Development of oil hydrocarbon fingerprinting and identification techniques

Oil, refined product, and pyrogenic hydrocarbons are the most frequently discovered contaminants in the environment. To effectively determine the fate of spilled oil in the environment and to successfully identify source(s) of spilled oil and petroleum products is, therefore, extremely important in many oil-related environmental studies and liability cases. This article briefly reviews the recent development of chemical analysis methodologies which are most frequently used in oil spill characterization and identification studies and environmental forensic investigations. The fingerprinting and data interpretation techniques discussed include oil spill identification protocol, tiered analytical approach, generic features and chemical composition of oils, effects of weathering on hydrocarbon fingerprinting, recognition of distribution patterns of petroleum hydrocarbons, oil type screening and differentiation, analysis of “source-specific marker” compounds, determination of diagnostic ratios of specific oil constituents, stable isotopic analysis, application of various statistical and numerical analysis tools, and application of other analytical techniques. The issue of how biogenic and pyrogenic hydrocarbons are distinguished from petrogenic hydrocarbons is also addressed.     

Modeling oil spill trajectory in coastal waters based on fractional Brownian motion

This paper proposes a numerical method to simulate oil spill trajectories, which are affected by the combination of advection, turbulent diffusion and mechanical spreading process, based on a particle tracking algorithm. Recent studies have shown that the trajectories of drifters on the ocean surface have a fractal structure that is far from being described using ordinary Brownian motion. Thus, in modeling the diffusion process, a discrete method has been employed for the generation of fractional Brownian motion (fBm) to illustrate superdiffusive transport. The algorithm is implemented to predict oil slick trajectories following the “Arteaga” oil spill accident that occurred near the Dalian coastal region in 2005. When compared with the observed data and the results of traditional diffusion modeling, the numerical results based on the fBm model are encouraging.     

Geomagnetic field variations between chrons 33r and 19r (83–41 Ma) from sea-surface magnetic anomaly profiles

Sea-surface magnetic profiles exhibit coherent short wavelength “micro-anomalies” (or “tiny wiggles”) superimposed to the main anomalies due to reversals. In this study, we investigate the nature and distribution of these tiny wiggles on oceanic crust formed during the  42 Myr-long period following the Cretaceous Normal Superchron. To this end, we compute stacks of anomaly profiles from different areas in the Indian and the Pacific oceans. Using a simple method based on upward continuation, we demonstrate that, the tiny wiggles are consistent worldwide although their patterns exhibit different resolutions at different spreading rates. They are therefore confidently ascribed to past fluctuations of the geomagnetic dipole moment. A high resolution record of these fluctuations is obtained by selecting and stacking profiles from areas with the highest spreading rates. Modeling the micro-anomalies as short magnetic polarity intervals yields durations for these intervals generally shorter than 10 kyr, likely too short to be indeed “true” subchrons. Moreover, the number of detected tiny wiggles clearly depends on the spreading rate. These results support geomagnetic intensity fluctuations as being the cause of most tiny wiggles, as also suggested by recent magnetostratigraphic data. The tiny wiggles are uniformly distributed within chrons, indicating that paleointensity fluctuations are neither inhibited after, nor enhanced before, a reversal beyond a “blind” zone of about 10 km (corresponding to 80 to 250 kyr depending on the spreading rate) for which the anomalies due to reversals prevent the detection of tiny wiggles. Most tiny wiggles probably represent a filtered record of a uniform secular variation regime, as suggested by their uniform spatial distribution over the whole investigated period.     

Deccan flood basalts at the Cretaceous/Tertiary boundary?

Joint consideration of new paleomagnetic, paleontological and geochronological data from the Deccan continental flood basalts in India and critical discussion of earlier results lead us to suggest that volcanic activity may have lasted less than 1 Ma, thus possibly ranking as one of the largest volcanic catastrophes in the last 200 Ma. Available data are best satisfied if volcanism spanned the Cretaceous/Tertiary boundary, followed shortly afterwards by rifting of the Arabian Sea. These results point out the need for further work which may help in choosing between “external” and “internal” models of the Cretaceous/Tertiary boundary events.     

