Factors Controlling In Situ Biogeochemical Transformation of Trichloroethene: Column Study

In situ biogeochemical transformation involves biological formation of reactive minerals in an aquifer that can destroy chlorinated solvents such as trichloroethene (TCE) without accumulation of intermediates such as vinyl chloride. There is uncertainty regarding the materials and geochemical conditions that are required to promote biogeochemical transformation. The objective of this study was to identify amendments and biogeochemical conditions that promote in situ biogeochemical transformation. Laboratory columns constructed with plant mulch were supplemented with different amendments and were operated under varying conditions of water chemistry and hydraulic residence time. Four patterns of TCE removal were observed: (1) no removal, (2) biotic transformation of TCE to cis‐1,2‐dichloroethene (cis‐1,2‐DCE), (3) biogeochemical transformation of TCE without accumulation of reductive dechlorination products, and (4) mixed behavior where a combination of patterns was observed either simultaneously or over time. Principal coordinates analysis and analysis of variance (ANOVA) identified factors that promoted biogeochemical transformation: (1) high influent sulfate concentration, (2) relatively high hydraulic retention time, (3) supplementation of mulch with vegetable oil, and (4) addition of hematite or magnetite. The combination of the first three factors promoted complete sulfate reduction and a high volumetric sulfate consumption rate. The fourth factor provided a source of ferrous iron and/or a surface to which sulfide could react to form reactive iron sulfides. Many columns demonstrated either no TCE removal or a biotic TCE transformation pattern. Modification of column operation to include all four factors identified above promoted biogeochemical transformation in these columns. These results support the importance of the factors in biogeochemical transformation.     

Ground water/surface water interaction in a fractured rock aquifer

In a recent field study of ground water/surface water interaction between a bedrock stream and an underlying fractured rock aquifer, it was determined that the majority of ground water discharge occurred through sparsely located vertical fractures. In this paper, the dominant mechanisms governing ground water/surface water exchange in such an environment are investigated using a numerical model. The study was conducted using several conceptual models based on the field study results. Although the field results provided the motivation for the modeling study, it was not intended to match modeling and field results directly. In addition, the extent of capture zones for discharging or recharging fractures was explored. The results of this study are intended to provide a better understanding of contaminant migration in the vicinity of bedrock streams. Based on the numerical results, the rate of ground water discharge (or recharge) was found to depend on the aperture size of the discharging feature, and on the distribution of hydraulic head with depth within the fracture network. It was determined that the extent of both the capture zone and reverse capture zone for an individual fracture can be extremely large, and will be determined by the height of the stream stage, the fracture apertures of the network, and the hydraulic-head distribution within the network. Because both the stream stage and the hydraulic-head distribution are transient, the size of the capture zone and/or the reverse capture zone for an individual fracture may change significantly over time. As a result, the migration path for contaminants within the fracture network and between the surface and subsurface will also vary significantly with time.     

The relative stabilities of the reverse and normal polarity states of the earth's magnetic field

Recent analyses of the geomagnetic reversal sequence have led to different conclusions regarding the important question of whether there is a discernible difference between the properties of the two polarity states. The main differences between the two most recent studies are the statistical analyses and the possibility of an additional 57 reversal events in the Cenozoic. These additional events occur predominantly during reverse polarity time, but it is unlikely that all of them represent true reversal events. Nevertheless the question of the relative stabilities of the polarity states is examined in detail, both for the case when all 57 “events” are included in the reversal chronology and when they are all excluded. It is found that there is not a discernible difference between the stabilities of the two polarity states in either case. Inclusion of these short events does, however, change the structure of the non-stationarity in reversal rate, but still allows a smooth non-stationarity. Only 7 of the 57 short events are pre-38 Ma, but the evidence suggests that this is a real geomagnetic phenomenon rather than degradation of the magnetic recording or a bias in observation. This could be tested by detailed magnetostratigraphic and oceanic magnetic surveys of the Paleogene and Late Cretaceous. Overall it would appear that the present geomagnetic polarity timescale for 0–160 Ma is probably a very good representation of the actual history, and that different timescales and additional events now represent only changes in detail.     

