Authigenic carbonates from methane seeps of the Congo deep-sea fan

Submersible investigations with the ROV Victor 6000 of some pockmark structures on the seafloor of the Congo deep-sea fan have shown that they are active venting sites of methane-rich fluids, associated with abundant fauna and carbonate crusts. Moreover, methane hydrates have been observed both outcropping and deep in the sediments in the centre of the “Regab” giant pockmark. Authigenic carbonates, mostly calcite sometimes mixed with aragonite, are cementing the sedimentary matrix components and fauna; diatoms are abundant but only as moulds, indicating that biogenic silica dissolution occurred in situ synchronous with carbonate precipitation. The occurrence of diagenetic barite and pyrite in some carbonate crusts demonstrates that they can be formed either within the sulphate/methane transition zone or deeper in sulphate-depleted sediments. The oxygen isotopic compositions of the diagenetic carbonates (3.17–6.01‰ V-PDB) indicate that precipitation occurred with bottom seawater mixed with a variable contribution of water from gas hydrate decomposition. The very low carbon isotopic compositions of the diagenetic carbonates (−57.1 to −27.75‰ V-PDB) demonstrate that carbon derives mostly from the microbial oxidation of methane.     

Particulate content of savanna fire emissions

As part of the FOS-DECAFE experiment at Lamto (Ivory Coast) in January 1991, various aerosol samples were collected at ground level near prescribed fires or under local background conditions, to characterize the emissions of particulate matter from the burning of savanna vegetation. This paper deals with total aerosol (TPM) and carbon measurements. Detailed trace element and polycyclic hydrocarbon data are discussed in other papers presented in this issue.Near the fire plumes, the aerosols from biomass burning are primarily of a carbonaceous nature (C%70% of the aerosol mass) and consist predominantly of submicron particles (more than 90% in mass.) They are characterized by their organic nature (black to total carbon ratio Cb/Ct in the range 3–20%) and their high potassium content (K/Cb0.6). These aerosols undergo aging during their first minutes in the atmosphere causing slight alterations in their size distribution and chemical composition. However, they remain enriched in potassium (K/Cb=0.21) and pyrene, a polycyclic aromatic hydrocarbon, such that both of these species may be used as tracers of savanna burning aerosols. We show that during this period of the year, the background atmosphere experiences severe pollution from both terrigenous sources and regional biomass burning (44% of the aerosol). Daynight variations of the background carbon concentrations suggest that fire ignition and spreading occur primarily during the day. Simultaneous TPM and CO₂ real-time measurements point to a temporal and spatial heterogeneity of the burning so that the ratio of the above background concentrations (TPM/CO₂) varies from 2 to 400 g/kg C. Smoldering processes are intense sources of particles but particulate emissions may also be important during the rapidly spreading heading fires in connection with the generation of heavy brown smoke. We propose emission factor values (EF) for aerosols from the savanna biomass burning aerosols: EF (TPM)=11.4±4.6 and 69±25 g/kg C_{dry plant} and EF(Ct)=7.4±3.4 and 56±16 g C/kg C_{dry plant} for flaming and smoldering processes respectively. In these estimates, the range of uncertainty is mostly due to the intra-fire variability. These values are significantly lower than those reported in the literature for the combustion of other types of vegetation. But due to the large amounts of vegetation biomass being burnt in African savannas, the annual flux of particulate carbon into the atmosphere is estimated to be of the order of 8 Tg C, which rivals particulate carbon emissions from anthropogenic activities in temperate regions.     

