Mário A. Gonçalves

Characterization of Geochemical Distributions Using Multifractal Models

The use of multifractals in the applied sciences has proven useful in the characterization and modeling of complex phenomena. Multifractal theory has also been recently applied to the study and characterization of geochemical distributions, and its relation to spatial statistics clearly stated. The present paper proposes a two-dimensional multifractal model based on a trinomial multiplicative cascade as a proxy to some geochemical distribution. The equations for the generalized dimensions, mass exponent, coarse Lipschitz–Hölder exponent, and multifractal spectrum are derived. This model was tested with an example data set used for geochemical exploration of gold deposits in Northwest Portugal. The element used was arsenic because a large number of sample assays were below detection limit for gold. Arsenic, however, has a positive correlation with gold, and the two generations of arsenopyrite identified in the gold quartz veins are consistent with different mineralizing events, which gave rise to different gold grades. Performing the multifractal analysis has shown problems arising in the subdivision of the area with boxes of constant side length and in the uncertainty the edge effects produce in the experimental estimation of the mass exponent. However, it was possible to closely fit a multifractal spectrum to the data with enrichment factors in the range 2.4–2.6 and constant K1 = 1.3. Such parameters may give some information on the magnitude of the concentration efficiency and heterogeneity of the distribution of arsenic in the mineralized structures. In a simple test with estimated points using ordinary lognormal kriging, the fitted multifractal model showed the magnitude of smoothing in estimated data. Therefore, it is concluded that multifractal models may be useful in the stochastic simulation of geochemical distributions.

Geodynamic evolution of the South Variscan Iberian Suture as recorded by mineral transformations

New structural, petrographic, mineralogical and geochemical data from the Beja-Acebuches Ophiolite Complex (BAOC) are presented, and reviewed together with data published elsewhere. The new data obtained shed light on questions such as: 1) the relative importance of the obduction event; 2) its geological record in the deep levels of BAOC; 3) the nature and intensity of the Variscan metamorphism and deformation during subsequent continental (arc) collision; 4) the age relationships between BAOC and the Beja Igneous Complex; and 5) by means of numerical modelling, the thermal metamorphism of the Ossa-Morena autochthonous terranes induced by the ophiolite obduction. The emerging picture is that of a fairly simple overall geological evolution for BAOC, seamlessly integrated within the evolution of the southern branch of the Iberian Variscides. Obduction of BAOC is a relatively minor early event in the general NE–SW convergence that gave rise to the orogen as seen regionally and is recorded by an anisotropic, high-temperature, metamorphic fabric at the gabbro levels and by subtle features of the chemical composition of primary minerals at the underlying peridotite level; it caused chilling of the obducted ophiolitic slab and no significant metamorphism on the autochtonous rocks of the Ossa-Morena Zone. BAOC underwent most of its deformation and (amphibolite facies) metamorphism during a later collisional event, that took place as the most primitive rocks of the Beja Igneous complex were being intruded, and whose waning stages are responsible for extensive serpentinisation of peridotites and for important aquocarbonic fluid discharges along the semibrittle–brittle shear zones meanwhile developed.

Base-Metals and Organic Content in Stream Sediments in the Vicinity of a Landfill

Landfill facilities are essential to modern societies as repositories for municipal solid wastes (MSW). However, irrespective of the regulations necessary to their construction there is always a certain risk of environmental impact. For this reason monitoring should be essential to their operation. In the present work, the environmental impact of such a landfill is studied, whose operation has been running for only 3 a. The approach used was to sample a series of stream sediments along two contaminated run-off water paths. These sediments were chemically analysed, and their mineralogy was also studied. Their most important feature is the existence of some contamination in Cu, Zn, and Pb above background levels in the first 200 m in the direction of water flow, whose concentration gradually decreases until background levels are reached. Although some artificial alloys and sulphides (sphalerite) were shown to be present, they could not account for the analysed concentrations, and cannot explain the negative gradient concentration by themselves. Sequential metal extraction methods together with solid phase extraction for the isolation of organic content, showed that metals adsorbed on the sediments are mostly associated with organic compounds. Although monocarboxylic organic acids were among the most important organic compounds present both in the contaminated waters and sediments, there is no clear correlation between these and base metal concentrations in the sediments. A stronger correlation exists if the total concentration of organic compounds is considered, which suggests that base metals can be easily partitioned into the sediments by the rapid adsorption onto their surfaces by organic compounds near the pollution source. The organic content identified decreases down stream as do base metal concentrations. This can be explained by the formation of complexes with organic acids as is extensively reported in natural and laboratory systems. The overall results point to the limited capacity for pollutant retention in this system, and suggest that in case of serious failure the contaminated plumes are likely to disperse rapidly into the environment.

