Site-specific Measurements Research Articles

Evaluating summarised radionuclide concentration ratio datasets for wildlife

Concentration ratios (CRwo-media) are used in most radioecological models to predict whole-body radionuclide activity concentrations in wildlife from those in environmental media. This simplistic approach amalgamates the various factors influencing transfer within a single generic value and, as a result, comparisons of model predictions with site-specific measurements can vary by orders of magnitude. To improve model predictions, the development of ‘condition-specific’ CRwo-media values has been proposed (e.g. for a specific habitat). However, the underlying datasets for most CRwo-media value databases, such as the wildlife transfer database (WTD) developed within the IAEA EMRAS II programme, include summarised data. This presents challenges for the calculation and subsequent statistical evaluation of condition-specific CRwo-media values. A further complication is the common use of arithmetic summary statistics to summarise data in source references, even though CRwo-media values generally tend towards a lognormal distribution and should, therefore, be summarised using geometric statistics. In this paper, we propose a statistically-defensible and robust method for reconstructing underlying datasets to calculate condition-specific CRwo-media values from summarised data and deriving geometric summary statistics. This method is applied to terrestrial datasets from the WTD. Statistically significant differences in sub-category CRwo-media values (e.g. mammals categorised by feeding strategy) were identified, which may justify the use of these CRwo-media values for specific assessment contexts. However, biases and limitations within the underlying datasets of the WTD explain some of these differences. Given the uncertainty in the summarised CRwo-media values, we suggest that the CRwo-media approach to estimating transfer is used with caution above screening-level assessments.

A new approach to estimation of methane emission rates from landfills

Methane emission monitoring has become increasingly essential for diffusive area sources, especially for landfills, which contribute to a significant fraction of the total anthropogenic methane emission globally. Statutorily, methane emission rate from landfills in Germany shall be examined on a semiannual basis; however, an appropriate approach has yet to be developed and adopted for general use. In this study, a new method is proposed based on experimental results, which utilizes a TDLAS (Tunable Diode Laser Absorption Spectroscopy) instrument – GasFinder2.0® system and a dispersion model LASAT (Lagrangian Simulation of Aerosol Transport) as the measurement device and calculation model, respectively. Between April 2010 and December 2011, a research project was conducted at a pilot scale landfill in the south of Germany. Drawing on the extensive research into this pilot project, an effective strategy of measurement setup was determined. Methane concentration was measured with GasFinder2.0® system in the upstream and downstream sections of the project site, while wind and turbulence data were measured simultaneously by an ultrasonic anemometer. The average methane emission rate from the source can be calculated by using the results as input data in the dispersion model. With this method, site-specific measurement approaches can be designed for not only landfills, but also different diffusive area sources with less workload and lower cost compared to conventional FID (Flame Ionization Detector) method.

Specific labeling and assignment strategies of valine methyl groups for NMR studies of high molecular weight proteins

The specific protonation of valine and leucine methyl groups in proteins is typically achieved by overexpressing proteins in M9/D2O medium supplemented with either labeled α-ketoisovalerate for the labeling of the four prochiral methyl groups or with 2-acetolactate for the stereospecific labeling of the valine and leucine side chains. However, when these labeling schemes are applied to large protein assemblies, significant overlap between the correlations of the valine and leucine methyl groups occurs, hampering the analysis of 2D methyl-TROSY spectra. Analysis of the leucine and valine biosynthesis pathways revealed that the incorporation of labeled precursors in the leucine pathway can be inhibited by the addition of exogenous l-leucine-d10. We exploited this property to label stereospecifically the pro-R and pro-S methyl groups of valine with minimal scrambling to the leucine residues. This new labeling protocol was applied to the 468 kDa homododecameric peptidase TET2 to decrease the complexity of its NMR spectra. All of the pro-S valine methyl resonances of TET2 were assigned by combining mutagenesis with this innovative labeling approach. The assignments were transferred to the pro-R groups using an optimally labeled sample and a set of triple resonance experiments. This improved labeling scheme enables us to overcome the main limitation of overcrowding in the NMR spectra of prochiral methyl groups, which is a prerequisite for the site-specific measurement of the structural and dynamic parameters or for the study of interactions in very large protein assemblies.

