Geochemical mass-balance and oxygen-isotope constrains on silcrete formation and its paleoclimatic implications in Southern Australia

Two geographically distinct silcrete associations are present in southern Australia, inland and eastern; these were sampled in central South Australia and central Victoria, respectively, At each site, both silicified and immediately adjacent unsilicified parent material were collected. Analytical data from these pairs were used to construct isocons, assuming Zr immobility, and to calculate the volume change and amount of silica introduced during silicification, These results, together with whole-rock oxygen isotope compositions, were used to determine the delta(18)O of th, introduced silica, The results show that the eastern silcretes in central Victoria are probably linked genetically to the associated basalts, weathering of which supplied the introduced silica, This conclusion is based on the close spatial connection between the two, as well as the substantial amount of introduced silica in the silcretes (greater than in the inland silcretes), resulting in volume increases in some eastern silcretes, Oxygen isotopic calculations for the silcretes indicate that the silica precipitated from groundwaters at temperatures slightly higher than present conditions. Silcrete formation apparently occurred during the Miocene and Pliocene (basalts in Victoria younger than Pliocene lack associated silcrete) and may reflect the much wetter climate in southeastern Australia at that time. The inland silcretes of central South Australia can be divided into pedogenic (the most common) and groundwater varieties. The pedogenic silcretes, which show typical soil features like columnar and nodular textures, contain moderate amounts of introduced silica that precipitated by evaporation from saline groundwaters, For the groundwater silcretes, which have massive textures and formed at or close to the water table, insufficient data are available to determine the mode of formation. The inland pedogenic silcretes have probably been farming from the Eocene-Miocene to the present, implying that conditions of seasonally high evaporation have occurred in central Australia during this time period. Thus silcrete formation depends on a complex interplay between climate and silica supply, and it is impossible to generalize that the presence of silcrete is indicative of a particular climate. Likewise, the elemental composition of silcretes, particularly Ti content, is not necessarily of climatic significance, Nevertheless, detailed geochemical and oxygen isotopic studies of a silcrete and its parent material can elucidate the mechanisms of silcrete formation, and if evaporation is indicated as a major factor in silcrete formation, then the climate at the time was likely to have been at least seasonally arid.

A review of the Apocreadiidae Skrjabin, 1942 (Trematoda : Digenea) and description of Australian species