Geochronology and geochemistry of eclogites from the Mariánské Lázně Complex,Czech Republic: Implications for Variscan orogenesis

The Mariánské Lázn complex (MLC) is located in the Bohemian Massif along the north-western margin of the Teplá-Barrandian microplate and consists of metagabbro, amphibolite and eclogite, with subordinate amounts of serpentinite, felsic gneiss and calcsilicate rocks. The MLC is interpreted as a metaophiolite complex that marks the suture zone between the Saxothuringian rocks to the north-west and the Teplá-Barrandian microplate to the south-east. Sm-Nd geochronology of garnet-omphacite pairs from two eclogite samples yields ages of 377±7, and 367±4 Ma. Samples of eclogite and amphibolite do not define a whole rock Sm-Nd isochron, even though there is a large range in Sm/Nd ratio, implying that the suite of samples may not be cogenetic. Eclogites do not have correlated _Nd values and initial ⁸⁷Sr/⁸⁶Sr ratios. Five of the eight eclogite samples have high _Nd values (+10.2 to +7.1) consistent with derivation from a MORB-like source, but variable ⁸⁷Sr/⁸⁶Sr ratios (0.7033 to 0.7059) which probably reflect hydrothermal seawater alteration. Three other eclogite samples have lower _Nd values (+ 5.4 to –0.8) and widely variable ⁸⁷Sr/⁸⁶Sr ratios (0.7033 to 0.7096). Such low _Nd values are inconsistent with derivation from a MORB, source and may reflect a subduction or oceanic island basalt component in their source. The MLC is an important petrotectonic element in the Bohemian Massif, providing evidence for Cambro-Ordovician formation of oceanic crust and interaction with seawater, Late Devonian (Frasnian-Famennian) high- and medium-pressure metamorphism related to closure of a Saxothuringian ocean basin, Early Carboniferous (Viséan) thrusting of the Teplá terrane over Saxothuringian rocks and Late Viséan extension.     

Lake Sediment Core Records of Sulphur Accumulation and Sulphur Isotopic Composition in Central Ontario, Canada Lakes

Stable isotopic compositions and concentrations of total sedimentary sulphur (S) were determined in cores from 6 lakes in the acid-sensitive Muskoka-Haliburton region of south-central Ontario. The isotopic composition of S in deep sediment (> ~ 20 cm) was approximately constant in all lakes, and indicated a pre-industrial δ ³⁴S value between +4.0 and +5.3‰, which is similar to current bulk deposition. Similarly, total S concentrations in deep sediment were relatively low (1.9–5 mg S g⁻¹ dwt) and approximately constant with depth within cores. All lakes exhibited up-core increases in total S and decreases in δ ³⁴S at a depth corresponding to the beginning of industrialization in the Great Lakes region ( ~ 1900), resulting in a generally reciprocal depth pattern between total S concentration and δ ³⁴S ratios. While initial shifts in total S and δ ³⁴S were likely due to enhanced SO₄ reduction of newly available anthropogenic SO₄, both the magnitude and pattern of up-core S enrichment and shifts in δ ³⁴S varied greatly among lakes, and did not match changes in S deposition post 1900. Differences between lakes in total S and δ ³⁴S were not related to any single hydrologic (e.g., residence time) or physical (e.g., catchment-area-to-lake area ratio) lake characteristic. This work indicates that sediment cores do not provide consistent records of changes in post-industrial S deposition in this region, likely due to redox-related mobility of S in upper sediment.     

3D numerical modelling of fluid flow in the Val-d’Or orogenic gold district: major crustal shear zones drain fluids from overpressured vein fields

Fluid flow patterns have been determined using oxygen isotope isopleths in the Val-d’Or orogenic gold district. 3D numerical modelling of fluid flow and oxygen isotope exchange in the vein field shows that the fluid flow patterns can be reproduced if the lower boundary of the model is permeable, which represents middle or lower crustal rocks that are infiltrated by a metamorphic fluid generated at deeper levels. This boundary condition implies that the major crustal faults so conspicuous in vein fields do not act as the only major channel for upward fluid flow. The upper model boundary is impermeable except along the trace of major crustal faults where fluids are allowed to drain out of the vein field. This upper impermeable boundary condition represents a low-permeability layer in the crust that separates the overpressured fluid from the overlying hydrostatic fluid pressure regime. We propose that the role of major crustal faults in overpressured vein fields, independent of tectonic setting, is to drain hydrothermal fluids out of the vein field along a breach across an impermeable layer higher in the crust and above the vein field. This breach is crucial to allow flow out of the vein field and accumulation of metals in the fractures, and this breach has major implications for exploration for mineral resources. We propose that tectonic events that cause episodic metamorphic dehydration create a short-lived pulse of metamorphic fluid to rise along zones of transient permeability. This results in a fluid wave that propagates upward carrying metals to the mineralized area. Earthquakes along crustal shear zones cause dilation near jogs that draw fluids and deposit metals in an interconnected network of subsidiary shear zones. Fluid flow is arrested by an impermeable barrier separating the hydrostatic and lithostatic fluid pressure regimes. Fluids flow through the evolving and interconnected network of shear zones and by advection through the rock matrix. Episodic breaches in the impermeable barrier along the crustal shear zones allow fluid flow out of the vein field.     

