Location of hydrogen atoms in hydronium jarosite

Various models for the crystal structure of hydronium jarosite were determined from Rietveld refinements against neutron powder diffraction patterns collected at ambient temperature and also single-crystal X-ray diffraction data. The possibility of a lower symmetry space group for hydronium jarosite that has been suggested by the literature was investigated. It was found the space group is best described as R3¯m, the same for other jarosite minerals. The hydronium oxygen atom was found to occupy the 3¯m site (3a Wyckoff site). Inadequately refined hydronium bond angles and bond distances without the use of restraints are due to thermal motion and disorder of the hydronium hydrogen atoms across numerous orientations. However, the acquired data do not permit a precise determination of these orientations; the main feature up/down disorder of hydronium is clear. Thus, the highest symmetry model with the least disorder necessary to explain all data was chosen: The hydronium hydrogen atoms were modeled to occupy an m (18 h Wyckoff site) with 50 % fractional occupancy, leading to disorder across two orientations. A rigid body description of the hydronium ion rotated by 60° with H–O–H bond angles of 112° and O–H distances of 0.96 Å was optimal. This rigid body refinement suggests that hydrogen bonds between hydronium hydrogen atoms and basal sulfate oxygen atoms are not predominant. Instead, hydrogen bonds are formed between hydronium hydrogen atoms and hydroxyl oxygen atoms. The structure of hydronium alunite is expected to be similar given that alunite supergroup minerals are isostructural.

Rapid identification of cytochrome P450cam variants by in vivo screening of active site libraries

The selection of cytochrome P450 enzymes from large variant libraries, and the subsequent use of these enzymes in preparative scale biotransformations, remains a formidable challenge due to the complexities of the associated electron transport systems. Here, a powerful approach for the generation and screening of P450cam libraries for new function is presented that is both flexible and robust. A targeted library was generated wherein only the P450cam active-site amino acids Y96 and F98 were fully randomized and biotransformations, using a novel P450cam whole-cell system, were screened by GC–MS for the hydroxylation of diphenylmethane. One in 50 of the reactions screened, including 16 different variants, produced 4-hydroxydiphenylmethane with up to 92% conversion observed in the case of the Y96A variant. These results demonstrate a primary example of the screening of P450cam libraries in a format that is compatible with extension to preparative scale reactions.

A nonlinear observer for estimating transverse stability parameters of marine surface vessels

This paper presents a nonlinear observer for estimating parameters associated with the restoring term of a roll motion model of a marine vessel in longitudinal waves. Changes in restoring, also referred to as transverse stability, can be the result of changes in the vessel's centre of gravity due to, for example, water on deck and also in changes in the buoyancy triggered by variations in the water-plane area produced by longitudinal waves -- propagating along the fore-aft direction along the hull. These variations in the restoring can change dramatically the dynamics of the roll motion leading to dangerous resonance. Therefore, it is of interest to estimate and detect such changes.

Calibration functions for estimating soil moisture from GPR dielectric constant measurements

Ground-penetrating radar (GPR) is widely used for assessment of soil moisture variability in field soils. Because GPR does not measure soil water content directly, it is common practice to use calibration functions that describe its relationship with the soil dielectric properties and textural parameters. However, the large variety of models complicates the selection of the appropriate function. In this article an overview is presented of the different functions available, including volumetric models, empirical functions, effective medium theories, and frequency-specific functions. Using detailed information presented in summary tables, the choice for which calibration function to use can be guided by the soil variables available to the user, the frequency of the GPR equipment, and the desired level of detail of the output. This article can thus serve as a guide for GPR practitioners to obtain soil moisture values and to estimate soil dielectric properties.

Revolving kaleidoscope : site-specificity and the part object in contemporary installation art

This practice-led research project explores the possibilities for restaging and reconfiguring contemporary art installations in multiple and different locations. By exploring ideas and art that demonstrate a kaleidoscopic approach to creative practice, this project examines how analysing artists' particular processes can achieve new understandings and experiences of installation art. This project achieves this through reflection on, and analysis of creative works made throughout the research, and a critical examination of contemporary art practices.

