Many coastal marine sediments display highly heterogeneous biogeochemistry due to complex biological and chemical interactions. Existing measurement techniques are limited in their ability to characterize the distributions of reduced species at high resolution in two dimensions. To obtain more detailed information than existing methods, a novel technique for the simultaneous high-resolution (1 mm), two-dimensional determination of porewater iron (II), and sulfide using a gel-based diffusive sampler was developed. A diffusive equilibration in a thin-film (DET) hydrogel was colorized by Ferrozine reagent, imaged electronically, and analyzed using computer imaging densitometry. With the selected gel parameters, the method detection limit for iron (II) was 0.6 μmol L -1
GCMs are used by many national weather services to produce seasonal outlooks of atmospheric and oceanic conditions and fluxes. Postprocessing is often a necessary step before GCM forecasts can be applied in practice. Quantile mapping (QM) is rapidly becoming the method of choice by operational agencies to postprocess raw GCM outputs. The authors investigate whether QM is appropriate for this task. Ensemble forecast postprocessing methods should aim to 1) correct bias, 2) ensure forecasts are reliable in ensemble spread, and 3) guarantee forecasts are at least as skillful as climatology, a property called “coherence.” This study evaluates the effectiveness of QM in achieving these aims by applying it to precipitation forecasts from the POAMA model. It is shown that while QM is highly effective in correcting bias, it cannot ensure reliability in forecast ensemble spread or guarantee coherence. This is because QM ignores the correlation between raw ensemble forecasts and observations. When raw forecasts are not significantly positively correlated with observations, QM tends to produce negatively skillful forecasts. Even when there is significant positive correlation, QM cannot ensure reliability and coherence for postprocessed forecasts. Therefore, QM is not a fully satisfactory method for postprocessing forecasts where the issues of bias, reliability, and coherence pre-exist. Alternative postprocessing methods based on ensemble model output statistics (EMOS) are available that achieve not only unbiased but also reliable and coherent forecasts. This is shown with one such alternative, the Bayesian joint probability modeling approach.
Environmental context. Microbial respiration generally occurs in distinct layers within coastal sediment, producing high porewater iron or sulfide concentrations, although this layering is dramatically modified by the activities of sediment-dwelling organisms. The present study describes use of a new technique to simultaneously measure two-dimensional concentrations of porewater iron and sulfide at millimetre resolution, allowing the patchiness of patterns of microbial respiration in sediment to be clearly observed. The measurements generally supported a conceptual model predicting the effects of animal burrows and seagrass roots on the porewater iron and sulfide distributions, although the addition of organic matter provided some unexpected observations that require further investigation.
Abstract. One of the most powerful predictive tools in sediment biogeochemistry is the electron acceptor layering model, which describes the order in which oxidised compounds are reduced by successions of respiring microbial populations, and how this layering is influenced by benthic macro-organism activity. However, techniques allowing convenient determination of heterogeneous distributions of reduced substances, such as iron(II) and sulfide, have been lacking. A combined diffusive gradients in thin films–diffusive equilibrium in thin films technique was used to quantitatively measure the two-dimensional iron(II) and sulfide distributions at high resolution in the vicinity of various sediment features, including macrofauna burrows, particulate organic matter and macrophyte roots. Substantial heterogeneity was observed for both analytes in all probes, especially in the vicinity of seagrass roots and particulate organic matter. Measured distributions tended to follow the general patterns predicted by the tertiary electron acceptor layering model. However, there was unexpected overlap of sulfide and iron(II) distributions at the millimetre to centimetre scale in several samples from different sediments, notably the more complex sediments containing particulate organic matter and seagrass roots. The cause of such overlap is unclear and further study is necessary to elucidate how such distributions can occur.
Samples of ash from the 18 May 1980 eruption of Mount St. Helens were collected from several locations in eastern Washington and Montana. The ash was subjected to a variety of analyses to determine its chemical, physical, mineralogical, and biological characteristics. Chemically, the ash samples were of dacitic composition. Particle size data showed bimodal distributions and differed considerably with location. However, all samples contained comparable amounts of particles less than 3.5 micrometers in diameter (respirable fraction). Mineralogically, the samples ranged from almost totally glassy to almost totally crystalline. Crystalline samples were dominated by plagioclase feldspar (andesine) and orthopyroxene (hypersthene), with smaller amounts of titanomagnetite and hornblende. All but one of the samples contained from less than 1 percent to 3 percent free crystalline silica (quartz, trydimite, or cristobalite) in both the bulk samples and 1 to 2 percent in the fractions smaller than 3.5 micrometers. The long-lived natural radionuclide content of the ash was comparable to that of crustal material; however, relatively large concentrations of short-lived radon daughters were present and polonium-210 content was inversely correlated with particle size. In vitro biological tests showed the ash to be nontoxic to alveolar macrophages, which are an important part of the lungs' natural clearance mechanism. On the basis of a substantial body of data that has shown a correlation between macrophage cytotoxicity and fibrogenicity of minerals, the ash is not predicted to be highly fibrogenic.
The method is absolute in the determination of single organic substances of known nature, but it is not absolute in the determination of the carbon content of water containing unknown impurities. However, in this case, it may be a very sensitive comparison method.The sensitivity and the precision may be affected by residual organic impurities in blank solutions. This limitation, also affecting the determination of a simple organic substance, can be overcome in industrial water quality evaluation if the cali-bration curve can be obtained with water at different carbon content but coming from the same plant. In this case, the nature of pollution is always the same and no dilution is needed to prepare samples of different carbon content.
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