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Geology, coal quality, and resources of the Antaramut-Kurtan-Dzoragukh coal field, north-central Armenia

The Antaramut-Kurta-Dzoragukh (AKD) coal deposit is a previously unrecognized coal field in north-central Armenia. Coal has been known to exist in the general vicinity since the turn of the century, but coal was thought to be restricted to a small (1 km2) area only near the village of Antaramut. However, through detailed field work and exploratory drilling, this coal deposit has been expanded to at least 20 km2, and thus renamed the Antaramut-Kurtan-Dzoragukh coal field, for the three villages that the coal field encompasses. The entire coal-bearing horizon, a series of tuffaceous sandstones, siltstones, and claystones, is approximately 50 m thick. The AKD coal field contains two coal beds, each greater than 1 m thick, and numerous small rider beds, with a total resource of approximately 31,000,000 metric tonnes. The coals are late Eocene in age, high volatile bituminous in rank, relatively high in ash yield (approximately 40%, as-determined basis) and moderate in sulfur content (approximately 3%, as-determined basis). The two coal beds (No. 1 and No. 2), on a moist, mineral-matter-free basis, have high calorific values of 32.6 MJ/kg (7796 cal/g) and 36.0 MJ/kg (8599 cal/g), respectively. Coal is one of the few indigenous fossil fuel resources occurring in Armenia and thus, the AKD coal field could potentially provide fuel for heating and possibly energy generation in the Armenian energy budget. Published by Elsevier Science B.V.

International Journal of Coal Geology↗

Coalbed methane: from hazard to resource

Coalbed gas, which mainly consists of methane, has remained a major hazard affecting safety and productivity in underground coal mines for more than 100 yr. Coalbed gas emissions have resulted in outbursts and explosions where ignited by open lights, smoking or improper use of black blasting powder, and machinery operations. Investigations of coal gas outbursts and explosions during the past century were aimed at predicting and preventing this mine hazard. During this time, gas emissions were diluted with ventilation by airways (eg, tunnels, vertical and horizontal drillholes, shsfts) and by drainage boreholes. The 1970s 'energy crisis' led to studies of the feasibility of producing the gas for commercial use. Subsequent research on the origin, accumulation, distribution, availability, and recoverability has been pursued vigorously during the past two decades. Since the 1970s research investigations on the causes and effects of coal mine outbursts and gas emissions have led to major advances towards the recovery and development of coalbed methane for commercial use. Thus, coalbed methane as a mining hazard was harnessed as a conventional gas resource.Coalbed gas, which mainly consists of methane, has remained a major hazard affecting safety and productivity in underground coal mines for more than 100 years. Coalbed gas emissions have resulted in outbursts and explosions where ignited by open lights, smoking or improper use of black blasting powder, and machinery operations. Investigations of coal gas outbursts and explosions during the past century were aimed at predicting and preventing this mine hazard. During this time, gas emissions were diluted with ventilation by airways (e.g., tunnels, vertical and horizontal drillholes, shafts) and by drainage boreholes. The 1970's `energy crisis' led to studies of the feasibility of producing the gas for commercial use. Subsequent research on the origin, accumulation, distribution, availability, and recoverability has been pursued vigorously during the past two decades. Since the 1970's research investigations on the causes and effects of coal mine outbursts and gas emissions have led to major advances towards the recovery and development of coalbed methane for commercial use. Thus, coalbed methane as a mining hazard was harnessed as a conventional gas resource.

International Journal of Coal Geology↗

The types of data needed for assessing the environmental and human health impacts of coal

Coal is one of the most important sources of energy. Its worldwide use will continue to expand during the next several decades, particularly in rapidly developing countries such as China and India. Unfortunately, coal use may bring with it environmental and human health costs. Many of the environmental and health problems attributed to coal combustion are due to mobilization of potentially toxic elements. Some of these problems could be minimized or even avoided if comprehensive databases containing appropriate coal quality information were available to decision makers so that informed decisions could be made regarding coal use. Among the coal quality parameters that should be included in these databases are: C, H, N, O, pyritic sulfur, organic sulfur, major, minor, and trace element concentrations, modes of occurrence of environmentally sensitive elements, cleanability, mineralogy, organic chemistry, petrography, and leachability.Coal is one of the most important sources of energy. Its worldwide use will continue to expand during the next several decades, particularly in rapidly developing countries such as China and India. Unfortunately, coal use may bring with it environmental and human health costs. Many of the environmental and health problems attributed to coal combustion are due to mobilization of potentially toxic elements. Some of these problems could be minimized or even avoided if comprehensive databases containing appropriate coal quality information were available to decision makers so that informed decisions could be made regarding coal use. Among the coal quality parameters that should be included in these databases are: C, H, N, O, pyritic sulfur, organic sulfur, major, minor, and trace element concentrations, modes of occurrence of environmentally sensitive elements, cleanability, mineralogy, organic chemistry, petrography, and leachability.