Comparison of 3 accelerometer data reduction approaches, step counts, and 2 self-report measures for estimating physical activity in free-living adults

Background Accelerometers have become one of the most common methods of measuring physical activity (PA). Thus, validity of accelerometer data reduction approaches remains an important research area. Yet, few studies directly compare data reduction approaches and other PA measures in free-living samples. Objective To compare PA estimates provided by 3 accelerometer data reduction approaches, steps, and 2 self-reported estimates: Crouter's 2-regression model, Crouter's refined 2-regression model, the weighted cut-point method adopted in the National Health and Nutrition Examination Survey (NHANES; 2003-2004 and 2005-2006 cycles), steps, IPAQ, and 7-day PA recall. Methods A worksite sample (N = 87) completed online-surveys and wore ActiGraph GT1M accelerometers and pedometers (SW-200) during waking hours for 7 consecutive days. Daily time spent in sedentary, light, moderate, and vigorous intensity activity and percentage of participants meeting PA recommendations were calculated and compared. Results Crouter's 2-regression (161.8 +/- 52.3 minutes/day) and refined 2-regression (137.6 +/- 40.3 minutes/day) models provided significantly higher estimates of moderate and vigorous PA and proportions of those meeting PA recommendations (91% and 92%, respectively) as compared with the NHANES weighted cut-point method (39.5 +/- 20.2 minutes/day, 18%). Differences between other measures were also significant. Conclusions When comparing 3 accelerometer cut-point methods, steps, and self-report measures, estimates of PA participation vary substantially.

Examining the effects of early cost drivers on contingencies

The accuracy of early cost estimates is critical to the success of construction projects. The selected tender price (clients' building cost) is usually seen in previous research as a holistic dependent variable when examining early stage estimates. Unlike other components of construction cost, the amount of contingencies is decided by clients/consultants with consideration of early project information. Cost drivers of contingencies estimates are associated with uncertainty and complexity, and include project size, schedule, ground condition, construction site access, market condition and so on. A path analysis of 133 UK school building contracts was conducted to identify impacts of nine major cost drivers on the determination of contingencies by different clients/cost estimators. This research finds that gross floor area (GFA), schedule and requirement of air conditioning have statistically significant impacts on the contingency determination. The mediating role of schedule between gross floor area and contingencies (GFA→Schedule→Contingencies) was confirmed with the Soble test. The total effects of the three variables on contingencies estimates were obtained with the consideration of this indirect effect. The squared multiple correlation (SMC) of contingencies (=0.624) indicates the identified three variables can explain 62.4% variance of contingencies, and it is comparatively satisfactory considering the heterogeneity among different estimators, unknown estimating techniques and different projects

Mode matching pursuit for estimating dominant modes in bulk power grid

This study presents a general approach to identify dominant oscillation modes in bulk power system by using wide-area measurement system. To automatically identify the dominant modes without artificial participation, spectral characteristic of power system oscillation mode is applied to distinguish electromechanical oscillation modes which are calculated by stochastic subspace method, and a proposed mode matching pursuit is adopted to discriminate the dominant modes from the trivial modes, then stepwise-refinement scheme is developed to remove outliers of the dominant modes and the highly accurate dominant modes of identification are obtained. The method is implemented on the dominant modes of China Southern Power Grid which is one of the largest AC/DC paralleling grids in the world. Simulation data and field-measurement data are used to demonstrate high accuracy and better robustness of the dominant modes identification approach.

Estimating local stream fish assemblage attributes: Sampling effort and efficiency at two spatial scales

As part of a wider study to develop an ecosystem-health monitoring program for wadeable streams of south-eastern Queensland, Australia, comparisons were made regarding the accuracy, precision and relative efficiency of single-pass backpack electrofishing and multiple-pass electrofishing plus supplementary seine netting to quantify fish assemblage attributes at two spatial scales (within discrete mesohabitat units and within stream reaches consisting of multiple mesohabitat units). The results demonstrate that multiple-pass electrofishing plus seine netting provide more accurate and precise estimates of fish species richness, assemblage composition and species relative abundances in comparison to single-pass electrofishing alone, and that intensive sampling of three mesohabitat units (equivalent to a riffle-run-pool sequence) is a more efficient sampling strategy to estimate reach-scale assemblage attributes than less intensive sampling over larger spatial scales. This intensive sampling protocol was sufficiently sensitive that relatively small differences in assemblage attributes (<20%) could be detected with a high statistical power (1-β > 0.95) and that relatively few stream reaches (<4) need be sampled to accurately estimate assemblage attributes close to the true population means. The merits and potential drawbacks of the intensive sampling strategy are discussed, and it is deemed to be suitable for a range of monitoring and bioassessment objectives.

