The behaviour of dissolved organic material,iron and manganese in estuarine mixing

Fractionation by ultra-filtration of the dissolved organic material (DOM) in the River Beaulieu, with typical concentrations of dissolved organic carbon (DOC) of 7–8 mg C/l, showed it to be mainly in the nominal molecular weight range of 10³–10⁵, with 16–23% of the total DOC in the fraction > 10⁵. The molecular weight distribution of DOM in the more alkaline River Test (average DOC, 2 mg C/l) was similar. In the River Beaulieu water, containing 136–314 βg Fe/l in ‘dissolved’ forms, 90% or more of this Fe was in the nominal molecular weight fraction > 10⁵. Experiments showed that DOM of nominal molecular weight <10⁵ could stabilize Fe(III) in ‘dissolved’ forms. The concentrations of ‘dissolved’ Fe in the river water probably reflect the presence of colloidal Fe stabilized by organic material and this process may influence the apparent molecular weight of the DOM. Dissolved. Mn (100–136 βg/l) in the River Beaulieu was mainly in true solution, probably as Mn(II), with some 30% in forms of molecular weight greater than ca 10⁴.During mi xing in the Beaulieu Estuary, DOC and dissolved Mn behave essentially conservatively. This contrasts with the removal of a large fraction of the dissolved Fe (Holliday and LISS, 1976, Est. Coastal Mar. Sci. 4, 349–353). Concentrations of lattice-held Fe and Mn in suspended particulate material were essentially uniform in the estuary, at 3.2 and 0.012%, respectively, whereas the non-lattice held fractions decreased markedly with increase in salinity. For Mn the decrease was linear and could be most simply accounted for by the physical mixing of riverborne and marine participates, although the possibility that some desorption occurs is not excluded. The non-linear decrease in the concentration of non-lattice held Fe in particulates reflected the more complex situation in which physical mixing is accompanied by removal of material from the ‘dissolved’ fraction.     

The Development of Laser Ablation ICP-MS and Calibration Strategies: Examples from the Analysis of Trace Elements in Volcanic Glass Shards and Sulfide Minerals

This contribution presents a review of the recent developments in laser ablation inductively coupled plasma-mass spectrometry. We describe the important developments which have occurred in the laser systems used, leading to a spatial resolution of around 20 (im, and give an overview of the major instrument developments which have affected the geological applications of laser ablation ICP-MS. We describe the calibration of laser ablation for the analysis of trace elements in two different matrices: volcanic glass shards and sulfide minerals. We show how single glass shards can be analysed using the National Institute of Standards and Technology (NIST) glass certified reference materials for calibration and demonstrate the effect of using single spot analyses compared to rastering of the calibration sample. We show the importance of inter-shard variation and demonstrate that averaged single shard analyses produce data which compare well with bulk analyses. The calibration of the laser system for sulfide mineral analysis is discussed and two different strategies are proposed, one using spiked pressed powder pellets of sulfides and the other metal reference materials. We present conclusions and recommendations for the calibration of laser ablation ICP-MS instruments.     

Cu(II) adsorption at the calcite-water interface in the presence of natural organic matter: Kinetic studies and molecular-scale characterization

We have characterized the adsorption of Suwannee River humic acid (SRHA) and Cu(II) on calcite from preequilibrated solutions at pH 8.25. Sorption isotherms of SRHA on calcite follow Langmuir-type behavior at SRHA concentrations less than 15 mg C L⁻¹, whereas non-Langmuirian uptake becomes evident at concentrations greater than 15 mg C L⁻¹. The adsorption of SRHA on calcite is rapid and mostly irreversible, with corresponding changes in electrostatic properties. At pH 8.25, Cu(II) uptake by calcite in the presence of dissolved SRHA decreases with increasing dissolved SRHA concentration, suggesting that formation of Cu-SRHA aqueous complexes is the primary factor controlling Cu(II) sorption at the calcite surface under the conditions of our experiments. We also observed that surface-bound SRHA has little influence on Cu(II) uptake by calcite, suggesting that Cu(II) coordinates to calcite surface sites rather than to surface-bound SRHA.Cu K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine-structure (EXAFS) spectroscopic results show that the local coordination of Cu adsorbed at the calcite surface is very similar in the presence and absence of SRHA. Ca backscatterers at ∼3.90 Å indicate that Cu(II) forms tetragonally distorted inner-sphere adsorption complexes in both binary and ternary systems. Subtle differences in the XANES and EXAFS between binary sorption samples and ternary sorption samples, however, prevent us from ruling out the formation of ternary Cu-SRHA surface complexes. Our findings demonstrate that SRHA plays an important role in controlling the fate and transport of Cu(II) in calcite-bearing systems.     

