Zero-Order Kinetics Model for the Christensen-Larsen Method for Fugitive Fuel Age Estimates

Estimating time of a middle distillate fuel release in soil can be performed under certain restricting environmental conditions using the Christensen-Larsen method (CLM). This method is based on the linear correlation between the time since a diesel fuel release and the corresponding value of n -heptadecane to pristane ratio ( n -C₁₇/Pr) but requires knowledge of the initial ratio value. The empirical nature of this method does not, however, allow accounting for variance in the initial fuel     value used by CLM. Based on the zero-order approximation of the Monod model, we have deduced a generalized equation that can be used for estimating release ages of middle distillate fuels with different initial     values. When combined with other site-specific factors, this equation provides a useful tool for the time of release estimates.     

Geochemical characteristics of crude oils from the Sagara oil field, Shizuoka Prefecture, Japan

Abstract   Six oil samples collected from the Sagara oil field, Shizuoka Prefecture, were geochemically analyzed. Unlike the Niigata oils, the Sagara oils: (i) are low-sulphur light oils dominated by gasoline and kerosene fractions; (ii) have low values of environment index in light hydrocarbon compositions; (iii) have high Pr/ n -C₁₇ and low Ph/ n -C₁₈ ratios and high oleanane/hopane ratios; (iv) have high relative abundance of C₂₉ and low relative abundance of C₂₈ regular steranes; and (v) have 'light' stable carbon isotope compositions. These characteristics show that the source rocks of the Sagara oils contain mainly marine organic matter, but with more input of terrigenous organic matter deposited under more oxic conditions compared to those of the Niigata oils. The light carbon isotope compositions and the low relative abundance of C₂₈ regular steranes of the Sagara oils suggest that their source rock is not Miocene, but probably Paleogene in age. The Sagara oils probably migrated along faults from deeper parts of the basin.     

Vitamin B12 and Reduced Titanium for Remediation of Residual Chlorinated Solvents: Field Experiment

A first pilot-scale field experiment using vitamin B₁₂ and reduced titanium was conducted in an in situ vertical circulation column at CFB Borden. The objective of the experiment was to test the applicability of the technology for restoring aquifer source zones contaminated by chlorinated solvents—tetrachloroethene (PCE) and 1,1,1-trichloroethane (1,1,1-TCA)—in a mixture of dense nonaqueous phase liquids (DNAPLs). Vitamin B₁₂ promotes the reductive dechlorination of chlorinated organics. A highly reducing and slightly alkaline environment must be maintained (Eh < - 480 mV and 7 < pH < 9) to maximize the rate of degradation. In this field test, PCE and 1,1,1-TCA degraded to a limited extent under experimental conditions, with 1,1,1-TCA degrading more readily. Indigenous bacteria were found to metabolize citrate, which caused titanium to precipitate, limiting degradation. The addition of glucose at the end of a second field season effectively limited citrate degradation and helped recover the optimal redox potential by keeping reduced titanium in solution. A laboratory column was used to confirm field results. The column also produced a significant biomass, which provided an additional source of organic carbon onto which the solvents sorbed.     

Origins of hydrocarbons in the Sagara oil field, central Japan

Abstract   We collected free-gas and in situ fluid samples up to a depth of 200.6 m from the Sagara oil field, central Japan (34°44'N, 138°15'E), during the Sagara Drilling Program (SDP) and measured the concentrations and stable carbon isotopic compositions of CH₄ and C₂H₆ in the samples. A combination of the CH₄/C₂H₆ ratios with the carbon isotope ratios of methane indicates that the hydrocarbon gases are predominantly of thermogenic origin at all depths. The isotope signature of hydrocarbon gases of δ¹³      < δ¹³     suggests that these gases in the Sagara oil field are not generated by polymerization, but by the decomposition of organic materials.     

Hydraulic Conductivity Measurements in the Unsaturated Zone Using Improved Well Analyses

The flow of ponded water into and through the unsaturated zone depends on both the saturated and unsaturated components of the hydraulic conductivity. Recent studies indicate that the ratio of the saturated (K_fs) to the unsaturated (φ_m) components (K_fs/φ_m=α*) of flow lies within prescribed bounds for most field soils, i.e., 1m⁻¹≤α*≤ 100 m⁻¹. In addition, the fact that the calculation of K_fs and φ_m is not strongly dependent on the choice of α*, suggests that a site estimation of α* leads to reasonable "best estimates" of K_fs and φ_m when using the constant head well permeameter technique. As a consequence, measurement of the steady flow rate using only one ponded head may be all that is necessary for many practical applications. Multiple head measurements or independent measurements of α* or φ_m can be used, however, to give more accurate estimates of K_fs if required.     

