Thermessaite-(NH4), (NH4)2AlF3(SO4), a new fumarole mineral from la Fossa crater at Vulcano, Aeolian Islands, Italy

Thermessaite-(NH4), ideally (NH4)2AlF3(SO4), is a new mineral found as a medium- to high-temperature (about 250-300°C) fumarole encrustation at the rim of La Fossa crater, Vulcano, Aeolian Islands, Italy. The mineral deposited as aggregates of micrometer-sized sharp prismatic crystals on the surface of a pyroclastic breccia in association with thermessaite, sulfur, arcanite, mascagnite, and intermediate members of the arcanite-mascagnite series. The new mineral is colorless to white, transparent, non-fluorescent, has a vitreous luster, and a white streak. The calculated density is 2.185 g/cm3. Thermessaite-(NH4) is orthorhombic, space group Pbcn, with a = 11.3005(3) Å, b = 8.6125(3) Å, c = 6.8501(2) Å, V = 666.69(4) Å3, Z = 4. The eight strongest reflections in the X-ray powder-diffraction data [d in Å (I) (hkl)] are: 5.65 (100) (200), 4.84 (89) (111), 6.85 (74) (110), 3.06 (56) (112), 3.06 (53) (221), 3.08 (47) (311), 2.68 (28) (022), 2.78 (26) (130). The average chemical composition, determined by quantitative SEM-EDS (N by difference), is (wt%): K2O 3.38, Al2O325.35, SO336.58, F 26.12, (NH4)2O 22.47, O = F -11.00, total 102.90. The empirical chemical formula, calculated on the basis of 7 anions pfu, is [(NH4)1.85K0.15]Σ2.00Al106F2.94-S0.98O3.06. The crystal structure, determined from single-crystal X-ray diffraction data [R(F) = 0.0367], is characterized by corner-sharing AlF4O2octahedra which form [001] octahedral chains by sharing two trans fluoride atoms [Al-F2 = 1.8394(6) Å]. Non-bridging Al-F1 distances are shorter [1.756(1) Å]. The two trans oxygen atoms [Al-O = 1.920(2) Å] are from SO4tetrahedra. NH4+ions occur in layers parallel to (100) which alternate regularly with (100) layers containing ribbons of corner-sharing AlF4O2octahedra and associated SO4 groups. The NH4+ions are surrounded by five oxygen atoms and by four fluorine atoms. The mineral is named as the (NH4)-analogue of thermessaite, K2AlF3(SO4), and corresponds to an anthropogenic phase found in the burning Anna I coal dump of the Anna mine, Aachen, Germany. Both mineral and mineral name have been approved by the IMA-CNMNC commission (IMA 2011-077)

Why Are Outcomes Different for Registry Patients Enrolled Prospectively and Retrospectively? Insights from the Global Anticoagulant Registry in the FIELD-Atrial Fibrillation (GARFIELD-AF).

Background: Retrospective and prospective observational studies are designed to reflect real-world evidence on clinical practice, but can yield conflicting results. The GARFIELD-AF Registry includes both methods of enrolment and allows analysis of differences in patient characteristics and outcomes that may result. Methods and Results: Patients with atrial fibrillation (AF) and ≥1 risk factor for stroke at diagnosis of AF were recruited either retrospectively (n = 5069) or prospectively (n = 5501) from 19 countries and then followed prospectively. The retrospectively enrolled cohort comprised patients with established AF (for a least 6, and up to 24 months before enrolment), who were identified retrospectively (and baseline and partial follow-up data were collected from the emedical records) and then followed prospectively between 0-18 months (such that the total time of follow-up was 24 months; data collection Dec-2009 and Oct-2010). In the prospectively enrolled cohort, patients with newly diagnosed AF (≤6 weeks after diagnosis) were recruited between Mar-2010 and Oct-2011 and were followed for 24 months after enrolment. Differences between the cohorts were observed in clinical characteristics, including type of AF, stroke prevention strategies, and event rates. More patients in the retrospectively identified cohort received vitamin K antagonists (62.1% vs. 53.2%) and fewer received non-vitamin K oral anticoagulants (1.8% vs . 4.2%). All-cause mortality rates per 100 person-years during the prospective follow-up (starting the first study visit up to 1 year) were significantly lower in the retrospective than prospectively identified cohort (3.04 [95% CI 2.51 to 3.67] vs . 4.05 [95% CI 3.53 to 4.63]; p = 0.016). Conclusions: Interpretations of data from registries that aim to evaluate the characteristics and outcomes of patients with AF must take account of differences in registry design and the impact of recall bias and survivorship bias that is incurred with retrospective enrolment. Clinical Trial Registration: - URL: http://www.clinicaltrials.gov . Unique identifier for GARFIELD-AF (NCT01090362)

Improved risk stratification of patients with atrial fibrillation: an integrated GARFIELD-AF tool for the prediction of mortality, stroke and bleed in patients with and without anticoagulation.

