Origins of high pH mineral waters from ultramafic rocks, Central Portugal

This paper reviews the geochemical, isotopic (²H, ¹⁸O, ¹³C, ³H and ¹⁴C) and numerical modelling approaches to evaluate possible geological sources of the high pH (11.5)/Na–Cl/Ca–OH mineral waters from the Cabeço de Vide region (Central-Portugal). Water–rock interaction studies have greatly contributed to a conceptual hydrogeological circulation model of the Cabeço de Vide mineral waters, which was corroborated by numerical modelling approaches. The local shallow groundwaters belong to the Mg–HCO₃ type, and are derived by interaction with the local serpentinized rocks. At depth, these type waters evolve into the high pH/Na–Cl/Ca–OH mineral waters of Cabeço de Vide spas, issuing from the intrusive contact between mafic/ultramafic rocks and an older carbonate sequence. The Cabeço de Vide mineral waters are supersaturated with respect to serpentine indicating that they may cause serpentinization. Magnesium silicate phases (brucite and serpentine) seem to control Mg concentrations in Cabeço de Vide mineral waters. Similar δ²H and δ¹⁸O suggest a common meteoric origin and that the Mg–HCO₃ type waters have evolved towards Cabeço de Vide mineral waters. The reaction path simulations show that the progressive evolution of the Ca–HCO₃ to Mg–HCO₃ waters can be attributed to the interaction of meteoric waters with serpentinites. The sequential dissolution at CO₂ (g) closed system conditions leads to the precipitation of calcite, magnesite, amorphous silica, chrysotile and brucite, indicating that the waters would be responsible for the serpentinization of fresh ultramafic rocks (dunites) present at depth. The apparent age of Cabeço de Vide mineral waters was determined as 2790 ± 40 a BP, on the basis of ¹⁴C and ¹³C values, which is in agreement with the ³H concentrations being below the detection limit.     

The impact of hydrological changes on travertine deposits related to thermal springs in the Pamukkale area (SW Turkey)

Pamukkale thermal waters (35 °C), exhibiting calcium-bicarbonate-sulfate composition and high carbon dioxide concentration, are of a predominantly meteoric origin. The meteoric fluid, circulating through faults and fractures, is heated by magmatic intrusions at great depth, and ascends from deep reservoirs to the surface. Mixing with relatively cold groundwater in the near surface zone promotes different saturation conditions with respect to calcium carbonate that later precipitates at depth and/or the surface. Dissolution-deposition processes of calcium carbonate both at surface and depth environments may help to reconstruct past climate direction in the field. During wet climate conditions a high-rate of calcium carbonate accumulation would be expected to occur at the surface because thermal fluid would be under-saturated with respect to calcium carbonate at depth because of a relatively higher mixing ratio with cold groundwater. During dry climate conditions the thermal fluid would be super-saturated at depth because of the highly acidic environment. Hydrometeorological studies reveal that the annual precipitation at the Pamukkale hydrothermal field tends to decrease with time. This climatic change in the area was also detected from geological records. While humid climate conditions prevailed during the late Quaternary, the area has recently been affected by arid/semi-arid climate conditions, followed by some episodic transitions. This study has shown how the system has possibly reacted to different climate conditions since antiquity.     

Nature and role of CO2 in some hot and cold HCO3/Na/CO2-rich Portuguese mineral waters: a review and reinterpretation

 At the northern part of the Portuguese mainland, the upflow zone of several hot and cold HCO₃/Na/CO₂-rich mineral waters is mainly associated with important NNE–SSW faults. Several geochemical studies have been carried out on thermal and non-thermal hydromineral manifestations that occur along or near these long tectonic alignments. The slight chemical differences that exist between these meteoric hot and cold HCO₃/Na/CO₂-rich mineral waters seem to be mainly caused by CO₂. δ¹³C_(TIDC) values observed in these groundwaters range between –6.00 and –1.00‰ versus V-PDB (V denotes Vienna, the site of the International Atomic Energy Agency; PDB originates from the CaCO₃ of the rostrum of a Cretaceous belemnite, Belemnitella americana, collected in the Peedee formation of South Carolina, USA) indicating a deep-seated (mantle) origin for most of the CO₂. Nevertheless, in the case of the heavier δ¹³C_(TIDC) values, the contribution of metamorphic CO₂ or the dissolution of carbonate rock levels at depth cannot be excluded. Concerning the hot waters, the lack of a positive ¹⁸O-shift should be attributed to water-rock interaction in a low temperature environment, rather than to the isotopic influence of CO₂ on the δ¹⁸O-value of the waters. Received: 9 August 1999 · Accepted: 8 March 2000     

Evidences of Holocene transgression on Domingos Petrolini Swamp, southern coastal plain, Rio Grande do Sul, Brazil

The Domingos Petrolini Swamp, located on the Southern Coastal Plain of Rio Grande do Sul, near the town of Rio Grande, constitutes an ample holocene lagoonal deposit. Events related to the holocene transgression and their diverse phases of glacial-eustatic ocillations were found through palynological analysis. Bases on these palynological data, four distinct phases to the paleoenvironmental evolution of the ecosystem were identified. It has also shown a transgressive restricted marine sequence on the base , which suggests the existence of a coastal brackish lagoon or a marisme type of environment. Later, there was a gradation for continentality conditions along with a scarce pollinical record. The third phase is characterized by the presence of marine components and halophyte vegetation, showing another transgressive event in that place. Lastly, the end of direct marine influence over the swamp was recorded and also the vegetation development as it appears these days.     