Nature and mechanism of ilmenite alteration: a Mössbauer and X-ray diffraction study of oxidized ilmenite from the Beja-Acebuches Ophiolite Complex(SE Portugal)

Abstract Ilmenites from the least-altered rocks of the Beja-Acebuches Ophiolite Complex (SE Portugal), with low Ti values and excess Fe, despite rare optical evidence of hematite exsolution, were studied by 57Fe Mössbauer spectroscopy and X-ray diffraction. According to single-crystal XRD the sequence of alternate layers characteristic of the ideal ilmenite structure is preserved, the excess Fe being accommodated in the Ti layers. No superparamagnetic oxides were detected by 57Fe Mössbauer spectroscopy. The typical spectra of bulk αFe2O3 and of Fe3+-containing ilmenite, in the paramagnetic state above 49 K and magnetically ordered at 6 K, are observed. The average degree of oxidation of the ilmenites, estimated from the chemical analysis assuming ideally stoichiometric full cation site occupancies, is also confirmed by 57Fe Mössbauer data. Since our crystal chemistry study gave no evidence of crypto-exsolution textures within the ilmenite with the observed compositions, fast cooling from magmatic temperatures and decomposition of ilmenite in supergene conditions is suggested.

Raman spectroscopic characterization of a synthetic, non-stoichiometric Cu–Ba uranyl phosphate

Crystals of phases belonging to the autunite group (general formula X(2+)(UO2)2(X(5+)O4)2·nH2O), specifically the uranyl phosphates (X(5+)=P) metauranocircite (X(2+)=Ba(2+)), metatorbernite (X(2+)=Cu(2+)) and a barian metatorbenite phase (X(2+)=Cu(2+)/Ba(2+)), have been synthesized in a silica gel medium and characterized by Raman spectroscopy. The Raman spectra showed bands in the range 750-1100 cm(-1), which were attributed to the ν1 and ν3 (PO(4))(3-) and (UO(2))(2+) stretching vibrations. By using the wavenumbers of the most intense and well defined ν1 (UO(2))(2+) vibration, the U-O bonds lengths were calculated for the three uranyl phosphate minerals. The results are in good agreement with previous single crystal structure analysis data. Bands in the spectra from 350 to 700 cm(-1) were attributed to the (PO(4))(3-) bending modes. Moreover, in the range 70-350 cm(-1), two groups of bands could be defined. The first group, with vibrations at lower wavenumbers, was attributed to the lattice modes and the second group, from 150 to 350 cm(-1), was assigned to the ν2 (UO(2))(2+) bending mode. Finally, in the case of the barian metatorbernite, bands in the range 1500-3800 cm(-1) were assigned to the OH stretching and the ν2 bending vibrations of water molecules. In this phase, all the vibrations show bandshifts when compared to the vibrations in metatorbernite. These bandshifts can be related to transitional Cu-O and Ba-O bond lengths.

In Situ Nanoscale Observations of Metatorbernite Surfaces Interacted with Aqueous Solutions

Metatorbernite (Cu(UO(2))(2)(PO(4))(2)·8H(2)O) has been identified in contaminated sediments as a phase controlling the fate of U. Here, we applied atomic force microscopy (AFM) to observe in situ the interaction between metatorbernite cleavage surfaces and flowing aqueous solutions (residence time = 1 min) with different pHs. In contact with deionized water the features of (001) surfaces barely modify. However, changes are remarkable both under acidic and basic conditions. In acidic solutions (pH = 2.5) metatorbernite surface develops a rough altered layer and large pits nucleate on it. The altered layer shows a low adhesion and is removed by the AFM tip during the scanning. The large pits spread rapidly, at few tens of nm/s, indicating a collapse of the structure. The combination of dissolution and the presence of defects in the metatorbernite structure can explain both the collapse process and the alteration of the surfaces under acidic conditions. Other mechanisms such as ion exchange reactions remain speculative. In NaOH solutions (pH = 11.5) metatorbernite dissolves by formation of etch pits bounded by steps parallel to [100], the direction of the most straight periodic bond chains (PBCs) in metatorbernite structure. These steps retreat at ∼0.15 nm/s. Under these conditions dissolution is promoted by the formation of stable uranyl carbonate complexes in solution.

