西江流域环境河水地球化学研究

River is a major component of the global surface water and CO2 cycles. The chemistry of river waters reveals the nature of weathering on a basin-wide scale and helps us understand the exogenic cycles of elements in the continent-river-ocean system. In particular, geochemical investigation of large river gives important information on the biogeochemical cycles of the elements, chemical weathering rates, physical erosion rates and CO2 consumption during the weathering of the rocks within the drainage basin. Its importance has led to a number of detailed geochemical studies on some of the world's large and medium-size river systems. Flowing in the south of China, the Xijiang River is the second largest river in the China with respect to its discharge, after the Yangtze River. Its headwaters drain the YunGui Plateau, where altitude is approximately 2000 meters. Geologically, the carbonate rocks are widely spread in the river drainage basin, which covers an area of about 0.17xl06 km2, i.e., 39% of the whole drainage basin. This study focuses on the chemistry of the Xijiang river system and constitutes the first geochemical investigation into major and trace elements concentrations for both suspended and dissolved loads of this river and its main tributaries, and Sr isotopic composition of the dissolved load is also investigated, in order to determine both chemical weathering and mechanical erosion rates. As compared with the other large rivers of the world, the Xijiang River is characterized by higher major element concentration. The dissolved major cations average 1.17, 0.33, 0.15, and 0.04 mmol I"1 for Ca, Mg, Na, and K, respectively. The total cation concentrations (TZ+) in these rivers vary between 2.2 and 4.4 meq I'1. The high concentration of Ca and Mg, high (Ca+Mg)/(Na+K) ratio (7.9), enormous alkalinity and low dissolved SiO2/HCO3 ratio (0.05) in river waters reveal the importance of carbonate weathering and relatively weak silicate weathering over the river drainage basin. The major elements in river water, such as the alkalis and alkaline-earths, are of different origins: from rain water, silicate weathering, carbonate and evaporite weathering. A mixing model based on mass budget equation is used in this study, which allows the proportions of each element derived from the different source to be calculated. The carbonate weathering is the main source of these elements in the Xijiang drainage basin. The contribution of rainwater, especially for Na, reaches to approximately 50% in some tributaries. Dissolved elemental concentration of the river waters are corrected for rain inputs (mainly oceanic salts), the elemental concentrations derived from the different rock weathering are calculated. As a consequence, silicate, carbonate and total rock weathering rates, together with the consumption rates of atmospheric CO2 by weathering of each of these lithologies have been estimated. They provide specific chemical erosion rates varying between 5.1~17.8 t/km2/yr for silicate, 95.5~157.2 t/km2/yr for carbonate, and 100.6-169.1 t/km2/yr for total rock, respectively. CO2 consumptions by silicate and carbonate weathering approach 13><109and 270.5x10 mol/yr. Mechanical denudation rates deduced from the multi-year average of suspended load concentrations range from 92-874 t/km2/yr. The high denudation rates are mainly attributable to high relief and heavy rainfall, and acid rain is very frequent in the drainage basin, may exceed 50% and the pH value of rainwater may be <4.0, result from SO2 pollution in the atmosphere, results in the dissolution of carbonates and aluminosilicates and hence accelerates the chemical erosion rate. The compositions of minerals and elements of suspended particulate matter are also investigated. The most soluble elements (e.g. Ca, Na, Sr, Mg) are strongly depleted in the suspended phase with respect to upper continent crust, which reflects the high intensity of rock weathering in the drainage basin. Some elements (e.g. Pb, Cu, Co, Cr) show positive anomalies, Pb/Th ratios in suspended matter approach 7 times (Liu Jiang) to 10 times (Nanpan Jiang) the crustal value. The enrichment of these elements in suspended matter reflects the intensity both of anthropogenic pollution and adsorption processes onto particles. The contents of the soluble fraction of rare earth elements (REE) in the river are low, and REE mainly reside in particulate phase. In dissolved phase, the PAAS-normalized distribution patterns show significant HREE enrichment with (La/Yb) SN=0.26~0.94 and Ce depletion with (Ce/Ce*) SN=0.31-0.98, and the most pronounced negative Ce anomalies occur in rivers of high pH. In the suspended phase, the rivers have LREE-enriched patterns relative to PAAS, with (La/Yb) SN=1 -00-1 .40. The results suggest that pH is a major factor controlling both the absolute abundances of REE in solution and the fractionation of REE of dissolved phase. Ce depletion in river waters with high pH values results probably from both preferential removal of Ce onto Fe-Mn oxide coating of particles and CeC^ sedimentation. This process is known to occur in the marine environment and may also occur in high pH rivers. Positive correlations are also observed between La/Yb ratio and DOC, HCO3", PO4", suggesting that colloids and (or) adsorption processes play an important role in the control of these elements.