Site-Specific Measurements of Lipid Membrane Interfacial Water Dynamics with Multidimensional Infrared Spectroscopy

One route to accessing site-specific dynamical information available with ultrafast multidimensional infrared spectroscopy is the development of robust and versatile vibrational probes. Here we synthesize and characterize a vibrationally labeled cholesterol derivative, (cholesteryl benzoate) chromium tricarbonyl, to probe model lipid membranes, focusing specifically on the membrane-water interface. Utilizing FTIR and polarized-ATR spectroscopies, we determine the location of the chromium tricarbonyl motif to be situated at the water-membrane interface with an orientation of 46 ± 2° relative to the vector normal to the membrane surface. We test the dynamical sensitivity of the (cholesteryl benzoate) chromium tricarbonyl label with two different nonlinear infrared spectroscopy methods, both of which show that the probe is well-suited to the study of membrane dynamics as well as the dynamics of water at the membrane interface. The metal carbonyl vibrational probe located at the surface of a bicelle exhibits spectral diffusion dynamics induced by membrane hydration water that is roughly three times slower than observed using a nearly identical vibrational probe in bulk water.

Trophic transfer of polychlorinated biphenyls (PCB) in a boreal lake ecosystem: Testing of bioaccumulation models

Understanding the fate of persistent organic chemicals in the environment is fundamental information for the successful protection of ecosystems and humans. A common dilemma in risk assessment is that monitoring data reveals contaminant concentrations in wildlife, while the source concentrations, route of uptake and acceptable source concentrations remain unsolved. To overcome this problem, different models have been developed in order to obtain more precise risk estimates for the food webs. However, there is still an urgent need for studies combining modelled and measured data in order to verify the functionality of the models. Studies utilising field-collected data covering entire food webs are particularly scarce. This study aims to contribute to tackling this problem by determining the validity of two bioaccumulation models, BIOv1.22 and AQUAWEBv1.2, for application to a multispecies aquatic food web.A small boreal lake, Lake Kernaalanjärvi, in Finland was investigated for its food web structure and concentrations of PCBs in all trophic levels. Trophic magnification factors (TMFs) were used to measure the bioaccumulation potential of PCBs, and the site-specific environmental parameters were used to compare predicted and observed concentrations.Site-specific concentrations in sediment pore water did not affect the modelling endpoints, but accurate site-specific measurements of freely dissolved concentrations in water turned out to be crucial for obtaining realistic model-predicted concentrations in biota. Numerous parameters and snapshot values affected the model performances, bringing uncertainty into the process and results, but overall, the models worked well for a small boreal lake ecosystem. We suggest that these models can be optimised for different ecosystems and can be useful tools for estimating the bioaccumulation and environmental fate of PCBs.

Development and validation of a lead emission inventory for the Greater Cairo area

Studies that investigate the environmental health risks to Cairo residents invariably conclude that lead is one of the area’s major health hazards. The Cairo Air Improvement Project (CAIP), which was implemented by a team led by Chemonics International, funded by USAID in partnership with the Egyptian Environmental Affairs Agency (EEAA), started developing a lead emission inventory for the greater Cairo (GC) area in 1998. The inventory contains a list by major source of the annual lead emissions in the GC area. Uses of the inventory and associated database include developing effective regulatory and control strategies, assessing emissions trends, and conducting modeling exercises. This paper describes the development of the current lead emissions inventory (1999–2010), along with an approach to develop site specific emission factors and measurements to validate the inventory. This paper discusses the major sources of lead in the GC area, which include lead smelters, Mazout (heavy fuel oil) combustion, lead manufacturing batteries factories, copper foundries, and cement factories. Included will be the trend in the lead emissions inventory with regard to the production capacity of each source category. In addition, the lead ambient measurements from 1999 through 2010 are described and compared with the results of Source Attribution Studies (SAS) conducted in 1999, 2002, and 2010. Due to EEAA/CAIP efforts, a remarkable decrease in more than 90% in lead emissions was attained for 2007.

