A study of methods used to analyze total oil and polycyclic aromatic hydrocarbons in produced water: steps towards the validation of molecularly imprinted polymers for use in marine environmetns

Produced water is a by-product of offshore oil and gas production, and is released in large volumes when platforms are actively processing crude oil. Some pollutants are not typically removed by conventional oil/water separation methods and are discharged with produced water. Oil and grease can be found dispersed in produced water in the form of tiny droplets, and polycyclic aromatic hydrocarbons (PAHs) are commonly found dissolved in produced water. Both can have acute and chronic toxic effects in marine environments even at low exposure levels. The analysis of the dissolved and dispersed phases are a priority, but effort is required to meet the necessary detection limits. There are several methods for the analysis of produced water for dispersed oil and dissolved PAHs, all of which have advantages and disadvantages. In this work, EPA Method 1664 and APHA Method 5520 C for the determination of oil and grease will be examined and compared. For the detection of PAHs, EPA Method 525 and PAH MIPs will be compared, and results evaluated. APHA Method 5520 C Partition-Infrared Method is a liquid-liquid extraction procedure with IR determination of oil and grease. For analysis on spiked samples of artificial seawater, extraction efficiency ranged from 85 – 97%. Linearity was achieved in the range of 5 – 500 mg/L. This is a single-wavelength method and is unsuitable for quantification of aromatics and other compounds that lack sp³-hybridized carbon atoms. EPA Method 1664 is the liquid-liquid extraction of oil and grease from water samples followed by gravimetric determination. When distilled water spiked with reference oil was extracted by this procedure, extraction efficiency ranged from 28.4 – 86.2%, and %RSD ranged from 7.68 – 38.0%. EPA Method 525 uses solid phase extraction with analysis by GC-MS, and was performed on distilled water and water from St. John’s Harbour, all spiked with naphthalene, fluorene, phenanthrene, and pyrene. The limits of detection in harbour water were 0.144, 3.82, 0.119, and 0.153 g/L respectively. Linearity was obtained in the range of 0.5-10 g/L, and %RSD ranged from 0.36% (fluorene) to 46% (pyrene). Molecularly imprinted polymers (MIPs) are sorbent materials made selective by polymerizing functional monomers and crosslinkers in the presence of a template molecule, usually the analytes of interest or related compounds. They can adsorb and concentrate PAHs from aqueous environments and are combined with methods of analysis including GC-MS, LC-UV-Vis, and desorption electrospray ionization (DESI)- MS. This work examines MIP-based methods as well as those methods previously mentioned which are currently used by the oil and gas industry and government environmental agencies. MIPs are shown to give results consistent with other methods, and are a low-cost alternative improving ease, throughput, and sensitivity. PAH MIPs were used to determine naphthalene spiked into ASTM artificial seawater, as well as produced water from an offshore oil and gas operation. Linearity was achieved in the range studied (0.5 – 5 mg/L) for both matrices, with R² = 0.936 for seawater and R² = 0.819 for produced water. The %RSD for seawater ranged from 6.58 – 50.5% and for produced water, from 8.19 – 79.6%.

Submarine slope failures in gassy soils

Submarine slope stability has become an important concern and a subject of research with increasing demand for offshore developments and technological advancement for harsh and challenging environments. The consequences of submarine slope failure adjacent to oil and gas facilities would have a large financial, safety and regulatory impact. This current research work investigates potential failure of submarine gassy slopes triggered by tidal variations. Due to tidal variations, failure of an unsaturated slope may occur under specific combinations of increasing degree of saturation and soil permeability, and decreasing tidal period. Novel physical model tests in a geotechnical centrifuge were undertaken to examine submarine slope failure mechanisms containing gassy sediments. The model preparation techniques, measurement systems and results are presented. The response observed in the model test is discussed and further developments proposed. The buried PPT’s response of the submarine slope are comparable in terms of attenuation and phase lag with Nagaswaran (1983) and with field measurements of Atigh and Byrne (2004) in terms of phase lag.

Genesis and character of thin-bedded turbidites associated with submarine channels

Acknowledgements We acknowledge the support of the PRACSS Joint Industry Project at University of Aberdeen, funded by BG Group, BP, DONG, RWE Dea, Petrochina, Statoil and Tullow Oil. We also acknowledge the entire crew of the Urania Research vessel which was used to acquire the CHIRP lines, bathymetric data and gravity cores from the Tyrrhenian Sea, Italy. Our colleagues Michal Janocko and Mike Mayall are thanked for the discussions and comments. Our colleagues Pan Li, Amanda Santa Catharina, Guilherme Bozetti and Matheus Silveira Sobiesiak are thanked for their assistance during field work where some of the ideas in this paper were synthesized. Finally we thank one anonymous reviewer and Brian Romans for their invaluable feedback which made some of the ideas introduced in this review much more succinct.

