Evidence for Multiple Diagenetic Episodes in Ancient Fluvial-Lacustrine Sedimentary Rocks in Gale Crater, Mars.

The Curiosity rover's exploration of rocks and soils in Gale crater has provided diverse geochemical and mineralogical data sets, underscoring the complex geological history of the region. We report the crystalline, clay mineral, and amorphous phase distributions of four Gale crater rocks from an 80-m stratigraphic interval. The mineralogy of the four samples is strongly influenced by aqueous alteration processes, including variations in water chemistries, redox, pH, and temperature. Localized hydrothermal events are evidenced by gray hematite and maturation of amorphous SiO2 to opal-CT. Low-temperature diagenetic events are associated with fluctuating lake levels, evaporative events, and groundwater infiltration. Among all mudstones analyzed in Gale crater, the diversity in diagenetic processes is primarily captured by the mineralogy and X-ray amorphous chemistry of the drilled rocks. Variations indicate a transition from magnetite to hematite and an increase in matrix-associated sulfates suggesting intensifying influence from oxic, diagenetic fluids upsection. Furthermore, diagenetic fluid pathways are shown to be strongly affected by unconformities and sedimentary transitions, as evidenced by the intensity of alteration inferred from the mineralogy of sediments sampled adjacent to stratigraphic contacts.

Smectite formation in the presence of sulfuric acid: Implications for acidic smectite formation on early Mars.

The excess of orbital detection of smectite deposits compared to carbonate deposits on the martian surface presents an enigma because smectite and carbonate formations are both favored alteration products of basalt under neutral to alkaline conditions. We propose that Mars experienced acidic events caused by sulfuric acid (H2SO4) that permitted phyllosilicate, but inhibited carbonate, formation. To experimentally verify this hypothesis, we report the first synthesis of smectite from Mars-analogue glass-rich basalt simulant (66 wt% glass, 32 wt% olivine, 2 wt% chromite) in the presence of H2SO4 under hydrothermal conditions (~200 °C). Smectites were analyzed by X-ray diffraction, Mossbauer spectroscopy, visible and near-infrared reflectance spectroscopy and electron microprobe to characterize mineralogy and chemical composition. Solution chemistry was determined by Inductively Coupled Plasma Mass Spectrometry. Basalt simulant suspensions in 11-42 mM H2SO4 were acidic with pH ≤ 2 at the beginning of incubation and varied from acidic (pH 1.8) to mildly alkaline (pH 8.4) at the end of incubation. Alteration of glass phase during reaction of the basalt simulant with H2SO4 led to formation of the dioctahedral smectite at final pH ~3 and trioctahedral smectite saponite at final pH ~4 and higher. Anhydrite and hematite formed in the final pH range from 1.8 to 8.4 while natroalunite was detected at pH 1.8. Hematite was precipitated as a result of oxidative dissolution of olivine present in Adirondack basalt simulant. Formation of secondary phases, including smectite, resulted in release of variable amounts of Si, Mg, Na and Ca while solubilization of Al and Fe was low. Comparison of mineralogical and solution chemistry data indicated that the type of smectite (i.e., dioctahedral vs trioctahedral) was likely controlled by Mg leaching from altering basalt and substantial Mg loss created favorable conditions for formation of dioctahedral smectite. We present a model for global-scale smectite formation on Mars via acid-sulfate conditions created by the volcanic outgassing of SO2 in the Noachian and early Hesperian.

Chemistry, mineralogy, and grain properties at Namib and High dunes, Bagnold dune field, Gale crater, Mars: A synthesis of Curiosity rover observations.

