Final dissolved organic carbon broad community intercalibration and preliminary use of DOC reference materials

A broad community intercalibration exercise for accurate measurement of dissolved organic carbon (DOC) in seawater has been carried out over a period of 5 years. A set of 10 natural samples with DOC content from 40 to 200 μM C were accompanied by two glucose standards and a “zero C” blank; all sealed in glass ampoules. Samples were sent to all interested analysts for “blind” analysis; 62 laboratories in 17 countries participated. A total of 59 separate analyses were determined to be acceptable by screening criteria based on standards and blank; another nine sets of analyses did not pass the screening. The majority of the analyses, both those passing and those that did not, were performed with high temperature combustion (HTC) methods, six sets of analyses were done using wet chemical oxidation methods.From the 53 sets of acceptable HTC analyses, the coefficient of variation (%CV) for analytical comparability of the samples was 10% (“community precision”). It is estimated that the individual replicate injection precision for most instruments was approximately 2% and that no additional variability was caused by differences within the ampoules of individual samples. The additional variability over 2% was likely a result of both random and systematic differences in analytical capabilities from instrument to instrument and from day to day for individual instruments. With an arbitrary selection after the fact, smaller subsets of analysts can show comparability better than 10% and duplicate or triplicate runs on different days of the full sets of samples in several laboratories showed comparability in the 2–6.5% range. Experienced oceanic analysts, with internal or shared reference materials, can now show reproducibility and comparability at a level closer to 2%.Preliminary use of DOC reference materials by 14 participants showed day-to-day reproducibilities for their laboratories in the 2–6% range in most cases; several with poorer reproducibility do not normally perform DOC analyses on samples with concentrations as low as the deep ocean reference used here. Use of these reference materials can also give a demonstration of comparability between laboratories. For credibility of DOC analyses, it is necessary for analysts to use community reference materials and report results of their analytical performance with these references.This paper does not identify individual data nor should it be considered an evaluation of individual laboratories or analysts. The purpose is to show the summary picture of the international community of DOC analysts as it existed in the mid- to late 1990s.     

Physical modeling and visualization of soil liquefaction under high confining stress

The mechanisms of seismically-induced liquefaction of granular soils under high confining stresses are still not fully understood. Evaluation of these mechanisms is generally based on extrapolation of observed behavior at shallow depths. Three centrifuge model tests were conducted at RPI‘s experimental facility to investigate the effects of confining stresses on the dynamic response of a deep horizontal deposit of saturated sand. Liquefaction was observed at high confining stresses in each of the tests. A system identification procedure was used to estimate the associated shear strain and stress time histories. These histories revealed a response marked by shear strength degradation and dilative patterns. The recorded accelerations and pore pressures were employed to generate visual animations of the models. These visualizations revealed a liquefaction front traveling downward and leading to large shear strains and isolation of upper soil layers.     

Quasi-Symmetry and Reversible Markov Sequences in Sedimentary Sections

Quasi-symmetry can be defined as a purely mathematical property of a matrix—that is, any matrix whose entries are strictly positive possesses quasi-symmetry if it can be written as a product of a diagonal and a symmetric matrix. A unique inverse solution for a quasi-symmetric matrix is readily obtained when the nondiagonal elements of the symmetric and quasi-symmetric matrix are set equal. Then it is shown that a Markov sequence is reversible if and only if it has a quasi-symmetric tally matrix. Because a properly counted Markov sequence must have marginal homogeneity, a simple chi-square test for symmetry on the tally matrix is sufficient to determine if an observed matrix is symmetrical and hence whether the Markov chain is reversible. Applications to sedimentary sequences are illustrated by the use of classical examples and with cyclothem data to determine if the sequence conforms to a reversible or nonreversible Markov process. Should the tally matrix lack marginal homogeneity, it is likely that a sampling bias was introduced by the counting procedure. However, a chi-square test for symmetry on a direct inverse of the tally matrix can be used to determine if the sedimentary sequence conforms to a reversible or a non-reversible Markov process.     