International Journal of Coal Geology↗

Environmental 90Sr measurements

90Sr (T1/2 = 28.5 years) is a long-lived radionuclide produced in nuclear fission. Fast radiochemical detection of 90Sr in environmental samples is not feasible using current analytical methods. Accelerator Mass Spectrometry (AMS) measurements of 90Sr were made with the Rehovot 14UD Pelletron accelerator at a terminal voltage of 11 or 12 MV using our standard detection system. Injection of hydride ions (SrH3-) was chosen owing to high beam intensity and low Coulomb explosion effects. 90Sr ions were identified and discriminated from isobaric 90Zr by measuring time of flight, total energy and three independent energy-loss signals in an ionization chamber. A reference sample and a ground-water sample were successfully measured. The detection limit determined for a laboratory blank by the residual counts in the 90Sr region is 90Sr/Sr = 3 ?? 10-13, corresponding in practice to (2-4) ?? 10790Sr atoms or about 0.5-1 pCi/L in environmental water samples.

Nuclear Instruments and Methods in Physics Researc↗

Paleoclimate simulations for North America over the past 21,000 years: Features of the simulated climate and comparisons with paleoenvironmental data

Maps of upper-level and surface winds and of surface temperature and precipitation illustrate the results of a sequence of global paleoclimatic simulations spanning the past 21,000 yr for North America. We review (a) the large-scale features of circulation, temperature, and precipitation that appear in the simulations from the NCAR Community Climate Model Version 1 (CCM 1), (b) the implications of the simulated climate for the past continental-scale distributions of three plant taxa ( Picea spp., Pseudotsuga menziesii , and Artemisia tridentata ), which are broadly representative of the vegetation across the continent, and (c) the potential explanations in terms of atmospheric circulation or surface energy- and water-balance processes for mismatches between the simulations and observations. Most of the broad-scale features of previous paleoclimatic simulations with the NCAR CCM 0 for North America are present in the current simulations. Many of the elements of a conceptual model (based on previous climate simulations) that describes the controls of paleoclimatic variations across North America during the past 21,000 yr are found in simulations reviewed here. These include (1) displacement of the jet stream by the Laurentide Ice Sheet to the south of its present position in both winter and summer, (2) generation of a ‘glacial anticyclone’ over the ice sheet at the LGM, and the consequent induction of large-scale sinking motions induced over eastern North America, (3) changes in the strength of surface atmospheric circulation features through time, including weakening of the Aleutian low in winter, and strengthening of the eastern Pacific and Bermuda high-pressure systems in summer as the ice sheet decreased in size, (4) development of a ‘heat low’ at the surface and a strengthened ridge in the upper-atmosphere over the continent at the time of the maximum summer insolation anomaly, (5) increases in summer temperature earlier in regions remote from the ice sheet (these increases appear earlier in the present (CCM 1) simulations than in the previous (CCM 0) ones, however), and (6) continuation of negative winter temperature anomalies into the middle Holocene. In general, simulated surface conditions that are discordant with paleoenvironmental observations can be attributed to the simulation of particular atmospheric circulation patterns (e.g. those that suppress precipitation or advect warm air into a region), with these mismatches amplified in Beringia and the southeastern United States by surface energy- and water-balance processes.

Quaternary Science Reviews↗

Applying linear programming to estimate fluxes in ecosystems or food webs: An example from the herpetological assemblage of the freshwater Everglades

We present the application of Linear Programming for estimating biomass fluxes in ecosystem and food web models. We use the herpetological assemblage of the Everglades as an example. We developed food web structures for three common Everglades freshwater habitat types: marsh, prairie, and upland. We obtained a first estimate of the fluxes using field data, literature estimates, and professional judgment. Linear programming was used to obtain a consistent and better estimate of the set of fluxes, while maintaining mass balance and minimizing deviations from point estimates. The results support the view that the Everglades is a spatially heterogeneous system, with changing patterns of energy flux, species composition, and biomasses across the habitat types. We show that a food web/ecosystem perspective, combined with Linear Programming, is a robust method for describing food webs and ecosystems that requires minimal data, produces useful post-solution analyses, and generates hypotheses regarding the structure of energy flow in the system.