Fully automated, high‐precision instrumentation for the isotopic analysis of tropospheric N2O using continuous flow isotope ratio mass spectrometry

Measurements of the isotopic composition of nitrous oxide in the troposphere have the potential to bring new information about the uncertain N2O budget, which mole fraction data alone have not been able to resolve. Characterizing the expected subtle variations in tropospheric N2O isotopic composition demands high-precision and high-frequency measurements. To enable useful observations of N2O isotopic composition in tropospheric air to reduce N2O source and sink uncertainty, it was necessary to develop a high-precision measurement system with fully automated capabilities for autonomous deployment at remote research stations. A fully automated pre-concentration system for high-precision measurements of N2O isotopic composition (δ(15)N(β) , δ(15)N(α), δ(18)O) in tropospheric air has been developed which combines a custom liquid-cryogen-free cryo-trapping system and gas chromatograph interfaced to a continuous flow isotope ratio mass spectrometry (IRMS) system. A quadrupole mass spectrometer was coupled in parallel to the IRMS system during development to evaluate peak interference. Multi-port inlet and fully-automated capabilities allow streamlined analyses between in situ air inlet, air standards, flask air sample, or other gas source in exactly replicated analysis sequences. The system has the highest precision to date for (15)N site-specific composition results (δ(15) N(α) ±0.11‰, δ(15)N(β) ±0.14‰ (1σ)), attributed mostly to uniformity of analytical cycles and particular attention to fluorocarbon interference noted for (15)N site-specific measurements by IRMS. Air measurements demonstrated the fully automated capacity and performance. The system makes substantial headway in measurement precision, possibly defining the limits of IRMS measurement capabilities in low concentration N2O air samples, with fully automated capabilities to enable high-frequency in situ measurements.

Radionuclide transfer in marine coastal ecosystems, a modelling study using metabolic processes and site data

This study implements new site-specific data and improved process-based transport model for 26 elements (Ac, Ag, Am, Ca, Cl, Cm, Cs, Ho, I, Nb, Ni, Np, Pa, Pb, Pd, Po, Pu, Ra, Se, Sm, Sn, Sr, Tc, Th, U, Zr), and validates model predictions with site measurements and literature data. The model was applied in the safety assessment of a planned nuclear waste repository in Forsmark, Öregrundsgrepen (Baltic Sea). Radionuclide transport models are central in radiological risk assessments to predict radionuclide concentrations in biota and doses to humans. Usually concentration ratios (CRs), the ratio of the measured radionuclide concentration in an organism to the concentration in water, drive such models. However, CRs vary with space and time and CR estimates for many organisms are lacking. In the model used in this study, radionuclides were assumed to follow the circulation of organic matter in the ecosystem and regulated by radionuclide-specific mechanisms and metabolic rates of the organisms. Most input parameters were represented by log-normally distributed probability density functions (PDFs) to account for parameter uncertainty. Generally, modelled CRs for grazers, benthos, zooplankton and fish for the 26 elements were in good agreement with site-specific measurements. The uncertainty was reduced when the model was parameterized with site data, and modelled CRs were most similar to measured values for particle reactive elements and for primary consumers. This study clearly demonstrated that it is necessary to validate models with more than just a few elements (e.g. Cs, Sr) in order to make them robust. The use of PDFs as input parameters, rather than averages or best estimates, enabled the estimation of the probable range of modelled CR values for the organism groups, an improvement over models that only estimate means. Using a mechanistic model that is constrained by ecological processes enables (i) the evaluation of the relative importance of food and water uptake pathways and processes such as assimilation and excretion, (ii) the possibility to extrapolate within element groups (a common requirement in many risk assessments when initial model parameters are scarce) and (iii) predictions of radionuclide uptake in the ecosystem after changes in ecosystem structure or environmental conditions. These features are important for the longterm (>1000 year) risk assessments that need to be considered for a deep nuclear waste repository.

