Identificación de los riesgos ambientales y sanitarios de la producción de gas mediante fracturación hidráulica y bases para una propuesta metodológica de vulnerabilidad de las aguas subterráneas

Hasta ahora, la gran mayoría de los recursos explotados de gas natural procedían de acumulaciones convencionales de gas aislado y de gas asociado y disuelto en el petróleo. Sin embargo, el gas natural se encuentra también en yacimientos que, debido a su baja porosidad y permeabilidad, tienen unas características que hacen que hasta muy recientemente no hayan sido económicamente rentables y que sólo puedan ser explotados mediante técnicas no convencionales, dando lugar al denominado gas no convencional. Las técnicas utilizadas para su extracción son la fracturación hidráulica o “fracking” y la perforación horizontal. Entre los diversos tipos de gas no convencional, es de prever que el gas de pizarra sea el que sufra mayor desarrollo a medio plazo en nuestro país, por lo que se están generando grandes debates, debido al riesgo de contaminación de las aguas superficiales y subterráneas del entorno, provocados por la elevada cantidad de agua utilizada, los aditivos empleados, los fluidos de retorno, por la alteración del medio físico, así como por la dificultad de monitorización de estos procesos. En este proyecto se identifican los riesgos ambientales y sanitarios asociados a la extracción de gas no convencional. El trabajo se basa principalmente en experiencias ocurridas en países donde el fracking se ha convertido en una práctica habitual. Se trata además de establecer las bases necesarias para la estimación de la vulnerabilidad de los acuíferos frente a la contaminación inducida por la fracturación hidráulica. Abstract Until now, most of the natural gas resources exploited were from isolated conventional gas accumulations and associated and dissolved gas in oil. However, the natural gas is also in reservoirs that, due to their low porosity and permeability, have characteristics that make until recently not been economically profitable and can be exploited only by unconventional techniques, leading to the so called unconventional gas. The techniques used for extraction are hydraulic fracturing or "fracking" and horizontal drilling. Among the various types of unconventional gas, it is expected that shale gas is the suffering greater medium-term development in our country, so it is generating much debate, due to the risks of contamination in surface waters and subterranean environment, caused by the high amount of water used, the additives used, the return fluid, by altering the physical environment, and the difficulty of monitoring these processes. In this project identifies the environmental and health risks associated with unconventional gas extraction. The work is mainly based on experiences that occurred in countries where fracking has become a common practice. This is for establish the necessary basis for estimating the vulnerability of aquifers from contamination induced by hydraulic fracturing.

Optimización del coste de aprovisionamiento de gas en el mercado mayorista español para una comercializadora

Los precios de compra de gas natural en el mercado mayorista español son los más altos de toda Europa. Este escenario provoca que haya que buscar alternativas para minimizar los costes de aprovisionamiento para una comercializadora de gas. En este proyecto se analizan distintas oportunidades de compra de gas en los mercados europeos y su importación al sistema gasista español para el suministro final a clientes, con el fin de optimizar los costes del gas natural para una comercializadora. En la búsqueda de nuevas oportunidades se incluye también un análisis del impacto económico en el mercado, de la producción de “shale gas” en España a medio - largo plazo. ABSTRACT The gas prices in the Spanish gas market are the highest in Europe. This scenario leads the Spanish gas trading companies to look for alternatives to minimize gas supply costs. In this project it is analyzed different opportunities of gas supply in the European markets and the gas import to the Spanish gas system, in order to optimize the costs of the natural gas for a gas trading company. Along with this, it is also studied, the economic impact of the “shale gas” production in Spain in a medium - long term on the Spanish gas market

Análisis del sector y mercado gasista nacional e internacional. : el Hub ibérico y su adaptación al sistema español