The Mars Science Laboratory Curiosity rover performed coordinated measurements to examine the textures and compositions of aeolian sands in the active Bagnold dune field. The Bagnold sands are rounded to subrounded, very fine to medium sized (~45-500 µm) with ≥6 distinct grain colors. In contrast to sands examined by Curiosity in a dust-covered, inactive bedform called Rocknest and soils at other landing sites, Bagnold sands are darker, less red, better sorted, have fewer silt-sized or smaller grains, and show no evidence for cohesion. Nevertheless, Bagnold mineralogy and Rocknest mineralogy are similar with plagioclase, olivine, and pyroxenes in similar proportions comprising >90% of crystalline phases, along with a substantial amorphous component (35% ± 15%). Yet Bagnold and Rocknest bulk chemistry differ. Bagnold sands are Si enriched relative to other soils at Gale crater, and H2O, S, and Cl are lower relative to all previously measured Martian soils and most Gale crater rocks. Mg, Ni, Fe, and Mn are enriched in the coarse-sieved fraction of Bagnold sands, corroborated by visible/near-infrared spectra that suggest enrichment of olivine. Collectively, patterns in major element chemistry and volatile release data indicate two distinctive volatile reservoirs in Martian soils: (1) amorphous components in the sand-sized fraction (represented by Bagnold) that are Si-enriched, hydroxylated alteration products and/or H2O- or OH-bearing impact or volcanic glasses and (2) amorphous components in the fine fraction (<40 µm; represented by Rocknest and other bright soils) that are Fe, S, and Cl enriched with low Si and adsorbed and structural H2O.

Organic molecules in the Sheepbed Mudstone, Gale Crater, Mars.

The Sample Analysis at Mars (SAM) instrument on board the Mars Science Laboratory Curiosity rover is designed to conduct inorganic and organic chemical analyses of the atmosphere and the surface regolith and rocks to help evaluate the past and present habitability potential of Mars at Gale Crater. Central to this task is the development of an inventory of any organic molecules present to elucidate processes associated with their origin, diagenesis, concentration, and long-term preservation. This will guide the future search for biosignatures. Here we report the definitive identification of chlorobenzene (150-300 parts per billion by weight (ppbw)) and C2 to C4 dichloroalkanes (up to 70 ppbw) with the SAM gas chromatograph mass spectrometer (GCMS) and detection of chlorobenzene in the direct evolved gas analysis (EGA) mode, in multiple portions of the fines from the Cumberland drill hole in the Sheepbed mudstone at Yellowknife Bay. When combined with GCMS and EGA data from multiple scooped and drilled samples, blank runs, and supporting laboratory analog studies, the elevated levels of chlorobenzene and the dichloroalkanes cannot be solely explained by instrument background sources known to be present in SAM. We conclude that these chlorinated hydrocarbons are the reaction products of Martian chlorine and organic carbon derived from Martian sources (e.g., igneous, hydrothermal, atmospheric, or biological) or exogenous sources such as meteorites, comets, or interplanetary dust particles. KEY POINTS: First in situ evidence of nonterrestrial organics in Martian surface sediments Chlorinated hydrocarbons identified in the Sheepbed mudstone by SAM Organics preserved in sample exposed to ionizing radiation and oxidative condition.

Volatile and organic compositions of sedimentary rocks in Yellowknife Bay, Gale crater, Mars.

H2O, CO2, SO2, O2, H2, H2S, HCl, chlorinated hydrocarbons, NO, and other trace gases were evolved during pyrolysis of two mudstone samples acquired by the Curiosity rover at Yellowknife Bay within Gale crater, Mars. H2O/OH-bearing phases included 2:1 phyllosilicate(s), bassanite, akaganeite, and amorphous materials. Thermal decomposition of carbonates and combustion of organic materials are candidate sources for the CO2. Concurrent evolution of O2 and chlorinated hydrocarbons suggests the presence of oxychlorine phase(s). Sulfides are likely sources for sulfur-bearing species. Higher abundances of chlorinated hydrocarbons in the mudstone compared with Rocknest windblown materials previously analyzed by Curiosity suggest that indigenous martian or meteoritic organic carbon sources may be preserved in the mudstone; however, the carbon source for the chlorinated hydrocarbons is not definitively of martian origin.

Volatile, isotope, and organic analysis of martian fines with the Mars Curiosity rover.