Ecological Modelling↗

Numerical modeling of coupled nitrification-denitrification in sediment perfusion cores from the hyporheic zone of the Shingobee River, MN

Nitrification and denitrification kinetics in sediment perfusion cores were numerically modeled and compared to experiments on cores from the Shingobee River MN, USA. The experimental design incorporated mixing groundwater discharge with stream water penetration into the cores, which provided a well-defined, one-dimensional simulation of in situ hydrologic conditions. Ammonium (NH 4 + ) and nitrate (NO 3 − ) concentration gradients suggested the upper region of the cores supported coupled nitrification–denitrification, where groundwater-derived NH 4 + was first oxidized to NO 3 − then subsequently reduced via denitrification to N 2 . Nitrification and denitrification were modeled using a Crank–Nicolson finite difference approximation to a one-dimensional advection–dispersion equation. Both processes were modeled using first-order reaction kinetics because substrate concentrations (NH 4 + and NO 3 − ) were much smaller than published Michaelis constants. Rate coefficients for nitrification and denitrification ranged from 0.2 to 15.8 h −1 and 0.02 to 8.0 h −1 , respectively. The rate constants followed an Arrhenius relationship between 7.5 and 22 °C. Activation energies for nitrification and denitrification were 162 and 97.3 kJ/mol, respectively. Seasonal NH 4 + concentration patterns in the Shingobee River were accurately simulated from the relationship between perfusion core temperature and NH 4 + flux to the overlying water. The simulations suggest that NH 4 + in groundwater discharge is controlled by sediment nitrification that, consistent with its activation energy, is strongly temperature dependent.

Minnesota↗

Trends in long-period seismicity related to magmatic fluid compositions

Sound speeds and densities are calculated for three different types of fluids: gas-gas mixture; ash-gas mixture; and bubbly liquid. These fluid properties are used to calculate the impedance contrast (Z) and crack stiffness (C) in the fluid-driven crack model (Chouet: J. Geophys. Res., 91 (1986) 13,967; 101 (1988) 4375; A seismic model for the source of long-period events and harmonic tremor. In: Gasparini, P., Scarpa, R., Aki, K. (Eds.), Volcanic Seismology, IAVCEI Proceedings in Volcanology, Springer, Berlin, 3133). The fluid-driven crack model describes the far-field spectra of long-period (LP) events as modes of resonance of the crack. Results from our calculations demonstrate that ash-laden gas mixtures have fluid to solid density ratios comparable to, and fluid to solid velocity ratios lower than bubbly liquids (gas-volume fractions <10%). This difference results in synthetic far-field spectra with higher impedance contrasts and narrower spectral bandwidths for ash-laden gas mixture than spectra for bubbly liquids. Spectral characteristics are described in terms of the quality factor Q-1. Q-1 is measured by the ratio of the frequency of the dominant spectral peak to the bandwidth of the peak measured at one half of its amplitude. This factor expresses the losses of energy due to elastic radiation Q-1r and other dissipative mechanisms Q-1i at the source, Q-1 = Q-1r + Q-1i. Spectra for LP events recorded at active volcanoes such as Galeras in Colombia and Kilauea in Hawaii, have Q-1 factors in the range of 0.1-0.002. The Q-1r factors due to radiation loss calculated for a sphere filled with a H2O-CO2 or H2O-SO2 gas mixture, vary between 0.0015 and 0.0040 with a change in wt% H2O at 800-1600 K and 10-50 MPa. For gas-rich mixtures, Q-1r has a strong dependence on resonator geometry (spherical versus rectangular). The spectra from a resonating sphere filled with gas-rich mixture yields values of Q-1r an order of magnitude smaller than those from a rectangular crack. For a resonating crack filled with an ash-gas mixture (or pseudogas), Q-1r varies parabolically from ???0.006 for an ash-rich mixture, to 0.0015 or 0.0023 for a H2O-rich or CO2-rich mixture at 800 K and 25 MPa. For low (<20%) gas-volume fraction fluids (foams, bubbly fluids and ash-rich pseudogases), the magnitudes for Q-1r are independent of crack geometry. Spectra associated with a foam (gas-volume fractions 10-90%) or bubbly basalt (gas-volume fractions <10%) may have a dominant spectral peak with values of Q-1r on the order of 0.01 and 0.1, respectively. The spectra from a resonating sphere filled with a foam containing >20% gas-volume fraction yields values of Q-1r similar to those for a rectangular crack. As with gas-gas and ash-gas mixtures, an increase in mass fraction narrows the bandwidth of the dominant mode and shifts the spectra to lower frequencies. Including energy losses due to dissipative processes in a bubbly liquid increases attenuation. Attenuation may also be higher in ash-gas mixtures and foams if the effects of momentum and mass transfer between the phases were considered in the calculations. ?? 2001 Elsevier Science B. V. All rights reserved.

