The Application of Petroleum Hydrocarbon Fingerprint Characterization in Site Investigation and Remediation

Tremendous resources have been and continue to be spent investigating and remediating petroleum hydrocarbon compounds (PHCs) in soil and ground water. Investigating and planning a remedial strategy for sites affected by PHCs is often a challenging task because of the complex chemical nature of the PHCs. the complex regulatory environment related to PHC cleanup, and the use of analytical methods that provide quantitation but not identification of PHCs. From a technical standpoint, the PHC impacting soil and/or ground water is frequently inadequately characterised, both in identification as well as in is general properties (solubility, toxicity). From a regulatory standpoint, promulgated or recommended total petroleum hydrocarbon (TPH) cleanup levels generally relate to assumed properties of specific unweathered products and are inconsistent among different agencies and regions. This produces a prime situation for unwillingly spending more resources on investigation or remediation than may be necessary, especially when the PHC in the subsurface has different properties from unweathered products such as gasoline or diesel.
Accurately identifying the PHC and its nature, a process known as fingerprint characterization, is critical to the determination of appropriate regulatory goals and design of cost-effective remedial approaches. This paper presents several case studies in which fingerprint characterization made a significant difference in the project outcome. In each instance the nature of the organic material was better understood, the regulatory cleanup levels were negotiated based on the nature of the material, and a remedial approach was implemented that differed significantly from and was generally less costly than what would have been required without fingerprint characterization data.     

Probability of earthquake recurrence with nonuniform stress rates and time-dependent failure

Current methods for calculation of long-term probabilities for the recurrence of large earthquakes on specific fault segments are based upon models of the faulting process that implicitly assume constant stress rates during the interval separating earthquakes and instantaneous failure at a critical stress threshold. However, observations indicate that the process of stress recovery following an earthquake involves rate variations at all time scales in addition to stress steps caused by nearby earthquakes. Additionally, the existence of foreshocks, aftershocks and possible precursory processes suggest that there may be significant time dependence of the earthquake nucleation process. A method for determining the conditional probabilities for earthquake occurrence under conditions of irregular stressing is developed that could be useful at all time scales including those pertinent to short-and intermediate-term prediction. Used with models for earthquake occurrence at a stress threshold, the addition of variable stressing introduces a simple scaling of the conditional probabilities by stress level and stress rate. A model for the time-dependent nucleation of earthquake slip has been proposed recently that is based upon laboratory observations of fault strength. This failure criterion results in large but relatively short duration changes in the probability of earthquake recurrence particularly following stress steps. Applied to populations of earthquakes the models predicts a 1/t decay of seismicity following stress steps as observed for aftershocks and for frequency of foreshock-mainshock pairs. The model suggests that variations of seismicity rates of small earthquakes in the nucleation zone of the expected earthquake directly indicate variations in probability of recurrence of the large earthquake.     

Assessing basin storage: Comparison of hydrometric- and tracer-based indices of dynamic and total storage

Storage is a fundamental but elusive component of drainage basin function, influencing synchronization between precipitation input and streamflow output and mediating basin sensitivity to climate and land use/land cover (LULC) change. We compare hydrometric and isotopic approaches to estimate indices of dynamic and total basin storage, respectively, and assess inter-basin differences in these indices across the Oak Ridges Moraine (ORM) region of southern Ontario, Canada. Dynamic storage indices for the 20 study basins included the ratio of baseflow to total streamflow (baseflow index BFI), Q ₉₉ flow and flow duration curve (FDC) slope. Ratios of the standard deviation of the streamflow stable isotope signal relative to that of precipitation were determined for each basin from a 1 year bi-weekly sampling program and used as indicators of total storage. Smaller ratios imply longer water travel times, smaller young water fractions (F _yw, < ~2–3 months in age) in streamflow and greater basin storage. Ratios were inversely related to BFI and Q ₉₉, and positively related to FDC slope, suggesting longer travel times and smaller F _yw for basins with stable baseflow-dominated streamflow regimes. Inter-basin differences in all indices reflected topographic, hydrogeologic and LULC controls on storage, which was greatest in steep, forest-covered headwaters underlain by permeable deposits with thick and relatively uniform unsaturated zones. Nevertheless, differential sensitivity of indices to controls on storage indicates the value of using several indices to capture more completely how basin characteristics influence storage. Regression relationships between storage indices and basin characteristics provided reasonable predictions of aspects of the streamflow regime of test basins in the ORM region. Such relationships and the underlying knowledge of controls on basin storage in this landscape provide the foundation for initial predictions of relative differences in streamflow response to regional changes in climate and LULC.     