中-新元古代海洋的硫和碳同位素的演化

Data on seawater carbon isotope in the Mesoproterozoic and Neoproterozoic is abundant. However, the sulfur isotopic age curve of seawater sulfates determined through the analysis of sulfur isotopic composition of marine evaporite is uncertain in the Mesoproterozoic and Neoproterozoic since evaporites are generally rare in Precambrian. The Mesoproterozoic and Neoproterozoic Carbonate Formations preserve not only the carbon isotopic records, but also the sulfur isotopic records of coeval seawater in the Huabei Platform and the Yangtze Platform, China. Sulfur isotopic composition can be determined by the extraction of trace sulfate from carbonate samples. Successive measurements of sulfur and carbon isotopic compositions of carbonate samples from the Mesoproterozoic and Neoproterozoic strata in the Huabei Platform and the Yangtze Platform was accomplished through the extracting of trace sulfate from carbonates. Sulfur and carbon isotopic compositions of coeval seawater were obtained from analytical results of sulfur and carbon isotopes of the same sample without diagenetic alteration. The high-resolution age curve of sulfur isotope given in this paper may reflect the trend of variations in sulfur isotope composition of seawater sulfates during the Mesoproterozoic and Neoproterozoic. It can be correlated with the characteristics of variation in age curve of carbon isotope of coeval seawater carbonates. The δ34S values of seawater varied from +10.3-37.0‰ during the Mesoproterozoic, which took on oscillated variation on the whole. The δ34S values took on high values in the Mesoproterozoic Chuanlinggou stage, Tuanshanzi stage Tieling stage and in Neoproterozoic Jing'eryu stage. The average of those was about +30‰. The sulfates have low δ34S values in the Mesoproterozoic Yangzhuang stage and Hongshuizhuang stage, The average of those was all lower than +20‰. There occured large-amplitude changs in δ34S values of seawater during the Mesoproterozoic. Large-amplitude oscillate of 534S values occured in the intervals of 1600~1400Ma and 1300~1200Ma. The δ13C values of seawater are mostly negative in Changcheng stage of late Paleoproterozoic, -0 ± 1‰ range in Jixian stage of Mesoproterozoic , and the positive 2±2‰ commonly in early Neoproterozoic Jing'eryu stage. From 1000 Ma to 900 Ma, about 108 years interval of oceanic 513C record is shortage. At the end of Paleoproterozoic (1700 - 1600 Ma), the oceanic 813C values change from -3‰ to 0‰, but strongly oscillate near 1600 Ma. Two larger variations of seawater 513C values occur in the Mesoproterozoic: one is a cycle of about 4%o happens at ca. 1400 Ma; another is rise from >2‰ to>5‰ at ca. 1250 Ma and then become stable at the near 1000 Ma. There appears a large positive excursion over +20‰ in 534S value of ancient seawater sulfates in the early Doushantuo stage. Simultaneously, 8 C values of ancient seawater occur a positive excursion reaching 10‰. These allow δ4S values and 513C values to reach high values of+51.7‰ and +6.9‰, respectively. The range of variation in 834S values of seawater is relatively narrow and 513C values are quite high in the middle Doushantuo stage. Then, δ34S values of seawater become oscillating, the same happens in δ13C values. Negative excursions in 834S values and 813C values occur simultaneously at the end of the Doushantuo stage, and the minimum of δ34S values and δ13C values dropped to -11.3‰ and -5.7‰, respectively. The ancient seawater in the Dengying stage has high δS values and δ13C values. Most of the δ34S values of the trace sulfate samples varied between +23.6‰ and +37.9‰ except two boundaries of the Dengying Formation, and the S13C values of the carbonate samples of the Dengying Formation varied between +0.5‰ and +5.0‰. There appeared large negative excursion in 834S values and δ13C values of ancient seawater at the bounder of Precambrian-Cambrian. The isotopic characteristics of sulfur and carbon implicated that the organic productivity and isotopic fractionation caused by biology were low and the palaeoceanic environment was quite unstable during the Mesoproterozoic. The increase and subsequent oscillation of seawater δ13C value occurred from 1700 to 1600 Ma and near 1300 Ma may be responsible to the two global tectonic events happened at coeval time. The characteristics of variation in sulfur and carbon isotopes of ancient seawater imply strong changes in oceanic environment, which became beneficial to inhabitation and propagation of organism. The organic production and the burial rate of organic carbon once reached a quite high level during the Doushantuo stage. However, the state of environment became unstable that means the global climate and the environment possibly were fluctuating and reiterating after the global glaciation. The negative excursions of S34S values and δ13C values occurring at the end of the Doushantuo stage represent a global event, which might be relative to the oxidation of deep seawater. The isotopic characteristics of sulfur and carbon implicated that there were a high organic productivity and a high burial rate of organic carbon in the Dengying stage. It is obvious that the palaeoceanic environment in Dengying stage was stable corresponding and beneficial for biology to inhabit and propagate except for the two boundaries. The tendency of sulfur and carbon isotopic variations maybe resulted from the gradual oxygenation of ocean environment during the Dengying stage. It has been reported that the secular variations of the sulfur isotopic compositions in seawater was negative correlated with that of carbon isotopic compositions. However, our results show that it is not the case. They were negatively correlated in some intervals and positively in some other intervals of the Mesoproterozoic and Neoproterozoic. The difference in correlation may be associated with the changes in conditions of redox in oceanic environment, e.g. sharp change of the oxidation-reduction interface. The strong changes in global environment may induce the abnormality to occur in the biogeo chemical S and C cycles in the ocean and accordingly sharp Variations in isotopic composition of seawater sulfur and carbon during the Mesoproterozoic and Neoproterozoic. Simultaneously, the global tectonism caused large changes of 87Sr/86Sr ratios. The leading factor that causes the variation in isotopic composition is different in the different intervals of the Mesoproterozoic and Neoproterozoic. Thus, there may exist different models of the biogeochemical S and C cycles in the ocean during the Mesoproterozoic and Neoproterozoic.

