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.

Oceans Deep: Lesson H (Oil Spill)

Teacher resources for Lesson H in the Discover Oceanography 'Scheme of Work' for use in schools.

Three dimensional modeling of contaminants transportation (oil spill) in Caspian Sea

Nowadays, Caspian Sea is in focus of more attentions than past because of its individualistic as the biggest lake in the world and the existing of very large oil and gas resources within it. Very large scale of oil pollution caused by development of oil exploration and excavation activities not only make problem for coastal facilities but also make severe damage on environment. In the first stage of this research, the location and quality of oil resources in offshore and onshore have been determined and then affected depletion factors on oil spill such as evaporation, emulsification, dissolution, sedimentation and so on have been studied. In second stage, sea hydrodynamics model is offered and tested by determination of governing hydrodynamic equations on sea currents and on pollution transportation in sea surface and by finding out main parameters in these equations such as Coriolis, bottom friction, wind and etc. this model has been calculated by using cell vertex finite volume method in an unstructured mesh domain. According to checked model; sea currents of Caspian Sea in different seasons of the year have been determined and in final stage different scenarios of oil spill movement in Caspian sea on various conditions have been investigated by modeling of three dimensional oil spill movement on surface (affected by sea currents) and on depth (affected by buoyancy, drag and gravity forces) by applying main above mentioned depletion factors.

Oil spill environmental risk assessment of stationary sources in offshore zones (Innovating a mathematical model)

Nowadays, risks arising from the rapid development of oil and gas industries are significantly increasing. As a result, one of the main concerns of either industrial or environmental managers is the identification and assessment of such risks in order to develop and maintain appropriate proactive measures. Oil spill from stationary sources in offshore zones is one of the accidents resulting in several adverse impacts on marine ecosystems. Considering a site's current situation and relevant requirements and standards, risk assessment process is not only capable of recognizing the probable causes of accidents but also of estimating the probability of occurrence and the severity of consequences. In this way, results of risk assessment would help managers and decision makers create and employ proper control methods. Most of the represented models for risk assessment of oil spills are achieved on the basis of accurate data bases and analysis of historical data, but unfortunately such data bases are not accessible in most of the zones, especially in developing countries, or else they are newly established and not applicable yet. This issue reveals the necessity of using Expert Systems and Fuzzy Set Theory. By using such systems it will be possible to formulize the specialty and experience of several experts and specialists who have been working in petroliferous areas for several years. On the other hand, in developing countries often the damages to environment and environmental resources are not considered as risk assessment priorities and they are approximately under-estimated. For this reason, the proposed model in this research is specially addressing the environmental risk of oil spills from stationary sources in offshore zones.

Coastal zone oil spill modeling

This work presents the development and application of a three-dimensional oil spill model for predicting the movement of an oil slick in the coastal waters of Singapore. In the model, the oil slick is divided into a number of small elements for simulating of the oil processes of spreading, advection, turbulent diffusion. This model is capable of predicting the horizontal movement of surface oil slick. Satellite images and field observations of oil slicks on the surface in the Singapore Straits are used to validate the newly developed model. Compared with the observations, the numerical results of the oil spill model show good conformity. In this study, the 3d model was generated using the geometrical data of Singapore Straits waters by GAMBIT which is a pre-processor of FLUENT programmed.

Puomiankkurin uudelleensuunnittelu ja valmistus

Tämän diplomityön tavoitteena on ollut suunnitella uusi öljyntorjunnassa käytettävä puomiankkuri. Nykyisin käytössä olevat ankkurit ovat painavia, paljon tilaa vieviä, jäykkiä rakenteeltaan ja hankalia käyttää. Työn tavoitteena on ollut suunnitella rakenne, jossa muotoilun avulla pyritään korvaamaan ankkurin painoa ja saavuttaa hyvä tunkeutuminen eri pohjalaaduissa. Ankkurin suunnitteluun kuuluu merkittävänä osana materiaalinvalintaprosessi, jonka perusteella materiaaliksi valittiin kulutusteräs. Kulutusteräksen korkea lujuus ja hyvä kulumiskestävyys mahdollistavat ohuemman materiaalin käytön rakenteessa, jonka seurauksena rakenteen painoa saatiin vähennettyä merkittävästi. Ankkurin rakenteen suunnittelussa käytettiin hyväksi nykyisiä ankkurin rakenteita, joiden pohjalta hahmoteltiin eri variaatioita ankkureista. Suunnittelutyössä käytettiin hyväksi tyypillisiä ankkurirakenteita hyvien puolien kannalta, joita pyrittiin toteuttamaan uudessa ankkuri- rakenteessa. Ankkurin suunnittelu toteutettiin järjestelmällisen suunnittelun avulla, jossa ensin laadittiin ankkurille vaatimuslista. Tämän jälkeen laadittiin ankkurille toimintorakenne ja jakaminen osatoimintoihin. Ankkurin rakenteista toteutettiin kaksi eri versiota: sisävesillä ja merialueilla käytettävät ankkurit, joille laadittiin mitoitus. Työssä suunnitellun terävän tunkeutumisosan ja optimaalisen tunkeutumiskulman avulla ankkureiden painoa saatiin huomattavasti alhaisemmaksi, jonka seurauksena ankkurille saatiin kevyempi rakenne ja materiaalikustannukset pienenivät merkittävästi. Uusien ankkurien rakenne on pienemmän koon ja painon ansiosta käyttäjäystävällisempi.