Samples from the Rocknest aeolian deposit were heated to ~835°C under helium flow and evolved gases analyzed by Curiosity's Sample Analysis at Mars instrument suite. H2O, SO2, CO2, and O2 were the major gases released. Water abundance (1.5 to 3 weight percent) and release temperature suggest that H2O is bound within an amorphous component of the sample. Decomposition of fine-grained Fe or Mg carbonate is the likely source of much of the evolved CO2. Evolved O2 is coincident with the release of Cl, suggesting that oxygen is produced from thermal decomposition of an oxychloride compound. Elevated δD values are consistent with recent atmospheric exchange. Carbon isotopes indicate multiple carbon sources in the fines. Several simple organic compounds were detected, but they are not definitively martian in origin.

Trabecular bone score (TBS): available knowledge, clinical relevance, and future prospects.

The diagnosis of osteoporosis rests on areal bone mineral density (BMD) measurement using DXA. Cancellous bone microarchitecture is a key determinant of bone strength but cannot be measured using DXA. To meet the need for a clinical tool capable of assessing bone microarchitecture, the TBS was developed. The TBS is a texture parameter that evaluates pixel gray-level variations in DXA images of the lumbar spine. The TBS variations may reflect bone microarchitecture. We explain the general principles used to compute the TBS, and we report the correlations between TBS and microarchitectural parameters. Several limitations of the TBS as it is used now are pointed out. We discuss data from currently available clinical studies on the ability of the TBS to identify patients with fractures and to evaluate the fracture risk. We conclude that this new index emphasizes the failure of the BMD T-score to fully capture the fragility fracture risk. However, although microarchitecture may influence the TBS, today, to the best of our understanding, there is no sufficient evidence that a TBS measurement provides reliable information on the status of the bone microarchitecture for a given patient. The TBS depends on gray-level variations and in a projectional image obtained in vivo, these variations can have many causes. Nevertheless, as clinical studies suggest that the TBS predicts the risk of fracture even after adjustment for BMD, we are encouraged to learn more about this score. Additional studies will have to be performed to assess the advantages and limitations of the TBS, in order to ensure that it is used appropriately in clinical practice.

Evidence for calcium carbonate at the Mars Phoenix landing site.

Carbonates are generally products of aqueous processes and may hold important clues about the history of liquid water on the surface of Mars. Calcium carbonate (approximately 3 to 5 weight percent) has been identified in the soils around the Phoenix landing site by scanning calorimetry showing an endothermic transition beginning around 725 degrees C accompanied by evolution of carbon dioxide and by the ability of the soil to buffer pH against acid addition. Based on empirical kinetics, the amount of calcium carbonate is most consistent with formation in the past by the interaction of atmospheric carbon dioxide with liquid water films on particle surfaces.

Use of simulations to assess the injury evaluation and management skills of advanced student athletic therapists at a Canadian university.

Simulations can provide exposure to cases that might not present themselves during a practicum assignment or rotation, allow students to make decisions without risk to a real patient, expose students to critical situations requiring a rapid response, allow students to observe the consequences (good or bad) of their management choices, and provide training to maintain infrequently used skills. Simulation has been used in a variety of medical fields such as anesthesia, emergency medicine, military trauma medicine, intensive care, trauma, and surgical critical care. Within athletic training (athletic therapy, in Canada), simulations might maximize the retention of knowledge, could increase the number of clinical experiences encountered, and aid in the transfer of training to real-life settings. Simulations could also be used as a method for evaluating student performance and assessing whether instructional objectives have been met. The primary purpose of this study was to investigate the use of simulations for the formative assessment of student athletic therapists enrolled in a Canadian University athletic therapy program.

Dissolution kinetics of iron-, manganese-, and copper-containing synthetic hydroxyapatites.