Identifying the influence of geology, land use, and anthropogenic activities on riverine sulfate on a watershed scale by combining hydrometric, chemical and isotopic approaches

Throughout the last few decades, sulfate concentrations in streamwater have received considerable attention due to their dominant role in anthropogenic acidification of surface waters. The objectives of this study conducted in the Oldman River Basin in Alberta (Canada) were to determine the influence of geology, land use and anthropogenic activities on sources, concentrations and fluxes of riverine sulfate on a watershed scale. This was achieved by combining hydrological, chemical and isotopic techniques. Surface water samples were collected from the main stem and tributaries of the Oldman River on a monthly basis between December 2000 and March 2003 and analyzed for chemical and isotopic compositions. At a given sampling site, sulfate sources were primarily dependent on geology and did not vary with time or flow condition. With increasing flow distance a gradual shift from ?34S values > 10 ‰ and ?18O values > 0 ‰ of riverine sulfate indicating evaporite dissolution and soil-derived sulfate in the predominantly forested headwaters, to negative ?34S and ?18O values suggested that sulfide oxidation was the predominant sulfate source in the agriculturally used downstream part of the watershed. Significant increases in sulfate concentrations and fluxes with downstream distance were observed, and were attributed to anthropogenically enhanced sulfide oxidation due to the presence of an extensive irrigation drainage network with seasonally varying water levels. Sulfate-S exports in an artificially drained subbasin (64 kg S/ha/yr) were found to exceed those in a naturally drained subbasin (4 kg S/ha/yr) by an order of magnitude. Our dataset suggests that the naturally occurring process of sulfide oxidation has been enhanced in the Oldman River Basin by the presence of an extensive network of drainage and irrigation canals.