Actualmente existe un gran interés orientado hacia el mercado del gas natural. Son muchas las razones por las que este combustible se posiciona como uno de los más importantes dentro del panorama energético mundial. Además de que salvaría el hueco dejado por el carbón y el petróleo, supone una alternativa mucho más limpia que se podría desarrollar aún más tanto a nivel doméstico, industrial como en el mundo de los transportes. La industria del gas natural está cambiando rápidamente fundamentalmente por la aparición del gas no convencional y sus técnicas de extracción. Por lo que se está produciendo un cambio en la economía de la producción de gas así como en la dinámica y los movimientos del GNL a lo largo de todo el planeta. El propósito de este estudio es enfocar el estado del sector y mercado del gas natural en todo el mundo y de esta forma subrayar las principales regiones que marcan la tendencia general de los precios de todo el planeta. Además, este trabajo reflejará los pronósticos esperados para los próximos años así como un resumen de las tendencias que se han seguido hasta el momento. Particularmente, se centrará la atención en el movimiento hacia los sistemas basados en forma de hub que comenzaron en EE.UU. y que llegaron a Reino Unido y al continente Europeo a principios del S.XX. Esta tendencia es la que se pretende implantar en España con el fin de conseguir una mayor competitividad, flexibilidad y liquidez en los precios y en el sistema gasista. De esta forma, poco a poco se irá construyendo la estructura hacia un Mercado Único Europeo que es el objetivo final que plantean los organismos de los estados miembros. Sin embargo, para la puesta en marcha de este nuevo modelo es necesario realizar una serie de cambios en el sistema como la modificación de la Ley de Hidrocarburos, la designación de un Operador de Mercado, elaboración de una serie de reglas para regular el mercado así como fomentar la liquidez del mercado. Cuando tenga lugar el cambio regulatorio, la liquidez del sistema español incrementará y se dará la oportunidad de crear nuevas formas para balancear las carteras de gas y establecer nuevas estrategias para gestionar el riesgo. No obstante, antes de que se hagan efectivos los cambios en la legislación, se implantaría uno de los modelos planteados en el “Gas Target Model”, el denominado “Modelo de Asignación de Capacidad Implícita”. La introducción de este modelo sería un primer paso para la integración de un mercado de gas sin la necesidad de afrontar un cambio legislativo, lo que serviría de VIII impulso para alcanzar el “Modelo de Área de Mercado” que sería el mejor para el sistema gasista español y se conectaría ampliamente con el resto de mercados europeos. Las conclusiones del estudio en relación a la formación del nuevo modelo en forma de hub plantean la necesidad de aprovechar al máximo la nueva situación y conseguir implantar el hub lo antes posible para poder dotar al sistema de mayor competencia y liquidez. Además, el sistema español debe aprovechar su gran capacidad y moderna infraestructura para convertir al país en la entrada de gas del suroeste de Europa ampliando así la seguridad de suministro de los países miembros. Otra conclusión que se puede extraer del informe es la necesidad de ampliar el índice de penetración del gas en España e incentivar el consumo frente a otros combustibles fósiles como el carbón y el petróleo. Esto situaría al gas natural como la principal energía de respaldo con respecto a las renovables y permitiría disminuir los precios del kilovatio hora del gas natural. El estudio y análisis de la dinámica que se viene dando en la industria del gas en el mundo es fundamental para poder anticiparse y planear las mejores estrategias frente a los cambios que poco a poco irán modificando el sector y el mercado gasista. ABSTRACT There is a great deal of focus on the natural gas market at the moment. Whether you view natural gas as bridging the gap between coal/oil and an altogether cleaner solution yet to be determined, or as a destination fuel which will be used not only for heating and gas fired generation but also as transportation fuel, there is no doubt that natural gas will have an increasingly important role to play in the global energy landscape. The natural gas industry is changing rapidly, as shale gas exploration changes the economics of gas production and LNG connects regions across the globe. The purpose of this study is to outline the present state of the global gas industry highlighting the differing models around the world. This study will pay particular attention to the move towards hub based pricing that has taken hold first in the US and over the past decade across the UK and Continental Europe. In the coming years the Spanish model will move towards hub based pricing. As gas market regulatory change takes hold, liquidity in the Spanish gas market will increase, bringing with it new ways to balance gas portfolios and placing an increasing focus on managing price risk. This study will in turn establish the links between the changes that have taken place in other markets as a way to better understanding how the Spanish market will evolve in the coming years.

Valoración de los indicios de gas no convencional en la cuenca del Guadiato

El “shale gas” es un gas no convencional que actualmente se está considerando como una fuente de energía primaria en el momento en que las reservas del petróleo y gas natural convencionales se agoten, razón por la que muchos países están interesados. No obstante, el procedimiento de extracción es complejo y conlleva muchos riesgos de contaminación. En este Proyecto Fin de Carrera se hace un estudio de las posibilidades de extracción en el futuro de “shale gas” o “shale oil” en la Cuenca del Guadiato. Para ello se evaluó el contenido de materia orgánica, el tipo y la madurez en muestras de la serie estratigráfica tipo del Carbonífero. Únicamente 3 niveles presentaban materia orgánica madura, que tendrían escaso potencial para extraer gas, descartándose la extracción de “shale oil”.

