Crude Oil Metabolites in Groundwater at Two Spill Sites

Two groundwater plumes in north central Minnesota with residual crude oil sources have 20 to 50 mg/L of nonvolatile dissolved organic carbon (NVDOC). These values are over 10 times higher than benzene and two to three times higher than Diesel Range Organics in the same wells. On the basis of previous work, most of the NVDOC consists of partial transformation products from the crude oil. Monitoring data from 1988 to 2015 at one of the sites located near Bemidji, MN show that the plume of metabolites is expanding toward a lakeshore located 335 m from the source zone. Other mass balance studies of the site have demonstrated that the plume expansion is driven by the combined effect of continued presence of the residual crude oil source and depletion of the electron accepting capacity of solid phase iron oxide and hydroxides on the aquifer sediments. These plumes of metabolites are not covered by regulatory monitoring and reporting requirements in Minnesota and other states. Yet, a review of toxicology studies indicates that polar metabolites of crude oil may pose a risk to aquatic and mammalian species. Together the results suggest that at sites where residual sources are present, monitoring of NVDOC may be warranted to evaluate the fates of plumes of hydrocarbon transformation products.     

Arsenic Cycling in Hydrocarbon Plumes: Secondary Effects of Natural Attenuation

Monitored natural attenuation is widely applied as a remediation strategy at hydrocarbon spill sites. Natural attenuation relies on biodegradation of hydrocarbons coupled with reduction of electron acceptors, including solid phase ferric iron (Fe(III)). Because arsenic (As) adsorbs to Fe‐hydroxides, a potential secondary effect of natural attenuation of hydrocarbons coupled with Fe(III) reduction is a release of naturally occurring As to groundwater. At a crude‐oil‐contaminated aquifer near Bemidji, Minnesota, anaerobic biodegradation of hydrocarbons coupled to Fe(III) reduction has been well documented. We collected groundwater samples at the site annually from 2009 to 2013 to examine if As is released to groundwater and, if so, to document relationships between As and Fe inside and outside of the dissolved hydrocarbon plume. Arsenic concentrations in groundwater in the plume reached 230 µg/L, whereas groundwater outside the plume contained less than 5 µg/L As. Combined with previous data from the Bemidji site, our results suggest that (1) naturally occurring As is associated with Fe‐hydroxides present in the glacially derived aquifer sediments; (2) introduction of hydrocarbons results in reduction of Fe‐hydroxides, releasing As and Fe to groundwater; (3) at the leading edge of the plume, As and Fe are removed from groundwater and retained on sediments; and (4) downgradient from the plume, patterns of As and Fe in groundwater are similar to background. We develop a conceptual model of secondary As release due to natural attenuation of hydrocarbons that can be applied to other sites where an influx of biodegradable organic carbon promotes Fe(III) reduction.     

Assessing marine debris in deep seafloor habitats off California

Marine debris is a global concern that pollutes the world’s oceans, including deep benthic habitats where little is known about the extent of the problem. We provide the first quantitative assessment of debris on the seafloor (20-365 m depth) in submarine canyons and the continental shelf off California, using the Delta submersible. Fishing activities were the most common contributors of debris. Highest densities occurred close to ports off central California and increased significantly over the 15-year study period. Recreational monofilament fishing line dominated this debris. Debris was less dense and more diverse off southern than central California. Plastic was the most abundant material and will likely persist for centuries. Disturbance to habitat and organisms was low, and debris was used as habitat by some fishes and macroinvertebrates. Future trends in human activities on land and at sea will determine the type and magnitude of debris that accumulates in deep water.     