Um estudo das condições de percolação e estabilidade em barragens de terra mediante métodos geofísicos: caso do dique de Sant Llorenç de Montgai - Espanha

The monitoring of Earth dam makes use of visual inspection and instrumentation to identify and characterize the deterioration that compromises the security of earth dams and associated structures. The visual inspection is subjective and can lead to misinterpretation or omission of important information and, some problems are detected too late. The instrumentation are efficient but certain technical or operational issues can cause restrictions. Thereby, visual inspections and instrumentation can lead to a lack of information. Geophysics offers consolidated, low-cost methods that are non-invasive, non-destructive and low cost. They have a strong potential and can be used assisting instrumentation. In the case that a visual inspection and strumentation does not provide all the necessary information, geophysical methods would provide more complete and relevant information. In order to test these theories, geophysical acquisitions were performed using Georadar (GPR), Electric resistivity, Seismic refraction, and Refraction Microtremor (ReMi) on the dike of the dam in Sant Llorenç de Montgai, located in the province of Lleida, 145 km from Barcelona, Catalonia. The results confirmed that the geophysical methods used each responded satisfactorily to the conditions of the earth dike, the anomalies present and the geological features found, such as alluvium and carbonate and evaporite rocks. It has also been confirmed that these methods, when used in an integrated manner, are able to reduce the ambiguities in individual interpretations. They facilitate improved imaging of the interior dikes and of major geological features, thus inspecting the massif and its foundation. Consequently, the results obtained in this study demonstrated that these geophysical methods are sufficiently effective for inspecting earth dams and they are an important tool in the instrumentation and visual inspection of the security of the dams

Ciclos e seqüências deposicionais das formações Rio da Batateira e Santana (Andar Alagoas), Bacia do Araripe, Brasil

The Rio da Batateira e Santana formations, the latter with Crato, Ipubi and Romualdo members (Alagoas Stage, Aptian), were studied in four cored and logged wells from the eastern portion of Araripe Basin, Northeastern Brazil. The investigated section is 230 m-thick, and PS-14 well is the most representative, because it is the only one which sampled the evaporites of Ipubi Member. Nine facies cycles were identified, being formed by siliciclastics (estuarine, deltaic and lacustrine), mixed lithologies (lacustrine), carbonates, black shales and marls (lacustrine), and gypsum-anhydrite (lacustrine evaporite). The ordering of facies cycles furnished six depositional sequences. They were formed by siliciclastic, regressive-transgressive R-T cycles (S1 and S4, corresponding to Rio da Batateira Formation and to Santana Formation/Romualdo Member), by siliciclastics and carbonates, R-T cycles (S2, S3.1 and S3.2, corresponding to Crato Member), and by siliciclastic-carbonate, R-T cycles followed by evaporitic cycles (S3.3, referred to Ipubi Member). The last cycles correspond to concentration-dilution, C-D cycles of marine brines, which precipitated gypsum in the restricted lacustrine basin.

Facies analysis of the Codó formation (Late Aptian) in the Grajaú area, Southern São Luís-Grajaú Basin

Facies descriptions of the Codó Formation in the Grajaú area are provided for the first time, and its sedimentary characteristics compared to those from the Codó area to allow paleoenvironmental reconstructions. Deposits in the Grajaú area include evaporites, limestones and argillites bearing features indicative of a shallow, low energy, subaqueous, saline environment exposed to meteoric and/or capillary conditions. Floodingevaporative concentration-desiccation cycles suggest a saline pan complex surrounded by extensive evaporitic mudflats. The location of the system, whether coastal or inland, is a matter open for debate. However, the later hypothesis is favored considering: 1. Sr isotopic data, with values higher than those expected for Late Aptian marine waters; 2. calcitic composition of limestones (instead of dolomitic and/or magnesitic as expected in coastal settings); and 3. presence of continental ostracods and lack of marine fauna. This interpretation is consistent with that proposed for UpperAptian deposits of the Codó area, but the depositional system there was one dominated by more stable, well-stratified, anoxic waters and evaporite precipitation in central lacustrine areas, while in the Grajaú area the salt pan was more oxygenated and ephemeral, with salt precipitation mainly in marginal areas or along surrounding mudflats.