How to recognise a kick : A cognitive task analysis of drillers’ situation awareness during well operations

Acknowledgements This article is based on a doctoral research project of the first author which was sponsored by an international drilling rig operator. The views presented are those of the authors and should not be taken to represent the position or policy of the sponsor. The authors wish to thank the industrial supervisor and the drilling experts for their contribution and patience, as well as Aberdeen Drilling School for allowing the first author to attend one of their well control courses.

Environmental Impacts of the Deep-Water Oil and Gas Industry : A Review to Guide Management Strategies

The authors would like to thank the leadership of the Deep Ocean Stewardship Initiative (DOSI), including Lisa Levin, Maria Baker, and Kristina Gjerde, for their support in developing this review. This work evolved from a meeting of the DOSI Oil and Gas working group supported by the J.M. Kaplan Fund, and associated with the Deep-Sea Biology Symposium in Aveiro, Portugal in September 2015. The members of the Oil and Gas working group that contributed to our discussions at that meeting or through the listserve are acknowledged for their contributions to this work. We would also like to thank the three reviewers and the editor who provided valuable comments and insight into the work presented here. DJ and AD were supported by funding from the European Union's Horizon 2020 research and innovation programme under the MERCES (Marine Ecosystem Restoration in Changing European Seas) project, grant agreement No 689518. AB was supported by CNPq grants 301412/2013-8 and 200504/2015-0. LH acknowledges funding provided by a Natural Environment Research Council grant (NE/L008181/1). This output reflects only the authors' views and the funders cannot be held responsible for any use that may be made of the information contained therein.

Advanced Aerogel Composites for Oil Remediation and Recovery

Oil spills in marine environments often damage marine and coastal life if not remediated rapidly and efficiently. In spite of the strict enforcement of environmental legislations (i.e., Oil Pollution Act 1990) following the Exxon Valdez oil spill (June 1989; the second biggest oil spill in U.S. history), the Macondo well blowout disaster (April 2010) released 18 times more oil. Strikingly, the response methods used to contain and capture spilled oil after both accidents were nearly identical, note that more than two decades separate Exxon Valdez (1989) and Macondo well (2010) accidents.

The goal of this dissertation was to investigate new advanced materials (mechanically strong aerogel composite blankets-Cabot® Thermal Wrap™ (TW) and Aspen Aerogels® Spaceloft® (SL)), and their applications for oil capture and recovery to overcome the current material limitations in oil spill response methods. First, uptake of different solvents and oils were studied to answer the following question: do these blanket aerogel composites have competitive oil uptake compared to state-of-the-art oil sorbents (i.e., polyurethane foam-PUF)? In addition to their competitive mechanical strength (766, 380, 92 kPa for Spaceloft, Thermal Wrap, and PUF, respectively), our results showed that aerogel composites have three critical advantages over PUF: rapid (3-5 min.) and high (more than two times of PUF’s uptake) oil uptake, reusability (over 10 cycles), and oil recoverability (up to 60%) via mechanical extraction. Chemical-specific sorption experiments showed that the dominant uptake mechanism of aerogels is adsorption to the internal surface, with some contribution of absorption into the pore space.

Second, we investigated the potential environmental impacts (energy and chemical burdens) associated with manufacturing, use, and disposal of SL aerogel and PUF to remove the oil (i.e., 1 m3 oil) from a location (i.e., Macondo well). Different use (single and multiple use) and end of life (landfill, incinerator, and waste-to-energy) scenarios were assessed, and our results demonstrated that multiple use, and waste-to-energy choices minimize the energy and material use of SL aerogel. Nevertheless, using SL once and disposing via landfill still offers environmental and cost savings benefits relative to PUF, and so these benefits are preserved irrespective of the oil-spill-response operator choices.

To inform future aerogel manufacture, we investigated the different laboratory-scale aerogel fabrication technologies (rapid supercritical extraction (RSCE), CO2 supercritical extraction (CSCE), alcohol supercritical extraction (ASCE)). Our results from anticipatory LCA for laboratory-scaled aerogel fabrication demonstrated that RSCE method offers lower cumulative energy and ecotoxicity impacts compared to conventional aerogel fabrication methods (CSCE and ASCE).