Puomiankkurin uudelleensuunnittelu ja valmistus

Tämän diplomityön tavoitteena on ollut suunnitella uusi öljyntorjunnassa käytettävä puomiankkuri. Nykyisin käytössä olevat ankkurit ovat painavia, paljon tilaa vieviä, jäykkiä rakenteeltaan ja hankalia käyttää. Työn tavoitteena on ollut suunnitella rakenne, jossa muotoilun avulla pyritään korvaamaan ankkurin painoa ja saavuttaa hyvä tunkeutuminen eri pohjalaaduissa. Ankkurin suunnitteluun kuuluu merkittävänä osana materiaalinvalintaprosessi, jonka perusteella materiaaliksi valittiin kulutusteräs. Kulutusteräksen korkea lujuus ja hyvä kulumiskestävyys mahdollistavat ohuemman materiaalin käytön rakenteessa, jonka seurauksena rakenteen painoa saatiin vähennettyä merkittävästi. Ankkurin rakenteen suunnittelussa käytettiin hyväksi nykyisiä ankkurin rakenteita, joiden pohjalta hahmoteltiin eri variaatioita ankkureista. Suunnittelutyössä käytettiin hyväksi tyypillisiä ankkurirakenteita hyvien puolien kannalta, joita pyrittiin toteuttamaan uudessa ankkuri- rakenteessa. Ankkurin suunnittelu toteutettiin järjestelmällisen suunnittelun avulla, jossa ensin laadittiin ankkurille vaatimuslista. Tämän jälkeen laadittiin ankkurille toimintorakenne ja jakaminen osatoimintoihin. Ankkurin rakenteista toteutettiin kaksi eri versiota: sisävesillä ja merialueilla käytettävät ankkurit, joille laadittiin mitoitus. Työssä suunnitellun terävän tunkeutumisosan ja optimaalisen tunkeutumiskulman avulla ankkureiden painoa saatiin huomattavasti alhaisemmaksi, jonka seurauksena ankkurille saatiin kevyempi rakenne ja materiaalikustannukset pienenivät merkittävästi. Uusien ankkurien rakenne on pienemmän koon ja painon ansiosta käyttäjäystävällisempi.

Integrated assessment for establishing an oil environmental vulnerability map: Case study for the Santos Basin region, Brazil

The growth of maritime transport and oil exploitation activities may increase the risk of oil spills. Thus, plans and actions to prevent or mitigate impacts are needed to minimize the effects caused by oil. However, tools used worldwide to support contingency plans have not been integrated, thus leading to failure in establishing priority areas. This investigation aimed to develop indices of environmental vulnerability to oil (IEVO), by combining information about environmental sensibility to oil and results of numerical modeling of spilled oil. To achieve that, a case study concerning to oil spills scenarios in a subtropical coastal area was designed, and IEVOs were calculated and presented in maps, in order to make the information about the areas' vulnerability more easily visualized. For summer, the extension of coastline potentially affected by oil was approximately 150. km, and most of the coastline presented medium to high vulnerability. For winter, 230. km coastline would be affected, from which 75% were classified as medium to high vulnerability. Thus, IEVO maps allowed a rapid and clearer interpretation of the vulnerability of the mapped region, facilitating the planning process and the actions in response to an oil spill. © 2013 Elsevier Ltd.