Aplicação do gravímetro de poço em problemas de avaliação de formação no Brasil

No período de outubro a novembro de 1990, foi realizado na Bacia Sergipe-Alagoas o primeiro levantamento gravimétrico de poço no Brasil, através de um programa com a participação da Universidade Federal do Pará, a PETROBRÁS e o U.S.G.S. (United States Geological Survey). Este levantamento teve como objetivos o teste do equipamento, a resposta dos perfis gravimétricos em relação aos problemas encontrados nas bacias sedimentares brasileiras e a comparação com os dados de densidade obtidos com o perfil de densidade compensada (CDL). Os levantamentos foram realizados em três poços e os dados obtidos passaram por um processo de redução, onde os valores foram transformados para miligals e corrigidos dos efeitos de maré, deriva e terreno, para obter as densidades preliminares. Porém, a região onde foram realizados os levantamentos apresenta além do embasamento muito raso, uma seqüência evaporítica com contraste de densidade grande em relação ao resto do pacote sedimentar, gerando gradientes verticais anômalos. Estes efeitos foram então corrigidos e obtidos os valores finais de densidade. Com base em uma caracterização litológica prévia, os valores de densidade foram então comparados com o perfil CDL. Verificou-se a boa qualidade dos dados, o que permitiu o cálculo de valores de porosidade, mostrando assim possíveis intervalos de interesse à exploração de hidrocarbonetos, tanto no embasamento, reservatório mais importante, quanto no intervalo sedimentar.

Reavaliação paleoambiental e estratigráfica da Formação Nobres do Grupo Araras, Neoproterozóico da Faixa Paraguai, região de Cáceres (MT)

A Formação Nobres representa a última deposição carbonática neoproterozoica do Grupo Araras, na porção sudoeste da Faixa Paraguai Norte. Estudos faciológicos e estratigráficos em afloramentos na região de Cáceres, no estado do Mato Grosso, subdividiram a Formação Nobres em: membro inferior, composto de dolomitos finos, dolopackstones intraclásticos, dolomitos arenosos, estromatólitos estratiformes e moldes evaporíticos, interpretados como depósitos de planície de maré/sabkha; e membro superior, composto por dolomitos finos, arenitos dolomíticos, estromatólitos estratiformes a dômicos e rugosos e moldes evaporíticos, além de arenitos e pelitos interpretados como depósitos de planície de maré mista. O empilhamento destes depósitos de até 200 m de espessura é composto por ciclos métricos de raseamento/salinidade ascendente relacionado a um clima árido. Os ciclos de perimaré também sugerem geração contínua e recorrente de espaço de acomodação provavelmente ligado à subsidência tectônica. O influxo de sedimentos siliciclásticos no final da deposição da Formação Nobres inibiu a sedimentação carbonática e é atribuída ao soerguimento de áreas-fontes ligado ao início do fechamento do Oceano Clymene, durante a colisão Pampeana-Araguaia, no limite Neoproterozoico-Cambriano.

Petrography of gypsum-bearing facies of the Codó Formation (Late Aptian), Northern Brazil