The final objective of this study was to investigate different surface coating techniques to enhance oil recovery by modifying the existing aerogel surface chemistries to develop chemically responsive materials (switchable hydrophobicity in response to a CO2 stimulus). Our results showed that studied surface coating methods (drop casting, dip coating, and physical vapor deposition) were partially successful to modify surface with CO2 switchable chemical (tributylpentanamidine), likely because of the heterogeneous fiber structure of the aerogel blankets. A possible solution to these non-uniform coatings would be to include switchable chemical as a precursor during the gel preparation to chemically attach the switchable chemical to the pores of the aerogel.

Taken as a whole, the implications of this work are that mechanical deployment and recovery of aerogel composite blankets is a viable oil spill response strategy that can be deployed today. This will ultimately enable better oil uptake without the uptake of water, potential reuse of the collected oil, reduced material and energy burdens compared to competitive sorbents (e.g., PUF), and reduced occupational exposure to oiled sorbents. In addition, sorbent blankets and booms could be deployed in coastal and open-ocean settings, respectively, which was previously impossible.

(Table 2) Grain composition of sediments from ODP Hole 161-974B and from beach samples

Miocene to Pleistocene sand and sandstone were recovered at Ocean Drilling Program Site 974 in the Tyrrhenian Basin and Sites 976 and 977 in the Alboran Basin. Sand detrital modes were determined for 45 samples from these sites, as well as 10 samples of Spanish beach sand. At Site 974, the Pleistocene section includes a number of volcaniclastic (vitric ash) and terrigenous sand layers; the latter are heterogeneous and contain sedimentary and metamorphic lithic fragments. Submarine canyon and onshore drainage patterns suggest that the most likely source of this sediment is the Tiber River drainage basin in central Italy, where a Pleistocene volcanic field is superimposed on Apennine orogenic rocks. In contrast, the Miocene sand in Unit III at Site 974 may have been derived from local basement highs. The quartzolithic composition and preponderance of metamorphic and sedimentary lithic debris in sand samples from Unit II at Site 976, Unit I at Sites 977 and 978, and Unit I at Site 979 are consistent with derivation from metamorphic rocks and sedimentary cover sequences that crop out in the Betic Cordillera of southern Spain (976-978) and in the Rif of Northern Africa (979). The sedimentary to metamorphic lithic fragment ratios in these samples reflect the relative proportion of metamorphic and sedimentary rocks exposed in onshore source terranes. In contrast, the source of the few quartzose Pleistocene sands at Site 976 was likely the Flysch Trough Units that crop out near Gibraltar. The significant volcanic component in certain intervals at Sites 976 (upper Miocene) and 977 (lower Pliocene to Miocene) is consistent with widespread volcanic activity during basin inception and development. Mean sand detrital modes for sand subgroups from both the Alboran and Tyrrhenian Basin sites plot in the Recycled Orogenic and Magmatic Arc compositional fields of Dickinson et al. (1983, doi:10.1130/0016-7606(1983)94<222:PONAPS>2.0.CO;2), reflecting the hybrid tectonic histories of these basins.

(Table 2) Terrigenous, authigenic and biogenic composition of sediments at DSDP Hole 93-603B

Pelagic sedimentation during the Early Cretaceous at Site 603 produced alternations of laminated marly limestone and bioturbated limestone-a facies typical of the "Blake-Bahama Formation" of the western Atlantic. This limestone is a nannofossil micrite, rich in calcified radiolarians, with variable amounts of organic matter, pyritized radiolarian tests, fish debris, and micaceous silt. The laminated marly limestone layers are enriched in organic matter when compared with the intervals of bioturbated limestone. The organic carbon is predominantly terrestrial plant debris; where the organic-carbon content is in excess of 1%, there is also a significant marine-derived component. Laminations can result either from bands of alternately enriched and depleted opaque material and clay, or from bands of elongate lenses (microflasers) of micrite, which could be plastically deformed pellets or diagenetic features. The alternating intervals of laminated and bioturbated structures may have resulted from combined changes in surface productivity, in the influx of terrigenous organic matter, and in the intensity of bottom circulation, which led to episodic oxygen depletion in the bottom water and sediments. Variations in the relative proportions of laminated clay-rich and bioturbated lime-rich limestone and in the development of cycles between these structures make it possible to subdivide the Lower Cretaceous pelagic facies into several subunits which appear to be regional in extent. Bioturbated limestone is dominant in the Berriasian, laminated marly limestone in the Valanginian and Barremian-lower Aptian, and well-developed alternations between these end members in the Hauterivian. The Hauterivian to lower Aptian sediments contain abundant terrigenous clastic turbidites associated with a submarine fan complex. These changes in the general characteristics of the pelagic sediment component of the Blake-Bahama Formation at Site 603 are synchronous with those in the Blake-Bahama Basin (Sites 534 and 391) to the south. Carbonate sedimentation ended in the early Aptian, probably because of a regional shoaling of the carbonate compensation depth.