The Apocreadiidae is reviewed and is considered to include genera recognised previously within the families Apocreadiidae, Homalometridae, Schistorchiidae, Sphincterostomatidae and Trematobrienidae. Key features of the family are extensive vitelline follicles, eye-spot pigment dispersed in forebody, I-shaped excretory vesicle, no cirrus-sac and genital pore opening immediately anterior to the ventral sucker (usually) or immediately posterior to it (Postporus Manter, 1949). Three subfamilies and 18 genera are recognised within the Apocreadiidae. The Apocreadiinae comprises Homalometron Stafford, 1904 (new syn. Barbulostomum Ramsey, 1965), Callohelmis n. g., Choanodera Manter, 1940, Crassicutis Manter, 1936, Dactylotrema Bravo-Hollis & Manter, 1957, Marsupioacetabulum Yamaguti, 1952, Microcreadium Simer, 1929, Myzotus Manter, 1940, Neoapocreadium Siddiqi & Cable, 1960, Neomegasolena Siddiqi & Cable, 1960, Pancreadium Manter, 1954, Procaudotestis Szidat, 1954 and Trematobrien Dollfus, 1950. The Schistorchiinae comprises Schistorchis Luhe, 1906, Sphincterostoma Yamaguti, 1937, Sphincteristomum Oshmarin, Mamaev & Parukhin, 1961 and Megacreadium Nagaty, 1956. The Postporinae comprises only Postporus. A key to subfamilies and genera of the Apocreadiidae is provided. It is argued that there is no convincing basis for the recognition of the genus Apocreadium Manter, 1937 and all its constituent species are combined with Homalometron. The following new combinations are proposed for species previously recognised within Apocreadium: Homalometron balistis (Manter, 1947), H. caballeroi (Bravo-Hollis, 1953), H. cryptum (Overstreet, 1969), H. longisinosum (Manter, 1937), H. manteri (Overstreet, 1970), H. mexicanum (Manter, 1937) and H. vinodae (Ahmad, 1985). Apocreadium uroproctoferum Sogandares-Bernal, 1959 is found to lack a uroproct and is made a synonym of H. mexicanum. Homalometron verrunculi nom. nov. is proposed to replace the secondarily pre-occupied H. caballeroi Lamothe-Argumedo, 1965. Barbulostomum is made a synonym of Homalometron and H. cupuloris (Ramsey, 1965) n. comb. is proposed. Neochoanodera is made a synonym of Choanodera and Choanodera ghanensis (Fischthal & Thomas, 1970) n. comb. is proposed. Species within the Apocreadiinae and Postporinae are reviewed and the following are recorded or described from Australian fishes: Homalometron wrightae n. sp. from Achlyopa nigra (Macleay), H. synagris (Yamaguti, 1953) n. comb. from Scolopsis monogramma (Cuvier), H. stradbrokensis n. sp. from Gerres subfasciatus Cuvier, Marsupioacetabulum opallioderma n. sp. from G. subfasciatus, Neoapocreadium karwarensis (Hafeezullah, 1970) n. comb. from G. subfasciatus, N. splendens n. sp. from S. monogramma and Callohelmis pichelinae n. g., n. sp. from Hemigymnus melapterus (Bloch), H. fasciatus (Bloch), Stethojulis bandanensis (Bleeker) andChoerodon venustus (De Vis). Callohelmis is recognised by the combination of absence of tegumental spines, caeca terminating midway between the testes and posterior end of body, ventral sucker enclosed in a tegumental pouch, prominent muscles radiating through the body from the ventral sucker, vitelline follicles not extending into the forebody, and a very short excretory vesicle that opens ventrally. New combinations for species previously recognised within Crassicutis are proposed as follows: Neoapocreadium caranxi (Bilqees, 1976) n. comb., N. gerridis (Nahhas & Cable, 1964) n. comb., N. imtiazi (Ahmad, 1984) n. comb. and N. marina (Manter, 1947) n. comb. The host-specificity and zoogeography of the Apocreadiinae are considered.

Bonding effects and the crystal structures of (NH4)(2)[Cu(H2O)(6)](SO4)(2) and its (H2O)-O-18 substituted form at 9.5 K

The crystal structures of the Tutton salts (NH4)(2)[Cu(H2O)(6)](SO4)(2), diammonium hexaaquacopper disulfate, formed with normal water and isotopically substituted (H2O)-O-18, have been determined by X-ray diffraction at 9.5 K and are very similar, with Cu-O(7) the longest of the Cu-O bonds of the Jahn-Teller distorted octahedral [Cu(H2O)(6)](2+) complex. It is known that structural differences accompany deuteration of (NH4)(2)[Cu(H2O)(6)](SO4)(2), the most dramatic of which is a switch to Cu-O(8) as the longest such bond. The present result suggests that the structural differences are associated with hydrogen-bonding effects rather than with increased mass of the water ligands affecting the Jahn-Teller coupling. The Jahn-Teller distortions and hydrogen-bonding contacts in the compounds are compared with those reported for other Tutton salts at ambient and high pressure.

Relationships between body mass index and well-being in young Australian women

OBJECTIVE: To explore relationships between body mass index (BMI, kg/m(2)) and indicators of health and well-being in young Australian women. DESIGN: Population based cohort study-baseline cross sectional data. SUBJECTS: 14,779 women aged 18-23 who participated in the baseline survey of the Australian Longitudinal Study on Women's Health in 1996. MEASUREMENTS: Self-reported height, weight, medical conditions, symptoms and SF-36. RESULTS: The majority of women (68%) had a BMI in the range 18.5-

Quantification of free mycophenolic acid by high-performance liquid chromatography-atmospheric pressure chemical ionisation tandem mass spectrometry