Celestite formation, bacterial sulphate reduction and carbonate cementation of Eocene reefs and basinal sediments (Igualada, NE Spain)

Petrographic and geochemical studies of an Upper Eocene reef and associated basinal sediments from the mixed carbonate–siliciclastic fill of the south‐eastern Pyrenean foreland basin near Igualada (NE Spain) provide new insights into the evolution of subsurface hydrology during the restriction of a marine basin. The reef deposits are located on delta‐lobe sandstones and prodelta marls, which are overlain by hypersaline carbonates and Upper Eocene evaporites. Authigenic celestite (SrSO₄) is an important component in the observed diagenetic sequences. Celestite is a significant palaeohydrological indicator because its low solubility constrains transportation of Sr²⁺ and SO₄^2? in the same diagenetic fluid. Stable isotopic analyses of carbonates in the reef indicate that meteoric recharge was responsible for aragonite stabilization and calcite cementation. Sulphur and oxygen isotope geochemistry of the celestite demonstrates that it formed from residual sulphate after bacterial sulphate reduction, but also requires that there was a prior episode of sulphate recycling. Meteoric water reaching the reef and basinal areas was most probably charged with SO₄^2? from the dissolution of younger Upper Eocene marine evaporites. This sulphate, combined with organic matter present in the sediments, fuelled bacterial sulphate reduction in the meteoric palaeoaquifer. Strontium for celestite precipitation was partly derived in situ from dissolution of aragonite corals in the reef and basinal counterparts. However, ⁸⁷Sr/⁸⁶Sr data also suggest that Sr²⁺ was partly derived from dissolution of overlying evaporites. Mixing of these two fluids promoted celestite formation. The carbonate stable isotopic data suggest that the local meteoric water was enriched in ¹⁸O compared with that responsible for stabilization of other reefs along the basin margin. Furthermore, meteoric recharge at Igualada post‐dated evaporite deposition in the basin, whereas other parts of the same reef complex were stabilized before evaporite formation. This discrepancy resulted from the spatial distribution of continental siliciclastic units that acted as groundwater conduits.     

Toxic Cyanobacteria in Greek Freshwaters, 1987—2000: Occurrence,Toxicity, and Impacts in the Mediterranean Region

In a survey in Greece from 1987 to 2000 hepatotoxic cyanobacterial blooms were observed in 9 out of 33 freshwaters. Microcystins (MCYSTs) were detected by HPLC in 7 of these lakes, and the total MCYST concentration per scum dry weight ranged from 50.3 to 1638 ± 464 μg g^—1. Cyanobacterial genera (Microcystis, Anabaena, Anabaenopsis, Aphanizomenon, Cylindrospermopsis) with known toxin producing taxa were present in 31 freshwaters. From our data and a review of the literature, it would appear that Mediterranean countries are more likely 1) to have toxic cyanobacterial blooms consisting of Microcystis spp. and 2) to have higher intracellular MCYST concentrations. A case study in Lake Kastoria is used to highlight seasonal patterns of cyanobacterial and MCYST‐LR occurrence and to assess cyanotoxin risk. Cyanobacterial biovolume was high (> 11 μL L^—1) throughout the year and was in excess of Guidance Level 2 (10 μL L^—1) proposed by WHO for recreational waters and Alert Level 2 for drinking water. Further, surface water samples from April to November exceeded Guidance Level 3, with the potential for acute cyanobacterial poisoning. Intracellular MCYST‐LR concentrations (max 3186 μg L^—1) exceeded the WHO guideline for drinking water (1 μg L^—1) from September to November with a high risk of adverse health effects. Preliminary evidence indicates that in 3 lakes microcystins are accumulated in some aquatic organisms. Generally, a high risk level can be deduced from the data for the Mediterranean region.     