Neste trabalho, é apresentado um estudo original e detalhado enfocando os aspectos petrográficos dos evaporitos de depósitos aptianos superiores expostos no sul e leste da Bacia de São Luís-Grajaú. O objetivo é o estabelecimento de critérios que permitam distinguir entre evaporitos primários e secundários, além da reconstrução de sua evolução pós-deposicional. Sete fases de evaporitos foram reconhecidas: 1. gipsita em chevron; 2. gipsita ou anidrita nodular a lenticular; 3. gipsita fibrosa a acicular; 4. gipsita em mosaico; 5. gipsita brechada a gipsarenito; 6. anidrita ou gipsita pseudo-nodular; e 7. gipsita em rosetas. As três primeiras fases apresentam características petrográficas condizentes com origem primária. Agipsita fibrosa a acicular e a gipsita em mosaico foramformadas por substituições de gipsita primária, com origem provável nos estágios iniciais da diagenêse, portanto ainda sob influência do ambiente deposicional. Estas morfologias de gipsita estão relacionadas com a fácies de evaporito laminado, tendo sido formadas por substituição, porém sem afetar a estruturação primária. A gipsita ou anidrita pseudo-nodular originou-se pela mobilização de soluções sulfatadas durante ou após soterramento, provavelmente associada à halocinese. A gipsita em rosetas, que intercepta todas as outras variedades de gipsita, representa o ultimo estágio de formação de evaporitos na área de estudo, tendo resultado de soluções intraestratais ou de águas superficiais durante intemperismo.

Aspectos petrográficos dos carbonatos da Formação Riachuelo - Albiano, bacia de Sergipe

The carbonatic rocks have great importance in petroleum geology, since most hydrocarbons reservoirs in the world are associated to this kind of rock. The new giant petroleum fields discovered in the Brazilian southeast Atlantic margin are directly connected to calcareous rocks, which are subjacent to the Aptian evaporite pack. This demand an increase in the number of geologists able to study such deposits. The Aptian carbonatic platform is completely exposed only in the Sergipe-Alagoas Basin. Therefore, it works as a natural laboratory to the study and understanding of this kind of rock. The Sergipe Basin is situated in the east Brazilian coast, and has its evolutional history is intimately related to the formation of the South Atlantic Ocean, through the break-up of the Gondwana supercontinent. The marine sequence of the Brazilian marginal basins is of Albian age and is marked by the development of carbonatic platforms. In doing so, this paper aims to analyze the Albian limestones from Riachuelo Formation of the Sergipe Basin. The project gave to the student the opportunity to increase his knowledge in carbonates, due to the laboratory and outdoor activities. The studied deposits, within a regional outline, were petrografically described, allowing interpretations about the evolution of the former South Atlantic Ocean. Ten points were visited where samples were collected for making of thin sheets. In this work several carbonatic facies were identified totaling 116 laminates described.

Sucessão estratigráfica e tratos de sistemas do Membro Romualdo, porção leste da Bacia do Araripe, nordeste do Brasil

Located in northeastern Brazil, the evolution of Araripe Basin has been associated with the fragmentation of Gondwana and opening of the South Atlantic. The Santana Formation belongs to the post-rift sequence of the basin and is characterized by the presence of laminated limestones in the lower portion (Mb. Crato), evaporite (Ipubi) and siliciclastics (Mb. Romualdo). For better understanding of the Romualdo's stratigraphy, depositional environments and tract of systems, a stratigraphic analysis was made with representative columnar sections of the unit. Sedimentary facies have been described in detail, as well as paleocurrents measured at different stratigraphic levels. It was found that the contact of Mb. Romualdo with the carbonate-evaporite section (Mbs. Crato and Ipubi) is a unconformity, evidenced by residual lags and thin layers of conglomerates above the contact. Above the conglomeratic levels predominate fine sandstones / medium interlayered with calciferous green shales. The percentage of shales increases towards the top, featuring retrogradational stacking culminating in layers of coquinas, excellent stratigraphic mark in the basin. Thin layers of coquins of gastropods comprising equinoids, located on the shale section, present in three sections marine deposits are associated with surfaces ravine. The upper section is characterized by recurrent facies of green shales, sandstones intercalated with sandstones progressively become more frequent towards the top of the unit, featuring the regressive part of the cycle. The sandstones present cross-stratification, often with mud clasts and clay layers in the foresets, and beddings of flaser type and wavy in heterolitic facies, suggesting the action of tidal currents. Paleocurrents measured in the sandstones show gaps with opposite flow directions outlining bipolar standards, which reinforce the interpretation of shallow marine environment influenced by tides during the sedimentation...