Initial stages of pollutants dispersion around municipal waste disposal facilities: a case study in Northern Portugal

The combined use of several geological, geochemical and geophysical observations during six years enabled the detection of a very faint halo of chemical contamination induced by the operation of a young waste disposal facility in Northern Portugal. The halo does not classify as pollution by any standards, but is observed to be intensifying and thus signals a potential hazardous situation in future years. The approach used shows that a comprehensive and diverse monitoring programme, although relatively inexpensive and easy to carry out, may detect concealed leaks long before any environmental concern is justified, and thus may help avert future complex remediation needs caused by the uncontrolled growth of undetected underground pollution plumes.

Copper, Zn and Pb soil geochemistry data from the NE domain of the Iberian Pyrite Belt in Portugal: implications for mineral exploration

The area-concentration multifractal modelling of a soil geochemical survey performed in the Alfarrobeira–Chança region (covering the Pulo do Lobo Terrane, PLT, and the Iberian Pyrite Belt, IPB) shows that the upper limit of Cu, Zn and Pb background concentrations in soils over PLT metasediments are c. 20, 55 and 20–30 ppm, respectively. In soils derived from the Volcano-Sedimentary Complex of IPB, the Cu, Zn and Pb regional threshold values are within the 25–45, 40–60 and 20–90 ppm intervals, respectively. The lower limit of Cu, Zn and Pb soil anomalies overlying metasediments are within the 30–50, 90–115 and 45–60 ppm intervals, respectively; over soils with abundant volcanic-derived components those lower limits are scattered in the 30–70, 70–90 and 33–100 ppm intervals. Proximity to mineralized rocks is indicated by Cu, Pb and Zn soil contents above c. 100, 120–150 and 250 ppm, respectively. Most of the anomalies display strong anisotropy. Separation of Cu, Zn and Pb soil anomalies reflects mostly the existence of distinct metal sources related to original compositional differences or to chemical changes developed during Variscan times. Metavolcanics represent the prevailing sources of Cu and, to a lesser extent, Pb; the prevalent sources of Zn are metasediments of the Phyllite-Quartzite (IPB) and Chança (PLT) Groups.

Geochemistry of stream sediments southwards of the SW Variscan suture in Portugal (Guadiana and Chança river basins): insights into element anomalies of variable origin and intensity

Abstract Stream sediment samples were collected in the Trindade–Chança region at 1034 sites for mineral exploration purposes during 1996–97. Concentrations of Cu, Zn, Pb, Co, Cr and Ni are high enough in most sample sites to allow data assessment by multi-element anomaly definition and threshold computation using the area concentration multifractal model technique. The regional threshold values are 20, 45, 30 and 15 ppm for Cu, Zn, Pb and Co respectively. Anomalies for Cu, Zn, Pb, Co, Cr and Ni are delimited by first order local threshold values at 40, 94, 70, 21, 37 and 42 ppm. The main anomalies are clustered to the east-southeast of the surveyed region and reflect mixed contributions from a variety of sources, namely different volcanic units with local contributions from pelite rocks, contamination from old (abandoned) mining activities and hydrothermal mineralisation controlled by different fault zones.

57Fe Mössbauer spectroscopy study of the correlation between the Fe3+ content and the magnetic properties of natural Cr-spinels

Both the Fe oxidation degree and the magnetic properties determined by 57 Fe Mossbauer spectroscopy were used to characterize the Cr-spinels from the Beja-Acebuches Ophiolite Complex (SE Portugal). Two different types of Cr-spinel were observed. The first one has an average Fe 3+ /(Fe total) ≈ 25%, and corresponds to unaltered Cr-spinel grains which remain paramagnetic down to 6K. The second one results from the alteration of the first type, has an average Fe 3+ /(Fe total) ≈40% and order magnetically between 222 K and 78 K. Fe 3+ /(total Fe) increases with the magnetic ordering temperature. The grain population ordering at the highest temperatures, in the range 202–222K, has the highest Fe 3+ /(total Fe) ≈ 58%. Quantitative Fe site distributions can be obtained from room-temperature Mossbauer data if the different recoilless factors for tetrahedral Fe 2+ and octahedral Fe 3+ are considered. The observed second-order Doppler shifts are consistent with Mossbauer temperatures of 330K and 605K, reported in the literature for tetrahedral Fe 2+ and octahedral Fe 3+ in other oxide spinels. The differences in the magnetic ordering temperatures allowed the characterization of both types of Cr-spinels using a single Mossbauer absorber, thus avoiding the need to separate them physically, which, in this case, would be very difficult. The results are compared to those obtained for other Cr-spinels and, for the first time in the case of natural Cr-spinels, the increase of their magnetic ordering temperatures with their oxidation degree, resulting from natural processes, is discussed in terms of the magnetic exchange interactions between the Fe cations.