OBJECTIVES: To provide an accurate, web-based tool for stratifying patients with atrial fibrillation to facilitate decisions on the potential benefits/risks of anticoagulation, based on mortality, stroke and bleeding risks. DESIGN: The new tool was developed, using stepwise regression, for all and then applied to lower risk patients. C-statistics were compared with CHA2DS2-VASc using 30-fold cross-validation to control for overfitting. External validation was undertaken in an independent dataset, Outcome Registry for Better Informed Treatment of Atrial Fibrillation (ORBIT-AF). PARTICIPANTS: Data from 39 898 patients enrolled in the prospective GARFIELD-AF registry provided the basis for deriving and validating an integrated risk tool to predict stroke risk, mortality and bleeding risk. RESULTS: The discriminatory value of the GARFIELD-AF risk model was superior to CHA2DS2-VASc for patients with or without anticoagulation. C-statistics (95% CI) for all-cause mortality, ischaemic stroke/systemic embolism and haemorrhagic stroke/major bleeding (treated patients) were: 0.77 (0.76 to 0.78), 0.69 (0.67 to 0.71) and 0.66 (0.62 to 0.69), respectively, for the GARFIELD-AF risk models, and 0.66 (0.64-0.67), 0.64 (0.61-0.66) and 0.64 (0.61-0.68), respectively, for CHA2DS2-VASc (or HAS-BLED for bleeding). In very low to low risk patients (CHA2DS2-VASc 0 or 1 (men) and 1 or 2 (women)), the CHA2DS2-VASc and HAS-BLED (for bleeding) scores offered weak discriminatory value for mortality, stroke/systemic embolism and major bleeding. C-statistics for the GARFIELD-AF risk tool were 0.69 (0.64 to 0.75), 0.65 (0.56 to 0.73) and 0.60 (0.47 to 0.73) for each end point, respectively, versus 0.50 (0.45 to 0.55), 0.59 (0.50 to 0.67) and 0.55 (0.53 to 0.56) for CHA2DS2-VASc (or HAS-BLED for bleeding). Upon validation in the ORBIT-AF population, C-statistics showed that the GARFIELD-AF risk tool was effective for predicting 1-year all-cause mortality using the full and simplified model for all-cause mortality: C-statistics 0.75 (0.73 to 0.77) and 0.75 (0.73 to 0.77), respectively, and for predicting for any stroke or systemic embolism over 1 year, C-statistics 0.68 (0.62 to 0.74). CONCLUSIONS: Performance of the GARFIELD-AF risk tool was superior to CHA2DS2-VASc in predicting stroke and mortality and superior to HAS-BLED for bleeding, overall and in lower risk patients. The GARFIELD-AF tool has the potential for incorporation in routine electronic systems, and for the first time, permits simultaneous evaluation of ischaemic stroke, mortality and bleeding risks. CLINICAL TRIAL REGISTRATION: URL: http://www.clinicaltrials.gov. Unique identifier for GARFIELD-AF (NCT01090362) and for ORBIT-AF (NCT01165710)

Two-year outcomes of patients with newly diagnosed atrial fibrillation: results from GARFIELD-AF.

AIMS: The relationship between outcomes and time after diagnosis for patients with non-valvular atrial fibrillation (NVAF) is poorly defined, especially beyond the first year. METHODS AND RESULTS: GARFIELD-AF is an ongoing, global observational study of adults with newly diagnosed NVAF. Two-year outcomes of 17 162 patients prospectively enrolled in GARFIELD-AF were analysed in light of baseline characteristics, risk profiles for stroke/systemic embolism (SE), and antithrombotic therapy. The mean (standard deviation) age was 69.8 (11.4) years, 43.8% were women, and the mean CHA2DS2-VASc score was 3.3 (1.6); 60.8% of patients were prescribed anticoagulant therapy with/without antiplatelet (AP) therapy, 27.4% AP monotherapy, and 11.8% no antithrombotic therapy. At 2-year follow-up, all-cause mortality, stroke/SE, and major bleeding had occurred at a rate (95% confidence interval) of 3.83 (3.62; 4.05), 1.25 (1.13; 1.38), and 0.70 (0.62; 0.81) per 100 person-years, respectively. Rates for all three major events were highest during the first 4 months. Congestive heart failure, acute coronary syndromes, sudden/unwitnessed death, malignancy, respiratory failure, and infection/sepsis accounted for 65% of all known causes of death and strokes for <10%. Anticoagulant treatment was associated with a 35% lower risk of death. CONCLUSION: The most frequent of the three major outcome measures was death, whose most common causes are not known to be significantly influenced by anticoagulation. This suggests that a more comprehensive approach to the management of NVAF may be needed to improve outcome. This could include, in addition to anticoagulation, interventions targeting modifiable, cause-specific risk factors for death. CLINICAL TRIAL REGISTRATION: http://www.clinicaltrials.gov. Unique identifier: NCT01090362

Risk profiles and one-year outcomes of patients with newly diagnosed atrial fibrillation in India: Insights from the GARFIELD-AF Registry.

