Inferring Hydrocarbon Migration and Sealing Potentials of Some Shales of the Anambra Basin (South-Eastern Nigeria) from Their Paragenesis and Geotechnical Index Properties

Shale samples from designated units of the Imo, Nsukka, Mamu, Enugu and Nkporo Formations of the Anambra Basin were subjected to X-ray diffraction and geotechnical index tests to determine the potential of the Formations to either create hydrocarbon migration pathways or to form seals for hydrocarbon entrapment. The X-ray diffraction results indicate that the shales are made up of silicate minerals with carbonates and sulphates. Results of the geotechnical index tests showed that the plasticity index (PI) for the Enugu shale ranges from 16 to 24 (average of 20) while the toughness index (TI) ranges from 0.4 to 0.8 (average of 0.7). The PI for the shales of Imo and Nsukka Formations ranges from 62 to 72 and 34–59 with averages of 67 and 46 respectively while their TIs range from 0.8 to 1.7 and 1.5–2.2 with averages of 1.3 and 1.9, respectively. These properties dispose the Enugu shale to easy amenability to loss of cohesion, deforming in a brittle manner, when subjected to shearing stress with the ability to create joints and faults that are pathways of hydrocarbon migration. Conversely, the properties of the shales of the Imo and Nsukka Formations give them the capacity to absorb high shearing stress without loss of cohesion thereby deforming in a ductile manner, which prevents the leakage of fluids in fluid migration. Hence, Enugu shale has the highest potential of creating hydrocarbon pathways while the shales of the Imo and Nsukka Formations are better seal rocks than others.     

Historically unprecedented erosion from Tropical Storm Irene due to high antecedent precipitation

Lacustrine sediment archives indicate that flooding during Tropical Storm Irene (2011) in the north‐eastern United States caused the most severe erosion of any flood in the historic record, surpassing that of events with greater precipitation and peak discharges. Compared to deposition from historic floods, Irene's event layer was more massive and more enriched in unweathered upland sediments, indicating an anomalously high incidence of mass wasting and sediment entrainment. Precipitation records indicate that neither precipitation intensity nor total accumulation distinguished Irene from less erosive historic floods. However, cumulative precipitation prior to Irene exceeded the 95th percentile of all days in the record. When allowing for non‐stationarity in the twentieth century background precipitation, we find a four‐fold increase in the probability of Irene‐like conditions, where impacts of extreme rainfall are enhanced by high antecedent precipitation. We conclude that irrespective of increases in extreme precipitation, the risk of highly erosive flooding in the region is increasing due to the influence of wetter baseline conditions associated with a changing climate. Copyright © 2015 John Wiley & Sons, Ltd.     

Continental-scale patterns in soil geochemistry and mineralogy: Results from two transects across the United States and Canada

In 2004, the US Geological Survey (USGS) and the Geological Survey of Canada (GSC) initiated a pilot study that involved collection of more than 1500 soil samples from 221 sites along two continental transects across Canada and the United States. The pilot study was designed to test and refine protocols for a soil geochemical survey of North America. The two transects crossed a wide array of soil parent materials, soil ages, climatic conditions, landforms, land covers and land uses. Sample sites were selected randomly at approximately 40-km intervals from a population defined as all soils of the continent. At each site, soils representing 0 to 5 cm depth, and the O, A, and C horizons, if present, were collected and analyzed for their near-total content of over 40 major and trace elements. Soils from 0–5 cm depth were also collected for analysis of organic compounds. Results from the transects confirm that soil samples collected at a 40-km spacing reveal coherent, continental- to subcontinental-scale geochemical and mineralogical patterns that can be correlated to aspects of underlying soil parent material, soil age and climate influence. The geochemical data also demonstrate that at the continental-scale the dominance of any of these major factors that control soil geochemistry can change across the landscape. Along both transects, soil mineralogy and geochemistry change abruptly with changes in soil parent materials. However, the chemical influence of a soil’s parent material can be obscured by changing climatic conditions. For the transects, increasing precipitation from west to east and increasing temperature from north to south affect both soil mineralogy and geochemistry because of climate effects on soil weathering and leaching, and plant productivity. Regional anomalous metal concentrations can be linked to natural variations in soil parent materials, such as high Ni and Cr in soils developed on ultramafic rocks in California or high P in soils formed on weathered Ordovician limestones in central Kentucky. On local scales, anomalous metal concentrations recognized in soil profiles, such as high P in soils from animal confinement sites, are consistent with local anthropogenic disturbances. At a larger scale, the distribution of Hg across the west to east transect demonstrates that it can be difficult to distinguish between natural or anthropogenic contributions and that many factors can contribute to an element’s spatial distribution.Only three samples in a subset of seventy-three 0–5 cm depth soil samples from the north to south transect had organochlorine pesticides values above the method detection limit, apparently related to historic usage of the pesticides DDT and dieldrin.     