Dispersant Use and a Bioremediation Strategy as Alternate Means of Reducing Impacts of Large Oil Spills on Mangroves: The Gladstone Field Trials

Over a three-year period (1995–1998), we studied short-term effects of dispersant use and a bioremediation strategy in two consecutive field trials in sub-tropical Australian mangroves. In each case, weathered oil was applied, and a large spill simulated, in mature Rhizophora stylosa trees around 4–9 m tall. In the first trial, we used Gippsland light crude oil with or without dispersant, Corexit 9527. In the second, a bioremediation strategy followed application of Gippsland oil or Bunker C fuel oil. Bioremediation involved forced aeration with supplemental application of nutrients. Dispersant use had an overall positive benefit shown as reduced tree mortality. By contrast, there was no apparent reduction in mortality of trees with bioremediation. However, one year after oiling, leaf densities of surviving trees were greater in bioremediation plots than in controls, and less in oil-only plots. These and other results have been incorporated into spill response management strategies in Australia.     

Persistent organic pollutants and stable isotopes in biopsy samples (2004/2006) from Southern Resident killer whales

“Southern Resident” killer whales include three “pods” (J, K and L) that reside primarily in Puget Sound/Georgia Basin during the spring, summer and fall. This population was listed as “endangered” in the US and Canada following a 20% decline between 1996 and 2001. The current study, using blubber/epidermis biopsy samples, contributes contemporary information about potential factors (i.e., levels of pollutants or changes in diet) that could adversely affect Southern Residents. Carbon and nitrogen stable isotopes indicated J- and L-pod consumed prey from similar trophic levels in 2004/2006 and also showed no evidence for a large shift in the trophic level of prey consumed by L-pod between 1996 and 2004/2006. ∑PCBs decreased for Southern Residents biopsied in 2004/2006 compared to 1993–1995. Surprisingly, however, a three-year-old male whale (J39) had the highest concentrations of ∑PBDEs, ∑HCHs and HCB. POP ratio differences between J- and L-pod suggested that they occupy different ranges in winter.     

Effects of sampling microhabitats with low coverage within the STAR/AQEM macroinvertebrate sampling protocol on stream assessment

In the STAR/AQEM protocol microhabitats covering less than 5% of the sampling area were neglected. Driven by an ongoing discussion on the importance of these underrepresented microhabitats we tested the influence of sampling them. We investigated 48 streams representing 14 different stream types from all over Germany. Macroinvertebrates of underrepresented microhabitats were sampled in addition to the STAR/AQEM protocol. To ensure the method remains feasible in routine monitoring programmes the total sampling and sorting effort of additional sampling was limited to 20 min. Particularly those taxa were picked, which were not recognised during the routine STAR/AQEM sorting.To identify the effect of additional sampling on stream assessment results, we calculated the stream type-specific Multimetric Index (MMI) with the “main” and the “main+additional” data for each sample. The mean and median difference in MMI values between “main” and “main+additional” samples was 0.02 and 0.01, respectively. In seven of 48 samples (14.6%) a different ecological quality class was calculated with the “main+additional” dataset. Regarding common metrics within the MMI as well as intercalibration metrics differences between “main” and “main+additional” samples were analysed. The values differed most in richness metrics (e.g., number of EPTCBO Taxa, number of Trichoptera Taxa). The results of the present study show that additional sampling of underrepresented microhabitats could alter multimetric assessment results.     

The Sea Empress oil spill (Wales, UK): effects on Common Scoter Melanitta nigra in Carmarthen Bay and status ten years later

Carmarthen Bay, UK, regularly supports internationally important numbers (>16,000) of non-breeding Common Scoters Melanitta nigra. The spill of 72,000 tonnes of crude oil from the Sea Empress in 1996 affected birds both through direct mortality and likely pollution of key food resources. Numbers were greatly reduced following the spill, whilst changes in the distribution of birds within Carmarthen Bay suggested that potentially sub-optimal foraging zones were used. However, ten years after the incident, numbers of Common Scoter were no different to those recorded immediately before the spill. Compared to some other spills, rapid revival is evident. Numbers increased to pre-spill levels within three winters and distributional changes suggested a concurrent return to previously contaminated feeding areas, implying that the ecosystem had regenerated sufficiently to support its top predator. The importance of prolonged, standardised monitoring of bird numbers and distribution as indicators of ecological recovery from environmental damage is emphasised.     

