Loss on ignition as a method for estimating organic and carbonate content in sediments: reproducibility and comparability of results

Five test runs were performed to assess possible bias when performing the loss on ignition (LOI) method to estimate organic matter and carbonate content of lake sediments. An accurate and stable weight loss was achieved after 2 h of burning pure CaCO3 at 950 °C, whereas LOI of pure graphite at 530 °C showed a direct relation to sample size and exposure time, with only 40-70% of the possible weight loss reached after 2 h of exposure and smaller samples losing weight faster than larger ones. Experiments with a standardised lake sediment revealed a strong initial weight loss at 550 °C, but samples continued to lose weight at a slow rate at exposure of up to 64 h, which was likely the effect of loss of volatile salts, structural water of clay minerals or metal oxides, or of inorganic carbon after the initial burning of organic matter. A further test-run revealed that at 550 °C samples in the centre of the furnace lost more weight than marginal samples. At 950 °C this pattern was still apparent but the differences became negligible. Again, LOI was dependent on sample size. An analytical LOI quality control experiment including ten different laboratories was carried out using each laboratory's own LOI procedure as well as a standardised LOI procedure to analyse three different sediments. The range of LOI values between laboratories measured at 550 °C was generally larger when each laboratory used its own method than when using the standard method. This was similar for 950 °C, although the range of values tended to be smaller. The within-laboratory range of LOI measurements for a given sediment was generally small. Comparisons of the results of the individual and the standardised method suggest that there is a laboratory-specific pattern in the results, probably due to differences in laboratory equipment and/or handling that could not be eliminated by standardising the LOI procedure. Factors such as sample size, exposure time, position of samples in the furnace and the laboratory measuring affected LOI results, with LOI at 550 °C being more susceptible to these factors than LOI at 950 °C. We, therefore, recommend analysts to be consistent in the LOI method used in relation to the ignition temperatures, exposure times, and the sample size and to include information on these three parameters when referring to the method.

Real-time analysis of δ13C- and δD-CH4 in ambient air with laser spectroscopy: method development and first intercomparison results

In situ and simultaneous measurement of the three most abundant isotopologues of methane using mid-infrared laser absorption spectroscopy is demonstrated. A field-deployable, autonomous platform is realized by coupling a compact quantum cascade laser absorption spectrometer (QCLAS) to a preconcentration unit, called trace gas extractor (TREX). This unit enhances CH4 mole fractions by a factor of up to 500 above ambient levels and quantitatively separates interfering trace gases such as N2O and CO2. The analytical precision of the QCLAS isotope measurement on the preconcentrated (750 ppm, parts-per-million, µmole mole−1) methane is 0.1 and 0.5 ‰ for δ13C- and δD-CH4 at 10 min averaging time. Based on repeated measurements of compressed air during a 2-week intercomparison campaign, the repeatability of the TREX–QCLAS was determined to be 0.19 and 1.9 ‰ for δ13C and δD-CH4, respectively. In this intercomparison campaign the new in situ technique is compared to isotope-ratio mass spectrometry (IRMS) based on glass flask and bag sampling and real time CH4 isotope analysis by two commercially available laser spectrometers. Both laser-based analyzers were limited to methane mole fraction and δ13C-CH4 analysis, and only one of them, a cavity ring down spectrometer, was capable to deliver meaningful data for the isotopic composition. After correcting for scale offsets, the average difference between TREX–QCLAS data and bag/flask sampling–IRMS values are within the extended WMO compatibility goals of 0.2 and 5 ‰ for δ13C- and δD-CH4, respectively. This also displays the potential to improve the interlaboratory compatibility based on the analysis of a reference air sample with accurately determined isotopic composition.

Evaluation of a solid phase microextraction method for community-based monitoring of 1,3-butadiene and benzene in Houston, Texas