To facilitate the investigation of free mycophenolic acid concentrations we developed a high-performance liquid chromatography tandem mass spectrometry method using indomethacin as an internal standard. Free drug was isolated from plasma samples (500 mul) using ultrafiltration, The analytes were extracted from the ultrafiltrate (200 mul) using C-18 solid-phase extraction. Detection was by selected reactant monitoring of mycophenolic acid (m/z 318.9-->190.9) and the internal standard (m/z 356.0-->297.1) with an atmospheric pressure chemical ionisation interface. The total chromatographic analysis time was 12 min. The method was found to be linear over the range investigated, 2.5-200 mug/l (r>0.990, n=6). The relative recovery of the method for the control samples studied (7.5, 40.0 and 150 mug/l) ranged from 95 to 104%. The imprecision of the method, expressed in terms of intra- and inter-day coefficients of variation, was

Energy expenditure and the body cell mass in cystic fibrosis

Poor nutritional status in patients with cystic fibrosis (CF) is associated with severe lung disease, and possible causative factors include inadequate intake, malabsorption, and increased energy requirements. Body cell mass (which can be quantified by measurement of total body potassium) provides an ideal standard for measurements of energy expenditure. The aim of this study was to compare resting energy expenditure (REE) in patients with CF with both predicted values and age-matched healthy children and to determine whether REE was related to either nutritional status or pulmonary function. REE was measured by indirect calorimetry and body cell mass by scanning with total body potassium in 30 patients with CF(12 male, mean age = 13.07 +/- 0.55 y) and 18 healthy children (six male, mean age = 12.56 +/- 1.25 y). Nutritional status was expressed as a percentage of predicted total body potassium; Lung function was measured in the CF group by spirometry and expressed as the percentage of predicted forced expiratory volume in 1 s. Mean REE was significantly increased in the patients with CF compared with healthy children (119.3 +/- 3.1% predicted versus 103.6 +/- 5% predicted, P < 0.001) and, using multiple regression techniques, REE for total body potassium was significantly increased in patients with CF (P = 0.0001). There was no relation between REE and nutritional status or pulmonary disease status in the CF group. In conclusion, REE is increased in children and adolescents with CF but is not directly related to nutritional status or pulmonary disease. Nutrition 2001;17:22-25. (C)Elsevier Science Inc. 2001.

Relating body mass index to figural stimuli: population-based normative data for Caucasians

OBJECTIVE: To establish body mass index (BMI) norms for standard figural stimuli using a large Caucasian population-based sample. In addition, we sought to determine the effectiveness of the figural stimuli to identify individuals as obese or thin. DESIGN: All Caucasian twins born in Virginia between 1915 and 1971 were identified by public birth record. In addition, 3347 individual twins responded to a letter published in the newsletter of the American Association of Retired Persons (AARP). All adult twins (aged 18 and over) from both of these sources and their family members were mailed a 16 page 'Health and Lifestyle' questionnaire. SUBJECTS: BMI and silhouette data were available on 16 728 females and 11 366 males ranging in age from 18- 100. MEASUREMENTS: Self-report information on height-weight, current body size, desired body size and a discrepancy score using standard figural stimuli. RESULTS: Gender- and age-specific norms are presented linking BMI to each of the figural stimuli. Additional norms for desired body size and discrepancy scores are also presented. Receiver operating curves (ROC) indicate that the figural stimuli are effective in classifying individuals as obese or thin. CONCLUSIONS: With the establishment of these norms, the silhouettes used in standard body image assessment can now be linked to BMI. Differences were observed between women and men in terms of desired body size and discrepancy scores, with women preferring smaller sizes. The figural stimuli are a robust technique for classifying individuals as obese or thin.