Potassium Permanganate Doped Geopolymers for Remedial Applications

This study investigates the use of KMnO₄ doped geopolymers as controlled‐release materials for remedial applications. The geopolymers were prepared by mixing alkali activated Na‐silicate solutions, metakaolin, and various amounts of granular KMnO₄. Samples were heat treated at 75 °C for 48 h. Concentrations of KMnO₄ in samples 1, 2, and 3 were 1.40 × 10^?1, 4.63 × 10^?1, and 6.07 × 10^?1 g/cm³, respectively. 1D column experiments showed that a high MnO₄^? release rate lasted for the first few hours, followed by a gradual decrease of MnO₄^? release. Neither cracks nor surface erosion of the geopolymers were observed throughout the experiments. Sample 1 approached exhaustion at the end of the Day 7. It took about 18 d for exhaustion of KMnO₄ releases in samples 2 and 3. Modeling of the observed KMnO₄ releases suggested diffusion and dissolution‐related fast transport as the most important mechanisms. This latter mechanism involves the creation of a connected secondary porosity in the geopolymers by dissolution of KMnO₄ granules. The contribution of Fickian diffusion to the total release decreased as the KMnO₄ content of the samples increased, and the dissolution mechanism became increasingly important.     

Microhabitat influences on stream insect emergence

Understanding the factors controlling insect emergence from streams has applications to ecological theory regarding cross-boundary flux, along with practical value for monitoring stream function after restoration projects. We hypothesized that stream microhabitat would have effects on emergence that were independent of those mediated by the local stock of benthic macroinvertebrates. We set 50 emergence traps in a third-order stream in northern Minnesota, USA, during two study periods and used structural equation modeling to examine direct and indirect effects of benthic stock and microhabitat features on emergence. Emergence by biomass showed direct positive relationships to substrates of fines and detritus in the first sampling period, and to shallow depth and wood area in the second period. Emergence by abundance had direct positive relationships with benthic stock, CPOM, and fewer macrophytes in the first period, and with benthic stock and periphyton in the second period. Fine substrates may act to concentrate burrowing larvae, whereas CPOM and particularly wood may intercept drifting pre-emergent insects and provide exiting surfaces. Shallow depths may reduce the extent to which resident insects drift downstream (and leave the sample area) while emerging. Periphyton may be an indicator for patches with greater illumination, which itself attracts emergers. Our results suggest emergence is sensitive to environmental conditions at the microhabitat scale, and that stream restoration activities should consider habitat for emerging insects when designing projects.     

Pleistocene geomorphology and geochronology of eastern Grand Canyon: linkages of landscape components during climate changes

We report new mapping, soils, survey, and geochronologic (luminescence, U-series, and cosmogenic-nuclide) data from Pleistocene deposits in the arid setting of eastern Grand Canyon. The result is a stratigraphic framework of inset fill gravels and associated terraces that provide a record of the responses of hillslopes, tributary streams, and the Colorado River to the last 400 kyr of glacial–interglacial climate change. The best-preserved last 80 kyr of this record indicates a stratigraphic–chronologic disconnect between both deposition and incision along the Colorado River versus along the trunks of local tributaries. For example, the Colorado River finished aggrading and had already begun incising before the main pulse of aggradation in the trunks of local catchments during Marine Isotope Stage 3, and then tributary incision followed during the millennial-scale fluctuations of the last glacial epoch, potentially concurrent with mainstem aggradation. The mainstem record appears to broadly correlate with regional paleoclimate and upstream geomorphic records and thus may be responding to climatic–hydrologic changes in its mountain headwaters, with aggradation beginning during full-glacial times and continuing into subsequent interglacials. The contrasting lag time in responses of the dryland catchments within Grand Canyon may be largely a function of the weathering-limited nature of hillslope sediment supply.