Micronutrient-substituted synthetic hydroxyapatite (SHA) is being evaluated by the National Aeronautics and Space Administration's (NASA) Advanced Life Support (ALS) Program for crop production on long-duration human missions to the International Space Station or for future Lunar or Martian outposts. The stirred-flow technique was utilized to characterize Ca, P, Fe, Mn, and Cu release characteristics from Fe-, Mn-, and Cu-containing SHA in deionized (DI) water, citric acid, and diethylene-triamine-pentaacetic acid (DTPA). Initially, Ca and P release rates decreased rapidly with time and were controlled by a non-SHA calcium phosphate phase(s) with low Ca/P solution molar ratios (0.91-1.51) relative to solid SHA ratios (1.56-1.64). At later times, Ca/P solution molar ratios (1.47-1.79) were near solid SHA ratios and release rates decreased slowly indicating that SHA controlled Ca and P release. Substituted SHA materials had faster dissolution rates relative to unsubstituted SHA. The initial metal release rate order was Mn >> Cu > Fe which followed metal-oxide/phosphate solubility suggesting that poorly crystalline metal-oxides/phosphates were dominating metal release. Similar metal release rates for all substituted SHA (approximately 0.01 cmol kg-1 min-1) at the end of the DTPA experiment indicated that SHA dissolution was supplying the metals into solution and that poorly crystalline metal-oxide/phosphates were not controlling metal release. Results indicate that non-SHA Ca-phosphate phases and poorly crystalline metal-oxide/phosphates will contribute Ca, P, and metals. After these phases have dissolved, substituted SHA will be the source of Ca, P, and metals for plants.

Mineralogical and chemical characterization of iron-, manganese-, and copper-containing synthetic hydroxyapatites.

The National Aeronautics and Space Administration's (NASA) Advanced Life Support (ALS) Program is evaluating the use of Fe-, Mn-, and Cu-containing synthetic hydroxyapatite (SHA) as a slow release fertilizer for crops that might be grown on the International Space Station or at Lunar and Martian outposts. Separate Fe-, Mn-, and Cu-containing SHA materials along with a transition-metal free SHA (pure-SHA) were synthesized using a precipitation method. Chemical and mineralogical analyses determined if and how Fe, Mn, and Cu were incorporated into the SHA structure. X-ray diffraction (XRD), Rietveld refinement, and transmission electron microscopy (TEM) confirmed that SHA materials with the apatite structure were produced. Chemical analyses indicated that the metal containing SHA materials were deficient in Ca relative to pure-SHA. The shift in the infrared PO4-mu 3 vibrations, smaller unit cell parameters, smaller particle size, and greater structural strain for Fe-, Mn-, and Cu-containing SHA compared with pure-SHA suggested that Fe, Mn, and Cu were incorporated into SHA structure. Rietveld analyses revealed that Fe, Mn, and Cu substituted into the Ca2 site of SHA. An Fe-rich phase was detected by TEM analyses and backscattered electron microscopy in the Fe-containing SHA material with the greatest Fe content. The substitution of metals into SHA suggests that metal-SHA materials are potential slow-release sources of micronutrients for plant uptake in addition to Ca and P.

Stereotactic radiosurgery for hypothalamic hamartomas.

Hypothalamic hamartomas are nonneoplastic lesions often characterized by central precocious puberty and gelastic epilepsy. Due to the delicate location surgery is often unsuccessful and associated with considerable risks. In the presented series, Gamma Knife radiosurgery was applied. Four cases (aged between 5-13 years) who presented with medically intractable gelastic epilepsy and increasing secondary generalization, abnormal behaviour and precocious puberty (3 cases) are reported. Hypothalamic hamartomas sized 11-17 mm had been diagnosed by MR imaging. Radiosurgical treatment was performed in general anaesthesia with margin doses of 12-14 Gy to the 50-90% isodoses covering volumes of 600-2300 mm3. After follow-up periods of 12 to 68 months, a continuing decrease both in seizure frequency and intensity was noted (outcome according to Engel: II a (3 cases) and III a (1 case)). All patients are socially reintegrated. MR imaging did not reveal significant changes concerning the size of the lesions. Gamma Knife radiosurgery can be an effective and safe alternative treatment modality for HH capable of achieving good seizure control and improving behavioural disorders in selected cases.

Preservation of cranial nerve function following Gamma Knife radiosurgery for benign skull base meningiomas: experience in 121 patients with follow-up of 5 to 9.8 years.