Upon closer inspection…

Article VII of the Antarctic Treaty opens “all areas of Antarctica, including all stations, installation and equipment… at all times” to inspection by observers of all Contracting Parties. Article VII guarantees this right of inspection as a means to “promote the objectives and ensure the observance of the provisions” of the Treaty. Freedom of inspection strengthens the Treaty's core principles of peace and international cooperation and more importantly, the provisions of Article IV temporarily reconcile the sovereignty issue between claimant and non-claimant states. To date, however, Article VII has been greatly underutilized as a means to better protect the Antarctic environment. Green-peace, through its experience in the Antarctic, has come to realize that a formal international inspectorate and regulatory authority is needed for compliance monitoring, comprehensive and long-term environmental baseline monitoring, information management and exchange, and the effective management of the natural resources and values of the entire Antarctic.     

Errors and uncertainty in physically-based rainfall-runoff modelling of catchment change effects

The error in physically-based rainfall-runoff modelling is broken into components, and these components are assigned to three groups: (1) model structure error, associated with the model’s equations; (2) parameter error, associated with the parameter values used in the equations; and (3) run time error, associated with rainfall and other forcing data. The error components all contribute to “integrated” errors, such as the difference between simulated and observed runoff, but their individual contributions cannot usually be isolated because the modelling process is complex and there is a lack of knowledge about the catchment and its hydrological responses. A simple model of the Slapton Wood Catchment is developed within a theoretical framework in which the catchment and its responses are assumed to be known perfectly. This makes it possible to analyse the contributions of the error components when predicting the effects of a physical change in the catchment. The standard approach to predicting change effects involves: (1) running “unchanged” simulations using current parameter sets; (2) making adjustments to the sets to allow for physical change; and (3) running “changed” simulations. Calibration or uncertainty-handling methods such as GLUE are used to obtain the current sets based on forcing and runoff data for a calibration period, by minimising or creating statistical bounds for the “integrated” errors in simulations of runoff. It is shown that current parameter sets derived in this fashion are unreliable for predicting change effects, because of model structure error and its interaction with parameter error, so caution is needed if the standard approach is to be used when making management decisions about change in catchments.     

Ökologische Bewertung von Tieflandbächen des Ladberger Mühlenbach-Systems im Norddeutschen Tiefland, basierend auf der Standorttypie der Trichopterenbiozönosen

In the last few years ecological evaluation of lowland freshwaters was controversely discussed. Due to the fact that most basic information of assessment systems derived from upland streams, the results could not be applied to the lowland situations. Additionally, it is not sufficient for an integral freshwater evaluation only to focus on the stream to show degradation in the tight coupling of running waters and their adjacent landscape. In this study we critically tested a new method, the Standorttypie-Index (STI), to assess lowland streams using caddis-fly communities.

During 1994 and 1996 we investigated the caddisfly community at 15 sampling sites of a river system in the “Westfälische Tieflandbucht” (Northrhine-Westphalia, Germany). As a result we found 72 species belonging to 16 families of the order Trichoptera. The calculation of the “Standorttypie-Index” is based on four defined ecological categories. Although the definitions were inaccurate, each species was classified into one category. In view of stream regulation and streamwidth, we calculated for all study sites the STI of the immature stages, the adults and a combined total STI.

Although there is a correlation between the “Standorttypie-Index” and the state of degradation of the study sites, the separate analysis of larval and adult communities showed that the results easily lead to misinterpretation. The STI of adults devalues the combined total STI of regulated as well as natural study sites. As a consequence, until now it is not possible to evaluate the state of degradation in the coupling of the stream and the adjacent landscape using the STI of the caddis-fly community.     

On the interest and the limits of using combined ESR/U-series model in the case of very late uranium uptake

Before ESR/U-series models were applied to ungulate teeth, it is generally assumed that calculated ages are close to the “real” ages when they range between the values obtained with the EU and LU models. When the samples show signs of uranium-leaching, a realistic mathematical modelling of the age is not possible. On the other hand, some samples have undergone a very late U-uptake “affecting” directly the U-series ages and rendering the calculated ages younger.

We present results obtained on two open-air sites, which show the limits of such combined models in the case of late uranium incorporation. For the Middle Pleistocene site of Isernia la Pineta (Italy), the ESR dates are expected to fall within the limits imposed by the Ar–Ar results. The other site, the Lower Palaeolithic deposits of Ambrona (Spain), yielded two sets of samples: some at the top of the sequence with uranium uptake ranging between EU and LU limits and thus giving a good idea of the “real” age of the site; others at the base displaying a very late U-uptake, which render an age determination difficult.     