Kinetics of Cd sorption, desorption and fixation by calcite: A long-term radiotracer study

Time-dependent sorption and desorption of Cd on calcite was studied over 210 days utilizing ¹⁰⁹Cd as a tracer to distinguish between ‘labile’ and ‘non-labile’ forms of sorbed Cd. Stabilizing the calcite suspensions for 12 months under atmospheric P_CO2 and controlled temperature was necessary to reliably follow Cd dynamics following initial sorption. Results revealed time-dependant Cd sorption and marked desorption hysteresis by calcite under environmentally relevant conditions. Data obtained were fitted to a first-order kinetic model and a concentric shell diffusion model. Both models described the progressive transfer of Cd²⁺ to a less reactive form within calcite and subsequent desorption of Cd subject to different initial contact times. The kinetic model provided a better fit to the combined sorption and desorption data (R² = 0.992). It differentiates between two ‘pools’ of sorbed Cd²⁺ on calcite, ‘labile’ and ‘non-labile’, in which labile sorbed Cd is in immediate equilibrium with the free Cd²⁺ ion activity in solution whereas non-labile Cd is kinetically restricted. For the diffusion model (R² = 0.959), the rate constants describing Cd dynamics in calcite produced a half-life for Cd desorption of ∼175 d, for release to a ‘zero-sink’ solution. Results from this study allow comment on the likely mechanisms occurring at the calcite surface following long-term Cd sorption.     

Sustainable Soil Particle Size Characterization Through Image Analysis

A rapid, clean, low-energy, image-based method for determining the grain size distribution of soils by image analysis has been developed. The method is called Sediment Imaging or “Sedimaging”. It develops the grain size distribution for particles in the range between a U.S. Standard Sieve No. 10 (2.0 mm openings) and U.S. Standard Sieve No. 200 (0.075 mm openings) range. The system utilizes a high resolution Nikon D7000 digital single lens reflex camera and image processing software developed specifically for interpreting the images and producing the resulting grain size distribution. The Sedimaging system is more sustainable and environmentally friendly than traditional sieving by virtue of its far lower power needs, less water consumption, longer equipment life and less maintenance. From the environmental and health perspectives, Sedimaging is less noisy, generates no vibrations and produces no airborne particulates. Sedimaging is also significantly faster than sieving and produces thousands of data points compared to typically 8 by sieving; it also automatically computes grain size distribution metrics such as the coefficients of uniformity and gradation.     

Clues from Current High CO2 Environments on the Effects of Ocean Acidification on CaCO3 Preservation

Acidification of surface seawater owing to anthropogenic activities has raised serious concerns on its consequences for marine calcifying organisms and ecosystems. To acquire knowledge concerning the future consequences of ocean acidification (OA), researchers have relied on incubation experiments with organisms exposed to future seawater conditions, numerical models, evidence from the geological record, and recently, observations from aquatic environments exposed to naturally high CO₂ and low pH, e.g., owing to volcanic CO₂ vents, upwelling, and groundwater input. In the present study, we briefly evaluate the distribution of dissolved CO₂–carbonic acid parameters at (1) two locations in the Pacific and the Atlantic Ocean as a function of depth, (2) a mangrove environment in Bermuda, (3) a seasonally stratified body of water in a semi-enclosed sound in Bermuda, and (4) in temporarily isolated tide pools in Southern California. We demonstrate that current in situ conditions of seawater pCO₂, pH, and CaCO₃ saturation state (Ω) in these environments are similar or even exceed the anticipated changes to these parameters in the open ocean over the next century as a result of OA. The observed differences between the Pacific and Atlantic Oceans with respect to seawater CO₂–carbonic acid chemistry, preservation of CaCO₃ minerals, and the occurrence and distribution of deep-sea marine calcifiers, support the hypothesized negative effects of OA on the production and preservation of CaCO₃ in surface seawater. Clues provided from shallow near-shore environments in Bermuda and Southern California support these predictions, but also highlight that many marine calcifiers already experience relatively high seawater pCO₂ and low pH conditions.     