The Houston region is home to arguably the largest petrochemical and refining complex anywhere. The effluent of this complex includes many potentially hazardous compounds. Study of some of these compounds has led to recognition that a number of known and probable carcinogens are at elevated levels in ambient air. Two of these, benzene and 1,3-butadiene, have been found in concentrations which may pose health risk for residents of Houston.^ Recent popular journalism and publications by local research institutions has increased the interest of the public in Houston's air quality. Much of the literature has been critical of local regulatory agencies' oversight of industrial pollution. A number of citizens in the region have begun to volunteer with air quality advocacy groups in the testing of community air. Inexpensive methods exist for monitoring of ozone, particulate matter and airborne toxic ambient concentrations. This study is an evaluation of a technique that has been successfully applied to airborne toxics.^ This technique, solid phase microextraction (SPME), has been used to measure airborne volatile organic hydrocarbons at community-level concentrations. It is has yielded accurate and rapid concentration estimates at a relatively low cost per sample. Examples of its application to measurement of airborne benzene exist in the literature. None have been found for airborne 1,3-butadiene. These compounds were selected for an evaluation of SPME as a community-deployed technique, to replicate previous application to benzene, to expand application to 1,3-butadiene and due to the salience of these compounds in this community. ^ This study demonstrates that SPME is a useful technique for quantification of 1,3-butadiene at concentrations observed in Houston. Laboratory background levels precluded recommendation of the technique for benzene. One type of SPME fiber, 85 μm Carboxen/PDMS, was found to be a sensitive sampling device for 1,3-butadiene under temperature and humidity conditions common in Houston. This study indicates that these variables affect instrument response. This suggests the necessity of calibration within specific conditions of these variables. While deployment of this technique was less expensive than other methods of quantification of 1,3-butadiene, the complexity of calibration may exclude an SPME method from broad deployment by community groups.^

A novel method for evaluating an interaction effect of correlated continuous covariates in a linear model

Interaction effect is an important scientific interest for many areas of research. Common approach for investigating the interaction effect of two continuous covariates on a response variable is through a cross-product term in multiple linear regression. In epidemiological studies, the two-way analysis of variance (ANOVA) type of method has also been utilized to examine the interaction effect by replacing the continuous covariates with their discretized levels. However, the implications of model assumptions of either approach have not been examined and the statistical validation has only focused on the general method, not specifically for the interaction effect.^ In this dissertation, we investigated the validity of both approaches based on the mathematical assumptions for non-skewed data. We showed that linear regression may not be an appropriate model when the interaction effect exists because it implies a highly skewed distribution for the response variable. We also showed that the normality and constant variance assumptions required by ANOVA are not satisfied in the model where the continuous covariates are replaced with their discretized levels. Therefore, naïve application of ANOVA method may lead to an incorrect conclusion. ^ Given the problems identified above, we proposed a novel method modifying from the traditional ANOVA approach to rigorously evaluate the interaction effect. The analytical expression of the interaction effect was derived based on the conditional distribution of the response variable given the discretized continuous covariates. A testing procedure that combines the p-values from each level of the discretized covariates was developed to test the overall significance of the interaction effect. According to the simulation study, the proposed method is more powerful then the least squares regression and the ANOVA method in detecting the interaction effect when data comes from a trivariate normal distribution. The proposed method was applied to a dataset from the National Institute of Neurological Disorders and Stroke (NINDS) tissue plasminogen activator (t-PA) stroke trial, and baseline age-by-weight interaction effect was found significant in predicting the change from baseline in NIHSS at Month-3 among patients received t-PA therapy.^

Table 2 Analytical data of the samples by the "Dipole CHIM" at the Yingezhuang gold deposit

CHIM method involves extracting metal ions of electromobile forms in either anodes or cathodes, facilitated by a man-made electric field. This paper presents two newly developed CHIM alternatives that are electrified by a low voltage dipole. The firstly improved technique enables cationic ions to be extracted in a single cathode, whereas the secondly improved technique allows both anionic and cationic species to be extracted simultaneously in an anode and in a cathode. Compared with the traditional CHIM methods, the innovative techniques developed in this paper are characterized by simple instrumentation, low cost and easy operation in field, and in particular enables simultaneous extraction of anionic and cationic species of elements, from which more information can be derived with higher extraction efficiency. Field tests at several well-known mine areas in China confirm the effectiveness and efficiency of the new techniques in exploring for deeply buried ore bodies.

Analytical study and evaluation results of power optimizers for distributed power conditioning in PV arrays

The use of modular or ‘micro’ maximum power point tracking (MPPT) converters at module level in series association, commercially known as “power optimizers”, allows the individual adaptation of each panel to the load, solving part of the problems related to partial shadows and different tilt and/or orientation angles of the photovoltaic (PV) modules. This is particularly relevant in building integrated PV systems. This paper presents useful behavioural analytical studies of cascade MPPT converters and evaluation test results of a prototype developed under a Spanish national research project. On the one hand, this work focuses on the development of new useful expressions which can be used to identify the behaviour of individual MPPT converters applied to each module and connected in series, in a typical grid-connected PV system. On the other hand, a novel characterization method of MPPT converters is developed, and experimental results of the prototype are obtained: when individual partial shading is applied, and they are connected in a typical grid connected PV array