Journal of Volcanology and Geothermal Research↗

Survival of lake trout eggs on reputed spawning grounds in Lakes Huron and Superior: In situ incubation, 1987-1988

Lake trout reproduce widely in Lake Superior but little in Lake Huron. We examined whether survival of lake trout eggs and fry in either lake was reduced by physical disturbances and swim-up mortality. Eggs were collected from feral lake trout in Lake Superior and placed in 108 plastic incubators. A total of 48 incubators was set at Partridge Island Reef in southern Lake Superior, 48 were set at Port Austin Reef in southern Lake Huron, and 12 were held as controls inflowing well water at a laboratory. Survival-to-hatching of these eggs at Partridge Island Reef (18%) was significantly different from that at Port Austin Reef (43%) and significantly different in the laboratory (88%) from that at either reef (P < 0.05). During egg-fry incubation from 28 October 1987 to 5 May 1988, 11&ndash;18 cm of sediment accumulated in sediment traps placed on the reefs but < 1 cm of sediment was present on each reef in May 1988. Analysis showed that 44% of the eggs at Port Austin Reef and 28% of those at Partridge Island Reef were buried and killed by sediments. During the first week after deployment, mean wave energy was 90% higher at Partridge Island Reef and significantly different from that at Port Austin Reef. Wave energy may be a habitat condition that makes Partridge Island Reef less suitable than Port Austin Reef for incubation of lake trout eggs. Fry from eggs incubated at all three sites experienced no swim-up mortality. We conclude that in 1987&ndash;88 habitat conditions required for survival of lake trout eggs were more suitable at Port Austin Reef than at Partridge Island Reef.

Journal of Great Lakes Research↗

Chapter 4 The meade peak member of the phosphoria formation: Temporal and spatial variations in sediment geochemistry

Variations in the geochemistry of rocks from the Meade Peak Member of the Phosphoria Formation were examined using ratios of elements associated with either the +terrigenous or marine sediment fractions. Inter-element relationships in the terrigenous fraction appear useful for chemo-stratigraphic correlation. A sharp decrease upsection in K 2 O/AI 2 O 3 ratios occurs in the lower half of all but the most northeasterly section, wherein an offset is still evident in average and minimum values. These offsets correspond closely to the lower Guadalupian Series boundary as defined by conodont zonations, coincident with a change from major low-stand to transgressive conditions. The offsets are possibly the result of increased transport distances or flooding of source areas related to transgres- sion of the Phosphoria sea on the Wyoming shelf. A series of intervals displaying high Fe 2 O 3 /Al 2 O 3 , Ba/Al 2 O 3 and Sc/Al 2 O 3 ratios occur in the upper beds of the easternmost sections. The intervals do not appear to reflect amplified marine signals, but rather the introduction of terrigenous sediment from a secondary source, or, simply, reworking of sediments under higher energy conditions. The westernmost section, presumably repre- senting the deepest parts of the Phosphoria basin, contains intervals with high Ba/Al 2 O 3 . We suggest these horizons represent periods of low sediment accumulation during maxi- mum flooding and high-stand conditions. Inter-element relationships in the marine-derived sediment fraction indicate that bottom waters of the Phosphoria basin were dominantly denitrifying (suboxic). Ratios of Cd and Mo to Zn and Cu closely approach those in modern plankton in most of the sections, implying a major biogenic source for these elements. Exceptions occur through- out the westernmost (distal) section, possibly due to changes in the dominant plankton populations and relative nutrient uptakes, and in the upper part of the most northeasterly (shoreward, ramp) section, which we suggest is due to increased oxygen levels. Relatively thick phosphatic layers occur in basinal areas due largely to lack of terrig- enous dilution during deposition. These basinal deposits appear to have lower concentra- tions of many trace elements than more shoreward deposits. This may reflect deposition away from areas of peak primary production. Alternatively, biogenic detritus in these areas may have been derived from differing populations of primary producers with differing nutrient requirements. Both mid-shelf (middle ramp) and marginal environments were sites of accumulation of rich phosphatic units with high concentrations of trace elements. Deposits from marginal areas have the most varied geochemistry, largely because they experienced greater variability in terrigenous sediment influx. Even moderate changes in sea level may have dramatically altered energy levels, sediment mixing, and the amount of organic detritus reaching the sediment surface in these shallower marginal areas.