Pain sensitivity and pericranial tenderness in children with tension-type headache: a controlled study

PurposeTo compare tenderness and pain sensitivity in children (aged 7–17 years) with tension-type headache (TTH) and healthy controls using total tenderness score (TTS), pressure pain threshold (PPT), and pain perceived at suprapressure pain threshold (supraPPT).Patients and methodsTwenty-three children with frequent episodic TTH, 36 with chronic TTH, and 57 healthy controls were included. TTS was measured bilaterally at seven pericranial myofascial structures. PPT and supraPPT were assessed in the finger, m. temporalis, and m. trapezius by a Somedic® algometer. SupraPPT was defined as the pain perceived at a stimulus calculated as the individual site-specific PPT + 50%.StatisticsThe effect of group, sex, age, headache frequency, intensity, and years on TTS, PPT, and supraPPT was analyzed by general linear models. Confirmatory factor analysis was analyzed for mutual relations between measurements.Results and conclusionTenderness increased uniformly in both frequent episodic TTH (median 14; interquartile range [IQR] 10–18; P < 0.001) and chronic TTH (median 13; IQR 9–20; P < 0.001) compared to controls (median 5, IQR 3–11). However, the children with frequent episodic TTH and chronic TTH did not show significantly increased sensitivity when measured by PPT or supraPPT. Factor analysis confirmed that the site-specific measurements depended on general latent variables. Consequently, the PPT and supraPPT tests can be assumed to measure central pain-processing levels.

Do site-specific radiocarbon measurements reflect localized distributions of 14C in biota inhabiting a wetland with point contamination sources?

Duke Swamp is a wetland ecosystem that receives 14C via a groundwater pathway originating from a waste management area on Atomic Energy Canada Limited's Chalk River Laboratories site. This groundwater reaches the surface of the swamp, resulting in relatively high 14C levels over an area of 146 m2. The objective of this study was to quantify 14C concentrations in flora and fauna inhabiting areas of Duke Swamp over the gradient of 14C activity concentrations in moss to determine whether 14C specific activities in receptor biota reflect the localized nature of the groundwater source in the swamp. Representative receptor plants and animals, and corresponding air and soil samples were collected at six sites in Duke Swamp with 14C specific activities in air that ranged from 1140 to 45,900 Bq/kg C. In general, it was found that specific activities of 14C in biota tissues reflected those measured in environmental media collected from the same sampling site. The findings demonstrate that mosses could be used in monitoring programs to ensure protection of biota in areas with elevated 14C, negating the need to capture and euthanize higher organisms.

Empirical Characterization of Propagation Path Loss and Performance Evaluation for Co-Site Urban Environment

The design of future generation communication systems depends so much on the suitability of path loss methods and their suitability to various regions. However, such models, no matter how accurate, will result in co-channel interference and wastage of power when they are used in environments for which they were not developed. So, the best bet is to perform site-specific measurements. This research work characterizes the propagation path loss in an urban environment for co-site CDMA2000-800MHz (CDMA2000 1x/UMTS800) and GSM900MHz. Received Signal Strength (RSS) measurements were gathered in Enugu from Mobile Telecommunications of Nigeria (MTN) Network (GSM900) and Visafone Network (CDMA2000 1x) in sites where each Network operates alone and where both Networks shared sites (co-site or coexistence). RSS data gathered was used to characterize Enugu Urban Environment and a propagation Path Loss model, suitable for scenario with Base Station antenna height above the average rooftop was subsequently developed. SINR was generated to evaluate the Link performance of co-site operation in comparison to Single Network operation in a site.

