Natural attenuation and bioremediation of Prestige fuel oil along the Atlantic coast of Galicia (Spain)

Heavy fuel oil spilled from the oil tanker Prestige in November 2002 affected hundreds of km of Spanish shoreline. We carried out a two year study at two highly contaminated sites in order to monitor natural attenuation of the residues coating shore rocks and to test the effectiveness of bioremediation with an oleophilic fertilizer (S200). The methodology included an innovative approach for oil load calculation (based on image analysis techniques), the analysis of the fate of hydrocarbons by means of chemical biomarkers and different microbiological techniques for isolating and examining hydrocarbon degraders.Considerable hydrocarbon depletion from shorelines (≈100% for light-medium linear alkanes and ≈35% for aromatics such as pyrene) was observed within the first months after the spill. However, this natural attenuation effect dramatically slowed down in the following year, although partial enhancement (especially for the aromatic fraction) was attained as a result of the application of S200 to stimulate indigenous microorganisms. In addition, one of the main outcomes of this work concerns the remarkable hydrocarbon depletion achieved at points where fresh water flowed through the shore rocks. The study of samples collected where this natural attenuation phenomenon took place made it possible to isolate heterotrophic bacteria and fungi that are likely to cooperate with cyanobacteria in hydrocarbon biodegradation. The overall results strongly advocate the implementation of new bioremediation approaches, including alternatives such as the use of natural fresh water to irrigate polluted areas.     

The petroleum generation potential and effective oil window of humic coals related to coal composition and age

A worldwide data set of more than 500 humic coals from the major coal-forming geological periods has been used to analyse the evolution in the remaining (Hydrogen Index, HI) and total (Quality Index, QI) generation potentials with increasing thermal maturity and the ‘effective oil window’ (‘oil expulsion window’). All samples describe HI and QI bands that are broad at low maturities and that gradually narrow with increasing maturity. The oil generation potential is completely exhausted at a vitrinite reflectance of 2.0–2.2%R_o or T_max of 500–510 °C. The initial large variation in the generation potential is related to the original depositional conditions, particularly the degree of marine influence and the formation of hydrogen-enriched vitrinite, as suggested by increased sulphur and hydrogen contents. During initial thermal maturation the HI increases to a maximum value, HI_max. Similarly, QI increases to a maximum value, QI_max. This increase in HI and QI is related to the formation of an additional generation potential in the coal structure. The decline in QI with further maturation is indicating onset of initial oil expulsion, which precedes efficient expulsion. Liquid petroleum generation from humic coals is thus a complex, three-phase process: (i) onset of petroleum generation, (ii) petroleum build-up in the coal, and (iii) initial oil expulsion followed by efficient oil expulsion (corresponding to the effective oil window). Efficient oil expulsion is indicated by a decline in the Bitumen Index (BI) when plotted against vitrinite reflectance or T_max. This means that in humic coals the vitrinite reflectance or T_max values at which onset of petroleum generation occurs cannot be used to establish the start of the effective oil window. The start of the effective oil window occurs within the vitrinite reflectance range 0.85–1.05%R_o or T_max range 440–455 °C and the oil window extends to 1.5–2.0%R_o or 470–510 °C. For general use, an effective oil window is proposed to occur from 0.85 to 1.7%R_o or from 440 to 490 °C. Specific ranges for HI_max and the effective oil window can be defined for Cenozoic, Jurassic, Permian, and Carboniferous coals. Cenozoic coals reach the highest HI_max values (220–370 mg HC/g TOC), and for the most oil-prone Cenozoic coals the effective oil window may possibly range from 0.65 to 2.0%R_o or 430 to 510 °C. In contrast, the most oil-prone Jurassic, Permian and Carboniferous coals reach the expulsion threshold at a vitrinite reflectance of 0.85–0.9%R_o or T_max of 440–445 °C.     

Visualization experiments of iron precipitates: Application for in-situ arsenic remediation

Laboratory experiments were carried out to acquire more insight and understanding of the phenomena associated with the in-situ arsenic remediation. Visualization techniques are the most informative for the detection of Fe(II) while flowing in soils. Green Rust (GR) was considered as representative of in-situ iron precipitates. In a visualization flat cell, the change in color of GR to orange, due to oxidation, was monitored by a digital camera and the images were analyzed giving the spatial and temporal distribution of Fe(II). Moreover, both oxygen and pH changes in time were recorded in two sections along the flow direction in the cell. The measured and calculated concentration profiles were compared and the actual reaction rates were predicted. The reaction rate constants measured in this study, under flowing conditions, are in a good agreement with the values obtained from batch experiments reported in the literature.     

Hydrochemical and isotopical tracers in the lacustrine aquifer of the Cerro Prieto area, Baja California, México

A series of patterns in the chemical and isotopic composition of the groundwater of the Cerro Prieto area have been recognized. These patterns were used to define four hydrochemical and isotopical zones in the area. One of these areas located at the east side was found to be the source of recharge, while another in the central part is where an older aquifer exist in lacustrine deposits. The low permeability of the area causes the aquifer to act as an aquitard, which at least is partly surrounded by an interface zone where mixing of waters occurs. Tritium and radiocarbon method revealed that the aquitard is an isolate system whose residence time is of 32 ka.     