A case study on fuel oil contamination in a mangrove swamp in Hong Kong

Mangroves commonly found along tropical and subtropical coastlines are susceptible to oil pollution. In December 2000, around 500 1 m tall Kandelia candel saplings at the age of 3–5 years old located at the foreshore region of Sheung Pak Nai swamp, Hong Kong SAR, were found to be damaged by oil pollution. More than 80% of the saplings were either dead or washed away and leaving less than 5% healthy saplings with dense green leaves. Elevated concentrations of light n-alkanes (ranging from n-C₁₄ to n-C₂₀), pristane and phytane were recorded in surface sediments collected in December 2000. The ratio between light and total n-alkanes was 0.4. The total petroleum hydrocarbons (60–80 μg g⁻¹ TPH) and unresolved complex mixtures (60–70 μg g⁻¹ UCM) were higher than the background values of other mangrove sediments in Hong Kong, which were 40 and 20 μg g⁻¹, respectively. In certain root zone sediments, TPH concentrations were above 1000 μg g⁻¹. These results suggest that surface sediments in Sheung Pak Nai were contaminated by petroleum oil, most likely by illegal discharge of fuel oil which occurred between 1998 and 2002. One year later, in December 2001, unhealthy saplings had recovered and re-grown. The concentrations of TPH and UCM in sediments declined to around 40 μg g⁻¹, pristane and phytane dropped by 80%, and the ratio of light to total n-alkanes was 0.15, suggesting that residual oil in sediments was weathered leading to a remarkable recovery of the unhealthy saplings.     

‘Fingerprinting’ petroleum hydrocarbons in bottom sediment,plankton, and sediment trap collected seston

Water carried particulate matter (seston) collected in sediment traps has been used for fingerprinting petrogenic hydrocarbons (PHC) along an urban influenced transect in the Stockholm archipelago. Gas-chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) have been used for identification and quantification of n-alkanes, the isoprenoids pristane and phytane, pentacyclic triterpanes, the unresolved complex mixture (UCM) and total hydrocarbon content (THC). Preserved seston has been compared with anoxic seston and anoxic bottom surface sediments to establish the effects of degradation processes, and with spring bloom plankton as a reference of biological material. The results show that samples of seston, collected and preserved in sediment traps, are very suitable for carrying out fingerprint analyses of petrogenic hydrocarbons. A gradient of increasing PHC downflux towards the urban area was found and petrogenic contamination of the waters was detected along the whole transect.     

Generation of Hydrogen Gas as a Result of Drilling Within the Saturated Zone

Hydrogen gas was discovered within the steel casing above standing water in a percussion-drilled borehole on the Hanlord Site in south-central Washington state. In situ measurements of the borehole fluids indicated anoxic, low-Eh (<-400 mV) conditions. Ground water sampled from adjacent wells in the same formation indicated that the ground water was oxygenated. H₂ was generated during percussion drilling, due to the decomposition of borehole waters as a result of aqueous reactions with drilled sediment and steel from the drilling tools or casing. The generation of H₂ within percussion-drilled boreholes that extend below the water table may be more common than previously realized. The ambient concentration of H₂ produced during drilling was limited by microbial activity within the casing-resident fluids. H₂ was generated abiotically in the laboratory, whereby sterilized borehole slurry samples produced 100 times more H₂ than unsterilizcd samples. It appears that H₂ is metabolized by microorganisms and concentrations might be significantly greater if not for microbial metabolism.     

Biodegradation and environmental behavior of biodiesel mixtures in the sea: An initial study

Biodiesel, a mixture of fatty acid methyl esters (FAMEs) derived from animal fats or vegetable oils, is rapidly moving towards the mainstream as an alternative source of energy. However, the behavior of biodiesel, or blends of biodiesel with fossil diesel, in the marine environment have yet to be fully understood. Hence, we performed a series of initial laboratory experiments and simple calculations to evaluate the microbial and environmental fate of FAMEs. Aerobic seawater microcosms spiked with biodiesel or mixtures of biodiesel and fossil diesel revealed that the FAMEs were degraded at roughly the same rate as n-alkanes, and more rapidly than other hydrocarbon components. The residues extracted from these different microcosms became indistinguishable within weeks. Preliminary results from physical-chemical calculations suggest that FAMEs in biodiesel mixtures will not affect the evaporation rates of spilled petroleum hydrocarbons but may stabilize oil droplets in the water column and thereby facilitate transport.     