Tuzla City (BiH): an example of geohazard induced by salt extraction

Salt deposits characterize the subsurface of Tuzla (BiH) and made it famous since the ancient times. Archeological discoveries demonstrate the presence of a Neolithic pile-dwelling settlement related to the existence of saltwater springs that contributed to make the most of the area a swampy ground. Since the Roman times, the town is reported as “the City of Salt deposits and Springs”; "tuz" is the Turkish word for salt, as the Ottomans renamed the settlement in the 15th century following their conquest of the medieval Bosnia (Donia and Fine, 1994). Natural brine springs were located everywhere and salt has been evaporated by means of hot charcoals since pre-Roman times. The ancient use of salt was just a small exploitation compared to the massive salt production carried out during the 20th century by means of classical mine methodologies and especially wild brine pumping. In the past salt extraction was practised tapping natural brine springs, while the modern technique consists in about 100 boreholes with pumps tapped to the natural underground brine runs, at an average depth of 400-500 m. The mining operation changed the hydrogeological conditions enabling the downward flow of fresh water causing additional salt dissolution. This process induced severe ground subsidence during the last 60 years reaching up to 10 meters of sinking in the most affected area. Stress and strain of the overlying rocks induced the formation of numerous fractures over a conspicuous area (3 Km2). Consequently serious damages occurred to buildings and infrastructures such as water supply system, sewage networks and power lines. Downtown urban life was compromised by the destruction of more than 2000 buildings that collapsed or needed to be demolished causing the resettlement of about 15000 inhabitants (Tatić, 1979). Recently salt extraction activities have been strongly reduced, but the underground water system is returning to his natural conditions, threatening the flooding of the most collapsed area. During the last 60 years local government developed a monitoring system of the phenomenon, collecting several data about geodetic measurements, amount of brine pumped, piezometry, lithostratigraphy, extension of the salt body and geotechnical parameters. A database was created within a scientific cooperation between the municipality of Tuzla and the city of Rotterdam (D.O.O. Mining Institute Tuzla, 2000). The scientific investigation presented in this dissertation has been financially supported by a cooperation project between the Municipality of Tuzla, The University of Bologna (CIRSA) and the Province of Ravenna. The University of Tuzla (RGGF) gave an important scientific support in particular about the geological and hydrogeological features. Subsidence damage resulting from evaporite dissolution generates substantial losses throughout the world, but the causes are only well understood in a few areas (Gutierrez et al., 2008). The subject of this study is the collapsing phenomenon occurring in Tuzla area with the aim to identify and quantify the several factors involved in the system and their correlations. Tuzla subsidence phenomenon can be defined as geohazard, which represents the consequence of an adverse combination of geological processes and ground conditions precipitated by human activity with the potential to cause harm (Rosenbaum and Culshaw, 2003). Where an hazard induces a risk to a vulnerable element, a risk management process is required. The single factors involved in the subsidence of Tuzla can be considered as hazards. The final objective of this dissertation represents a preliminary risk assessment procedure and guidelines, developed in order to quantify the buildings vulnerability in relation to the overall geohazard that affect the town. The historical available database, never fully processed, have been analyzed by means of geographic information systems and mathematical interpolators (PART I). Modern geomatic applications have been implemented to deeply investigate the most relevant hazards (PART II). In order to monitor and quantify the actual subsidence rates, geodetic GPS technologies have been implemented and 4 survey campaigns have been carried out once a year. Subsidence related fractures system has been identified by means of field surveys and mathematical interpretations of the sinking surface, called curvature analysis. The comparison of mapped and predicted fractures leaded to a better comprehension of the problem. Results confirmed the reliability of fractures identification using curvature analysis applied to sinking data instead of topographic or seismic data. Urban changes evolution has been reconstructed analyzing topographic maps and satellite imageries, identifying the most damaged areas. This part of the investigation was very important for the quantification of buildings vulnerability.