A sensitive and specific assay for glutathione with potential application to glutathione disulphide, using high-performance liquid chromatography-tandem mass spectrometry

We have utilised the combination of sensitivity and specificity afforded by coupling high-performance liquid chromatography (HPLC) to a tandem mass spectrometer (MS-MS) to produce an assay which is suitable for assaying glutathione (GSH) concentrations in liver tissue. The sensitivity suggests it may also be suitable for extrahepatic tissues, The method has been validated for GSH using mouse liver samples and also allows the assay of GSSG. The stability of GSH under conditions relevant to the assay has been determined. A 20-mul amount of a diluted methanol extract of tissue is injected with detection limits of 0.2 pmol for GSH and 2 pmol for GSSG. The HPLC uses an Altima C-18 (150X4.6 mm, 5 mum) column at 35 degreesC. Chromatography utilises a linear gradient from 0 to 10% methanol in 0.1% formic acid over 5 min, with a final isocratic stage holding at 10% methanol for 5 min. Total flow rate is 0.8 ml/min. The transition from the M+H ion (308.1 m/z for GSH, and 613.3 m/z for GSSG) to the 162.0 m/z (GSH) and 355.3 m/z (GSSG) fragments are monitored. (C) 2001 Elsevier Science B.V. All rights reserved.

Quantification and stability of everolimus (SDZ RAD) in human blood by high-performance liquid chromatography-electrospray tandem mass spectrometry

We report here a validated method for the quantification of a new immunosuppressant drug, everolimus (SDZ RAD), using HPLC-tandem mass spectrometry. Whole blood samples (500 mul) were prepared by protein precipitation, followed by C-18 solid-phase extraction. Mass spectrometric detection was by selected reaction monitoring with an electrospray interface operating in positive ionization mode. The assay was linear from 0.5 to 100 mug/l (r(2) > 0.996, n = 9). The analytical recovery and inter-day imprecision, determined using whole blood quality control samples (n = 5) at 0.5, 1.2, 20.0, and 75.0 mug/l, was 100.3-105.4% and less than or equal to7.6%, respectively. The assay had a mean relative recovery of 94.8 +/- 3.8%. Extracted samples were stable for up to 24 h. Fortified everolimus blood samples were stable at -80 degreesC for at least 8 months and everolimus was found to be stable in blood when taken through at least three freeze-thaw cycles. The reported method provides accurate, precise and specific measurement of everolimus in blood over a wide analytical range and is currently supporting phase 11 and III clinical trials. (C) 2002 Elsevier Science B.V. All rights reserved.

Estimation of body fatness from body mass index and bioelectrical impedance: comparison of New Zealand European, Maori and Pacific Island children

Objective: To compare percentage body fat (%BF) for a given body mass index (BMI) among New Zealand European, Maori and Pacific Island children. To develop prediction equations based on bioimpedance measurements for the estimation of fat-free mass (FFM) appropriate to children in these three ethnic groups. Design: Cross-sectional study. Purposive sampling of schoolchildren aimed at recruiting three children of each sex and ethnicity for each year of age. Double cross-validation of FFM prediction equations developed by multiple regression. Setting: Local schools in Auckland. Subjects: Healthy European, Maori and Pacific Island children (n = 172, 83 M, 89 F, mean age 9.4 +/- 2.8(s. d.), range 5 - 14 y). Measurements: Height, weight, age, sex and ethnicity were recorded. FFM was derived from measurements of total body water by deuterium dilution and resistance and reactance were measured by bioimpedance analysis. Results: For fixed BMI, the Maori and Pacific Island girls averaged 3.7% lower % BF than European girls. For boys a similar relation was not found since BMI did not significantly influence % BF of European boys ( P = 0.18). Based on bioimpedance measurements a single prediction equation was developed for all children: FFM (kg) = 0.622 height (cm)(2)/ resistance +0.234 weight (kg)+1.166, R-2 = 0.96, s. e. e. = 2.44 kg. Ethnicity, age and sex were not significant predictors. Conclusions: A robust equation for estimation of FFM in New Zealand European, Maori and Pacific Island children in the 5 - 14 y age range that is more suitable than BMI for the determination of body fatness in field studies has been developed. Sponsorship: Maurice and Phyllis Paykel Trust, Auckland University of Technology Contestable Grants Fund and the Ministry of Health.