History and Progress of the North American Soil Geochemical Landscapes Project,2001-2010

In 2007,the U.S.Geological Survey,the Geological Survey of Canada,and the Mexican Geological Survey initiated a low-density(1 site per 1600 km2,13323 sites) geochemical and mineralogical survey of North American soils(North American Soil Geochemical Landscapes Project).Sampling and analytical protocols were developed at a series of workshops in 2003-2004 and pilot studies were conducted from 2004-2007.The ideal sampling protocol at each site includes a sample from 0-5 cm depth,a composite of the soil A horizon,and a sample from the soil C horizon.The <2-mm fraction of each sample is analyzed for Al,Ca,Fe,K,Mg,Na,S,Ti,Ag,Ba,Be,Bi,Cd,Ce,Co,Cr,Cs,Cu,Ga,In,La,Li,Mn,Mo,Nb,Ni,P,Pb,Rb,Sb,Sc,Sn,Sr,Te,Th,Tl,U,V,W,Y,and Zn by inductively coupled plasma-mass spectrometry and inductively coupled plasma-atomic emission spectrometry following a near-total digestion in a mixture of HCl,HNO3,HClO4,and HF.Separate methods are used for As,Hg,Se,and total C on this same size fraction.The major mineralogical components are determined by a quantitative X-ray diffraction method.Sampling in the conterminous U.S.was completed in 2010(c.4800 sites) with chemical and mineralogical analysis currently underway.In Mexico,approximately 66% of the sampling(871 sites) had been done by the end of 2010 with completion expected in 2012.After completing sampling in the Maritime provinces and portions of other provinces(472 sites,7.6% of the total),Canada withdrew from the project in 2010.Preliminary results for a swath from the central U.S.to Florida clearly show the effects of soil parent material and climate on the chemical and mineralogical composition of soils.A sample archive will be established and made available for future investigations.     

Pilot studies for the North American Soil Geochemical Landscapes Project – Site selection, sampling protocols, analytical methods, and quality control protocols

In 2004, the US Geological Survey (USGS) and the Geological Survey of Canada sampled and chemically analyzed soils along two transects across Canada and the USA in preparation for a planned soil geochemical survey of North America. This effort was a pilot study to test and refine sampling protocols, analytical methods, quality control protocols, and field logistics for the continental survey. A total of 220 sample sites were selected at approximately 40-km intervals along the two transects. The ideal sampling protocol at each site called for a sample from a depth of 0–5 cm and a composite of each of the O, A, and C horizons. The <2-mm fraction of each sample was analyzed for Al, Ca, Fe, K, Mg, Na, S, Ti, Ag, As, Ba, Be, Bi, Cd, Ce, Co, Cr, Cs, Cu, Ga, In, La, Li, Mn, Mo, Nb, Ni, P, Pb, Rb, Sb, Sc, Sn, Sr, Te, Th, Tl, U, V, W, Y, and Zn by inductively coupled plasma-mass spectrometry and inductively coupled plasma-atomic emission spectrometry following a near-total digestion in a mixture of HCl, HNO₃, HClO₄, and HF. Separate methods were used for Hg, Se, total C, and carbonate-C on this same size fraction. Only Ag, In, and Te had a large percentage of concentrations below the detection limit. Quality control (QC) of the analyses was monitored at three levels: the laboratory performing the analysis, the USGS QC officer, and the principal investigator for the study. This level of review resulted in an average of one QC sample for every 20 field samples, which proved to be minimally adequate for such a large-scale survey. Additional QC samples should be added to monitor within-batch quality to the extent that no more than 10 samples are analyzed between a QC sample. Only Cr (77%), Y (82%), and Sb (80%) fell outside the acceptable limits of accuracy (% recovery between 85 and 115%) because of likely residence in mineral phases resistant to the acid digestion.A separate sample of 0–5-cm material was collected at each site for determination of organic compounds. A subset of 73 of these samples was analyzed for a suite of 19 organochlorine pesticides by gas chromatography. Only three of these samples had detectable pesticide concentrations. A separate sample of A-horizon soil was collected for microbial characterization by phospholipid fatty acid analysis (PLFA), soil enzyme assays, and determination of selected human and agricultural pathogens. Collection, preservation and analysis of samples for both organic compounds and microbial characterization add a great degree of complication to the sampling and preservation protocols and a significant increase to the cost for a continental-scale survey. Both these issues must be considered carefully prior to adopting these parameters as part of the soil geochemical survey of North America.     