The comparative effects of oil dispersants and oil/dispersant conjugates on germination of the marine macroalga Phyllospora comosa (Fucales: Phaeophyta)

Germination inhibition of the marine macrophyte Phyllospora comosa was utilized as a sub-lethal end-point to assess and compare the effects of four oil dispersants and dispersed diesel fuel and crude oil combinations. Inhibition of germination by the water-soluble fraction of diesel fuel increased following the addition of each of the dispersants; the nominal 48-h EC₅₀ concentration of diesel fuel declined from 6800 to approximately 400 μl l⁻¹ nominal for each dispersed combination. This contrasted with crude oil, where the addition of two dispersants resulted in an enhanced germination rate and an increase in nominal EC₅₀ concentrations from 130 μl l⁻¹ for the undispersed crude to 4000 and 2500 μl l⁻¹. The results indicate that, while germination inhibition of P. comosa may be enhanced by the chemical dispersal of oil, the response varies with type of both oil and oil dispersant.     

Quartz microtextures of the Sambagawa schists and their implications in convergent margin processes

Abstract Quartz c-axis fabrics of the Sambagawa schists produced along a late Mesozoic convergent plate margin were analysed so that their tectono-metamorphic history could be clarified. It has been noted by many authors that quartz fabrics produced by earlier phase deformation are easily modified by strain increment during later phase deformation. This paper attempts to elucidate the high-temperature phases of prograde metamorphism (Sim-Bim phase) and of retrograde metamorphism (Sb₁ phase and Sb₂₋₁ phase) from quartz grains included in garnet and plagioclase porphyroblasts. Quartz c-axis fabrics for all these phases are explained in terms of a type I crossed girdle, without (only rarely with) higher concentration in the principal axis of strain Y (X>Y>Z), that must have been produced by the activity of a dominant slip system such as rhomb and basal. As a result, the plastic deformation of quartz, which was responsible for the formation of the type I crossed girdle, occurred even under temperatures greater than 500°C and pressures a little greater than 10–11 kb, which correspond to the physical condition of the Sim-Bim phase. It has been assumed that a high strain rate (and/or low H₂O content) caused rhomb and basal to be active as dominant slip systems in the subduction zone related to the formation of the Sambagawa schists even under high temperatures (> 500°C).     

Chemical evolution of Macondo crude oil during laboratory degradation as characterized by fluorescence EEMs and hydrocarbon composition

The fluorescence EEM technique, PARAFAC modeling, and hydrocarbon composition were used to characterize oil components and to examine the chemical evolution and degradation pathways of Macondo crude oil under controlled laboratory conditions. Three major fluorescent oil components were identified, with Ex/Em maxima at 226/328, 262/315, and 244/366 nm, respectively. An average degradation half-life of ～20 d was determined for the oil components based on fluorescence EEM and hydrocarbon composition measurements, showing a dynamic chemical evolution and transformation of the oil during degradation. Dispersants appeared to change the chemical characteristics of oil, to shift the fluorescence EEM spectra, and to enhance the degradation of low-molecular-weight hydrocarbons. Photochemical degradation played a dominant role in the transformation of oil components, likely an effective degradation pathway of oil in the water column. Results from laboratory experiments should facilitate the interpretation of field-data and provide insights for understanding the fate and transport of oil components in the Gulf of Mexico.     

Estimation of Biodegradation Rates Using Respiration Tests During In Situ Bioremediation of Weathered Diesel NAPL

Respiration tests were carried out during a seven month bioremediation field trial to monitor biodegradation rates of weathered diesel non-aqueous phase liquid (NAPL) contaminating a shallow sand aquifer. Multiple depth monitoring of oxygen concentrations and air-filled porosity were carried out in nutrient amended and nonamended locations to assess the variability of degradation rate estimates calculated from respiration tests.
The field trial consisted of periodic addition of nutrients (nitrogen and phosphorus) and aeration of a 100 m² trial plot. During the bioremediation trial, aeration was stopped periodically, and decreases in gaseous oxygen concentrations were logged semi-continuously using data loggers attached to recently developed in situ oxygen probes placed at multiple depths above and within a thin NAPL-contaminated zone. Oxygen usage rate coefficients were determined by fitting zero-and first-order rate equations to the oxygen concentration reduction curves, although only zero-order rates were used to calculate biodegradation rates. Air-filled porosity estimates were found to vary by up to a factor of two between sites and at different times.
NAPL degradation rates calculated from measured air-filled porosity and oxygen usage rate coefficients ranged up to 69 mg kg^-1 day^-1. These rates are comparable to and higher than rates quoted in other studies, despite the high concentrations and weathered state of the NAPL at this test site. For nutrient-amended sites within the trial plot, estimates of NAPL degradation rates were two to three times higher than estimates from nonamended sites. Rates also increased with depth.     