Geothermal springs of the West Florida continental shelf: Evidence for dolomitization and radionuclide enrichment

On the sea bed of the West Florida continental shelf about 45 km SSW of Ft. Myers, Florida, an 85-km² area has been discovered in which six thermal springs discharge warm, chemically altered seawater from vents and seepage zones. The spring water apparently originates in the subsurface ocean around the Florida Platform and penetrates the highly porous strata of the platform about 500–1000 meters below sea level. It percolates toward the interior of the platform and is geothermally heated to about 40°C en route. Then it rises along more vertical flow channels and is discharged in warm submarine springs.Beneath the platform, several chemical processes alter the percolating seawater. One process seems to be a secondary dolomitization of the limestone of the platform because, in the discharging seawater, magnesium is lower by 2.7 mmole/kg and calcium higher by 3.6 mmole/kg than in normal seawater with the same chlorinity. Other reactions within the sediments of the platform enrich the spring effluents 1000-fold in²²⁶Ra, 10,000-fold in²²²Rn, and 90-fold in²²⁸Ra compared to the seawater surrounding the platform. Thus, the springs may be important sources of radionuclides for the Gulf of Mexico. The percolating seawater also loses all of its oxygen and nitrate to reduction processes, loses most of its phosphate and 40% of its²³⁸U, and roughly quadruples its silica content.Coastal carbonate platforms are fairly common geological features. Thus, processes like those beneath the West Florida Shelf may function on a world-wide basis to play an important role in the diagenesis of carbonate sediments.     

Nutrient availability in support of Karenia brevis blooms on the central West Florida Shelf: What keeps Karenia blooming?

Identifying nutrient sources, primarily nitrogen (N) and phosphorus (P), sufficient to support high biomass blooms of the red tide dinoflagellate, Karenia brevis, has remained problematic. The West Florida Shelf is oligotrophic, yet populations >10⁶ cells L⁻¹ frequently occur and blooms can persist for months. Here we examine the magnitude and variety of sources for N and P that are available to support blooms. Annual average in situ or background concentrations of inorganic N in the region where blooms occur range 0.02–0.2 μM while inorganic P ranges 0.025–0.24 μM. Such concentrations would be sufficient to support the growth of populations up to ∼3×10⁴ cells L⁻¹ with at least a 1 d turnover rate. Organic N concentrations average 1–2 orders of magnitude greater than inorganic N, 8–14 μM while organic P concentrations average 0.2–0.5 μM. Concentrations of organic N are sufficient to support blooms >10⁵ cells L⁻¹ but the extent to which this complex mixture of N species is utilizable is unknown. Other sources of nutrients included in our analysis are aerial deposition, estuarine flux, benthic flux, zooplankton excretion, N₂-fixation, and subsequent release of organic and inorganic N by Trichodesmium spp., and release of N and P from dead and decaying fish killed by the blooms. Inputs based on atmospheric deposition, benthic flux, and N₂-fixation, were minor contributors to the flux required to support growth of populations >2.6×10⁴ cells L⁻¹. N and P from decaying fish could theoretically maintain populations at moderate concentrations but insufficient data on the flux and subsequent mixing rates does not allow us to calculate average values. Zooplankton excretion rates, based on measured zooplankton population estimates and excretion rates could also supply all of the N and P required to support populations of 10⁵ and 10⁶ cells L⁻¹, respectively, but excretion is considered as “regenerated” nutrient input and can only maintain biomass rather than contribute to “new” biomass. The combined estuarine flux from Tampa Bay, Charlotte Harbor, and the Caloosahatchee River can supply a varying, but at times significant level of N and P to meet growth and photosynthesis requirements for populations of approximately 10⁵ cells L⁻¹ or below. Estimates of remineralization of dead fish could supply a significant proportion of bloom maintenance requirements but the rate of supply must still be determined. Overall, a combination of sources is required to maintain populations >10⁶ cells L⁻¹.