Fitting and evaluation of height-diameter models for <Emphasis Type="Italic">Alnus japonica</Emphasis> in La Trinidad,Benguet, Philippines

The study was conducted to develop height-diameter at breast height (HT-DBH) models for Alnus japonica in La Trinidad, Benguet, Philippines and evaluate their predictive capability. The six widely used nonlinear growth models that were selected in this study were the Chapman-Richards, Schnute, Modified logistic, Korf/Lundqvist, Weibull and Exponential. A total of 208 Alnus japonica trees were measured using standard diameter tape for DBH (1.3 m above the ground) and Vertex and transponder was used for the total height measurement. The performance of the developed models were evaluated using the fit statistics including coefficient of determination (R²), root mean square error (RMSE), mean bias (ē), absolute mean difference (AMD), and Akaike Information Criterion (AIC). The lack-of-fit statistics was also performed for further evaluation of the performance of the models. Based on the evaluation criteria, all six models were able to determine the DBH-height relationships and fitted the data well. Using the rank analysis, the Weibull HT-DBH model had the best performance among the six commonly used nonlinear growth models. The results of this study will help forest managers especially in La Trinidad, Benguet to easily predict the total height using the Weibull model for Alnus japonica utilizing the DBH as the predicting variable.     

The stratigraphy and structure of the Galley Head culmination zone: An area of enhanced shortening related to basin geometry within the Irish Variscides

In southwest Ireland an Upper Devonian to Lower Carboniferous clastic succession was deposited in an ENE–WSW trending half-graben, known as the South Munster Basin. Across the Galley Head peninsula on the south coast, this stratigraphical succession is attenuated due to the presence of a palaeogeographical feature called the Glandore High. Evidence suggests that the Glandore High was an east–west feature, faulted to the north and east, which was part of the southern flank (hangingwall rollover) of the South Munster Basin. During post-Carboniferous Variscan deformation the relatively thin stratigraphy of Galley Head underwent prolonged folding, causing a local periclinal fold pair to develop within the hinge zone of a regional syncline. The main cleavage then developed parallel to bedding on the overturned south limb of the anticline of this fold pair. The local enhanced shortening caused the development of a structural culmination, and south facing, tight to isoclinal folds. The culmination was enhanced and tightened by a fault system of contractional, strike-parallel faults linked by cross faults. Secondary folds occur across the hinges of regional anticlines and also on major fold limbs as isolated fold pairs and in monoclinal fold zones, some of which may have nucleated on irregular sandstone bodies. Local crenulation cleavages are related to late fault movements. Syn-cleavage, conjugate, wrench faults record 10 per cent to 15 per cent strike-parallel extension in the culmination. The deformation chronology of the Galley Head area is somewhat anomalous for the Irish Variscides in that the folds were well established before the onset of the main cleavage development. The enhanced shortening across the area was compartmentalized by major cross faults and a minor component of north–south sinistral shear was also active across the area causing a swing in strike and a late set of minor cross faults. Structural facing directions in southwest Ireland appear to be directly linked with the geometry of the deformed basins. Hence the southward facing along the south coast is due to the proximity of the southern margin of the South Munster Basin. Structural facing directions fan northwards across the basin and major folds are overturned to the north at the northern margin of the basin.     

Biomarker induction in tropical fish species on the Northwest Shelf of Australia by produced formation water

Normal operation of oil well platforms results in the discharge of produced formation water (PFW). The expression of CYP1A, CYP2M1- and 2K1-like proteins was examined for use as possible biomarkers of PFW exposure. A pilot study on the Northwest Shelf of Australia had indicated that PFW contamination possibly contributes to induction of CYP1A-like proteins in Gold-Spotted Trevally (Carangoides fulvoguttatus). The pilot study samples were re-examined for CYP1A, and, in addition, CYP2K1/2M1-like proteins. In a subsequent caged fish study in the same location a second species, Stripey seaperch (Lutjanus carponotatus), caught at a clean site, were distributed to three caging sites in a PFW gradient from the Harriet A production platform: A (near-field), B (far-field) and C (a non-impacted reference site). Fish were sampled at time (T) T = 0, T = 3 and T = 10 days. Significant increases of CYP1A, one CYP2K1- and two CYP2M1-like proteins were noted at Site A at T = 10d. For another CYP2K1-like protein, a significant increase was observed at Site A only at T = 3d. These results support a previous study indicating that CYP1A protein is sensitive to PFW exposure. Importantly, statistically significant environmental induction of both CYP2M1- and CYP2K1-like proteins in tropical fish due to PFW exposure had not previously been described and induction of enzymes in the CYP2 family suggest new biomarkers for PFW. In addition, the novel response of one CYP2K-like protein requires further verification, but offers promise for improved monitoring of sub-lethal responses in marine organisms.     