Tab. 1+2+3: Selected principal soil properties in the oil exploitation region of KomiArcticOil (Usinsk) in the Russian tundra

Oil polluted and not oil polluted soils (crude oil hydrocarbons contents: 20-92500 mg/kg dry soil mass) under natural grass and forest vegetation and in a bog in the Russian tundra were compared in their principal soil ecological parameters, the oil content and the microbial indicators. CFE biomass-C, dehydrogenase and arylsulfatase activity were enhanced with the occurrence of crude oil. Using these parameters for purposes of controlling remediation and recultivation success it is not possible to distinguish bctween promotion of microbial activity by oil carbon or soil organic carbon (SOC). For this reason we think that these parameters are not appropriate to indicate a soil damage by an oil impact. In contrast the metabolie quotient (qC02), calculated as the ratio between soil basal respiration and the SIR biomass-C was adequate to indicate a high crude oil contamination in soil. Also, the ß-glucosidase activity (parameter ß-GL/SOC) was correlated negatively with oil in soil. The indication of a soil damage by using the stress parameter qCO, or the specific enzyme activities (activity/SOC) minimizes the promotion effect of the recent SOC content on microbial parameters. Both biomass methods (SIR, CFE) have technical problems in application for crude oil-contaminated and subarctic soils. CFE does not reflect the low C_mic level of the cold tundra soils. We recommend to test every method for its suitability before any data collection in series as well as application for cold soils and the application of ecophysiological ratios as R_mic/C_mic, C_mic/SOC or enzymatic activity/SOC instead of absolute data.

Annotated record of the detailed examination of Mn deposits on the coral banks of the continental shelf in the south-western coastal area of the Gulf of Mexico off Texas

During U.S. Department of Interior, Bureau of Land Management (BLM) public hearings held in 1973, 1974 and 1975 prior to Texas Outer Continental Shelf (OCS) oil and gas lease sales, concern was expressed by the National Marine Fisheries Service, scientists from Texas A&M and the University of Texas and private citizens over the possible environmental impact of oil and gas drilling and production operations on coral reefs and fishing banks in or adjacent to lease blocks to be sold. As a result, certain restrictive regulations concerning drilling operations in the vicinity of the well documented coral reefs and biostromal communities at the East and West Flower Gardens were established by BLM, and Signal Oil Company was required to provide a biological and geological baseline study of the less well known Stetson Bank before a drilling permit could be issued. Considering the almost total lack of knowledge of the geology and biotic communities associated with the South Texas OCS banks lying in or near lease blocks to be offered for sale in 1975, BLM contracted with Texas A&M University to provide the biological and geological baseline information required to facilitate judgments as to the extent and nature of restrictive regulations on drilling near these banks which might be required to insure their protection. In pursuit of this, scientists from Texas A&M University were to direct their attention toward assessments of ground fish populations, unique biological and geological features, substratum type and distribution, and the biotic and geologic relationships between these banks and those farther north.

(Table 1) Strontium concentration and isotope ratios of carbonates from DSDP Holes 69-504B as well as 83-504B and fish debris samples from Indian and Pacific Ocean sediments

Recent revisions of the geological time scale by Kent and Gradstein (in press) suggest that, on the average, Cretaceous magnetic anomalies are approximately 10 m.y. older than in Larson and Hilde's (1975) previous time scale. These revised basement ages change estimates for the duration of alteration in the ocean crust, based on the difference between secondary-mineral isochron ages and magnetic isochron-crustal ages, from 3 to approximately 13 m.y. In addition to the revised time scale, Burke et al.'s (1982) new data on the temporal variation of 87Sr/86Sr in seawater allow a better understanding of the timing of alteration and more realistic determinations of water/rock ratios during seawater-basalt interaction. Carbonates from all DSDP sites which reached Layer 2 of Atlantic crust (Sites 105, 332, 417, and 418) are deposited within 10-15 m.y. of crustal formation from solutions with 87Sr/86Sr ratios identical to unaltered or contemporaneous seawater. Comparisons of the revised seawater curve with the 87Sr/86Sr of basement carbonates is consistent with a duration of approximately 10-15 m.y. for alteration in the ocean crust. Our preliminary Sr and 87Sr/86Sr data for carbonates from Hole 504B, on 5.9-m.y.-old crust south of the Costa Rica Rift, suggest that hydrous solutions from which carbonates precipitated contained substantial amounts of basaltic Sr. For this reason, carbonate 87Sr/86Sr cannot be used to estimate the duration of alteration at this site. A basalt-dominated alteration environment at Hole 504B is consistent with heat-flow evidence which indicates rapid sediment burial of crust at the Costa Rica Rift, sealing it from access by seawater and resulting in unusually low water/rock ratios during alteration.