Oxygen isotopic determinations of sequentially erupted plagioclases in the 1974 magma of Fuego Volcano,Guatemala

Plagioclases in the 1974 high-Al basalt from Fuego Volcano have δO¹⁸ values of +6.0 to +8.5 per mil. Meteoric water cannot have played a significant role in Fuego’s magma. Large, weakly zone clear phenocrysts had δO¹⁸ values in the accepted mantle range, while patchyzoned and oscillatory-zoned plagioclases inferred to have formed later and shallower levels have slightly heavier oxygen isotopic ratios.     

Evolution of tholeiitic diabase sheet systems in the eastern United States: examples from the Culpeper Basin, Virginia-Maryland, and the Gettysburg Basin, Pennsylvania

High-TiO₂, quartz-normative (HTQ) tholeiite sheets of Early Jurassic age have intruded mainly Late Triassic sedimentary rocks in several early Mesozoic basins in the eastern United States. Field observations, petrographic study, geochemical analyses and stable isotope data from three HTQ sheet systems in the Culpeper basin of Virginia and Maryland and the Gettysburg basin of Pennsylvania were used to develop a general model of magmatic differentiation and magmatic-hydrothermal interaction for HTQ sheets. The three sheet systems have remarkably similar major-oxide and trace-element compositions. Cumulus and evolved diabase in comagmatic sheets separated by tens of kilometers are related by igneous differentiation. Differentiated diabase in all three sheets have petrographic and geochemical signatures and fluid inclusions indicating hydrothermal alteration beginning near magmatic temperatures and continuing to relatively low temperatures. Sulfur and oxygen isotope data are consistent with a magmatic origin for the hydrothermal fluid.The three sheet systems examined apparently all had a similar style of crystal-liquid fractionation that requires significant lateral migration of residual magmatic liquid. The proposed magmatic model for HTQ sheets suggests that bronzite-laden magma was intruded in an upper crustal magma chamber, with bronzite phenocrysts collecting in the lower part of the magma chamber near the feeder dike. Early crystallization of augite and Ca-poor pyroxene before significant plagioclase crystallization resulted in density-driven migration of lighter residual magmatic liquids along lateral and vertical pressure gradients towards the upper part of the sheet. The influence of water on the physical properties of the residual liquid, including density, viscosity and liquidus temperature, may have facilitated the lateral movement more than 15 km up dip in the sheets. Exsolution of a Cl- and S-rich metal-bearing aqueous fluid from residual magma resulted in concentration and redistribution of incompatible and aqueoussoluble elements in late-stage differentiated rocks. This proposed hydrothermal mechanism has important economic implications as it exerts a strong control on the final distribution of noble metals in these types of diabase sheets.     

Hydrothermal manganese oxide deposits from Galapagos mounds,DSDP Leg 70, hole 509B and “Alvin” dives 729 and 721

During DSDP Leg 70, a 1.60 m thick manganese oxide layer was sampled in hole 509B. This deposit is formed of alternating layers of hard plates of pure todorokite, about 2 mm thick, and of a more powdery material deeply impregnated with manganese oxide, about 3 mm thick. A SEM study of the plates and the associated powder shows that the powdery material is a transformation of a pre-existing sediment, while the plates are a direct precipitation from a hydrothermal solution.The uranium series disequilibrium method was used to determine the ages of the plates. They are found to be in good chronological sequence and in accordance with the sedimentation rate of the area (4.9 cm/10³ years) which implies that they have been formed at the sediment-seawater interface during a pulsed injection of hydrothermal solution. The powder presents systematically an “older age” which is explained by a slowing down of the injection while the normal sediment settles; the older age is due to the²³⁰Th excess of the sediment.     

Salinity detection and associated behavior in the dungeness crab,Cancer magister

Dungeness crabs, Cancer magister, showed the same antennular flicking response to brief (<2 min) salinity fluctuations as they have previously shown in detecting chemical food cues during other studies. The threshold concentrations at which 50% of the crabs detected the salinity changes were 29.9‰ and 32.7‰ or 96% and 105% of ambient seawater (31.0‰). At the maximum salinity changes used, other behaviors accompanied the flicking response. In a second experiment where salinity rose or fell continuously, two previously undescribed behaviors, pulsing and closure, occurred. In pulsing, crabs showed a rapid coordinated opening and closing of the outer maxillipeds with rapid beating of the maxillipedal flagellae. In closure, crabs stopped all overt activity, retracted their appendages and tightly closed the buccal cavity with the outer maxillipeds. Under increasing salinity crabs exhibited pulsing at 34.9‰ or 113% of ambient seawater and closure at 36.2‰ or 117% of ambient. Under decreasing salinity crabs showed pulsing at 23.2‰ or 75% of ambient seawater and closure at 15.5‰ or 50% of ambient.