MINERALOGICAL AND TEXTURAL EVOLUTION OF THE ECONOMIC MANGANESE MINERALIZATION IN WESTERN RHODOPE MASSIF, N GREECE

The western Rhodope massif contains a significant number of 'battery grade' Mn-oxide deposits which are best developed in the area near Kato Nevrokopi, Drama district, N. Greece. Economic Mn-oxide ore concentrations are confined to fault zones and related karsts in marbles. The mineralisation has formed by weathering of hydrothermal veins that were genetically related to Oligocene magmatism. At Kato Nevrokopi, progressive and continuous weathering of primary, hydrothermal veins of rhodochrosite, mixed sulphide, quartz and 'black calcite' (calcite and todorokite) has resulted in the formation of the assemblage MnO-gel-(amorphous Mn-oxide)-todorokite-azurite-goethite-cerussite in the veins and the assemblage MnO-gel-nsutite-chalcophanite-birnessite-cryptomelane-pyrolusite and malachite and amorphous Fe-oxides in karstic cavities. The f(S)2 and f(O)2 of the hydrothermal fluids increased with time. The breakdown of the hypogene Mn-carbonate was aided by the production of an acidic fluid due to the oxidation of sulphides. Precipitation of the supergene ores was caused by neutralisation of the fluids due to reaction with the host marble and to mixing of relatively reduced fluids with oxygenated surface water in a fluctuation water table regime. Zinc was also mobile during weathering and became concentrated in the intermediate Mn-oxides, effectively stabilising their structures. The mineral paragenesis records the progressive oxidation of the ore and the appearance of less hydrated Mn-oxides, low in alkalis and alkaline earths

A TEM investigation of optical variations in sphalerite.

Sphalerites from the Force Crag Pb-Zn vein, N England, show darker coloured zones found not only to be richer in Cu, Fe, Sb, Ag and Pb but also to contain precipitates of tetrahedrite-like composition. Sphalerites from Silvermines, Ireland, also showed trace-element enriched colour banding but were devoid of precipitates. A low-iron sphalerite from Tyndrum, Scotland, showed opaque bands found to be enriched in Cu and Fe related to the intergrowths of digenite. -R.A.H

Silver substitution into synthetic zinc, cadmium, and iron tetrahedrites.

The limit of Ag substitution in natural zincian tetrahedrites is approx 4 Ag per half unit cell, (Cu,Ag)10(Zn,Fe)2Sb4S13, and into iron tetrahedrites approx 6.5 Ag. The cell size increases with increasing Ag up to 4 Ag but then decreases. In synthetic material the highest substitution achieved was 4.7 Ag in Zn2-tetrahedrite, 7.02 Ag in Cd2-tetrahedrite and 6.80 Ag in Fe2-tetrahedrite. For these synthetic phases the largest cell size was a 10.927 A for the 7.02 Ag in Cd2- tetrahedrite. An explanation for the limit of 7 Ag substitution is given on the basis of a combined electron band/molecular orbital approach.- R.A.H

Clinical Utility of Random Anti–Tumor Necrosis Factor Drug–Level Testing and Measurement of Antidrug Antibodies on the Long-Term Treatment Response in Rheumatoid Arthritis

Objective: To investigate whether antidrug antibodies and/or drug non-trough levels predict the long-term treatment response in a large cohort of patients with rheumatoid arthritis (RA) treated with adalimumab or etanercept and to identify factors influencing antidrug antibody and drug levels to optimize future treatment decisions.  Methods: A total of 331 patients from an observational prospective cohort were selected (160 patients treated with adalimumab and 171 treated with etanercept). Antidrug antibody levels were measured by radioimmunoassay, and drug levels were measured by enzyme-linked immunosorbent assay in 835 serial serum samples obtained 3, 6, and 12 months after initiation of therapy. The association between antidrug antibodies and drug non-trough levels and the treatment response (change in the Disease Activity Score in 28 joints) was evaluated.  Results: Among patients who completed 12 months of followup, antidrug antibodies were detected in 24.8% of those receiving adalimumab (31 of 125) and in none of those receiving etanercept. At 3 months, antidrug antibody formation and low adalimumab levels were significant predictors of no response according to the European League Against Rheumatism (EULAR) criteria at 12 months (area under the receiver operating characteristic curve 0.71 [95% confidence interval (95% CI) 0.57, 0.85]). Antidrug antibody–positive patients received lower median dosages of methotrexate compared with antidrug antibody–negative patients (15 mg/week versus 20 mg/week; P = 0.01) and had a longer disease duration (14.0 versus 7.7 years; P = 0.03). The adalimumab level was the best predictor of change in the DAS28 at 12 months, after adjustment for confounders (regression coefficient 0.060 [95% CI 0.015, 0.10], P = 0.009). Etanercept levels were associated with the EULAR response at 12 months (regression coefficient 0.088 [95% CI 0.019, 0.16], P = 0.012); however, this difference was not significant after adjustment. A body mass index of ≥30 kg/m2 and poor adherence were associated with lower drug levels.  Conclusion: Pharmacologic testing in anti–tumor necrosis factor–treated patients is clinically useful even in the absence of trough levels. At 3 months, antidrug antibodies and low adalimumab levels are significant predictors of no response according to the EULAR criteria at 12 months

Harnessing the extracellular bacterial production of nanoscale cobalt ferrite with exploitable magnetic properties

Nanoscale ferrimagnetic particles have a diverse range of uses from directed cancer therapy and drug delivery systems to magnetic recording media and transducers. Such applications require the production of monodisperse nanoparticles with well-controlled size, composition, and magnetic properties. To fabricate these materials purely using synthetic methods is costly in both environmental and economical terms. However, metal-reducing microorganisms offer an untapped resource to produce these materials. Here, the Fe(III)-reducing bacterium Geobacter sulfurreducens is used to synthesize magnetic iron oxide nanoparticles. A combination of electron microscopy, soft X-ray spectroscopy, and magnetometry techniques was employed to show that this method of biosynthesis results in high yields of crystalline nanoparticles with a narrow size distribution and magnetic properties equal to the best chemically synthesized materials. In particular, it is demonstrated here that cobalt ferrite (CoFe2O4) nanoparticles with low temperature coercivity approaching 8 kOe and an effective anisotropy constant of ∼106 erg cm−3 can be manufactured through this biotechnological route. The dramatic enhancement in the magnetic properties of the nanoparticles by the introduction of high quantities of Co into the spinel structure represents a significant advance over previous biomineralization studies in this area using magnetotactic bacteria. The successful production of nanoparticulate ferrites achieved in this study at high yields could open up the way for the scaled-up industrial manufacture of nanoparticles using environmentally benign methodologies