Hammond Hill Research Catchment: Supporting hydrologic investigations of rooting zone and vegetation water dynamics under climate change

The Hammond Hill Research Catchment (HH) is a small (120 ha), temperate, second order tributary to Six Mile Creek, Cayuga Lake, and the Great Lakes (42.42°, −76.32°). The HH has been monitored since January 2017 for the purpose of understanding how recent infiltration mixes with antecedent soil water on hillslope forest floors and the spatial and temporal patterns of Root Water Uptake (RWU) by temperate northeastern US tree species (eastern hemlock [Tsuga canadensis], American beech [Fagus grandifolia], and sugar maple [Acer saccharum]). These data are informing us about the hydrologic consequences of anticipated tree species composition change and supporting the development of more refined ecohydrological models. The glaciated catchment is underlain by a shallow confining siltstone layer (1–1.5 m depth) and densely covered with an approximately 60 year old regrowth mixed species forest of hemlock, beech, and other deciduous tree species common to the northeastern US. Current datasets from the HH include precipitation snow water equivalent, discharge, and associated isotopic water compositions, δ²H & δ¹⁸O. Measurements of (top 10 cm) soil water content, as well as bulk soil water and hemlock and beech xylem isotopic compositions are made at several locations across a topographic wetness gradient. The near-term role of the HH is to support an understanding of the environmental and ecological drivers of plant RWU competition. All data from the HH are publicly available.     

Prediction of thermal conductivity in reservoir rocks using fabric theory

An accurate prediction of the thermal conductivity of reservoir rocks in the subsurface is extremely important for a quantitative analysis of basin thermal history and hydrocarbon maturation. A model for calculating the thermal conductivity of reservoir rocks as a function of mineral composition, porosity, fluid type, and temperature has been developed based on fabric theory and experimental data. The study indicates that thermal conductivities of reservoir rocks are dependent on the volume fraction of components (minerals, porosity, and fluids), the temperature, and the fraction of series elements (FSE) which represents the way that the mineral components aggregate. The sensitivity test of the fabric model shows that quartz is the most sensitive mineral for the thermal conductivity of clastic rocks. The study results indicate that the FSE value is very critical. Different lithologies have different optimum FSE values because of different textures and sedimentary structures. The optimum FSE values are defined as those which result in the least error in the model computation of the thermal conductivity of the rocks. These values are 0.444 for water-saturated clay rocks, 0.498 for water-saturated sandstones, and 0.337 for water-saturated carbonates. Compared with the geometric mean model, the fabric model yields better results for the thermal conductivity, largely because the model parameters can be adjusted to satisfy different lithologies and to minimize the mean errors. The fabric model provides a good approach for estimating paleothermal conductivity in complex rock systems based on the mineral composition and pore fluid saturation of the rocks.     

Effects of finite rifting times on the development of sedimentary basins

Most thermo-mechanical models for the development of sedimentary basins have assumed that the rifting responsible for the formation of the basin occurred instantaneously and have examined the post-rift development of the basin. This assumption greatly simplifies the mathematical treatment, but is not in accord with what is found in nature, where 10-to 50-m.y. rifting events commonly accompany the formation of sedimentary basins and continental margins. The effects of a finite rifting time on the development of sedimentary basins are examined using an analytic technique which allows an arbitrary rifting history in both time and space and which considers the effects of both vertical and horizontal heat transfer. This technique allows the thermal structure of the lithosphere to be calculated throughout the rifting event and thus permits the subsidence history and surface heat flow of the developing basin to be traced.The effect of a finite-duration extension event is that heat is lost during rifting increasing the syn-rift subsidence at the expense of the post-rift. Lateral heat flow, which was not included in previous studies of the effect of finite rifting times, has a significant effect on the subsidence history, distribution of sediments and thermal history. In particular, the post-rift subsidence is decreased by more than 25% for a 20-m.y. rifting event and by more than 10–15% for a rifting event as short as 10 m.y. This will significantly decrease the subsidence rates in the post-rift stage and implies that inferences concerning the structure, development and thermal history of the basin derived from using “β-curves” to interpret backstripped subsidence can be greatly in error.Variations in syn-rift sediment accumulation and lithospheric thermal structure at the end of rifting resulting from different rifting histories can interact with other factors, such as the flexural response of the lithosphere to sediment loading, to affect the final width of the basin, the total amount of sediments that accumulate and the basin stratigraphy.     