Site specific measurements and propagation models for GSM in three cities in Northern Nigeria

Site specific measurements and propagation models for GSM in three cities in Northern Nigeria

Magic Angle Spinning NMR of Paramagnetic Proteins

Metal ions are ubiquitous in biochemical and cellular processes. Since many metal ions are paramagnetic due to the presence of unpaired electrons, paramagnetic molecules are an important class of targets for research in structural biology and related fields. Today, NMR spectroscopy plays a central role in the investigation of the structure and chemical properties of paramagnetic metalloproteins, linking the observed paramagnetic phenomena directly to electronic and molecular structure. A major step forward in the study of proteins by solid-state NMR came with the advent of ultrafast magic angle spinning (MAS) and the ability to use (1)H detection. Combined, these techniques have allowed investigators to observe nuclei that previously were invisible in highly paramagnetic metalloproteins. In addition, these techniques have enabled quantitative site-specific measurement of a variety of long-range paramagnetic effects. Instead of limiting solid-state NMR studies of biological systems, paramagnetism provides an information-rich phenomenon that can be exploited in these studies. This Account emphasizes state-of-the-art methods and applications of solid-state NMR in paramagnetic systems in biological chemistry. In particular, we discuss the use of ultrafast MAS and (1)H-detection in perdeuterated paramagnetic metalloproteins. Current methodology allows us to determine the structure and dynamics of metalloenzymes, and, as an example, we describe solid-state NMR studies of microcrystalline superoxide dismutase, a 32 kDa dimer. Data were acquired with remarkably short times, and these experiments required only a few milligrams of sample.

A Global and Spatially Explicit Assessment of Climate Change Impacts on Crop Production and Consumptive Water Use

Food security and water scarcity have become two major concerns for future human's sustainable development, particularly in the context of climate change. Here we present a comprehensive assessment of climate change impacts on the production and water use of major cereal crops on a global scale with a spatial resolution of 30 arc-minutes for the 2030s (short term) and the 2090s (long term), respectively. Our findings show that impact uncertainties are higher on larger spatial scales (e.g., global and continental) but lower on smaller spatial scales (e.g., national and grid cell). Such patterns allow decision makers and investors to take adaptive measures without being puzzled by a highly uncertain future at the global level. Short-term gains in crop production from climate change are projected for many regions, particularly in African countries, but the gains will mostly vanish and turn to losses in the long run. Irrigation dependence in crop production is projected to increase in general. However, several water poor regions will rely less heavily on irrigation, conducive to alleviating regional water scarcity. The heterogeneity of spatial patterns and the non-linearity of temporal changes of the impacts call for site-specific adaptive measures with perspectives of reducing short- and long-term risks of future food and water security.

Site-Specific Measurement of Terbium and Calcium Binding to Calmodulin and Calmodulin Fragments

Calcium controls a variety of cellular processes including muscle contraction, cellular motility, and synaptic function. A key player in many of these signaling events is the evolutionarily conserved Ca2+ sensor, calmodulin (CaM), a 148 amino acid protein consisting of four EF hand Ca2+-binding domains arranged as pairs in two globular domains (N- and C-lobe) connected by a flexible linker. Though extensive work has investigated Ca2+ binding to CaM, published Ca2+ association constants and cooperativity factors vary by several orders of magnitude. Surprisingly little of this variability is attributable to differences in experimental conditions. We have determined through simulations that macroscopic total binding curves are fundamentally insufficient to constrain a complete, quantitative model of Ca2+ binding to CaM. To improve estimates of Ca2+ affinity and cooperativity in binding to CaM we have conducted site-specific binding measurements at each binding site. To detect metal occupancy at individual sites, terbium (Tb3+) ions, which have been shown to effectively substitute for Ca2+ in activating CaM, are sensitized via energy transfer from a minimally invasive tryptophan residue inserted in each EF hand. Through competition experiments, both Ca2+ and Tb3+ association constants can be determined. We have obtained site-specific Tb3+ binding isotherms at all four sites in full CaM and measurements of Tb3+ binding and Ca2+ competition in an isolated, N-lobe CaM fragment. These data suggest distinct Ca2+ and Tb3+ affinities at each of the sites in the N-lobe CaM fragment and distinct Tb3+ affinities at all four sites in full CaM. The additional information obtained through site-specific binding measurements enhances estimates of Ca2+ affinity and cooperativity in binding to CaM. This technique is powerful in its applicability to a variety of EF-hand containing calcium-sensing proteins in isolation or in complex with signaling partners.