Chemical Fate of Injected Wastes

The chemical fate of wastes put into disposal wells can be determined using standard chemical engineering techniques. The concentration of hazardous constituents is typically reduced by reactions within the waste itself or by reactions with the injection zone material, thus reducing any potential impact on the environment. Such reactions include neutralization, hydrolysis, ion exchange, adsorption, precipitation, co-precipitation and microbial degradation.
Extensive research was done to quantify these phenomena, so they could be used in a predictive model.
Neutralization, hydrolysis and precipitation were modeled using data from the open literature: reaction rates and equilibrium constants for the dominant reactions were incorporated into a sophisticated computer simulation that calculates solid-liquid equilibria of aqueous electrolyte solutions.
The model predicted the fate of two waste streams: (1) high-pH, cyanide-containing waste injected into sandstone is made less hazardous by hydrolysis and sand dissolution, and (2) FeCl₃-FeCl₂ HCl-H₂ O waste is made non-hazardous by reaction with dolomite. Experiments are planned to confirm certain model predictions. Further development and public access of the model are planned.     

Geographical distribution of helium isotope ratios in northeastern Japan

In order to study the precise geographical distribution of helium isotope ratios in northeastern Japan and compare it with geophysical data, we collected 43 gas and water samples from hot and mineral springs in the region where the ratio had never been reported, and measured the ³He/⁴He and ⁴He/²⁰Ne ratios of these samples. It was found that the ³He/⁴He ratios show clear contrasts between the forearc and the back-arc regions in the Tohoku district in northeastern Japan. In the forearc region, the ratios are smaller than 1 R_A (1 R_A = 1.4 × 10⁻⁶; R_A means the ³He/⁴He ratio of the atmosphere). On the other hand, those along the volcanic front and in the back-arc region are apparently higher. Moreover, we found a variation in the ³He/⁴He ratios along the volcanic front. In Miyagi Prefecture (38–39°N), the ratios range from 2 to 5 R_A. On the other hand, the ratios are less than 1 R_A in and around the southern border between Iwate and Akita Prefectures (39–39.5°N). Comparing the distribution of helium isotope ratios to results of recent geophysical studies, we found that the features in geographical distribution of helium isotope ratios are similar to those of seismic low-velocity zone distributions and high Qp⁻¹ distributions in the uppermost mantle. These observations strongly suggest that the helium isotope ratios reflect the distribution of melts in the uppermost mantle and are a useful tool for investigating the origin, behavior, and distribution of deep fluids and melts.     

Origin and Extent of Fresh Paleowaters on the Atlantic Continental Shelf, USA

While the existence of relatively fresh groundwater sequestered within permeable, porous sediments beneath the Atlantic continental shelf of North and South America has been known for some time, these waters have never been assessed as a potential resource. This fresh water was likely emplaced during Pleistocene sea-level low stands when the shelf was exposed to meteoric recharge and by elevated recharge in areas overrun by the Laurentide ice sheet at high latitudes. To test this hypothesis, we present results from a high-resolution paleohydrologic model of groundwater flow, heat and solute transport, ice sheet loading, and sea level fluctuations for the continental shelf from New Jersey to Maine over the last 2 million years. Our analysis suggests that the presence of fresh to brackish water within shallow Miocene sands more than 100 km offshore of New Jersey was facilitated by discharge of submarine springs along Baltimore and Hudson Canyons where these shallow aquifers crop out. Recharge rates four times modern levels were computed for portions of New England's continental shelf that were overrun by the Laurentide ice sheet during the last glacial maximum. We estimate the volume of emplaced Pleistocene continental shelf fresh water (less than 1 ppt) to be 1300 km³ in New England. We also present estimates of continental shelf fresh water resources for the U.S. Atlantic eastern seaboard (10⁴ km³) and passive margins globally (3 × 10⁵ km³). The simulation results support the hypothesis that offshore fresh water is a potentially valuable, albeit nonrenewable resource for coastal megacities faced with growing water shortages.     