On the mode theory of V. L. F. ionospheric propagation

Summary The space between the earth and the ionosphere is considered as a wave-guide with sharply bounded walls. Employing a representation in terms of spherical wave functions of complex order, the field of a vertical dipole source is calculated for very low frequencies. It is shown that the dominant mode for 16 kc is of order one and not zero as has been commonly supposed. Good agreement is obtained with the experimental results ofJ. Heritage.Paper presented at «Colloque International sur la propagation des Ondes Radio électriques» Paris, September 1956.     

Subsurface electric fields of a grounded cable of finite length for both frequency and time domain

Summary The subsurface electric fields of a current-carrying cable are examined for both steady-state and transient situations. Closed form expressions are obtained for two of the electric field components, and a numerical integration is used to obtain the third component. Waveforms for a stepfunction current excitation are displayed. The results have possible application to pulsed downlink communication in mine rescue operations.     

Oxygen and hydrogen in the primitive atmosphere

From time to time there appears in the literature the assertion that photolysis of water vapor could have maintained an appreciable concentration of oxygen in the primitive (prebiological) atmosphere. The implausibility of this assertion is argued in this paper.By itself, photolysis does not provide a source of oxygen because it is usually followed by recombination of the products of photolysis. Only the escape to space (at a much smaller rate) of the hydrogen produced by photolysis of water results in a net source of oxygen. The oxidation state of the primitive atmosphere depended on the relative magnitudes of this net source of oxygen and a volcanic source of hydrogen and other reduced gases. Today the volcanic source of reduced gases is approximately equal to the oxygen source provided by photolysis followed by escape. The oxygen source depends on the mixing ratio of water vapor in the stratosphere, which ultimately determines the rate of escape of hydrogen produced from water vapor. Its magnitude may not have been very different in the past. The volcanic source of hydrogen, on the other hand, is likely to have been much larger when the earth was tectonically young. Hydrogen was therefore released to the primitive atmosphere more rapidly than oxygen, probably. Photochemical reactions with the excess hydrogen maintained oxygen mixing ratios at negligibly small levels. The hydrogen mixing ratio was determined by a balance between the volcanic source (reduced by recombination with oxygen) and escape to space.In time, either because of decline of the volcanic source of hydrogen or because of addition of a biological source of oxygen, the input of oxygen to the atmosphere rose above the input of hydrogen. The oxidation state of the atmosphere changed rapidly. Volcanic hydrogen was now consumed by photochemical reactions with excess oxygen, while the oxygen mixing ratio was determined by a balance between the source (reduced by recombination with volcanic hydrogen) and consumption in reactions with reduced material at the surface.     

Ferromanganoan sediments in the equatorial East Pacific

Ferromanganoan sediments containing little or no CaCO₃ have been found to occur extensively throughout the region between the East Pacific Rise and the Galapagos Rise. Concentrations of Fe and Mn of up to 18 and 6.5%, respectively, accompany low concentrations of Al and Ti. The concentrations of Cu, Ni, and Zn are also high relative to more typical pelagic sediments.While chemically similar to the non-carbonate fraction of metalliferous sediments previously described from the East Pacific Rise, the mineralogy is markedly different. A non-detrital smectite makes up the bulk of sediment (70 to 90%) and is the most important iron bearing phase. Fe and Mn oxides, occurring primarily as micro-nodules, comprise 10 to 20% of the sediment. Detrital material is relatively rare, amounting to less than 10% in all samples.