Colorado, Idaho, Montana, Nebraska, North Dakota, ↗

Formation of pedestalled, relict lakes on the McMurdo Ice Shelf, Antarctica

Surface debris covers much of the western portion of the McMurdo Ice Shelf and has a strong influence on the local surface albedo and energy balance. Differential ablation between debris-covered and debris-free areas creates an unusual heterogeneous surface of topographically low, high-ablation, and topographically raised (‘pedestalled’), low-ablation areas. Analysis of Landsat and MODIS satellite imagery from 1999 to 2018, alongside field observations from the 2016/2017 austral summer, shows that pedestalled relict lakes (‘pedestals’) form when an active surface meltwater lake that develops in the summer, freezes-over in winter, resulting in the lake-bottom debris being masked by a high-albedo, superimposed, ice surface. If this ice surface fails to melt during a subsequent melt season, it experiences reduced surface ablation relative to the surrounding debris-covered areas of the ice shelf. We propose that this differential ablation, and resultant hydrostatic and flexural readjustments of the ice shelf, causes the former supraglacial lake surface to become increasingly pedestalled above the lower topography of the surrounding ice shelf. Consequently, meltwater streams cannot flow onto these pedestalled features, and instead divert around them. We suggest that the development of pedestals has a significant influence on the surface-energy balance, hydrology and flexure of the ice shelf.

Journal of Glaciology↗

Importance of fish in the diet of Adélie penguins across multiple life stages

Over recent decades, the Adélie penguin ( Pygoscelis adeliae ) population has grown across most of its range, the exception being the northern coast of the western Antarctic Peninsula (WAP). In the Ross Sea, the very large Cape Crozier colony grew to reach ~9% of the global population. Demographic factors driving the Cape Crozier trend have yet to be identified. However, low chick fledging mass - a negative influence in the northern WAP where the diet is mostly less-energy-dense krill - is not showing an effect in the Cape Crozier colony. Previously, we hypothesized that Cape Crozier fledglings, and post-breeding adults, must be finding sufficient higher-quality prey once free of the prey-depleted colony foraging area, with subsequent higher survival. Here we explore penguin diet within and outside the colony foraging area using stable isotope analysis (SIA) of feathers: those grown by post-breeding adults outside the foraging area, prior to moult, compared to those of near-fledged chicks raised on meals obtained within the foraging area. Second, we explore whether a major difference occurs between breeding and post-breeding diet of adults from a small, nearby colony (Cape Royds) that exploits a smaller, little-depleted preyscape. Finally, we compare the results to SIA analyses published by others to explore whether the pre-moult diet of Ross Island adults, mostly foraging within the north-eastern Ross Sea, compares with that of adults nesting in the southern WAP (Bellingshausen Sea coast). At the latter, populations are not decreasing, with diet containing an appreciable contribution of fish. The results confirmed that fish contributed greatly to chick diets at both Ross Island colonies (δ 15 N 10.6–11.4). Once adults were released from central-place foraging, SIA levels (δ 15 N 9.7–12.9) were similar to those of the southern WAP. Foraging on energy-dense fish in coastal Antarctic waters could be one reason Adélie penguins are among the most abundant and therefore most ecologically successful penguin species.