Water-use efficiency and productivity trends in Australian irrigated cotton: a review

The aim of this review is to report changes in irrigated cotton water use from research projects and on-farm practice-change programs in Australia, in relation to both plant-based and irrigation engineering disciplines. At least 80% of the Australian cotton-growing area is irrigated using gravity surface-irrigation systems. This review found that, over 23 years, cotton crops utilise 6–7 ML/ha of irrigation water, depending on the amount of seasonal rain received. The seasonal evapotranspiration of surface-irrigated crops averaged 729 mm over this period. Over the past decade, water-use productivity by Australian cotton growers has improved by 40%. This has been achieved by both yield increases and more efficient water-management systems. The whole-farm irrigation efficiency index improved from 57% to 70%, and the crop water use index is &gt;3 kg/mm.ha, high by international standards. Yield increases over the last decade can be attributed to plant-breeding advances, the adoption of genetically modified varieties, and improved crop management. Also, there has been increased use of irrigation scheduling tools and furrow-irrigation system optimisation evaluations. This has reduced in-field deep-drainage losses. The largest loss component of the farm water balance on cotton farms is evaporation from on-farm water storages. Some farmers are changing to alternative systems such as centre pivots and lateral-move machines, and increasing numbers of these alternatives are expected. These systems can achieve considerable labour and water savings, but have significantly higher energy costs associated with water pumping and machine operation. The optimisation of interactions between water, soils, labour, carbon emissions and energy efficiency requires more research and on-farm evaluations. Standardisation of water-use efficiency measures and improved water measurement techniques for surface irrigation are important research outcomes to enable valid irrigation benchmarks to be established and compared. Water-use performance is highly variable between cotton farmers and farming fields and across regions. Therefore, site-specific measurement is important. The range in the presented datasets indicates potential for further improvement in water-use efficiency and productivity on Australian cotton farms.

Locally delivered antioxidant gel as an adjunct to nonsurgical therapy improves measures of oxidative stress and periodontal disease

PurposeThe present study has two aims; firstly, it attempts to verify the presence of oxidative stress by estimating the reactive oxygen species (ROS) levels in periodontal pockets ≥5 mm as compared to controls. The second aim is to evaluate the effect of lycopene as a locally delivered antioxidant gel on periodontal health and on the gingival crevicular fluid (GCF) levels of 8-hydroxydeoxyguanosine (8-OHdG), a marker of oxidative injury.MethodsThirty-one subjects participated in this study. In the pretreatment phase, the ROS levels in pockets ≥5 mm were measured by flow cytometry. Three sites in each subject were randomly assigned into each of the following experimental groups: sham group, only scaling and root planing (SRP) was done; placebo group, local delivery of placebo gel after SRP; and lycopene group, local delivery of lycopene gel after SRP. Clinical parameters included recording site-specific measures of GCF 8-OHdG, plaque, gingivitis, probing depth, and clinical attachment level.ResultsThe gel, when delivered to the sites with oxidative stress, was effective in increasing clinical attachment and in reducing gingival inflammation, probing depth, and 8-OHdG levels as compared to the placebo and sham sites.ConclusionsFrom this trial conducted over a period of 6 months, it was found that locally delivered lycopene seems to be effective in reducing the measures of oxidative stress and periodontal disease.