Natural Tracers in recent groundwaters from different Alpine aquifers

Groundwater with underground residence times between days and a few years have been investigated over more than 20 years from 487 remote sites located in different aquifer types in the Alpine belt. Analysis of the data reveals that groundwaters evolved in crystalline, evaporite, carbonate, molasse, and flysch aquifers can be clearly distinguished based on their major and trace element composition and degree of mineralisation. A further subdivision can be made even within one aquifer type based on the trace element compositions, which are characteristic for the lithologic environment. Major and trace element concentrations can be quantitatively described by interaction of the groundwater with the aquifer- specific mineralogy along the flow path. Because all investigated sites show minimal anthropogenic influences, the observed concentration ranges represent the natural background concentrations and can thus serve as a “geo-reference” for recent groundwaters from these five aquifer types. This “geo-reference” is particularly useful for the identification of groundwater contamination. It further shows that drinking water standards can be grossly exceeded for critical elements by purely natural processes

Strontium isotopic ratios of evaporites of the Tyrrhenian Sea

Strontium isotopic ratios of gypsums recovered from upper Miocene (Messinian) evaporites at ODP Leg 107 Holes 652A, 653B, and 654A (Tyrrhenian Sea) are lower than expected. The values for the Messinian balatino-like gypsum, single gypsum crystals, and anhydrites range from 0.70861 to 0.70886 and are approximately 25 * 10**-5 less than would be expected for evaporites precipitated from Messinian seawater (0.70891-0.70902). Pre-evaporitic planktonic foraminifers from Hole 654A show variable degrees of dolomitization and 87Sr/86Sr values that irregularly decrease upward from normal marine values approximately 81m below the lowest evaporite occurrence. This suggests diagenetic alteration by advecting interstitial water with a low 87Sr/86Sr ratio or that the lower Sr isotopic ratios for the Messinian evaporites could have resulted from a greater influence of fresh water on the Sr isotopic composition of the desiccating Tyrrhenian Sea. Fluctuations of the 87Sr/86Sr-ratio for evaporites in the sedimentary cycles recognized for Holes 653B and 654A, the generally low Sr isotopic ratio of river water entering the Mediterranean Sea, and the presence of dwarf marine microfossils suggest that the 87Sr/86Sr ratio of the evaporites responded to hydrologic variations in a very restricted basin with variable rates of marine and fresh water input. The strontium isotopic ratios of the Messinian anhydrites from the proposed lacustrine sequence at Hole 652A fall in the same range as the marine evaporites from Holes 654A and 653B. This suggests a common or similar origin of the brines at the three locations. The complex depositional and hydrologic conditions in the Mediterranean during the Messinian salinity crisis preclude the use of Sr isotopic values from the evaporites for stratigraphic correlation and dating. They are, however, very useful in the interpretation of the depositional history of the basin. General calculations assuming a closed system suggest that the 87Sr/86Sr ratio of Messinian seawater (-0.7090) could be reduced to that of the evaporites (-0.7087) by mixing with fresh water (e.g., Nile River) in times of 10**4 to 10**5 yr.

Geochemistry and isotopes at DSDP Hole 79-546

At Site 546, below the Mazagan Escarpment at a water depth of 4 km, 36 m of salt rock was cored from the top of one of a field of salt domes. The core was studied by thin section and a variety of geochemical procedures. The salt rock contains 0.1 to 3% carnallite and lesser amounts of sylvite and polyhalite, which with the corresponding high level of bromide place it within the potash evaporite facies. The bromide profile is of a dominantly marine evaporite deposited in moderately shallow brine which, however, was not repeatedly desiccated. A mineralogical argument suggests that the brine surface was not below sea level. An average of about 5% elastics, with dispersed anhydrite, darken the salt rock to deep shades of red, brown, and gray green. Most of the included materials are in highly deformed boudins or dispersions in the salt rock that has also undergone cataclasis in a subsequent, probably tectonic, deformation. The salt rock is slightly deficient in anhydrite, and the usual separate beds and laminae of anhydrite are virtually absent. Stable isotope ratios of sulfur and oxygen in the sulfate are clearly derived from sea water of Permian to Scythian age, in contrast to the late Triassic or Early Jurassic age of evaporites onshore in Morocco and Portugal and the corresponding evaporites offshore Maritime Canada. In contrast to those evaporites off the axis of Atlantic rifting, the salt at Site 546 may have been deposited in a very early central rift fed by marine waters from Tethys through the Gibraltar or South Atlas fracture zones.