Antarctic Science↗

Hubble Space Telescope observations of Europa in and out of eclipse

Europa is a prime target for astrobiology and has been prioritized as the next target for a National Aeronautics and Space Administration flagship mission. It is important, therefore, that we advance our understanding of Europa, its ocean and physical environment as much as possible. Here, we describe observations of Europa obtained during its orbital eclipse by Jupiter using the Hubble Space Telescope. We obtained Advanced Camera for Surveys Solar Blind Channel far ultraviolet low-resolution spectra that show oxygen line emission both in and out of eclipse. We also used the Wide-Field and Planetary Camera-2 and searched for broad-band optical emission from fluorescence of the surface material, arising from the very high level of incident energetic particle radiation on ices and potentially organic substances. The high-energy particle radiation at the surface of Europa is extremely intense and is responsible for the production of a tenuous oxygen atmosphere and associated FUV line emission. Approximately 50% of the oxygen emission lasts at least a few hours into the eclipse. We discuss the detection limits of the optical emission, which allow us to estimate the fraction of incident energy reradiated at optical wavelengths, through electron-excited emission, Cherenkov radiation in the ice and fluorescent processes. ?? 2010 Cambridge University Press.

Conference Paper↗

Comparison of two U.S. power-plant carbon dioxide emissions data sets

Estimates of fossil-fuel CO2 emissions are needed to address a variety of climate-change mitigation concerns over a broad range of spatial and temporal scales. We compared two data sets that report power-plant CO 2 emissions in the conterminous U.S. for 2004, the most recent year reported in both data sets. The data sets were obtained from the Department of Energy's Energy Information Administration (EIA) and the Environmental Protection Agency's eGRID database. Conterminous U.S. total emissions computed from the data sets differed by 3.5% for total plant emissions (electricity plus useful thermal output) and 2.3% for electricity generation only. These differences are well within previous estimates of uncertainty in annual U.S. fossil-fuel emissions. However, the corresponding average absolute differences between estimates of emissions from individual power plants were much larger, 16.9% and 25.3%, respectively. By statistical analysis, we identified several potential sources of differences between EIA and eGRID estimates for individual plants. Estimates that are based partly or entirely on monitoring of stack gases (reported by eGRID only) differed significantly from estimates based on fuel consumption (as reported by EIA). Differences in accounting methods appear to explain differences in estimates for emissions from electricity generation from combined heat and power plants, and for total and electricity generation emissions from plants that burn nonconventional fuels (e.g., biomass). Our analysis suggests the need for care in utilizing emissions data from individual power plants, and the need for transparency in documenting the accounting and monitoring methods used to estimate emissions.

Environmental Science & Technology↗

Partition characteristics of polycyclic aromatic hydrocarbons on soils and sediments

The partition behavior was determined for three polycyclic aromatic hydrocarbons (PAHs), i.e., naphthalene, phenanthrene, and pyrene, from water to a range of soil and sediment samples. The measured partition coefficients of the individual PAHs between soil/sediment organic matter (SOM) and water (i.e., K(oc) values) are relatively invariant either for the 'clean' (uncontaminated) soils or for the clean sediments; however, the mean K(oc) values on the sediments are about twice the values on the soils. This disparity is similar to the earlier observation for other nonpolar solutes and reflects the compositional differences between soil and sediment organic matters. No significant differences in K(oc) are observed between a clean coastal marine sediment and freshwater sediments. The coastal sediments that are significantly impacted by organic contaminants exhibit higher K(oc) values. At given K(ow) values (octanol-water), the PAHs exhibit much higher K(oc) values than other relatively nonpolar solutes (e.g., chlorinated hydrocarbons). This effect is shown to result from the enhanced partition of PAHs to SOM rather than from lower K(ow) values of PAHs at given supercooled liquid solute solubilities in water. The enhanced partition of PAHs over other nonpolar solutes in SOM provides an account of the markedly different correlations between log K(oc) and log K(ow) for PAHs and for other nonpolar solutes. The improved partition of PAHs in SOM stems apparently from the enhanced compatibility of their cohesive energy densities with those of the aromatic components in SOM. The approximate aromatic fraction in soil/sediment organic matter has been assessed by solid-state 13C-NMR spectroscopy.The partition behavior was determined for three polycyclic aromatic hydrocarbons (PAHs), i.e., naphthalene, phenanthrene, and pyrene, from water to a range of soil and sediment samples. The measured partition coefficients of the individual PAHs between soil/sediment organic matter (SOM) and water (i.e., Koc values) are relatively invariant either for the `clean' (uncontaminated) soils or for the clean sediments; however, the mean Koc values on the sediments are about twice the values on the soils. This disparity is similar to the earlier observation for other nonpolar solutes and reflects the compositional differences between soil and sediment organic matters. No significant differences in Koc are observed between a clean coastal marine sediment and freshwater sediments. The coastal sediments that are significantly impacted by organic contaminants exhibit higher Koc values. At given Kow values (octanol-water), the PAHs exhibit much higher Koc values than other relatively nonpolar solutes (e.g., chlorinated hydrocarbons). This effect is shown to result from the enhanced partition of PAHs to SOM rather than from lower Kow values of PAHs at given supercooled liquid solute solubilities in water. The enhanced partition of PAHs over other nonpolar solutes in SOM provides an account of the markedly different correlations between log Koc and log Kow for PAHs and for other nonpolar solutes. The improved partition of PAHs in SOM stems apparently from the enhanced compatibility of their cohesive energy densities with those of the aromatic components in SOM. The approximate aromatic fraction in soil/sediment organic matter has been assessed by solid-state 13C-NMR spectroscopy.