BACKGROUND: The Global Anticoagulant Registry in the FIELD-Atrial Fibrillation (GARFIELD-AF) is an ongoing prospective noninterventional registry, which is providing important information on the baseline characteristics, treatment patterns, and 1-year outcomes in patients with newly diagnosed non-valvular atrial fibrillation (NVAF). This report describes data from Indian patients recruited in this registry. METHODS AND RESULTS: A total of 52,014 patients with newly diagnosed AF were enrolled globally; of these, 1388 patients were recruited from 26 sites within India (2012-2016). In India, the mean age was 65.8 years at diagnosis of NVAF. Hypertension was the most prevalent risk factor for AF, present in 68.5% of patients from India and in 76.3% of patients globally (P < 0.001). Diabetes and coronary artery disease (CAD) were prevalent in 36.2% and 28.1% of patients as compared with global prevalence of 22.2% and 21.6%, respectively (P < 0.001 for both). Antiplatelet therapy was the most common antithrombotic treatment in India. With increasing stroke risk, however, patients were more likely to receive oral anticoagulant therapy [mainly vitamin K antagonist (VKA)], but average international normalized ratio (INR) was lower among Indian patients [median INR value 1.6 (interquartile range {IQR}: 1.3-2.3) versus 2.3 (IQR 1.8-2.8) (P < 0.001)]. Compared with other countries, patients from India had markedly higher rates of all-cause mortality [7.68 per 100 person-years (95% confidence interval 6.32-9.35) vs 4.34 (4.16-4.53), P < 0.0001], while rates of stroke/systemic embolism and major bleeding were lower after 1 year of follow-up. CONCLUSION: Compared to previously published registries from India, the GARFIELD-AF registry describes clinical profiles and outcomes in Indian patients with AF of a different etiology. The registry data show that compared to the rest of the world, Indian AF patients are younger in age and have more diabetes and CAD. Patients with a higher stroke risk are more likely to receive anticoagulation therapy with VKA but are underdosed compared with the global average in the GARFIELD-AF. CLINICAL TRIAL REGISTRATION-URL: http://www.clinicaltrials.gov. Unique identifier: NCT01090362

Description and unique crystal-structure of waterhouseite, a new hydroxy manganese phosphate species from the Iron Monarch deposit, middleback ranges, South Australia

Waterhouseite from the Iron Monarch mine, Iron Knob, South Australia, is a new hydroxy manganese phosphate species that has a unique crystal-structure. The mineral was found in a carbonate-rich zone with gatehouseite, seamanite, rhodochrosite, shigaite, barite, hausmannite and hematite. It occurs as divergent sprays of orange-brown to dark brown bladed crystals up to 1 mm in length but only up to 20 μm in thickness. The crystals are transparent with a pearly luster on cleavages, but it is vitreous to pearly on the tabular faces. The mineral is brittle, with a conchoidal fracture and a yellowish brown streak. There is a perfect cleavage on (100) and a probable cleavage on (001). The crystals show the principal forms {100} (dominant), {010}, {011} and {001}. All crystals are twinned on (100) by non-merohedry. The Mohs hardness is estimated to be ∼4, and the measured density is 3.55(5) g/cm3 (calculated density is 3.591 g/cm3). Crystals are biaxial negative and length-slow, with α 1.730(3), β ∼1.738 and γ 1.738(4), but 2V could not be measured. Interference colors are normal, implying the absence of optical dispersion. The optical orientation is XYZ = bac (pseudo-orthorhombic), and the pleochroism is X pale brownish, Y brown-yellow, Z pale brownish, with absorption Z = X > Y. Electron-microprobe analyses yielded the empirical formula Mn7.29[(P1.81As0.07 V0.04)∑1.92O7.68](OH,O) 8.32, calculated on the basis of 16 O atoms. The simplified formula is Mn7(PO4)2(OH)8, in agreement with the crystal-structure determination. The strongest five lines in the powder X-ray-diffraction pattern [d in Å(I)(hkl)] are: 4.436(70)(111), 3.621(100)(202), 3.069 (50)(311), 2.941(40)(013), and 2.780(35)(020). Unit-cell parameters refined from powder-diffraction data, a 11.364(6), b 5.570(2), c 10.455(3) Å, β 96.61(3)°, V 657.4(2) Å 3 (Z = 2), agree very well with those refined from the single-crystal data. The crystal structure was solved by direct methods and refined in space group P21/c to R1(F) = 5.15% and wR2all(F2) = 16.28% using data from a twinned crystal (by non-merohedry) with 1400 "observed" reflections with Fo. > 4o-(Fo). The crystal structure is characterized by a dense, complex framework of Mn(O,OH)6 octahedra and PO4 tetrahedra, which are linked by both edges and comers. Two different subunits can be recognized in the structure: arsenoclasite-type strips of edge-sharing octahedra (fragments of brucite-pyrochroite-type sheets of octahedra) and finite chains of edge-sharing octahedra (fragments of infinite rutile-type chains). The PO4 tetrahedra provide a connection between the strips and the chains. Single-crystal Raman spectra confirm weak hydrogen bonding. A unique feature of the structure is that the single PO4 tetrahedron shares two of its edges with Mn(O,OH)6 octahedra. Only two synthetic anhydrous metal arsenates are known that show a corresponding sharing of two edges. The structure of waterhouseite has no equivalent, although the unit-cell parameters reveal some relations with the two chemical analogues allactite, Mn7(AsO4)2(OH)8, and raadeite, M97(PO4)2 (OH)8