Identifying the major spilled oil constituents and fate in harsh offshore environments

The behaviour and fate of spilled oil in harsh marine environments, such as the North Atlantic and the Arctic Ocean are complex due to environmental factors and the composition of the crude. In order to develop appropriate oil spill prevention and management methods, we must first understand how the oil behaves in these harsh environmental conditions. This study focuses on determining the fate of oil in harsh marine environments by first identifying target compounds in the oil that can be used to determine the fate of a spill. This thesis presents the partitioning behaviour of six polycyclic aromatic hydrocarbons (PAHs), which represent different groups, and phenols in cold conditions. The smallest PAH, naphthalene, dominated in terms of concentration in water accommodated fraction (WAF) of oil, while the larger ringed PAHs presented at lower concentrations. The smallest oil-water partition coefficient was recorded by phenol which partitioned into the seawater more quickly than PAHs. The partitioning of larger PAHs was slower and they indicated high partition coefficients. The oil partitioning increased slightly as temperature increased from 4ᴼC to 15ᴼC. The oil loading (0.1 g/L to 10 g/L) also contributed in deciding the concentrations in water. The use of chemical dispersants is a common response to spills. This study identified that chemical dispersants can change the fate of an oil spill by increasing the availability of oil in seawater. The concentration of larger PAHs such as pyrene and chrysene increased significantly with the application of dispersants. The information obtained are used in developing a molecular imprinted polymer (MIP) sensor to identify oil spills in the North Atlantic Ocean.

Characterisation of the effect of a simulated hydrocarbon spill on diazotrophs in mangrove sediment mesocosm

An analysis of the effect of an oil spill on mangrove sediments was carried out by contamination of mesocosms derived from two different mangroves, one with a history of contamination and one pristine. The association between N(2) fixers and hydrocarbon degradation was assessed using quantitative PCR (qPCR) for the genes rrs and nifH, nifH clone library sequencing and total petroleum hydrocarbon (TPH) quantification using gas chromatography. TPH showed that the microbial communities of both mangroves were able to degrade the hydrocarbons added; however, whereas the majority of oil added to the mesocosm derived from the polluted mangrove was degraded in the 75 days of the experiment, there was only partially degradation in the mesocosm derived from the pristine mangrove. qPCR showed that the addition of oil led to an increase in rrs gene copy numbers in both mesocosms, having almost no effect on the nifH copy numbers in the pristine mangrove. Sequencing of nifH clones indicated that the changes promoted by the oil in the polluted mangrove were greater than those observed in the pristine mesocosm. The main effect observed in the polluted mesocosm was the selection of a single phylotype which is probably adapted to the presence of petroleum. These results, together with previous reports, give hints about the relationship between N(2) fixation and hydrocarbon degradation in natural ecosystems.

Unlike PAHs from Exxon Valdez crude oil, PAHs from Gulf of Alaska coals are not readily bioavailable.

In the wake of the 1989 Exxon Valdez oil spill, spatially and temporally spill-correlated biological effects consistent with polycyclic aromatic hydrocarbon (PAH) exposure were observed. Some works have proposed that confounding sources from local source rocks, prominently coals, are the provenance of the PAHs. Representative coal deposits along the southeast Alaskan coast (Kulthieth Formation) were sampled and fully characterized chemically and geologically. The coals have variable but high total organic carbon content technically classifying as coals and coaly shale, and highly varying PAH contents. Even for coals with high PAH content (approximately 4000 ppm total PAHs), a PAH-sensitive bacterial biosensor demonstrates nondetectable bioavailability as quantified, based on naphthalene as a test calibrant. These results are consistent with studies indicating that materials such as coals strongly diminish the bioavailability of hydrophobic organic compounds and support previous work suggesting that hydrocarbons associated with the regional background in northern Gulf of Alaska marine sediments are not appreciably bioavailable.

Vuosaaren sataman palon-, öljyn- ja vaarallisten aineiden torjuntasuunnitelmat

Työn tavoitteena oli laatiavuonna 2008 valmistuvaan Vuosaaren satamaan palon-, öljyn- ja vaarallisten aineiden torjuntasuunnitelmat. Suunnitelmat perustuvat eri lain-säädännön sekä sataman ympäristöluvan vaatimuksiin. Ne otetaan käyttöön jo sata-man rakentamisen yhteydessä. Suunnitelmissa on Vuosaaren satamassa työskentelevälle henkilöstölle toimintaohjei-ta erilaisten onnettomuuksien varalle. Suunnitelmat täyttävät viranomaisten niille asettamat vaatimukset. Liitteillä on tarkentavia piirroksia ja toimintaohjeita, joita voi tarvittaessa hyödyntää työpisteissä tai torjuntakonteissa. Suunnitelmien laadinnassa ovat olleet mukana Helsingin Sataman ao. toiminnasta vastaavat henkilöt sekä eri viranomaiset (ympäristö- ja pelastusviranomaiset). Varsinainen diplomityö on kuvaus ja tiivistelmä eri suunnitelmista ja siitä, miten ne ovat syntyneet.

Generalist hydrocarbon-degrading bacterial communities in the oil-polluted water column of the North Sea.