Palaeozoic and Mesozoic tectonic evolution and palaeogeography of East Asian crustal fragments: The Korean Peninsula in context

East and Southeast Asia comprises a complex assembly of allochthonous continental lithospheric crustal fragments (terranes) together with volcanic arcs, and other terranes of oceanic and accretionary complex origins located at the zone of convergence between the Eurasian, Indo-Australian and Pacific Plates. The former wide separation of Asian terranes is indicated by contrasting faunas and floras developed on adjacent terranes due to their prior geographic separation, different palaeoclimates, and biogeographic isolation. The boundaries between Asian terranes are marked by major geological discontinuities (suture zones) that represent former ocean basins that once separated them. In some cases, the ocean basins have been completely destroyed, and terrane boundaries are marked by major fault zones. In other cases, remnants of the ocean basins and of subduction/accretion complexes remain and provide valuable information on the tectonic history of the terranes, the oceans that once separated them, and timings of amalgamation and accretion. The various allochthonous crustal fragments of East Asia have been brought into close juxtaposition by geological convergent plate tectonic processes. The Gondwana-derived East Asia crustal fragments successively rifted and separated from the margin of eastern Gondwana as three elongate continental slivers in the Devonian, Early Permian and Late Triassic–Late Jurassic. As these three continental slivers separated from Gondwana, three successive ocean basins, the Palaeo-Tethys,. Meso-Tethys and Ceno-Tethys, opened between these and Gondwana. Asian terranes progressively sutured to one another during the Palaeozoic to Cenozoic. South China and Indochina probably amalgamated in the Early Carboniferous but alternative scenarios with collision in the Permo–Triassic have been suggested. The Tarim terrane accreted to Eurasia in the Early Permian. The Sibumasu and Qiangtang terranes collided and sutured with Simao/Indochina/East Malaya in the Early–Middle Triassic and the West Sumatra terrane was transported westwards to a position outboard of Sibumasu during this collisional process. The Permo–Triassic also saw the progressive collision between South and North China (with possible extension of this collision being recognised in the Korean Peninsula) culminating in the Late Triassic. North China did not finally weld to Asia until the Late Jurassic. The Lhasa and West Burma terranes accreted to Eurasia in the Late Jurassic–Early Cretaceous and proto East and Southeast Asia had formed. Palaeogeographic reconstructions illustrating the evolution and assembly of Asian crustal fragments during the Phanerozoic are presented.     

Neoproterozoic alkaline magmatism at Sivamalai, southern India

The Sivamalai alkaline complex lies at the southern margin of the Cauvery Shear System that separates the Archaean and Proterozoic domains of the Southern Granulite Terrain in India. U–Pb TIMS dating of zircon from a pegmatitic syenite sample in the complex yields a concordant age of 590.2 ± 1.3 (2σ) Ma which is interpreted to date the intrusion of the alkaline rocks. A lower concordia intercept at 168 ± 210 Ma defined by two grains with high common lead may indicate post-magmatic disturbances due to recrystallisation which is also evident in the CL images of the zircons. EPMA dating of monazite from a post-kinematic pegmatite which intrudes the crystalline basement hosting the alkaline rocks yields an age of 478 ± 29 (2σ) Ma and provides a lower bracket for the main phase of tectonism in this part of the Southern Granulite Terrain. The Pan-African high-grade metamorphism and ductile deformation has thus most likely affected the alkaline rocks. This is supported by the presence of a metamorphic foliation and extensive recrystallisation textures seen in the rocks. The major and trace element concentrations measured on selected samples reveals the presence of both enriched and depleted rock types. The enriched group includes ferrosyenite and nepheline syenite while the depleted group has only nepheline syenites. The trace element depletion of some nepheline syenites is interpreted to be a result of fractional crystallization involving the removal of accessory phases like zircon, titanite, apatite and allanite.     

The timing of ultrahigh-temperature metamorphism in Southern India: U–Th–Pb electron microprobe ages from zircon and monazite in sapphirine-bearing granulites

We report here U–Pb electron microprobe ages from zircon and monazite associated with corundum- and sapphirine-bearing granulite facies rocks of Lachmanapatti, Sengal, Sakkarakkottai and Mettanganam in the Palghat–Cauvery shear zone system and Ganguvarpatti in the northern Madurai Block of southern India. Mineral assemblages and petrologic characteristics of granulite facies assemblages in all these localities indicate extreme crustal metamorphism under ultrahigh-temperature (UHT) conditions. Zircon cores from Lachmanapatti range from 3200 to 2300 Ma with a peak at 2420 Ma, while those from Mettanganam show 2300 Ma peak. Younger zircons with peak ages of 2100 and 830 Ma are displayed by the UHT granulites of Sengal and Ganguvarpatti, although detrital grains with 2000 Ma ages are also present. The Late Archaean-aged cores are mantled by variable rims of Palaeo- to Mesoproterozoic ages in most cases. Zircon cores from Ganguvarpatti range from 2279 to 749 Ma and are interpreted to reflect multiple age sources. The oldest cores are surrounded by Palaeoproterozoic and Mesoproterozoic rims, and finally mantled by Neoproterozoic overgrowths. In contrast, monazites from these localities define peak ages of between 550 and 520 Ma, with an exception of a peak at 590 Ma for the Lachmanapatti rocks. The outermost rims of monazite grains show spot ages in the range of 510–450 Ma.While the zircon populations in these rocks suggest multiple sources of Archaean and Palaeoproterozoic age, the monazite data are interpreted to date the timing of ultrahigh-temperature metamorphism in southern India as latest Neoproterozoic to Cambrian in both the Palghat–Cauvery shear zone system and the northern Madurai Block. The data illustrate the extent of Neoproterozoic/Cambrian metamorphism as India joined the Gondwana amalgam at the dawn of the Cambrian.