Oil Market Modelling: A Comparative Analysis of Fundamental and Latent Factor Approaches

We formally compare fundamental factor and latent factor approaches to oil price modelling. Fundamental modelling has a long history in seeking to understand oil price movements, while latent factor modelling has a more recent and limited history, but has gained popularity in other financial markets. The two approaches, though competing, have not formally been compared as to effectiveness. For a range of short- medium- and long-dated WTI oil futures we test a recently proposed five-factor fundamental model and a Principal Component Analysis latent factor model. Our findings demonstrate that there is no discernible difference between the two techniques in a dynamic setting. We conclude that this infers some advantages in adopting the latent factor approach due to the difficulty in determining a well specified fundamental model.

Advances in single-shot, dry drilling of composite/metal stacks

Carbon fibre reinforced polymers (CFRP) are increasingly being used in the aerospace, automotive and defence industry due to their high specific stiffness and good corrosion resistance. In a modern aircraft, 50-60% of its structure is made up of CFRP material while the remainder is mostly a combination of metallic alloys (typically aluminium or titanium alloys). Mechanical fastening (bolting or riveting) of CFRP and metallic components has thus created a pressing requirement of drilling several thousand holes per aircraft. Drilling of stacks in a single-shot not only saves time, but also ensures proper alignment when fasteners are inserted, achieving tighter geometric tolerances. However, this requirement poses formidable manufacturing challenges due to the fundamental differences in the material properties of CFRP and metals e.g. a drill bit entering into the stack encounters brittle and abrasive CFRP material as well as the plastic behaviour of the metallic alloy, making the drilling process highly non-linear.

Over the past few years substantial efforts have been made in this direction and majority of the research has tried to establish links between how the process parameters (feed, depth of cut, cutting speed), tooling (geometry, material and coating) and the wear of the cutting tool affect the hole quality. Similarly, multitudes of investigations have been conducted to determine the effects of non-traditional drilling methods (orbital, helical and vibration assisted drilling), cutting zone temperatures and efficiency of chip extraction on the hole quality and rate of tool wear during single shot drilling of CFRP/alloy stacks.

In a timely effort, this paper aims at reviewing the manufacturing challenges and barriers faced when drilling CFRP/alloy stacks and to summarise various factors influencing the drilling process while detailing the advances made in this fertile research area of single-shot drilling of stack materials. A survey of the key challenges associated with avoiding workpiece damage and the effect these challenges have on tool design and process optimisation is presented. An in depth critique of suitable hole making methods and their aptness for commercialisation follows. The paper concludes by summarising the future work required to achieve repeatable, high quality single shot drilled holes in CFRP/alloy stacks.

Oil Flow Rate Measurements Using 198au And Total Count Technique

In industrial plants, oil and oil compounds are usually transported by closed pipelines with circular cross-section. The use of radiotracers in oil transport and processing industrial facilities allows calibrating flowmeters, measuring mean residence time in cracking columns, locate points of obstruction or leak in underground ducts, as well as investigating flow behavior or industrial processes such as in distillation towers. Inspection techniques using radiotracers are non-destructive, simple, economic and highly accurate. Among them, Total Count, which uses a small amount of radiotracer with known activity, is acknowledged as an absolute technique for flow rate measurement. A viscous fluid transport system, composed by four PVC pipelines with 13m length (12m horizontal and 1m vertical) and ½, ¾, 1 and 2-inch gauges, respectively, interconnected by maneuvering valves was designed and assembled in order to conduct the research. This system was used to simulate different flow conditions of petroleum compounds and for experimental studies of flow profile in the horizontal and upward directions. As 198Au presents a single photopeak (411,8 keV), it was the radioisotope chosen for oil labeling, in small amounts (6 ml) or around 200 kBq activity, and it was injected in the oil transport lines. A NaI scintillation detector 2”x 2”, with well-defined geometry, was used to measure total activity, determine the calibration factor F and, positioned after a homogenization distance and interconnected to a standardized electronic set of nuclear instrumentation modules (NIM), to detect the radioactive cloud.