INTRODUCTION: Microsurgical excision with preservation of juxtaposed neurovascular structures is considered the treatment of choice for skull base meningiomas, but there exists a great controversy regarding surgical resectability, potential risk for subsequent postoperative Cranial Nerve Deficit (CND) and the role of adjuvant or adjunctive treatment options. In this study we evaluated the effect of Gamma Knife Radiosurgery (GKRS) in 121 patients with benign basal meningiomas after a follow-up of 5 to 9.8 years. METHODS: Sixty patients had undergone open resections prior to radiosurgical treatment and 61 patients were treated by GKRS alone. Tumour volumes of 0.5 to 89.9 ccm (median 6.8 ccm) received a median marginal dose of 13 Gy (range 7-25 Gy) at the covering 25% to 80% isodose volume curves (median 45%). RESULTS: Neuroradiological controls demonstrated decreased tumour size in 73 patients (60.3%), stable meningioma volume in 47 cases (38.9%) and tumour enlargement in one patient (0.8%). Clinically, 54 patients (44.6%) improved and 61 cases (50.4%) remained unchanged. Four patients (3.3%) showed temporary and two patients (1.7%) permanent neurological deterioration (unrelated to tumour or treatment in one patient). Two patients (1.7%) developed radiation induced new or aggravated pre-existent CND (1 transient, 1 permanent) and two patients (1.7%) required further surgical resection. CONCLUSION: In our long-term experience, GKRS proved to be an attractive additional and save alternative primary treatment option in selected patients with basal meningiomas. The tumour control rate of 98.3% associated with excellent clinical outcome and low incidence for treatment related CND (1.7%) compares favourably with the reported microsurgical series.

Cranial nerve preservation after radiosurgery of vestibular schwannomas.

Radiosurgery is a management approach used to treat patients with vestibular schwannomas. The goals are long-term tumour growth control, maintenance of cranial nerve function and prevention of new deficiencies. We sought to determine long-term outcomes measuring the potential benefits against the neurological risks of primary radiosurgery. Gamma Knife radiosurgery was applied as a treatment modality for 289 patients with vestibular schwannomas from April 1992 to April 2002. The long-term results of 100 patients who underwent radiosurgery were evaluated. 60 patients received a primary treatment, 40 other cases presented with previously performed subtotal microsurgical resection or recurrence of disease (12-96 months, median 39). The median treatment volume was 3.4 ccm and the median dose to the tumour margin was 13 Gy. The median patient follow-up time was 76 months (range 60-120 months). Four tumours progressed after primary radiosurgery. Tumour control rate was 96%. Useful hearing (Gardner-Robertson I/II) was preserved in 16 patients (55%). Clinical neurological improvement occurred in 50%. Adverse effects comprised neurological symptoms (incomplete facial palsy) (House-Brackman II/III) in six cases (four recovered completely), mild transient trigeminal neuropathy in five cases, and morphological changes displaying rapid enlargement of preexisting macrocysts in two patients and tumour growth in two other patients. Microsurgical resection was performed in four cases (4%) and two patients underwent a shunting procedure because of hydrocephalus formation (2%). In patients who had undergone previous microsurgery, no new cranial nerve deficit was observed. Radiosurgery is an effective method for growth control of vestibular schwannomas and is associated with both a low mortality rate and a good quality of life. Accordingly, for the preservation of cranial nerve function radiosurgery is a useful method for the management of properly selected patients and is comparable to microsurgery.

Gamma Knife radiosurgery of brainstem gliomas.

From August 1992 until December 1999 Gamma Knife radiosurgery (GKRS) was applied to 21 patients (male to female ratio 14:7) with brainstem gliomas. Patient's median age was 23 years (8-56 years). All tumours were histologically confirmed by biopsy or open surgery: 12 low-grade gliomas and 9 malignant growths. Two lesions were located primarily in the medulla, 12 in the pons and 7 in the midbrain. A median dose of 12 Gy (9-20 Gy) was applied to the tumour margin by the median isodose of 45%. Prior to radiosurgery 4 patients were treated by conventional radiotherapy, 1 had radiotherapy and chemotherapy, 1 patient underwent chemotherapy, and 1 patient was shunted due to hydrocephalus. Neuroimaging controls (MR, CT) were obtained from 19 patients. The median interval between radiosurgery and the last neuroimaging control was 11.8 months (1-74 months). Neuroimaging depicted tumour progression in 2 patients, stable disease in 10 patients and regression in 3 cases. Follow-up periods ranged between 3 and 99 months (median 29 months). The neurological state improved in 5 patients. Microsurgical cyst fenestration was performed in 1 patient after GKRS, shunting procedure was necessary for 2 patients. Nine patients died unrelated to radiosurgery within 3 to 45 months (median 20.7 months). GKRS is an effective treatment modality for brainstem gliomas with satisfying tumour control and functional outcome.