Environmental Science & Technology↗

Application of the surface complexation concept to complex mineral assemblages

Two types of modeling approaches are illustrated for describing inorganic contaminant adsorption in aqueous environments: (a) the component additivity approach and (b) the generalized composite approach. Each approach is applied to simulate Zn2+ adsorption by a well-characterized sediment collected from an aquifer at Cape Cod, MA. Zn2+ adsorption by the sediment was studied in laboratory batch experiments with a range of pH and Zn(II) concentrations selected to encompass conditions observed in the aquifer. In the generalized composite approach, one, and two-site surface complexation model parameters were calibrated with the experimental data using FITEQL. The pH dependence of Zn2+ adsorption was simulated without explicit representation of electrostatic energy terms. Surface acidity constants and ion pair formation by major electrolyte ions were also not required in the model thereby minimizing the number of fitted parameters. Predictions of Zn2+ adsorption with the component additivity modeling approach did not simulate the experimental data adequately without manipulation of surface area or site density parameter values. To apply the component additivity approach to environmental sorbents, further research is needed to better characterize the composition of sediment surface coatings. The generalized composite modeling approach requires less information and can be viewed as more practical for application within solute transport models. With only three adjustable parameters, this approach could simulate Zn2+ adsorption over a range of chemical conditions that would cause several orders of magnitude variation in the distribution coefficient (K(d)) for Zn2+ within the aquifer.Two types of modeling approaches are illustrated for describing inorganic contaminant adsorption in aqueous environments: (a) the component additivity approach and (b) the generalized composite approach. Each approach is applied to simulate Zn2+ adsorption by a well-characterized sediment collected from an aquifer at Cape Cod, MA. Zn2+ adsorption by the sediment was studied in laboratory batch experiments with a range of pH and Zn(II) concentrations selected to encompass conditions observed in the aquifer. In the generalized composite approach, one- and two-site surface complexation model parameters were calibrated with the experimental data using FITEQL. The pH dependence of Zn2+ adsorption was simulated without explicit representation of electrostatic energy terms. Surface acidity constants and ion pair formation by major electrolyte ions were also not required in the model, thereby minimizing the number of fitted parameters. Predictions of Zn2+ adsorption with the component additivity modeling approach did not simulate the experimental data adequately without manipulation of surface area or site density parameter values. To apply the component additivity approach to environmental sorbents, further research is needed to better characterize the composition of sediment surface coatings. The generalized composite modeling approach requires less information and can be viewed as more practical for application within solute transport models. With only three adjustable parameters, this approach could simulate Zn2+ adsorption over a range of chemical conditions that would cause several orders of magnitude variation in the distribution coefficient (Kd) for Zn2+ within the aquifer.