Palaeoclimatic implications of the growth history and stable isotope (delta O-18 and delta C-13) geochemistry of a Middle to Late Pleistocene stalagmite from central-western Italy

The age structure and, stable isotope composition of a stalagmite (CC I) from an upland cave in central-western Italy were studied to investigate regional response to global climatic changes. Four growth phases are constrained by 28 thermal ionization and multi-collector inductively coupled plasma mass spectrometry Th-U ages and reveal intermittent deposition through the period between Marine isotope Stage (MIS) 11 and 3 (similar to380 and similar to43 kyr). Most of the growth took place between similar to380 and similar to280 kyr, a period punctuated briefly by a hiatus in deposition through the glacial maximum of MIS 10. Growth was terminated abruptly at 280 kyr just prior to the MIS 8 glacial maximum. With a present-day chamber temperature of 7.5 degreesC, the timing of hiatuses close to these glacial maxima point to freezing conditions at the time. No deposition was recorded through the entirety of MIS 7 and most of MIS 6, whilst two minor growth phases occurred at similar to141-125 and similar to43 kyr. Growth at 141 kyr indicates temperatures >0 degreesC at a time when MIS 6 ice volumes were close to their maximum. High stable carbon isotope (delta(13)C) values (similar to2.8parts per thousand to +3.1parts per thousand) throughout the stalagmite's growth reflect a persistently low input of biogenic CO2, indicating that the steep, barren and alpine-like recharge area of today ha's been in existence for at least the last similar to380 kyr. During MIS 9, the lowest delta(13)C values occur well after maximum interglacial conditions, suggesting a lag in the development of post-glacial soils in this high-altitude karst. The stable oxygen isotope (delta(18)O) trends match the main structural features of the major climate proxy records (SPECMAP, Vostok and Devils Hole), suggesting that the delta(18)O of CC1 has responded to global-scale climate changes, whilst remarkable similarity exists between CC1 delta(18)O and regional sea-surface temperature reconstructions from North Atlantic core ODP980 and southwest Pacific marine core MD97-2120 through the most detailed part of the CC1 record, MIS 9-8. The results suggest that CC1 and other stalagmites from the cave have the potential to capture a long record of regional temperature trends, particularly in regards to the relative severity of Pleistocene glacial stages. (C) 2004 Elsevier B.V. All rights reserved.

A rapid HPLC-mass spectrometry cyclosporin method suitable for current monitoring practices

Objectives: Cyclosporin is an immunosuppressant drug with a narrow therapeutic window. Trough and 2-h post-dose blood samples are currently used for therapeutic drug monitoring in solid organ transplant recipients. The aim of the current study was to develop a rapid HPLC-tandem mass spectrometry (HPLC-MS) method for the measurement of cyclosporin in whole blood that was not only suitable for the clinical setting but also considered a reference method. Methods: Blood samples (50 mu L) were prepared by protein precipitation followed by C-18 solid-phase extraction while using d(12) cyclosporin as the internal standard. Mass spectrometric detection was by selected reaction monitoring with an electrospray interface in positive ionization mode. Results: The assay was linear from 10 to 2000 mu g/L (r(2) > 0.996, n = 9). Inter-day,analytical recovery and imprecision using whole blood quality control samples at 10, 30, 400, 1500, and 2000 mu g/L were 94.9-103.5% and

Novel cuticular hydrocarbons from the cane beetle Antitrogus parvulus - 4,6,8,10,16-penta- and 4,6,8,10,16,18-hexamethyldocosanes - Unprecedented anti-anti-anti-stereochemistry in the 4,6,8,10-methyltetrad

[GRAPHICS] The major cuticular hydrocarbons from the cane beetle species Antitrogus parvulus are 4,6,8,10,16-penta- and 4,6,8,10,16,18-hexamethyldocosanes, I and 2, respectively. Stereoisomers of 2,4,6,8-tetramethylundecanal of established relative stereochemistry were derived from 2,4,6-trimethylphenol and were then coupled with appropriate methyl-substituted phosphoranes 62 and 25 to furnish alkenes, which on reduction provided diastereomers of I and 2, respectively. Capillary gas chromatography, mass spectrometry, and high resolution C-13 NMR spectroscopy confirmed 1 as either 84a or 84b and 2 as either 15a or 15b. The novelty of these structures and their relative stereochemistry is briefly related to polyketide assembly.