Analytical properties of horizontal visibility graphs in the Feigenbaum scenario

Time series are proficiently converted into graphs via the horizontal visibility (HV) algorithm, which prompts interest in its capability for capturing the nature of different classes of series in a network context. We have recently shown [B. Luque et al., PLoS ONE 6, 9 (2011)] that dynamical systems can be studied from a novel perspective via the use of this method. Specifically, the period-doubling and band-splitting attractor cascades that characterize unimodal maps transform into families of graphs that turn out to be independent of map nonlinearity or other particulars. Here, we provide an in depth description of the HV treatment of the Feigenbaum scenario, together with analytical derivations that relate to the degree distributions, mean distances, clustering coefficients, etc., associated to the bifurcation cascades and their accumulation points. We describe how the resultant families of graphs can be framed into a renormalization group scheme in which fixed-point graphs reveal their scaling properties. These fixed points are then re-derived from an entropy optimization process defined for the graph sets, confirming a suggested connection between renormalization group and entropy optimization. Finally, we provide analytical and numerical results for the graph entropy and show that it emulates the Lyapunov exponent of the map independently of its sign.

A three-dimensional self-adaptive hp finite element method for the characterization of waveguide discontinuities

We propose the use of a highly-accurate three-dimensional (3D) fully automatic hp-adaptive finite element method (FEM) for the characterization of rectangular waveguide discontinuities. These discontinuities are either the unavoidable result of mechanical/electrical transitions or deliberately introduced in order to perform certain electrical functions in modern communication systems. The proposed numerical method combines the geometrical flexibility of finite elements with an accuracy that is often superior to that provided by semi-analytical methods. It supports anisotropic refinements on irregular meshes with hanging nodes, and isoparametric elements. It makes use of hexahedral elements compatible with high-order H(curl)H(curl) discretizations. The 3D hp-adaptive FEM is applied for the first time to solve a wide range of 3D waveguide discontinuity problems of microwave communication systems in which exponential convergence of the error is observed.

Application of the Boundary Element Method to the Analysis of Bridge Abutments

The B.E. technique is applied to an interesting dynamic problem: the interaction between bridges and their abutments. Several two-dimensional cases have been tested in relation with previously published analytical results. A three-dimensional case is also shown and different considerations in relation with the accuracy of the method are described.

Impedance of foundations using the Boundary Integral Equation Method

Dynamic soil-structure interaction has been for a long time one of the most fascinating areas for the engineering profession. The building of large alternating machines and their effects on surrounding structures as well as on their own functional behavior, provided the initial impetus; a large amount of experimental research was done,and the results of the Russian and German groups were especially worthwhile. Analytical results by Reissner and Sehkter were reexamined by Quinlan, Sung, et. al., and finally Veletsos presented the first set of reliable results. Since then, the modeling of the homogeneous, elastic halfspace as a equivalent set of springs and dashpots has become an everyday tool in soil engineering practice, especially after the appearance of the fast Fourier transportation algorithm, which makes possible the treatment of the frequency-dependent characteristics of the equivalent elements in a unified fashion with the general method of analysis of the structure. Extensions to the viscoelastic case, as well as to embedded foundations and complicated geometries, have been presented by various authors. In general, they used the finite element method with the well known problems of geometric truncations and the subsequent use of absorbing boundaries. The properties of boundary integral equation methods are, in our opinion, specially well suited to this problem, and several of the previous results have confirmed our opinion. In what follows we present the general features related to steady-state elastodynamics and a series of results showing the splendid results that the BIEM provided. Especially interesting are the outputs obtained through the use of the so-called singular elements, whose description is incorporated at the end of the paper. The reduction in time spent by the computer and the small number of elements needed to simulate realistically the global properties of the halfspace make this procedure one of the most interesting applications of the BIEM.

Effect of control method on impedance-based interactions in a buck converter

All the interconnected regulated systems are prone to impedance-based interactions making them sensitive to instability and transient-performance degradation. The applied control method affects significantly the characteristics of the converter in terms of sensitivity to different impedance interactions. This paper provides for the first time the whole set of impedance-type internal parameters and the formulas according to which the interaction sensitivity can be fully explained and analyzed. The formulation given in this paper can be utilized equally either based on measured frequency responses or on predicted analytic transfer functions. Usually, the distributed dc-dc systems are constructed by using ready-made power modules without having thorough knowledge on the actual power-stage and control-system designs. As a consequence, the interaction characterization has to be based on the frequency responses measureable via the input and output terminals. A buck converter with four different control methods is experimentally characterized in frequency domain to demonstrate the effect of control method on the interaction sensitivity. The presented analytical models are used to explain the phenomena behind the changes in the interaction sensitivity.