Discourses and values underpin public debate on fracking in Spain: a case study at the crossroad

In the EU context extraction of shale and oil gas by hydraulic fracturing (fracking) differs from country to country in terms of legislation and implementation. While fossil fuel extraction using this technology is currently taking place in the UK, Germany and France have adopted respective moratoria. In between is the Spanish case, where hydrocarbon extraction projects through fracking have to undergo mandatory and routine environmental assessment in accordance with the last changes to environmental regulations. Nowadays Spain is at the crossroad with respect to the future of this technology. We presume a social conflictt in our country since the position and strategy of the involved and confronted social actors -national, regional and local authorities, energy companies, scientists, NGO and other social organization- are going to play key and likely divergent roles in its industrial implementation and public acceptance. In order to improve knowledge on how to address these controverted situations from the own engineering context, the affiliated units from the Higher Technical School of Mines and Energy Engineering at UPM have been working on a transversal program to teach values and ethics. Over the past seven years, this pioneering experience has shown the usefulness of applying a consequentialist ethics, based on a case-by-case approach and costs-benefits analysis both for action and inaction. As a result of this initiative a theoretical concept has arisen and crystallized in this field: it is named Inter-ethics. This theoretical perspective can be very helpful in complex situations, with multi-stakeholders and plurality of interests, when ethical management requires the interaction between the respective ethics of each group; professional ethics of a single group is not enough. Under this inter-ethics theoretical framework and applying content analysis techniques, this paper explores the articulation of the discourse in favour and against fracking technology and its underlying values as manifested in the Spanish traditional mass media and emerging social media such as Youtube. Results show that Spanish public discourse on fracking technology includes the costs-benefits analysis to communicate how natural resources from local communities may be affected by these facilities due to environmental, health and economic consequences. Furthermore, this technology is represented as a solution to the "demand of energy" according to the optimistic discourse while, from a pessimistic view, fracking is often framed as a source "environmental problems" and even natural disasters as possible earthquakes. In this latter case, this negative representation could have been influenced by the closure of a macro project to store injected natural gas in the Mediterranean Sea using the old facilities of an oil exploitation in Amposta (Proyecto Cástor). The closure of this project was due to the occurrence of earthquakes whose intensity was higher than the originally expected by the experts in the assessment stage of the project.

Estudo em laboratório do desempenho de concreto asfáltico usinado a quente empregando ligante tipo asfalto-borracha

Pesquisas sobre aplicação de borracha de pneus descartados em pavimentação asfáltica vêm sendo desenvolvidas desde a década de 1960, especialmente nos Estados Unidos e, desde o início da década de 1990, no Brasil, como alternativa para diminuição dos problemas ambientais gerados por estes resíduos sólidos. Esta pesquisa tem por objetivo avaliar o desempenho de três misturas asfálticas do tipo concreto asfáltico usinado à quente: duas empregando teores diferentes de borracha moída e óleo de xisto (CAP 40 + 12% de borracha + 10% de óleo de xisto e CAP 40 + 20% de borracha + 15% de óleo de xisto) e uma convencional. Este estudo faz parte de um programa de pesquisa coordenado pela Escola de Engenharia de São Carlos da Universidade de São Paulo (EESC-USP), Universidade Estadual de Maringá (UEM) e Petrobrás, envolvendo a execução de misturas com borracha e óleo de xisto em trechos experimentais. Foram realizadas dosagens Marshall e ensaios de resistência à tração, módulo de resiliência e fluência por compressão uniaxial estática. Os corpos-de-prova empregados nos ensaios foram moldados no teor ótimo de cimento asfáltico referente a cada uma das misturas. Constatou-se a viabilidade técnica da adição de óleo extensor para a incorporação de borracha de pneus descartados em concreto asfáltico, permitindo a obtenção de resultados satisfatórios quanto aos projetos de dosagem das misturas pelo método Marshall. Com base nos resultados dos ensaios realizados, acredita-se ser viável a execução de trechos experimentais empregando as duas misturas modificadas.

Fisiologia e formação de partículas lipídicas durante o crescimento da levedura Yarrowia lipolytica IMUFRJ 50682.