The aim of this work was to determine the effect of light crude oil on bacterial communities during an experimental oil spill in the North Sea and in mesocosms (simulating a heavy, enclosed oil spill), and to isolate and characterize hydrocarbon-degrading bacteria from the water column. No oil-induced changes in bacterial community (3 m below the sea surface) were observed 32 h after the experimental spill at sea. In contrast, there was a decrease in the dominant SAR11 phylotype and an increase in Pseudoalteromonas spp. in the oiled mesocosms (investigated by 16S rRNA gene analysis using denaturing gradient gel electrophoresis), as a consequence of the longer incubation, closer proximity of the samples to oil, and the lack of replenishment with seawater. A total of 216 strains were isolated from hydrocarbon enrichment cultures, predominantly belonging to the genus Pseudoaltero monas; most strains grew on PAHs, branched and straight-chain alkanes, as well as many other carbon sources. No obligate hydrocarbonoclastic bacteria were isolated or detected, highlighting the potential importance of cosmopolitan marine generalists like Pseudoalteromonas spp. in degrading hydrocarbons in the water column beneath an oil slick, and revealing the susceptibility to oil pollution of SAR11, the most abundant bacterial clade in the surface ocean.

Immediate ecotoxicological effects of short-lived oil spills on marine biota.

Marine environments are frequently exposed to oil spills as a result of transportation, oil drilling or fuel usage. Whereas large oil spills and their effects have been widely documented, more common and recurrent small spills typically escape attention. To fill this important gap in the assessment of oil-spill effects, we performed two independent supervised full sea releases of 5 m(3) of crude oil, complemented by on-board mesocosm studies and sampling of accidentally encountered slicks. Using rapid on-board biological assays, we detect high bioavailability and toxicity of dissolved and dispersed oil within 24 h after the spills, occurring fairly deep (8 m) below the slicks. Selective decline of marine plankton is observed, equally relevant for early stages of larger spills. Our results demonstrate that, contrary to common thinking, even small spills have immediate adverse biological effects and their recurrent nature is likely to affect marine ecosystem functioning.

Toimintamalli asuinkiinteistö öljyvahingon hoitamiseksi

Pienkiinteistöjen öljyvahingot ovat viime vuosina lisääntyneet. Tämän työn tarkoituksena on luoda öljyvahingon torjuntaan ja jälkihoitoon osallistuvalle urakoitsijalle toimintamalli asuinkiinteistön öljyvahingon hoitamiseksi. Mallin halutaan erityisesti kuvaavan öljyvahingon hoitoon osallistuvien viranomaisten ja muiden tahojen vastuita ja velvollisuuksia. Työn tavoitteena on myös tunnistaa pienkiinteistöissä tapahtuvat öljyvahinkotyypit sekä niille altistavat riskitekijät. Öljyn päästäminen ympäristöön sekä öljyn käsittely ja varastointi niin, että siitä aiheutuu öljyvahingon vaara, kielletään laissa. Vahinkojen torjumiseksi on annettu määräyksiä muun muassa öljylämmityslaitteistojen turvallisuutta koskien. Asuinkiinteistöjen öljyvahingot liittyvät yleensä öljysäiliön täyttötilanteisiin. Vahinkojen syynä on usein säiliön ja sen varusteiden puutteellisuus tai huono kunto. Asuinrakennusten lämmitykseen käytetään kevyttä polttoöljyä. Maahan joutuessaan polttoöljy imeytyy sora- ja hiekkamaahan nopeasti, jolloin vaarana on öljyn kulkeutuminen pohjaveteen ja vesistöihin. Asuinkiinteistön öljyvahingossa öljyä joutuu usein myös rakenteisiin. Öljyvahingosta tulee ilmoittaa aina hätäkeskukseen. Vastuu öljyvahinkojen torjunnasta kuuluu alueelliselle pelastustoimelle. Torjuntatoimiin osallistuu usein myös urakoitsija. Jos vahinkokohdetta ei torjuntatoimin saada kunnostettua, alueellinen ympäristökeskus voi määrätä puhdistamisesta vastuussa olevan selvittämään pilaantuneen alueen laajuuden ja puhdistamistarpeen sekä toteuttamaan mahdollisen kunnostuksen. Pilaantuneen maaperän kunnostus voidaan toteuttaa massan vaihtona tai paikan päällä maata kaivamatta. Likaantuneiden rakenteiden saneerausta tarvitaan sisäilman hajuhaittojen poistamiseksi. Öljyvahingon kustannukset voivat nousta hyvinkin suuriksi. Ensisijainen vastuu niistä kuuluu vahingonaiheuttajalle.