The role of Gamma Knife radiosurgery in the management of glomus jugular tumours.

BACKGROUND: Glomus jugular tumours are usually managed by microsurgical resection and/or radiotherapy with considerable risk for treatment-related morbidity. The role of Gamma Knife Radiosurgery (GKRS) in the management of these lesions remains to be defined. METHOD: Between May 1992 and November 2000, 19 patients with glomus tumours underwent GKRS at our department. Nine patients received radiosurgery for residual or recurrent paragangliomas following microsurgical resection and in 10 cases GKRS was performed as primary treatment. The median tumour volume was 5.22 ccm (range: 0.38-33.5 ccm). Marginal doses of 12-20 Gy (median 14 Gy) were applied to enveloping isodose volume curves (Range: 30-55%, median 50%). FINDINGS: Except for an 81-year-old patient who died 9 months after radiosurgery the observation time ranged from 1.5 to 10 years (median 7.2 yrs). The total tumour control rate was 94.7% (7 cases with decreased and 11 with stable tumour size). The only patient with tumour progression (5.3%) underwent repeated radiosurgical treatment 85 months after initial GKRS. A newly diagnosed second lesion in the cavernous sinus was treated radiosurgically as well 53 months after the first Gamma Knife procedure. On clinical examination 10 patients (52.6%) presented with improved and 8 patients (42.1%) with unchanged neurological status. Deterioration in one patient (5.3%) was not related to tumour or radiosurgery. INTERPRETATION: As GKRS demonstrated to be a minimally invasive treatment alternative to microsurgery and radiotherapy with no acute or chronic toxicity it should be considered more frequently in the primary or adjuvant strategy for glomus jugular tumours.

Combination of surgery and gamma knife radiosurgery--a therapeutic option for patients with tumors of nasal cavity or paranasal sinuses infiltrating the skull base.

UNLABELLED: The purpose of this study was to investigate whether patients operated for skull base-infiltrating malignant tumors of the nasal cavity and/or the paranasal sinuses benefit from an additional Gamma knife radiosurgery. CASE SERIES: eight consecutive patients, (male: female ratio = 1:1, mean age = 52 years, range 34 to 79 years) presented with 2 cyclindric cell carcinomas, 2 adenocarcinomas, 2 malignant neuroblastomas, 1 squamous cell carcinoma, 1 amelanotic melanoma. Tumor stages (UICC) were: 1 T1, 3 T2, 3 T3, 1 T4, all N0, all M0. All patients were primarily treated surgically and 4 weeks later received additional stereotactic radiosurgery. Follow-up was based on computerized tomography (CT), magnetic resonance imaging (MRI), endoscopy, and biopsy. The course of disease was compared to tumor courses with surgery but without radiosurgery reported in literature. Four times endoscopic endonasal surgery (EES), once EES in combination with fluorescein technique, once EES plus external approach of frontal sinus, once lateral rhinotomy was performed. All 8 cases underwent radiosurgery (Leksell gamma knife) 4 weeks after surgery. Thirty six months after radiosurgery 6 patients were alive (4 patients without evidence of disease, 1 patient with pulmonary metastasis but without local recurrence, 1 patient with regional metastasis but no local recurrence), 1 patient died 11 months after treatment due to disease, 1 patient died due to a second malignancy. No negative or adverse effects due to radiosurgery were observed. The combination of microsurgery with Leksell Gamma knife radiosurgery appears to be an encouraging therapeutic option. To date no adverse effects have been observed in the presented cases.

Solid state 31phosphorus nuclear magnetic resonance of iron-, manganese-, and copper-containing synthetic hydroxyapatites.