Geochemical characteristics of stream sediments,sediment fractions,soils, and basement rocks from the Mahaweli River and its catchment,Sri Lanka

Geochemical variations in stream sediments (n = 54) from the Mahaweli River of Sri Lanka have been evaluated from the viewpoints of lithological control, sorting, heavy mineral concentration, influence of climatic zonation (wet, intermediate, and dry zones), weathering, and downstream transport. Compositions of soils (n = 22) and basement rocks (n = 38) of the catchment and those of <180 μm and 180–2000 μm fractions of the stream sediments were also examined. The sediments, fractions, soils and basement rocks were analyzed by X-ray fluorescence to determine their As, Pb, Zn, Cu, Ni, Cr, V, Sr, Y, Nb, Zr, Th, Sc, Fe₂O₃, TiO₂, MnO, CaO, P₂O₅ and total sulfur contents. Abundances of high field strength and ferromagnesian elements in the sediments indicate concentration of durable heavy minerals including zircon, tourmaline, rutile, monazite, garnet, pyriboles, and titanite, especially in <180 μm fractions. The sediments show strong correlation between Ti and Fe, further suggesting presence of heavy mineral phases containing both elements, such as ilmenite and magnetite. The basement rocks range from mafic through to felsic compositions, as do the soils. The river sediments lack ultrabasic components, and overall have intermediate to felsic compositions. Elemental spikes in the confluences of tributary rivers and high values in the <180 μm fractions indicate sporadic inputs of mafic detritus and/or heavy minerals to the main channel. Al₂O₃/(K₂O + Na₂O) and K₂O/Na₂O ratios of the sediments and LOI values of the soils correlate well with the climatic zones, suggesting intense weathering in the wet zone, lesser weathering in the intermediate zone, and least weathering in the dry zone. Low Sr and CaO contents and Cr/V ratios in stream sediments in the wet zone also suggest climatic influence. Fe-normalized enrichment factors (EFs) for As, Pb, Zn, Cu, Ni and Cr in stream sediments in the main channel are nearly all <1.5, indicating there is no significant environmental contamination. The chemistry of the sediments, rocks and the soils in the Mahaweli River are thus mainly controlled by source lithotype, weathering, sorting, and heavy mineral accumulation.     

Garnet polycrystals and the significance of clustered crystallization

Polycrystalline garnets are common in metamorphic rocks and may form as a result of close spacing of nuclei (if clustering is early) or impingement of larger grains (if clustering occurs later in the growth history). The timing of clustering relative to garnet growth is relevant to understanding the formation and evolution of porphyroblasts and evaluating the significance (if any) of clustering. Electron backscattered diffraction (EBSD) analysis of garnet-bearing metamorphic rocks reveals the presence of polycrystalline garnet in nine localities examined in this study: the northern Appalachians (Vermont, Maine, New York, USA); North American Cordillera (North Cascades Range, Washington; Snake Range, Nevada, USA); western Rocky Mountains (British Columbia, Canada); southern Menderes Massif (Turkey); Santander Massif (Colombia); and the Sanandaj–Sirjan zone (Hamadan, Iran). In some samples, polycrystals comprise ~20–30% of garnets analyzed, and chemical and textural evidence suggests that early coalescence of garnet polycrystals is common. Some early-coalescing polycrystals exhibit growth zoning that is concentric about the geometric center of the polycrystal. In thin section, these garnets may be undetectable as polycrystals based on morphology or zoning. In some polycrystals, zoning is unrelated to the location of internal grain boundaries; in others, Fe–Mn–Mg zoning has a different pattern than that of Ca; zoning patterns may vary on the scale of a single thin section. In addition, some polycrystals are characterized by high-angle misorientation boundaries that may be in special (non-random) orientations, an observation that indicates that these polycrystals are not random clusters of grains. The presence of internal grain boundaries may affect diffusion pathways and length scales, and may facilitate communication of porphyroblast interiors with matrix phases, thereby influencing reaction history of the rock and the composition/zoning of garnet.     

Asteroid rotation: III. 1978 Observations

Photoelectric observations of 32 asteroids observed from Table Mountain Observatory during the second half of 1978 are reported. Rotation periods were obtained for most objects. Absolute magnitudes and phase functions were not determined for any of these asteroids. The geometric mean rotation period of the 32 asteroids observed is 14.2 ± 1.6 hr, as compared to 9.38 ± 0.35 hr for 182 asteroids analyzed in Paper I (A. W. Harris and J. A. Burns, 1979, Icarus 40, 115–144). We attribute this difference to an observational selection effect which favors detection of fast rotation, as discussed in Paper I. If this is true, then the present sample contains the reverse bias, since it is complete in that a period (in some cases very approximate) was obtained for each object observed, but fast rotators are underrepresented due to prior discovery of their rotation properties.