eocene fauna is as diverse as the Recent fauna, for the hexactinellid sponges and astrophorid demosponges, and much more diverse for lithistid sponges. The paleoecology of the Tutuiri Greensand has been interpreted as inner to mid shelf water depths (50–250 m) but the poriferan fauna described here is more like that of the present‐day soft sediment benthic environment of the Chatham Rise at 800–1200 m.     

Laboratory simulations of prebiotic molecule stability in the jarosite mineral group; end member evaluation of detection and decomposition behavior related to Mars sample return

Recently, the prebiotic amino acid glycine has been found associated with natural jarosite samples from locations around the world. Since the discovery of jarosite on Mars, extensive research focuses on linking this mineral group with possible detection of biosignatures in the geologic record on Earth and Mars. Multiple analytical methods, including extraction and mass spectrometry techniques, have identified glycine and other biomolecules in jarosite samples. The jarosite end members jarosite (sensu stricto-potassium jarosite), natrojarosite (sodium jarosite), and ammoniojarosite (ammonium jarosite) have different thermodynamic stabilities, decompose at different rates, and have potentially different susceptibilities to substitution. The relationship between the thermodynamic stability of the jarosite end members and the effect that glycine has on the thermal decomposition behavior of each end member was investigated using thermal gravimetric analysis. Introducing glycine into the synthesis procedure (75 ppm) of the potassium, sodium, and ammonium jarosite end member has elucidated the effects that glycine has on the thermal stability of the mineral group. Potassium jarosite appears to be the least susceptible to the effects of glycine, with the sodium and ammonium end members showing marked changes in thermal decomposition behavior and decomposition rates. These results suggest that the sodium and ammonium jarosites are more suitable targets for identifying signs of prebiotic or biotic activity on Mars and Earth than the potassium jarosites. These results have implications for current in situ investigations of the martian surface and future sample return missions.     

Young-of-the-year oyster,Crassostrea virginica,reproduction in coastal Georgia

Young-of-the-year (YOY) oysters (Crassostrea virginica) in the Gulf of Mexico mature sexually and spawn in their first year. This study determined whether YOY oysters in the southeastern United States also mature and spawn in their first year. In 1991 and 1993, 300 YOY oysters were marked in May and 20–30 were sampled in subsequent months along with 20 adult controls. Two sites were chosen in 1991 (House Creek and Skidaway River) and one in 1993 (Skidaway River). At House Creek, YOY oysters were mature and spawned in September. YOY oysters at Skidaway spawned in October. Adult oysters did not appear to spawn in 1991. In 1993, the adult oysters spawned in August and September whereas, the YOY oysters spawned heavily in October. Oyster recruitment in coastal Georgia extends through October. The potential contribution of YOY oysters to this late season set is substantial, given that the YOY oysters are relatively large (≈4 cm) and are found in greater numbers than the adults. Oysters are capable of having two, if not more, generations within one year, prior to exposure of disease-causing organisms. Also, this particular reproductive strategy would increase the oysters suitability as a test subject in population genetic studies.     

Nitrogen microanalysis of glass inclusions in chondritic olivines by nuclear reaction

Measured were the abundance and distribution of nitrogen in glasses of glass inclusions in olivines of CV3, CO3, CR, C4, CH3, and LL chondritic meteorites by means of the ¹⁴N(d, p)¹⁵N nuclear reaction. Similar to what was observed with carbon, nitrogen is present in low concentrations (<20 ppm) in the structure of olivines but can by stored in variable amounts in glasses of glass inclusions. These primitive glasses, characterized by a Si-Al-Ca-rich composition, have highly variable nitrogen contents (30 to 1500 ppm) and highly inhomogeneous nitrogen distribution. Nitrogen contents are independent of the chemical composition of the glasses. The heterogeneous distribution is a common feature of all studied inclusions, as is evidenced by the variable contents of nitrogen in glass inclusions occurring in the same olivine grain. Nitrogen heterogeneity is suggestive of trapping of solid nitrogen carrier phases during formation of the constituents of chondrules. However, part of the originally trapped nitrogen appears to have been lost, possibly, by ulterior oxidation and subsequent transformation into volatile species.