Late pleistocene to holocene composite speleothem O-18 and C-13 chronologies from south island, new Zealand-did a global younger dryas really exist?

Oxygen and carbon data from eight stalagmites from northwest South Island are combined to produce composite records of delta(18)O and delta(13)C from 23.4 ka to the present. The chronology is anchored by 43 thermal ionization mass spectrometry (TIMS) uranium series ages. Delta O-18 values are interpreted as having a first order positive relationship to temperature, but also to be influenced by precipitation in a complex manner. Delta C-13 is interpreted as responding negatively to increases in atmospheric CO, concentration, biological activity and precipitation amount. Six climatic phases are recognized. After adjustment of 1.2parts per thousand for the ice volume effect, the delta(18)O record between 23 and 18 ka varies around -3.72parts per thousand compared to the Holocene average of -3.17parts per thousand. Late-glacial warming commenced between 18.2 and 17.8 ka and accelerated after 16.7 ka, culminating in a positive excursion between 14.70 and 13.53 ka. This was followed by a significant negative excursion between 13.53 and 11.14 ka of up to 0.55parts per thousand depth that overlapped the Antarctic Cold Reversal (ACR) and spanned the Younger Dryas (YD). Positive delta(18)O excursions at 11.14 ka and 6.91-6.47 ka represent the warmest parts of the Holocene. The mid-Holocene from 6 to 2 ka was marked by negative excursions that coincide with increased glacial activity in the South Island. A short positive excursion from 0.71 to 0.57 ka was slightly later than the Medieval Warm Period of Europe. Delta C-13 values were high until 17.79 ka after which there was an abrupt decrease to 17.19 ka followed by a steady decline to a minimum at 10.97 ka. Then followed a general increase, suggesting a drying trend, to 3.23 ka followed by a further general decline. The abrupt decrease in delta-values after 17.79 ka probably corresponds to an increase in atmospheric CO2 concentration, biological activity and wetness at the end of the Last Glaciation, but the reversal identified in the delta(18)O record from 13.53 to 11.14 ka was not reflected in delta(13)C changes. The lowest delta(13)C values coincided with the early Holocene climatic suboptimum when conditions were relatively wet as well as mild. Major trends in the delta(18)O(c) record are similar to the Northern Hemisphere, but second order detail is often distinctly different. Consequently, at the millennial scale, a more convincing case can be made for asymmetric climatic response between the two hemispheres rather than synchronicity. (C) 2004 Elsevier B.V. All rights reserved.

Structure and dynamics of the Shapley Supercluster - Velocity catalogue, general morphology and mass

We present results of our wide-field redshift survey of galaxies in a 285 square degree region of the Shapley Supercluster (SSC), based on a set of 10 529 velocity measurements (including 1201 new ones) on 8632 galaxies obtained from various telescopes and from the literature. Our data reveal that the main plane of the SSC (v approximate to 14 500 km s(-1)) extends further than previous estimates, filling the whole extent of our survey region of 12 degrees by 30 degrees on the sky (30 x 75 h(-1) Mpc). There is also a connecting structure associated with the slightly nearer Abell 3571 cluster complex (v approximate to 12 000 km s(-1)). These galaxies seem to link two previously identified sheets of galaxies and establish a connection with a third one at v = 15 000 km s(-1) near RA = 13(h). They also tend to fill the gap of galaxies between the foreground Hydra-Centaurus region and the more distant SSC. In the velocity range of the Shapley Supercluster (9000 km s(-1) < cz < 18 000 km s(-1)), we found redshift-space overdensities with b(j) < 17.5 of similar or equal to 5.4 over the 225 square degree central region and similar or equal to 3.8 in a 192 square degree region excluding rich clusters. Over the large region of our survey, we find that the intercluster galaxies make up 48 per cent of the observed galaxies in the SSC region and, accounting for the different completeness, may contribute nearly twice as much mass as the cluster galaxies. In this paper, we discuss the completeness of the velocity catalogue, the morphology of the supercluster, the global overdensity, and some properties of the individual galaxy clusters in the Supercluster.