A levedura Yarrowia lipolytica tem sido muito investigada, especialmente por ser um microrganismo oleaginoso, ou seja, capaz de acumular grandes quantidades de lipídios, o que ocorre majoritariamente em organelas denominadas partículas lipídicas. Estes lipídios apresentam várias potenciais aplicações biotecnológicas, como por exemplo na produção de óleo microbiano (single cell oil) e na produção de biodiesel. Durante este projeto de mestrado, objetivou-se estudar a fisiologia de duas linhagens da levedura Y. lipolytica, sendo uma tradicionalmente estudada pela comunidade científica internacional (linhagem w29) e outra isolada da Baía da Guanabara, no Rio de Janeiro (linhagem IMUFRJ 50682). Foram realizados cultivos em frascos agitados tipo Erlenmeyer com defletores tampados com algodão (volume total 500 mL, volume de meio 100 mL, 28 oC e 200 rotações por minuto), durante os quais foi possível: 1) escolher um meio de cultivo de composição totalmente definida, com tiamina como único fator de crescimento, adequado a estudos de fisiologia quantitativa com esta levedura; 2) verificar que Y. lipolytica não é capaz de crescer com sacarose ou xilose como única fonte de carbono; 3) verificar que Y. lipolytica cresce com velocidade específica de crescimento máxima (Máx) de 0,49 h-1 num meio complexo contendo glicose, extrato de levedura e peptona (meio YPD), 0,31 h-1 em meio definido com glicose como única fonte de carbono e 0,35 h-1 no mesmo meio, mas com glicerol como única fonte de carbono, sem excreção de metabólitos para o meio de cultivo; 4) verificar que ocorreu limitação por oxigênio nos cultivos em frasco agitado, sendo este o motivo pelo qual as células deixaram de crescer exponencialmente; 5) verificar que o uso de ureia, em vez de sulfato de amônio, como fonte de nitrogênio, contribui para uma variação menor do pH durante os cultivos, sem prejuízo ao crescimento da levedura; 6) observar que, ao se restringir a oferta de nitrogênio à levedura (aumento da relação C/N inicial no meio de 12,6 para 126), as células têm sua morfologia alterada e apresentam maior quantidade de partículas lipídicas; 7) determinar uma composição elementar para a biomassa de Y. lipolytica (CH1,98O0,58N0,13), em que os átomos de carbono encontram-se em média mais reduzidos do que na biomassa de leveduras como Saccharomyces cerevisiae e Dekkera bruxellensis. Foram também realizados cultivos em biorreator em batelada (1 L de volume útil, 28 oC, aerobiose plena e pH controlado em 5,0), durante os quais foi possível: a) estabelecer um protocolo de cultivo para Y. lipolytica em biorreator (que envolvem agitação mecânica, aeração e uso de anti-espumante, entre outras diferenças em relação aos cultivos em frasco); b) confirmar os valores dos principais parâmetros fisiológicos apresentados por esta levedura, anteriormente obtidos a partir de cultivos em frasco; c) confirmar que o fator de conversão de substrato a células (Yx/s) é maior para cultivos realizados com glicerol como fonte única de carbono (0,53 g/g para a linhagem IMUFRJ 50682), do que com glicose (0,48 g/g para a mesma linhagem). Finalmente, cultivos realizados em quimiostato com glicerol como fonte de carbono e energia, limitados por amônio (fonte de nitrogênio, relação C/N 126), às vazões específicas de 0,25 h-1 e 0,15 h-1, permitiram observar que o número de partículas lipídicas por célula de Y. lipolytica permaneceu em torno de 2 em ambas as situações e houve uma diminuição no teor de nitrogênio nas células quando a velocidade específica de crescimento diminuiu de 0,25 para 0,15 h-1.

Social License to Operate: Hydraulic Fracturing-Related Challenges Facing the Oil & Gas Industry

The crossroads of urban development and improved technology allowing oil and gas development in new areas can result in contentious community issues. The debate over one of the improved technologies – i.e., hydraulic fracturing – can be highly emotional. Consequently, industry must address community issues, earning trust and therefore a “social license to operate.” This paper provides fundamental knowledge of the social license to operate concept, validates its application to the oil and gas industry, particularly with respect to shale gas development, discusses the current status of social license in the unconventional development sphere, analyzes current ongoing efforts for shale gas developers to monitor and establish a social license, and identifies potential new methods of encouraging, establishing, and monitoring a social license to operate. The paper also proposes a new institutional framework in which to promote the social license to operate, “The Center for Social License to Operate in the Oil & Gas Industry.”