The incorporation of micronutrients into synthetic hydroxyapatite (SHA) is proposed for slow release of these nutrients to crops in the National Aeronautics and Space Administration's (NASA's) Advanced Life Support (ALS) program for Lunar or Martian outposts. Solid state 31P nuclear magnetic resonance (NMR) was utilized to examine the paramagnetic effects of Fe3+, Mn2+, and Cu2+ to determine if they were incorporated into the SHA structure. Separate Fe3+, Mn2+, and Cu2+ containing SHA materials along with a transition metal free SHA (pure-SHA) were synthesized using a precipitation method. The proximity (<1 nm) of the transition metals to the 31P nuclei of SHA were apparent when comparing the integrated 31P signal intensities of the pure-SHA (87 arbitrary units g-1) with the Fe-, Mn-, and Cu-SHA materials (37-71 arbitrary units g-1). The lower integrated 31P signal intensities of the Fe-, Mn-, and Cu-SHA materials relative to the pure-SHA suggested that Fe3+, Mn2+, and Cu2+ were incorporated in the SHA structure. Further support for Fe3+, Mn2+, and Cu2+ incorporation was demonstrated by the reduced spin-lattice relaxation constants of the Fe-, Mn-, and Cu-SHA materials (T'=0.075-0.434s) relative to pure-SHA (T1=58.4s). Inversion recovery spectra indicated that Fe3+, Mn2+, and Cu2+ were not homogeneously distributed about the 31P nuclei in the SHA structure. Extraction with diethylene-triamine-penta-acetic acid (DTPA) suggested that between 50 and 80% of the total starting metal concentrations were incorporated in the SHA structure. Iron-, Mn-, and Cu-containing SHA are potential slow release sources of Fe, Mn, and Cu in the ALS cropping system.

Characterization of iron, manganese, and copper synthetic hydroxyapatites by electron paramagnetic resonance spectroscopy.

The incorporation of micronutrients (e.g., Fe, Mn, Cu) into synthetic hydroxyapatite (SHA) is proposed for slow release of these nutrients to crops in NASA's Advanced Life Support (ALS) program for long-duration space missions. Separate Fe3+ (Fe-SHA), Mn2+ (Mn-SHA), and Cu2+ (Cu-SHA) containing SHA materials were synthesized by a precipitation method. Electron paramagnetic resonance (EPR) spectroscopy was used to determine the location of Fe3+, Mn2+, and Cu2+ ions in the SHA structure and to identify other Fe(3+)-, Mn(2+)-, and Cu(2+)-containing phases that formed during precipitation. The EPR parameters for Fe3+ (g=4.20 and 8.93) and for Mn2+ (g=2.01, A=9.4 mT, D=39.0 mT and E=10.5 mT) indicated that Fe3+ and Mn2+ possessed rhombic ion crystal fields within the SHA structure. The Cu2+ EPR parameters (g(z)=2.488, A(z)=5.2 mT) indicated that Cu2+ was coordinated to more than six oxygens. The rhombic environments of Fe3+ and Mn2+ along with the unique Cu2+ environment suggested that these metals substituted for the 7 or 9 coordinate Ca2+ in SHA. The EPR analyses also detected poorly crystalline metal oxyhydroxides or metal-phosphates associated with SHA. The Fe-, Mn-, and Cu-SHA materials are potential slow release sources of Fe, Mn, and Cu for ALS and terrestrial cropping systems.

[Preoperative management of hip osteochondritis: comparison of MRI and arthrography with abduction views]. / Bilan préopératoire des ostéochondrites de hanches: comparaison de l'arthrographie et de l'IRM avec des clichés en abduction.

PURPOSE: Comparison between conventional arthrography and MRI in the preoperative work up of Legg-Calvé-Perthes disease. MATERIAL: ans methods. We studied 17 children (18 hips) who had arthrography and MRI (open-magnet configuration) the same day. Coronal and sagittal T1 weighted were realised with the hip in neutral position. Additional coronal T1 weighted with abduction of the hip were obtained. Two readers analysed individually MRI and arthrographic findings: shape of femoral head, index of Heyman (antero-external covering), came effect, recentering of femoral head and quality of examimation. RESULTS: No statistical difference between MRI and arthrography could be noted-exception made for the index of Heyman. CONCLUSION: MRI can replace arthrography in Legg-Calvé-Perthes disease.