Estimating present day extreme total water level exceedance probabilities around the Australian coastline

The occurrence of extreme water level events along low-lying, highly populated and/or developed coastlines can lead to devastating impacts on coastal infrastructure. Therefore it is very important that the probabilities of extreme water levels are accurately evaluated to inform flood and coastal management and for future planning. The aim of this study was to provide estimates of present day extreme total water level exceedance probabilities around the whole coastline of Australia, arising from combinations of mean sea level, astronomical tide and storm surges generated by both extra-tropical and tropical storms, but exclusive of surface gravity waves. The study has been undertaken in two main stages. In the first stage, a high-resolution (~10 km along the coast) hydrodynamic depth averaged model has been configured for the whole coastline of Australia using the Danish Hydraulics Institute’s Mike21 modelling suite of tools. The model has been forced with astronomical tidal levels, derived from the TPX07.2 global tidal model, and meteorological fields, from the US National Center for Environmental Prediction’s global reanalysis, to generate a 61-year (1949 to 2009) hindcast of water levels. This model output has been validated against measurements from 30 tide gauge sites around Australia with long records. At each of the model grid points located around the coast, time series of annual maxima and the several highest water levels for each year were derived from the multi-decadal water level hindcast and have been fitted to extreme value distributions to estimate exceedance probabilities. Stage 1 provided a reliable estimate of the present day total water level exceedance probabilities around southern Australia, which is mainly impacted by extra-tropical storms. However, as the meteorological fields used to force the hydrodynamic model only weakly include the effects of tropical cyclones the resultant water levels exceedance probabilities were underestimated around western, northern and north-eastern Australia at higher return periods. Even if the resolution of the meteorological forcing was adequate to represent tropical cyclone-induced surges, multi-decadal periods yielded insufficient instances of tropical cyclones to enable the use of traditional extreme value extrapolation techniques. Therefore, in the second stage of the study, a statistical model of tropical cyclone tracks and central pressures was developed using histroic observations. This model was then used to generate synthetic events that represented 10,000 years of cyclone activity for the Australia region, with characteristics based on the observed tropical cyclones over the last ~40 years. Wind and pressure fields, derived from these synthetic events using analytical profile models, were used to drive the hydrodynamic model to predict the associated storm surge response. A random time period was chosen, during the tropical cyclone season, and astronomical tidal forcing for this period was included to account for non-linear interactions between the tidal and surge components. For each model grid point around the coast, annual maximum total levels for these synthetic events were calculated and these were used to estimate exceedance probabilities. The exceedance probabilities from stages 1 and 2 were then combined to provide a single estimate of present day extreme water level probabilities around the whole coastline of Australia.

A dynamic Web agent for verifying the security and integrity of a Web site's contents

To harness safe operation of Web-based systems in Web environments, we propose an SSPA (Server-based SHA-1 Page-digest Algorithm) to verify the integrity of Web contents before the server issues an HTTP response to a user request. In addition to standard security measures, our Java implementation of the SSPA, which is called the Dynamic Security Surveillance Agent (DSSA), provides further security in terms of content integrity to Web-based systems. Its function is to prevent the display of Web contents that have been altered through the malicious acts of attackers and intruders on client machines. This is to protect the reputation of organisations from cyber-attacks and to ensure the safe operation of Web systems by dynamically monitoring the integrity of a Web site's content on demand. We discuss our findings in terms of the applicability and practicality of the proposed system. We also discuss its time metrics, specifically in relation to its computational overhead at the Web server, as well as the overall latency from the clients' point of view, using different Internet access methods. The SSPA, our DSSA implementation, some experimental results and related work are all discussed

Late Pleistocene stratigraphy of IODP Site U1396 and compiled chronology offshore of south and south west Montserrat, Lesser Antilles

Marine sediments around volcanic islands contain an archive of volcaniclastic deposits, which can be used to reconstruct the volcanic history of an area. Such records hold many advantages over often incomplete terrestrial datasets. This includes the potential for precise and continuous dating of intervening sediment packages, which allow a correlatable and temporally-constrained stratigraphic framework to be constructed across multiple marine sediment cores. Here, we discuss a marine record of eruptive and mass-wasting events spanning ~250 ka offshore of Montserrat, using new data from IODP Expedition 340, as well as previously collected cores. By using a combination of high-resolution oxygen isotope stratigraphy, AMS radiocarbon dating, biostratigraphy of foraminifera and calcareous nannofossils and clast componentry, we identify five major events at Soufriere Hills volcano since 250 ka. Lateral correlation of these events across sediment cores collected offshore of the south and south west of Montserrat, have improved our understanding of the timing, extent and associations between events in this area. Correlations reveal that powerful and potentially erosive density-currents travelled at least 33 km offshore, and demonstrate that marine deposits, produced by eruption-fed and mass-wasting events on volcanic islands, are heterogeneous in their spatial distribution. Thus, multiple drilling/coring sites are needed to reconstruct the full chronostratigraphy of volcanic islands. This multidisciplinary study will be vital to interpreting the chaotic records of submarine landslides at other sites drilled during Expedition 340 and provides a framework that can be applied to the stratigraphic analysis of sediments surrounding other volcanic islands.