Structural evolution of the Lesser Himalayan fold-thrust belt of west central Nepal

The Lesser Himalayan fold-thrust belt on the south flank of the Jajarkot klippe in west central Nepal was mapped in detail between the Main Central thrust in the north and the Main Boundary thrust in the south. South of the Jajarkot klippe, the fold-thrust belt involves sandstone, shale and carbonate rocks that are unmetamorphosed in the foreland and increase in metamorphic grade with higher structural position to sub-greenschist facies towards the hinterland. The exposed stratigraphy is correlative with the Proterozoic Ranimata, Sangram, Galyang, Syangia Formations and Lakharpata Group of Western Nepal and overlain by the Paleozoic Tansen and Kali Gandaki Groups. Based on field mapping and cross-section construction, three distinct thrust sheets were identified separated by top-to-the-south thrust faults. From the foreland (south) to the hinterland (north), the first thrust sheet in the immediate hanging wall of the Main Boundary thrust defines an open syncline. The second thrust sheet contains a very broad synformal duplex, which is structurally stacked against the third thrust sheet containing a homoclinal panel of the oldest exposed Proterozoic stratigraphy. Outcrop scale folds throughout the study area are predominantly south vergent, open, and asymmetric reflecting the larger regional scale folding style, which corroborate the top-to-the-south deformation style seen in the faults of the region. Field techniques were complemented with microstructural and quartz crystallographic c-axis preferred orientation analyses using a petrographic microscope and a fabric analyzer, respectively. Microstructural analysis identified abundant strain-induced recrystallization textures and occasional occurrences of top-to-the-south shear-sense indicators primarily in the hinterland rocks in the immediate footwall of the Main Central Thrust. Top-to-the-south shearing is also supported by quartz crystallographic c-axis preferred orientations. Quartz recrystallization textures indicate an increase in deformation temperature towards the Main Central thrust. A line balance estimate indicates that approximately 15 km of crustal shortening was accommodated by folding and faulting in the fold-thrust belt south of the Jajarkot klippe. Additionally, estimations of shortening velocity suggest that the shortening velocity operating in this section of the fold-thrust belt between 23 to 14 Ma was slower than what is currently observed as a result of the ongoing deformation of the Sub-Himalayan fold-thrust belt.

The 2030 framework on climate and energy - Getting Europe on the right track? EPC Commentary, 30 January 2014

Climate vs competitiveness? The European Commission published its proposal on the 2030 climate and energy framework on 22 January. Reflective of the current economic climate, it was accompanied by a report on energy prices and the Commission decided not to propose regulation on shale gas but to issue recommendations on environmental standards. The same day also saw the publication of a communication “For a European Industrial Renaissance”. Climate considerations no longer drive the agenda. The enthusiasm of 2007, when the “20/20/20” climate and energy targets were set for 2020, has diminished. The new reality has brought competitiveness to the top of the EU’s priority agenda.

Kyiv's gas strategy: closer cooperation with Gazprom or a genuine diversification. OSW Commentary No. 110, 2013-07-16

In recent months Kyiv has been intensifying its efforts to diversify Ukraine’s gas supply routes with a view to reducing the country’s dependence on imports from Russia. One of the steps which Kyiv has taken has been to make the unprecedented decision to start importing gas from its Western neighbours. In November 2012, Ukraine’s state-owned Naftogaz began importing gas through Poland under a two-month contract with RWE (the imports continued into 2013 under a separate deal), while in the spring of 2013 Ukraine started importing gas from Hungary. Kyiv is also currently looking into the possibility of purchasing gas from Slovakia. Furthermore, since 2010 the Ukrainian government has been working on the construction of an LNG terminal near Odesa. The authorities have declared that this will allow Ukraine to import up to 5 billion m3 of LNG a year by 2015. The government has also taken measures to increase domestic production, including from non-traditional sources, and it plans to replace gas-based with coal-based technologies in local power stations. Finally, in January 2013, the government signed a 50-year production sharing agreement with Shell. This paves the way for the development of Ukraine’s shale gas deposits.