Analysis of Petroleum-Contaminated Water by GC/FID with Direct Aqueous Injection

A direct aqueous injection capillary gas chromatography/flame ionization (GC/FID) procedure for the analysis of petroleum-contaminated water was developed and applied to seven water samples saturated with different petroleum products. Separation of C₁ to C₄ alcohols, C₆ to C₉ monoaromatics, MTBE, phenol, aniline, and other compounds, and the detection of BTEX compounds at concentrations at or below their maximum contaminant levels (MCLs) is reported. Among the test compounds analyzed, the only pair found to coelute were 1-butanol and benzene. A method for confirmation of alcohols and polar compounds in the presence of dissolved petroleum hydrocarbons was also evaluated. In this case, water samples were analyzed before and after purging. Polar compounds were found to be significant components of the water soluble fractions of commercial petroleum products.     

Petrology and retrograde P-T path for eclogites of the Maksyutov Complex, Southern Ural Mountains, Russia

Abstract The Maksyutov Complex, situated in the southern Ural Mountains of Russia, is the first location where quartz aggregates within garnets exhibiting radial fractures were identified as coesite pseudomorphs (Chesnokov & Popov 1965). The complex consists of two tectonic units: a structurally lower eclogite-bearing schist unit and an overlying meta-ophiolite unit. Both units show evidence for multiple stages of metamorphism and deformation. The high-pressure metamorphism of the eclogite-bearing schist unit, discussed in this report, is suspected to be related to a collision between the Russian platform and a fragment of the Siberian continent during the early Cambrian. At least three stages of metamorphism (M_1-3) and two stages of deformation (S₁ and S₂) were observed in thin sections: M₁) garnet (Alm_55-60, Prp_22-28, Grs_16-20) + omphacite (Jd_46-56) + phengite (Si ≅ 3.5) + rutile; M₂) garnet + glaucophane ± lawsonite + white mica; and M₃) epidote + chlorite ± albite ± actinolite + white mica. Observed mineral parageneses define a retrograde P-T path for the eclogite. Mineral assemblages within the most representative eclogite from the lower unit of the Maksyutov Complex indicate minimum peak pressures of 15 kbar at temperatures of approximately 600°C. If the presence of coesite pseudomorph is confirmed, the peak ultrahigh-pressure metamorphism may be as high as 27 kbar at 615°C.     

Hydrogen Peroxide Treatment of Septic Systems and Its Negative Effects on Shallow Ground Water

Soil-solution samplers and shallow ground water monitoring wells were utilized to monitor nitrate movement to ground water following H₂O₂ application to a clogged soil absorption system. Nitrate-nitrogen concentrations in soil water and shallow ground water ranged from 29 to 67 mg/L and 9 to 22 mg/L, respectively, prior to H₂O₂ treatment. Mean nitrate-nitrogen concentrations in soil water and ground water increased and ranged from 67 to 115 mg/L and 23 to 37 mg/L, respectively, one week after H₂O₂ application. Elevated concentrations of nitrate-nitrogen above background persisted for several weeks following H₂O₂ treatment. The H₂O₂ treatment was unsuccessful in restoring the infiltrative capacity of a well-structured soil. Application of H₂O₂ to the soil absorption system poses a threat of nitrate contamination of ground water and its usefulness should be fully evaluated before rehabilitation is attempted.     

Vitamin B12-Catalyzed Dechlorination of Perchloroethylene Present as Residual DNAPL

The goal of this study was the cleanup of residual solvents in the saturated zone using an in situ biochemical treatment. Perchloroethylene (PCE) was chosen as a model compound because it is the most commonly found organic ground water contaminant. A mixture of vitamin B₁₂ with titanium citrate was pumped as the remedial solution through a column containing 100 μL of PCE residual. The rate of reaction was found to be first order with respect 10 the concentration of PCE and to the concentration of vitamin B₂. At 10 ppm B₁₂, more than 85 percent PCM was degraded to trichloroelhylene (TCE) and dichloroelhylene (DCE) in two hours. The presence of low to moderate concentrations of organic carbon had no significant effect on the reaction. Vitamin B₁₂ reduced by titanium citrate was found lo be compatible with the survival of anaerobic bacteria. The four major advantages of the biochemical system over the use of anaerobic bacteria are that (1) the rate is faster: (2) there is no need for the careful balance of nutrients or the addition of an extraneous carbon source: (3) there is no restriction in the concentration range of the compound to be treated; and (4) the remedial solution is mobile, even in the presence of organic carbon.