New occurrences of watanabeite, colusite, &quot;arsenosulvanite&quot; and &quot;Cu-excess&quot; tetrahedrite-tennantite at the Pef ka high-sulfidation epithermal deposit, northeastern Greece

The high-to intermediate-sulfidation epithermal Cu-Au-Ag-Te deposit at Pefka in northeastern Greece reveals an extraordinary and rare polymetallic ore-mineralogy including several Cu-, Bi-, Sn-, Ge-, V-, As-, Hg-, Au- and Ag-bearing sulfides, sulfosalts, tellurides, native elements and the rare Cu-sulfosalts and chalcogeno-salts watanabeite, colusite, &quot;arsenosuvanite&quot; and &quot;Cu-excess&quot; tetrahedrite-tennantite. Paragenetic sequences suggest deposition of an earlier high-sulfidation metallic ore assemblage (e.g. enargite/luzonite, goldfieldite and native gold), followed by an intermediate-sulfidation ore assemblage (composed of tetrahedrite-tennantite and various tellurides). Watanabeite, colusite and &quot;arsenosulvanite&quot; are intergrown with enargite/luzonite and native copper, thus clearly belonging to the high-sulfidation stage of ore deposition at Pefka. &quot;Cu-excess&quot; tetrahedrite-tennantite postdates enargite/luzonite, thus suggesting deposition at the transition from high-towards intermediate-sulfidation fluid states. Of all known occurrences worldwide, the As:Sb ratio of the Pefka watanabeite is the closest to the type material from the Teine mine, Hokkaido. An extremely Sb-rich analog to watanabeite (with up to 1.4 apfu Sb) detected during this study at Pefka mine, seems to fill the gap within the solid solution between the As-rich member and an unnamed Sb-dominant phase. Colusite at Pefka ranges in composition from colusite sensu stricto to stibiocolusite. In comparison to colusite, &quot;arsenosulvanite&quot; is Sn-free or relatively Sn-poor and moderately anisotropic. The fahlore-group minerals at Pefka reveal an excess in Cu-contents of up to 11.73 and 11.03 apfu for tennantite and tetrahedrite, respectively. Thus, our results suggest that the term &quot;Cu-excess&quot; can be applied for the whole tetrahedrite-tennantite solid solution series. We also detected &quot;Cu-excess&quot; compositions for Zn-bearing, Fe-free tennantite that has not been previously reported. We suggest a continuous evolution of the Pefka hydrothermal system from initial high-temperature (&gt;280°C) high-sulfidation, oxidizing conditions, towards lower-temperature and lower-sulfidation, more reduced conditions with time. This evolution is also reflected in the paragenetic sequence of the fahlore group minerals (e.g. early extreme &quot;Cu-excess&quot; tennantite and tetrahedrite with &gt; 11 apfu Cu was followed by moderate to weak &quot;Cu-excess&quot;-, and finally by fully substituted tennantite and tetrahedrite), being the result of decreasing copper content in the hydrothermal system. The abundance of tellurides and native tellurium in the mineralization is compatible with direct deposition of metals from the vapor phase of a buried porphyry body. © 2015 E. Schweizerbart&apos;sche Verlagsbuchhandlung, Stuttgart, Germany