Kimberlite metasomatism at Murowa and Sese pipes, Zimbabwe

Metasomatism accompanying kimberlite emplacement is a worldwide phenomenon, although infrequently described or recognised. At the Cambrian-aged Murowa and Sese kimberlite clusters located within the Archean Zimbabwe Craton just north of the boundary with the Limpopo Mobile Zone in southern central Zimbabwe, the metasomatism is intense and well exposed and the processes can be readily studied. Dykes, sills and the root zones of pipes are exposed at the current erosion level. Kimberlite lithologies present are hypabyssal macrocrystic kimberlite (“HMK”), HMK breccia, and tuffisitic kimberlite breccia (“TKB”) including minor lithic tuffisitic kimberlite breccia (“LTKB”). Country rocks are 2.6 Ga Chibi and Zimbabwe granite batholiths emplaced into 2.6–2.9 Ga or earlier Archean tonalitic gneiss and greenstones. During initial metasomatism, the granites become spotted with green chlorite, needles of alkaline amphiboles (winchite, riebeckite, arfvedsonite) and pyroxenes (aegirine–augite) with minor carbonate and felts of talc. Oligoclase feldspar becomes converted to albite, extensively altered, dusted and reddened with hematite, whereas K-feldspar remains unaffected. The granites become converted to syenite through removal of quartz. More intense metasomatism at Murowa and Sese results in veins of green metasomatite which cut and disrupt the granite. Progressive disruption entrains granite blocks, breaking down the granite still further, spalling off needle-like granite slivers, and so giving rise to LTKB. This process of disruption and entrainment appears to be the manner of initial development of the pipe structure. The chemistry of the metasomatite is intermediate between granite and kimberlite. Compared to granite country rock it has markedly higher Mg, Cr, Ni, CO₂ and H₂O+, higher Ca, Mn, Nb, Sr, P, Fe³⁺/Fe²⁺ ratio, U, Co, and Cu, approximately equal TiO₂, K₂O, Na₂O, La, Ta, Rb, Zr, Zn and resultant lower SiO₂, Al₂O₃, Ga and Y. The metasomatite Na₂O/K₂O ratio is slightly higher than that of the granite. The metasomatic process is broadly analogous to fenitisation of granitic wall rock accompanying carbonatite complex emplacement. The metasomatism at Murowa and Sese was caused by fluids from the rising but confined proto-kimberlite melt penetrating into cracks and matrix of granite country rock and reacting with it. These fluids were CO₂-rich, hydrous, oxidising, enhanced in ultramafic elements and carried low levels of Na.     

Modeling Spatially and Temporally Complex Land‐Cover Change: The Case of Western Honduras*

This article presents an econometric analysis of land‐cover change in western Honduras. Ground‐truthed satellite image analysis indicates that between 1987 and 1996 net reforestation occurred in the 1,015‐km² study region. While some reforestation can be attributed to a 1987 ban on logging, the area of reforestation greatly exceeds that of previously clear‐cut areas. Further, new area was also deforested between 1987 and 1996. Thus, the observed land‐cover changes represent a complex mosaic of changing land‐use patterns across time and space. The analysis contributes to the literature on land‐cover change modeling in that: (1) it compares two econometric approaches to capture complex and often bidirectional changes in land cover from 1987 to 1996 as a function of agricultural suitability and transportation costs, and (2) it addresses techniques to identify and correct for spatial autocorrelation in a categorical regression framework.