Uptake of estradiol from sediment by hornyhead turbot (Pleuronichthys verticalis) and effects on oxidative DNA damage in male gonads

Male and female hornyhead turbot (Pleuronichthys verticalis) were exposed to four concentrations (0, 0.75, 14.7 and 46.5 ng/g dry weight) of E2-amended sediment for 7 days. Sediment-derived E2 was bioavailable to the flatfish, though the route of uptake was unclear. A concentration of 46.5 ng/g E2 in sediment led to a significant increase in vitellogenin concentrations in the plasma in both sexes after 7 days of exposure. Though plasma E2 concentrations increased significantly in males at sediment E2 concentrations of 0.75 ng/g dry weight and above, a dose-dependent increase was not observed. There was also no correlation between sediment E2 concentrations, plasma E2 concentrations, and oxidative DNA damage in male gonads. The results suggest that the DNA damage previously seen in the gonads of feral hornyhead turbot at a sewage outfall is likely not caused by acute exposure to exogenous E2 from sediments.     

Comparative biomass structure and estimated carbon flow in food webs in the deep Gulf of Mexico

A budget of the standing stocks and cycling of organic carbon associated with the sea floor has been generated for seven sites across a 3-km depth gradient in the NE Gulf of Mexico, based on a series of reports by co-authors on specific biotic groups or processes. The standing stocks measured at each site were bacteria, Foraminifera, metazoan meiofauna, macrofauna, invertebrate megafauna, and demersal fishes. Sediment community oxygen consumption (SCOC) by the sediment-dwelling organisms was measured at each site using a remotely deployed benthic lander, profiles of oxygen concentration in the sediment pore water of recovered cores and ship-board core incubations. The long-term incorporation and burial of organic carbon into the sediments has been estimated using profiles of a combination of stable and radiocarbon isotopes. The total stock estimates, carbon burial, and the SCOC allowed estimates of living and detrital carbon residence time within the sediments, illustrating that the total biota turns over on time scales of months on the upper continental slope but this is extended to years on the abyssal plain at 3.6 km depth. The detrital carbon turnover is many times longer, however, over the same depths. A composite carbon budget illustrates that total carbon biomass and associated fluxes declined precipitously with increasing depth. Imbalances in the carbon budgets suggest that organic detritus is exported from the upper continental slope to greater depths offshore.The respiration of each individual “size” or functional group within the community has been estimated from allometric models, supplemented by direct measurements in the laboratory. The respiration and standing stocks were incorporated into budgets of carbon flow through and between the different size groups in hypothetical food webs. The decline in stocks and respiration with depth were more abrupt in the larger forms (fishes and megafauna), resulting in an increase in the relative predominance of smaller sizes (bacteria and meiofauna) at depth. Rates and stocks in the deep northern GoM appeared to be comparable to other continental margins where similar comparisons have been made.     

High-pressure behaviour of serpentine minerals: a Raman spectroscopic study

Four main serpentine varieties can be distinguished on the basis of their microstructures, i.e. lizardite, antigorite, chrysotile and polygonal serpentine. Among these, antigorite is the variety stable under high pressure. In order to understand the structural response of these varieties to pressure, we studied well-characterized serpentine samples by in situ Raman spectroscopy up to 10 GPa, in a diamond-anvil cell. All serpentine varieties can be metastably compressed up to 10 GPa at room temperature without the occurrence of phase transition or amorphization. All spectroscopic pressure-induced changes are fully reversible upon decompression. The vibrational frequencies of antigorite have a slightly larger pressure dependence than those of the other varieties. The O–H-stretching modes of the four varieties have a positive pressure dependence, which indicates that there is no enhancement of hydrogen bonding in serpentine minerals at high pressure. Serpentine minerals display two types of hydroxyl groups in the structure: inner OH groups lie at the centre of each six-fold ring while outer OH groups are considered to link the octahedral sheet of a given 1:1 layer to the tetrahedral sheet of the adjacent 1:1 layer. On the basis of the contrasting behaviour of the Raman bands as a function of pressure, we propose a new assignment of the OH-stretching bands. The strongly pressure-dependent modes are assigned to the vibrations of the outer hydroxyl groups, the less pressure-sensitive peaks to the inner ones.