Environmental Science & Technology↗

Methane hydrates in nature - Current knowledge and challenges

Recognizing the importance of methane hydrate research and the need for a coordinated effort, the United States Congress enacted the Methane Hydrate Research and Development Act of 2000. At the same time, the Ministry of International Trade and Industry in Japan launched a research program to develop plans for a methane hydrate exploratory drilling project in the Nankai Trough. India, China, the Republic of Korea, and other nations also have established large methane hydrate research and development programs. Government-funded scientific research drilling expeditions and production test studies have provided a wealth of information on the occurrence of methane hydrates in nature. Numerous studies have shown that the amount of gas stored as methane hydrates in the world may exceed the volume of known organic carbon sources. However, methane hydrates represent both a scientific and technical challenge, and much remains to be learned about their characteristics and occurrence in nature. Methane hydrate research in recent years has mostly focused on: (1) documenting the geologic parameters that control the occurrence and stability of methane hydrates in nature, (2) assessing the volume of natural gas stored within various methane hydrate accumulations, (3) analyzing the production response and characteristics of methane hydrates, (4) identifying and predicting natural and induced environmental and climate impacts of natural methane hydrates, (5) analyzing the methane hydrate role as a geohazard, (6) establishing the means to detect and characterize methane hydrate accumulations using geologic and geophysical data, and (7) establishing the thermodynamic phase equilibrium properties of methane hydrates as a function of temperature, pressure, and gas composition. The U.S. Department of Energy (DOE) and the Consortium for Ocean Leadership (COL) combined their efforts in 2012 to assess the contributions that scientific drilling has made and could continue to make to advance our understanding of methane hydrates in nature. COL assembled a Methane Hydrate Project Science Team with members from academia, industry, and government. This Science Team worked with COL and DOE to develop and host the Methane Hydrate Community Workshop, which surveyed a substantial cross section of the methane hydrate research community for input on the most important research developments in our understanding of methane hydrates in nature and their potential role as an energy resource, a geohazard, and/or as an agent of global climate change. Our understanding of how methane hydrates occur in nature is still growing and evolving, and it is known with certainty that field, laboratory, and modeling studies have contributed greatly to our understanding of hydrates in nature and will continue to be a critical source of the information needed to advance our understanding of methane hydrates.

Journal of Chemical and Engineering Data↗

Vertical accretion and shallow subsidence in a mangrove forest of southwestern Florida, U.S.A

Simultaneous measurements of vertical accretion from artificial soil marker horizons and soil elevation change from sedimentation-erosion table (SET) plots were used to evaluate the processes related to soil building in range, basin, and overwash mangrove forests located in a low-energy lagoon which recieves minor inputs of terregenous sediments. Vertical accretion measures reflect the contribution of surficial sedimentation (sediment deposition and surface root growth). Measures of elevation change reflect not only the contributions of vertical accretion but also those of subsurface processes such as compaction, decomposition and shrink-swell. The two measures were used to calculate amounts of shallow subsidence (accretion minus elevation change) in each mangrove forest. The three forest types represent different accretionary envrionments. The basin forest was located behind a natural berm. Hydroperiod here was controlled primarily by rainfall rather than tidal exchange, although the basin flooded during extreme tidal events. Soil accretion here occurred primarily by autochthonous organic matter inputs, and elevation was controlled by accretion and shrink-swell of the substrate apparently related to cycles of flooding-drying and/or root growth-decomposition. This hydrologically-restricted forest did not experience an accretion or elevation deficit relative to sea-level rise. The tidally dominated fringe and overwash island forests accreted through mineral sediment inputs bound in place by plant roots. Filamentous turf algae played an important role in stabilizing loose muds in the fringe forest where erosion was prevalent. Elevation in these high-energy environments was controlled not only by accretion but also by erosion and/or shallow subsidence. The rate of shallow subsidence was consistently 3-4 mm y-1 in the fringe and overwash island forests but was negligible in the basin forest. Hence, the vertical development of mangrove soils was influenced by both surface and subsurface processes and the procces controlling soil elevation differed among forest types. The mangrove ecosystem at Rookery Bay has remained stable as sea level has risen during the past 70 years. Yet, lead-210 accretion data suggest a substantial accretion deficit has occurred in the past century (accretion was 10-20 cm < sea-level rise from 1930 to 1990) in the fringe and island forests at Rookery Bay. In contrast, our measures of elevation change mostly equalled the estimates of sea-level rise and shallow subsidence. These data suggest that (1) vertical accretion in this system is driven by local sea-level rise and shallow subsidence, and (2) the mangrove forests are mostly keeping pace with sea-level rise. Thus, the vulnerability of this mangrove ecosystem to sea-level rise is best described in terms of an elevation deficit (elevation change minus sea-level rise) based on annual measures rather than an accretion deficit (accretion minus sea-level rise) based on decadal measures.

Mangroves and Salt Marshes↗