A model for estimating grid side harmonics of matrix converter based bi-directional IPT systems

Matrix converter (MC) based bi-directional inductive power transfer (BD-IPT) systems are gaining popularity as an efficient and reliable technique with single stage grid integration as opposed to two stage grid integration of conventional grid connected BD-IPT systems. However MCs are invariably rich in harmonics and thus affect both power quality and power factor on the grid side. This paper proposes a mathematical model through which the grid side harmonics of MC based BD-IPT systems can accurately be estimated. The validity of the proposed mathematical model is verified using simulated results of a 3 kW BD-IPT system and results suggest that the MC based BD-IPT systems have a better power factor with higher power quality over conventional grid connected rectifier based systems.

Rapid on-site evaluation of fine needle aspiration specimens by cytology scientists : a review of 3032 specimens

Objectives To determine: (1) the accuracy of cytology scientists at assessing specimen adequacy by rapid on-site evaluation (ROSE) at fine needle aspiration (FNA) cytology collections; and (2) whether thyroid FNA with ROSE has lower inadequacy rates than non-attended FNAs. Methods The ROSE of adequacy for 3032 specimens from 17 anatomical sites collected over a 20-month period was compared with the final report assessment of adequacy. ROSE was performed by 19 cytology scientists. The report profile for 1545 thyroid nodules with ROSE was compared with that for 1536 consecutive non-ROSE thyroid FNAs reported by the same cytopathologists during the study period. Results ROSE was adequate in 75% (2276/3032), inadequate in 12% (366/3032) and in 13% (390/3032) no opinion was rendered. Of the 2276 cases assessed as adequate by ROSE, 2268 (99.6%) were finally reported as adequate for assessment; eight specimens had adequacy downgraded on the final report. Fifty eight per cent of cases with a ROSE assessment of inadequate were reported as adequate (212/366), whereas 93% (363/390) with no opinion rendered were reported as adequate. The overall final report adequacy rate for the 3032 specimens was 94% (2843/3032). Confirmation of a ROSE of adequacy at reporting was uniformly high amongst the 19 scientists, ranging from 98% to 100%. The inadequacy rate for thyroid FNAs with ROSE (6%) was significantly (P < 0.0001) lower than for non-ROSE thyroid FNAs (17%). A significantly (P = 0.02) higher proportion of adequate ROSE thyroid specimens was reported with abnormalities, compared with non-ROSE thyroid collections. Conclusions Cytology scientists are highly accurate at determining specimen adequacy at ROSE for a wide range of body sites. ROSE of thyroid FNAs can significantly reduce inadequate reports.

A robust methodological approach for mine site water accounting

Over the past decade, the mining industry has come to recognise the importance of water both to itself and to others. Water accounting is a formalisation of this importance that quantifies and communicates how water is used by individual sites and the industry as a whole. While there are a number of different accounting frameworks that could be used within the industry, the Minerals Council of Australia’s (MCA) Water Accounting Framework (WAF) is an industry-led approach that provides a consistent representation of mine site water interactions regardless of their operational, social or environmental context that allows for valid comparisons between sites and companies. The WAF contains definitions of offsite water sources and destinations and onsite water use, a methodology for applying the definitions and a set of metrics to measure site performance. The WAF is comprised of two models: the Input-Output Model, which represents the interactions between sites and their surrounding community and the Operational Model, which represents onsite water interactions. Members of the MCA have recently adopted the WAF’s Input-Output Model to report on their external water interactions in their Australian operations with some adopting it on a global basis. To support this adoption, there is a need for companies to better understand how to implement the WAF in their own operations. Developing a water account is non-trivial, particularly for sites unfamiliar with the WAF or for sites with the need to represent unusual features. This work describes how to build a water account for a given site using the Input-Output Model with an emphasis on how to represent challenging situations.