Farm-level assessment of CO2 and N2O emissions in Lower Saxony and comparison of implementation potentials for mitigation measures in Germany and England

Greenhouse gases (GHG) emissions from agricultural farming practice contribute significantly to European GHG inventories. For example, CO2 is emitted when grassland is converted to cropland or when peatlands are drained and cultivated. N2O emissions result from fertilization. Enabling farmers to reduce their GHG emissions requires sufficient information about its pressure–impact relations as well as incentives, such as regulations and funding, that support climate-friendly agricultural management. This paper discusses potentials to improve the supply of information on: farm-specific climate services or impacts, present policy incentives in Germany and England that support climate-friendly farm management and related adaptation requirements. Tools which have been developed for a farm environmental management software (to be added after review because of potential identification) are presented. These tools assess CO2 emissions from grassland conversion to cropland and peatland cultivation, as well as N2O emissions from nitrogen fertilization. As input data, the CO2 tool requires a classification of soil types according to soil organic carbon storage. The input data based on soil profile samples was compared with reference data from the literature. The N2O tool relies on farm data concerning fertilization. These tools were tested on three farms in order to determine their viability with respect to the availability of required data and the differentiation of results, which determines how well site-specific conservation measures can be identified. Assessing CO2 retention function of grassland conservation to cropland on the test farms leads to spatially differentiated results (~100 to ~900 potentially mitigated t CO2 ha−1). Assessed N2O emissions varied from 0.41 to 1.1 t CO2eq. ha−1 a−1. The proposed methods support policies that promote a more differentiated funding of climate conservation measures. Conservation measures and areas can be selected so that they will have the greatest mitigation effects. However, even though present policy instruments in Germany and England, such as Cross Compliance and agri-environmental measures, have the potential to reduce agricultural GHG, they do not appear to guide measures effectively or site-specifically. In order to close this gap, agri-environmental measures with the potential to support climate protection should be spatially optimized. Additionally, the wetland restoration measures which are most effective in reducing GHG emissions should be included in funding schemes.

Site-Specific Measurement of Water Dynamics in the Substrate Pocket of Ketosteroid Isomerase Using Time-Resolved Vibrational Spectroscopy

Little is known about the reorganization capacity of water molecules at the active sites of enzymes and how this couples to the catalytic reaction. Here, we study the dynamics of water molecules at the active site of a highly proficient enzyme, Δ(5)-3-ketosteroid isomerase (KSI), during a light-activated mimic of its catalytic cycle. Photoexcitation of a nitrile-containing photoacid, coumarin183 (C183), mimics the change in charge density that occurs at the active site of KSI during the first step of the catalytic reaction. The nitrile of C183 is exposed to water when bound to the KSI active site, and we used time-resolved vibrational spectroscopy as a site-specific probe to study the solvation dynamics of water molecules in the vicinity of the nitrile. We observed that water molecules at the active site of KSI are highly rigid, during the light-activated catalytic cycle, compared to the solvation dynamics observed in bulk water. On the basis of this result, we hypothesize that rigid water dipoles at the active site might help in the maintenance of the preorganized electrostatic environment required for efficient catalysis. The results also demonstrate the utility of nitrile probes in measuring the dynamics of local (H-bonded) water molecules in contrast to the commonly used fluorescence methods which measure the average behavior of primary and subsequent spheres of solvation.

Latent Class Modeling for Site- and Non-Site-Specific Classification Accuracy Assessment Without Ground Data

Accuracy assessment should be a fundamental component of an image classification analysis and is typically undertaken following either a non-site- or a site-specific methodology. The assessment of classification accuracy is, however, often difficult, with many challenges associated with the ground data typically required. Using a series of classifications of two test sites, this paper shows that accuracy assessment from both perspectives is possible through the use of a latent class modeling approach in the absence of ground data. This is possible because the parameters of a latent class model that explains the observed associations in class labeling made by a series of classifications provide estimates of class cover and conditional probabilities of class membership that equate to popular non-site- and site-specific (producer's accuracy) measures of accuracy, respectively. Additionally, the latent class model provides a new classification that could be evaluated by traditional means if ground data are available. The classification of each test site derived from the latent class model was accurate, being of equivalent accuracy to a conventional ensemble classification that was based on the same series of classifications for a site. The ability to derive a highly accurate classification and yield estimates of classification accuracy without ground data to form a testing set indicates the considerable promise of the method and a means to reduce demands for costly ground data that may also be a source of error due to imperfections.