Impacts of a fuel oil spill on seagrass meadows in a subtropical port,Gladstone, Australia – The value of long-term marine habitat monitoring in high risk areas

We used an established seagrass monitoring programme to examine the short and longer-term impacts of an oil spill event on intertidal seagrass meadows. Results for potentially impacted seagrass areas were compared with existing monitoring data and with control seagrass meadows located outside of the oil spill area.Seagrass meadows were not significantly affected by the oil spill. Declines in seagrass biomass and area 1 month post-spill were consistent between control and impact meadows. Eight months post-spill, seagrass density and area increased to be within historical ranges. The declines in seagrass meadows were likely attributable to natural seasonal variation and a combination of climatic and anthropogenic impacts. The lack of impact from the oil spill was due to several mitigating factors rather than a lack of toxic effects to seagrasses. The study demonstrates the value of long-term monitoring of critical habitats in high risk areas to effectively assess impacts.     

Hebei Spirit oil spill monitored on site by fluorometric detection of residual oil in coastal waters off Taean, Korea

The spatiotemporal distributions of dissolved and/or dispersed oil in seawater and pore water were monitored on site by fluorometric detection method after the Hebei Spirit oil spill. The oil concentrations in intertidal seawater, 15 days after the spill, were as high as 16,600 μg/L and appeared to decrease below the Korean marine water quality standard of 10 μg/L at most sites 10 months after the spill. Fluorometric detection of oil in pore water was introduced to eliminate the effects of grain size for the quantification of oil in sediments and to better explain spatial and temporal distribution of oil pollution at sandy beaches. The fluorescence detection method was compared with the conventional laboratory technique of total petroleum hydrocarbon analysis using gas chromatography. The method of fluorescence detection of oil was capable of generating results much faster and more cost-effectively than the traditional GC technique.     

Two tiltmeters and an integrating seismometer for the monitoring of volcanic activity, and the results of some trials on Mount Etna

Two types of continuously recording tiltmeter and a new “integrating seismometer” were tested on Etna during the period September to December 1976. The primary object was the investigation of techniques for the surveillance and prediction of volcanic activity, but some information on the internal structure and mechanism of Etna was also obtained. It was concluded that a network of tiltmeters combined with seismic monitoring (using standard and/or integrating seismometers) offers the best dual approach to the problem of determining the true state of dormant volcanoes, and predicting the date and site of possible future eruptions.     

Meso-scale testing and development of test procedures to maintain mass balance

The Conrad Blucher Institute for Surveying and Science (Texas A&M University––Corpus Christi) has conducted numerous petroleum experiments at the Shoreline Environmental Research Facility (Corpus Christi, Texas, USA). The meso-scale facility has multiple wave tanks, permitting some control in experimental design of the investigations, but allowing for real-world conditions. This paper outlines the evolution of a materials balance approach in conducting petroleum experiments at the facility. The first attempt at a materials balance was during a 1998 study on the fate/effects of dispersant use on crude oil. Both water column and beach sediment samples were collected. For the materials balance, the defined environmental compartments for oil accumulation were sediments, water column, and the water surface, while the discharge from the tanks was presumed to be the primary sink. The “lessons learned” included a need to quantify oil adhesion to the tank surfaces. This was resolved by adhering strips of the polymer tank lining to the tank sides that could be later removed and extracted for oil. Also, a protocol was needed to quantify any floating oil on the water surface. A water surface (oil slick) quantification protocol was developed, involving the use of solid-phase extraction disks. This protocol was first tested during a shoreline cleaner experiment, and later refined in subsequent dispersant effectiveness studies. The effectiveness tests were designed to simulate shallow embayments which created the need for additional adjustments in the tanks. Since dispersant efficacy is largely affected by hydrodynamics, it was necessary to scale the hydrodynamic conditions of the tanks to those expected in our prototype system (Corpus Christi Bay, Texas). The use of a scaled model permits the experiment to be reproduced and/or evaluated under different conditions. To minimize wave reflection in the tank, a parabolic wave dissipater was built. In terms of materials balance, this design reduced available surface area as a sink for oil adsorption.     

Determination of hydraulic conductivity from auger holes and pits — An approximation

A steady-state solution is developed which relates saturated hydraulic conductivity to rate of rise in auger holes and pits of arbitrary geometries. The analysis assumes axial symmetric cavities and steady-state conditions and uses the solution for a disc source in infinite space together with the method of images. Numerical results and a table are presented for “arc” and “trapezoidal” shaped pits.     

