Chemistry of sulfide deposits from ODP Site 106-649

In Snake Pit massive sulfide fragments and friable, unconsolidated material recovered during ODP Leg 106, isocubanite and pyrite are generally the predominant phases, followed by marcasite, chalcopyrite, sphalerite, and pyrrhotite. Detailed analyses of paragenetic relations of minerals indicate that isocubanite first precipitated together with pyrrhotite. With decreasing temperature, chalcopyrite and sphalerite precipitated, and at the latest stage colloform sphalerite-pyrite (or colloform marcasite) formed. Isocubanite usually has exsolution lamellae of chalcopyrite and less commonly of pyrrhotite. The average bulk chemical composition of the friable, unconsolidated material indicates that it is rich in copper, reflecting the dominance of isocubanite in the specimens, and is characterized by high Co, low Pb, and Ag contents. Sulfur isotope ratios are very uniform, ranging in d34S from +1.2 to +2.8 per mil. The obtained values are apparently low, compared to those for the eastern Pacific sulfide samples, reflecting a smaller contribution of seawater sulfate in the Snake Pit sulfide deposit.

Chemistry of sulfide deposites of ODP Site 106-649

The Snake Pit active hydrothermal field was discovered at 23°22'N on the Mid-Atlantic Ridge during ODP Leg 106. Among the ten holes drilled in the mound at the foot of an active chimney, only three (649B, 649F, and 649G) had substantial recovery, and produced cores of unconsolidated hydrothermal deposit made up of porous sulfide fragments with minor talc pellets and biological debris, and a few pieces of brassy massive sulfides. Eight representative samples from the 6.5-m-long core from Hole 649B were analyzed for bulk chemistry, both by XRF (major elements) and NAA (trace elements). Major elements average compositions show high Fe (36 wt%), S (37 wt%), and Cu (12 wt%) contents, and minor Zn (6.7 wt%), reflecting a mostly high-temperature deposit. Trace elements are characterized by a high Au content (600 ppb) which could express the maturity of the mound. Mineralogical assemblages show evidence of sequential precipitation, and absence of equilibrium. Major sulfide phases are pyrrhotite, pyrite, Fe, Cu sulfides, marcasite, and sphalerite. Three types of samples are distinguished on the basis of textures and mineral assemblages: type 1, rich in pyrrhotite, with approximately equivalent amounts of Cu, Fe sulfides, and sphalerite and minor pyrite; type 2, rich in Cu, Fe sulfides, which are cubic cubanite with exsolutions and rims of chalcopyrite; and type 3, essentially made up of sphalerite. Type 2 samples likely represent fragments of the inner chimney wall. The presence of talc intergrown with cubic cubanite/chalcopyrite in one big piece from Hole 649G is probably related to mixing of the hydrothermal fluid with seawater.

Chemistry of hydrothermal clasy and sulfides of ODP Site 106-649

Several meters of unconsolidated hydrothermal sediment were recovered from the Snake Pit hydrothermal field during ODP Leg 106. Polymetallic sulfides comprise most of the sediment with minor fragments of massive sulfide, organic debris, clay minerals, and fresh glass shards. Trace element and Sr-isotope contents of hydrothermal clays and sulfides from Holes 649B and 649G indicate that these minerals precipitated from a mixed hydrothermal fluid-seawater solution. Evaluation of the REE mineral data and the Snake Pit hydrothermal fluids shows that the REE distribution coefficients between the hydrothermal fluids and clay-sulfide mixes range from 100-500. This indicates that hydrothermal fluids originating in the root-zone of the Snake Pit hydrothermal system may be modified by the precipitation of hydrothermal minerals, either in the shallow subsurface or within chimney structures. Contrasting REE profiles of clay-sulfide aggregates and massive sulfides from Holes 649B and 649G may be accounted for by spatial and/or temporal variations in redox conditions in the plumbing system.

Difração de raios X por policristais: uma ferramenta para caracterização e determinação estrutural do protótipo a fármaco LASSBio-1755

Novos protótipos de fármacos estão constantemente a ser sintetizados e muitas estruturas cristalinas de outros ainda são desconhecidas. Tão importante quanto o planejamento e síntese de novos fármacos é a sua caracterização estrutural, uma vez que a sua estrutura (conformação) pode estar diretamente relacionada com a ação terapêutica. O uso da difração de raios X tem sido muito importante na determinação estrutural dos novos compostos sintetizados. Neste trabalho foi feita a determinação da estrutura de LASSBio-1755 com os dados de difração de raios X por policristais. Este composto foi sintetizado no Laboratório de Avaliação e Síntese de Substâncias Bioativas (LASSBio) da Universidade Federal do Rio de Janeiro. O composto LASSBio-1755 pertence a uma nova série de compostos cicloalquil-N-acilidrazônicos planejados para o desenvolvimento de protótipos com atividades antinociceptiva e anti-inflamatórios. Este composto cristalizou-se num sistema triclínico com grupo espacial (P ), com parâmetros de cela unitária a = 4,86647(9) Å, b = 9,3108(2) Å, c = 11,3402(2) Å, α = 106,649(1), β = 101,958(1), γ = 82,629(2) e V = 480,30(2) Å3. A estrutura cristalina de LASSBio-1755 consiste em duas fórmulas unitárias por cela unitária (Z = 2), acomodando uma molécula na unidade assimétrica (Z' = 1). O Método de Rietveld foi utilizado para refinar a estrutura cristalina e o indicador de qualidade do ajuste, bem como os fatores R foram, respectivamente: χ2 = 1,131, RBragg = 0,856%, Rwp =4,174% e o Rexp= 3,692%. As técnicas de calorimetria exploratória diferencial, termogravimetria e espectroscopia no infravermelho por transformada de Fourier também foram utilizadas para análise do composto LASSBio-1755 e os seus resultados corroboraram com os obtidos através da técnica de difração de raios X por policristais.