First steps towards into the unknown. The possibilities prospects of unconventional gas extraction in Ukraine. OSW Commentary No. 106, 2013-04-24

Ukraine’s deposits of unconventional gas (shale gas, tight gas trapped in non-porous sandstone formations, and coal bed methane) may form a significant part of Europe’s gas reserves. Initial exploration and test drilling will be carried out in two major deposits: Yuzivska (Kharkiv and Donetsk Oblasts) and Oleska (Lviv and Ivano-Frankivsk Oblasts), to confirm the volume of the reserves. Shell and Chevron, respectively, won the tenders for the development of these fields in mid 2012. Gas extraction on an industrial scale is expected to commence in late 2018/ early 2019 at the earliest. According to estimates presented in the draft Energy Strategy of Ukraine 2030, annual gas production levels may range between 30 billion m3 and 47 billion m3 towards the end of the next decade. According to optimistic forecasts from IHS CERA, total gas production (from both conventional and unconventional reserves) could reach as much as 73 billion m3. However, this will require multi-billion dollar investments, a significant improvement in the investment climate, and political stability. It is clear at the present initial stage of the unconventional gas extraction project that the private interests of the Ukrainian government elite have played a positive role in initiating unconventional gas extraction projects. Ukraine has had to wait nearly four decades for this opportunity to regain its status of a major gas producer. Gas from unconventional sources may lead not only to Ukraine becoming self-sufficient in terms of energy supplies, but may also result in it beginning to export gas. Furthermore, shale gas deposits in Poland and Ukraine, including on the Black Sea shelf (both traditional natural gas and gas hydrates) form a specific ‘European methane belt’, which could bring about a cardinal change in the geopolitics and geo-economics of Eastern and Central Europe over the next thirty years.

Energising the TTIP: Political economy of the trade policy rationale. Paper No. 9 in the CEPS-CTR project “TTIP in the Balance’’and CEPS Special Report No. 113/July 2015

Despite accounting for a significant share of global trade and the resulting interdependencies from it, energy governance remains largely fragmented and there is no global framework or agreement defining the rules of energy trade. This paper, after presenting the main global and regional energy market developments, discusses the opportunities to ‘energise the TTIP’, i.e. to include a chapter dedicated to trade and cooperation in the sphere of energy. The shale revolution in the US, the ever-rising interconnectedness of energy markets (recently proven by the disappearance of the ‘Asian gas premium’) and the EU’s quest to diversify its energy supplies generally sets favourable conditions to reinforce energy relations between the EU and the US. The question, as is often the case, is whether there is sufficient political will to tighten relations in a strategic sphere with connotations for national security and sovereignty.

(Table 2) Trace metal concentrations in ODP Hole 169-1033B

We measured the concentrations of redox-sensitive trace metals (Mn, V, Mo, U, Cd and Re) in sediments from ODP Leg 169S Hole 1033B in Saanich Inlet, British Columbia, to determine changes in redox conditions associated with the onset of laminated sediments at ~12.5 kyr. The most striking result is a large peak in authigenic Re along with detrital levels of Mo at the glacial terrigenous clay-diatomaceous sediment transition. In contrast, the underlying glacial terrigenous clay, which extends throughout the bottom section of the core, is chemically similar to detrital concentrations, either Cowichan River particulates or average shale values. These data suggest a period of oxic bottom waters but reducing pore-waters. This could be due to the dramatic transformation of Saanich Inlet during the late deglaciation from an open bay to an inlet, which restricted circulation and slowed bottom water oxygen renewal. A peak and gradual increase in authigenic Mn in younger sediments subsequent to the Re peak suggests that increasingly oxic conditions followed the authigenic enrichment in Re. These conditions could be connected to the Younger Dryas cooling period, which was coincident with an increase in well oxygenated upwelled waters on the west coast of North America that form the bottom waters of Saanich Inlet. Metal concentrations in a gray clay bed (~11 kyr) are similar to their concentrations in the glacial terrigenous clay, implying that they have a common source. Authigenic enrichments of Re with little authigenic Mo and Cd suggest that before the deposition of this bed, bottom waters were oxic and pore-water oxygen was consumed in the top centimeter or less. Laminations above the clay layer suggest anoxic conditions, which are also indicated by higher authigenic Mo and Cd and slightly lower Re/Mo ratios in these sediments. The basin remained mostly anoxic after the gray clay was emplaced, as seen by continuous authigenic enrichment of the redox-sensitive trace metals. These results are consistent with increased stratification of the water column, brought about by an influx of fresh water to the basin by a large flood.