Mantle-derived carbon in Hercynian granites. Stable isotopes signatures and C/He associations in the thermomineral waters,N-Portugal

Na–HCO₃–CO₂-rich thermomineral waters issue in the N of Portugal, within the Galicia-Trás-os-Montes region, linked to a major NNE-trending fault, the so-called Penacova-Régua-Verin megalineament. Along this tectonic structure different occurrences of CO₂-rich thermomineral waters are found: Chaves hot waters (67 °C) and also several cold (16.1 °C) CO₂-rich waters. The δ²H and δ¹⁸O values of the thermomineral waters are similar to those of the local meteoric waters. The chemical composition of both hot and cold mineral waters suggests that water–rock reactions are mainly controlled by the amount of dissolved CO₂ (g) rather than by the water temperature. Stable carbon isotope data indicate an external CO₂ inorganic origin for the gas. δ¹³C_CO2 values ranging between ? 7.2‰ and ? 5.1‰ are consistent with a two-component mixture between crustal and mantle-derived CO₂. Such an assumption is supported by the ³He/⁴He ratios measured in the gas phase, are between 0.89 and 2.68 times the atmospheric ratio (Ra). These ratios which are higher than that those expected for a pure crustal origin (≈ 0.02 Ra), indicating that 10 to 30% of the He has originated from the upper mantle. Release of deep-seated fluids having a mantle-derived component in a region without recent volcanic activity indicates that extensive neo-tectonic structures originating during the Alpine Orogeny are still active (i.e., the Chaves Depression).     

Climatic trends and different drought adaptive capacity and vulnerability in a mixed Abies pinsapo�CPinus halepensis forest

The projected temperature rise, rainfall decrease and concentration of rainfall in extreme events could induce growth decline and die-off on tree populations located at the geographical distribution limit of the species. Understanding of adaptive capacity and regional vulnerability to climate change in Mediterranean forests is not well developed and requires more focused research efforts. We studied the relationships between spatiotemporal patterns of temperature and precipitation along the southwestern edge of the Betic range (southern Spain) and measured basal area increment (BAI) and carbon isotope (??) in tree ring series of Abies pinsapo and Pinus halepensis, two Mediterranean conifer trees with contrasting drought adaptive capacity. Climatic information was obtained from a network covering a wide range of elevations and distances from the Atlantic and Mediterranean coasts. Temperature trends were tested by the Mann?CKendall test, and precipitation was thoroughly analyzed by quantile regression. Climatic data showed a warming trend, enhanced since the 1970s, while quantile regressions revealed that drought events worsened during the course of the twentieth century. Long-term decrease of A. pinsapo BAI was related to regional warming and changing precipitation patterns, suggesting increasing drought stress on this species. Both temperature and precipitation in the summer influenced wood ?? in P. halepensis, whereas negative correlation between wood ?? and current autumn temperature was yielded for A. pinsapo. Increased intrinsic water use efficiency was inferred from wood ?? in both species; however, A. pinsapo showed sudden growth reductions under drier conditions, while pine trees were able to maintain almost constant BAI values and lower water costs under increasing long-term water stress.     

Hydrocarbon composition and distribution in a coastal region under influence of oil production in northeast Brazil

Waters and sediments from the Potiguar Basin (NE Brazilian coast) were investigated for the presence and nature of polycyclic aromatic hydrocarbons (PAH) and aliphatic hydrocarbons. The region receives treated produced waters through a submarine outfall system serving the industrial district. The total dispersed/dissolved concentrations in the water column ranged from 10-50 ng L⁻¹ for ∑16PAH and 5-10 μg L⁻¹ for total aliphatic hydrocarbons. In the sediments, hydrocarbon concentrations were low (0.5-10 ng g⁻¹for ∑16PAH and 0.01-5.0 μg g⁻¹ for total aliphatic hydrocarbons) and were consistent with the low organic carbon content of the local sandy sediments. These data indicate little and/or absence of anthropogenic influence on hydrocarbon distribution in water and sediment. Therefore, the measured values may be taken as background values for the region and can be used as future reference following new developments of the petroleum industry in the Potiguar Basin.     

Assessment of pollution risk ascribed to Santa Margarida Military Camp activities (Portugal)

Santa Margarida Military Camp (S.M.M.C.) is the only one Portuguese military training area, including firing ranges for tactical military manoeuvres of mechanised divisions. For this reason, various negative effects on the environment were expected due to the military activities, as the Military Camp’s area is classified as a high vulnerability area to pollution of its multilayer porous aquifers. The aim of this study was to identify and characterise local/regional geochemical impacts caused by the continuing military training activities performed at S.M.M.C. in the course of 52 years. An overview of the geochemical research issues as a basis for risk assessment is presented. A special attention has been put on the quality of local and regional surface waters, shallow groundwaters and groundwaters. Local soils and sediments as well as fragments of shells and bullets were sampled and analysed. The results so far obtained, indicated that none pollution effects were a consequence of the military training activities. Till now, the geochemical signatures such as, high levels of K, Cl and NO₃ in waters, detected in particular sites, should be faced as tracers of diffuse pollution ascribed to urban waste disposal and cattle breading.