“Andesitic water”: a phantom of the isotopic evolution of water-silicate systems. Comment on “Isotopic shifts in waters from geothermal and volcanic systems along convergent plate boundaries and their origin” by W.F. Giggenbach

On account of the low porosity of the lithosphere, intracrustal fluids behave very differently from surface fluids, in that they are changing their geochemical and isotopic labels according to the geological environment. Given a heat source, meteoric waters can be supplied plentifully and their rates of throughput in geothermal systems are sufficiently high to exhaust the compositional signals of a given rock buffer. In contrast, fluids exsolved from magma, and subducted fluids, would be supplied at less than about one tenth of the meteoric rate over the life time of a system. Based on up-to-date flow models, the isotopic evolution of meteoric water interacting with crustal rock follows a curved to L-shaped track in the δD versus δ¹⁸O plot. Instantaneous (present-day) tie-lines between recharge and discharge are secants of such tracks and can have a range of slopes. At the start of an interaction, waters have δD and δ¹⁸O values approaching equilibrium with the original rock composition (water “W1”). Using known hydrogen isotope fractionation factors, W1 values generally plot in the region of “andesite” or “andesitic” waters of various authors. Since the W1 waters have δD values that are on average more positive, and also less variable than those of the meteoric recharges, most tracks and tie-lines have positive slopes, and the plotting of a large number of tie-lines will produce a focus on the field of W1 waters, regardless of the original water source.     

Evidence for mantle metasomatism: an oxygen and strontium isotope study of the Vulsinian District, Central Italy

This paper presents new O and Sr isotope data for lavas from the northern part of the Roman perpotassic province. The samples comprise the tephritic leucititic to leucite phonolitic lavas and the saturated lavas from the Vulsinian District, the olivine leucite melilitite of San Venanzo, and the kalsilite diopside melilitite of Cupaello. Previous oxygen isotope work on the lavas of the Vulsinian District suggested crustal contamination of “normal” mantle-derived magmas. The new data cover the ranges previously found. O and Sr isotope ratios of evolved lavas of the undersaturated suite indicate assimilation in variable amounts of up to ca. 10% of continental crustal material. The saturated lavas probably assimilated large amounts (up to ca. 50%) of crust. Lavas chemically identified as corresponding to little modified mantle-derived liquids are high in both⁸⁷Sr/⁸⁶Sr andδ¹⁸O: 0.7103−0.7107, +7.8 to +9.4 (Vulsini), 0.7104, +12.3 (San Venanzo) and 0.7112, +14.4 (Cupaello). These high values are interpreted to have been inherited from a metasomatized parental mantle. Hydrous fluids enriched in large-ion lithophile elements and high inδ¹⁸O and⁸⁷Sr/⁸⁶Sr are thought to have mixed with mantle of “normal”δ¹⁸O and⁸⁷Sr/⁸⁶Sr. The fluids probably origi dehydration of continent-derived sediments, which were subducted beneath a mantle wedge in the continent-continent collision of the Corsica-Sardinia block and the Adriatic (Italian) plate. This hypothesis is supported by Pb and Nd isotopic evidence and is probably valid for the entire Roman Province.     

The role of collisional tectonics in the metallogeny of the Central Andean tin belt

The Inner Arc of the Central Andes, broadly corresponding to the Eastern Cordillera, is the location of a rich Tertiary and Triassic Sn–W–(Ag-base metal) metallogenic province, commonly referred to as the Bolivian tin belt. We propose that the Tertiary metallogeny, which generated most of the tin ores, was a direct consequence of discrete “collisions” between the South American plate and the Nazca slab and sub-slab mantle, during the ongoing Andean orogeny. Evidence supporting this proposal include: (1) the coincidence of the tin province and the Inner Arc in a marked “hump” in the Andean orogen, which may represent tectonic indentation; (2) the symmetry of the tin province with respect to the Bolivian orocline, the axis of which corresponds to the direction of highest compression; (3) the relative symmetry of the magmatism and tin mineralization with respect to this axis; (4) the concurrent timing of mineralization and compressional pulses; (5) the similar host rock geochemistry and ore lead isotope data, testifying to a common crustal reservoir; and (6) the striking similarity of the igneous suites, associated with the ore deposits to those from “typical” collisional orogens. A number of studies have called upon a persistent tin anomaly to explain the metallogeny of the region. We propose, instead, that the latter is better explained by periodic compressional interaction between the Farallon/Nazca oceanic plate and the South American continent. This led to the generation of peraluminous magmas, which during fractional crystallization exsolved the fluids responsible for the voluminous Sn–W mineralization.