An Atomic Force Microscopy study of the growth of calcite in the presence of sodium sulfate

In situ atomic force microscopy (AFM) has been used to compare the growth of pure calcite and the growth of calcite in the presence of sulfate ions from aqueous solutions at a constant value of supersaturation (S.I. = 0.89) with respect to calcite. The effect of sulfate ions on calcite growth rates is determined and a potential incorporation of sulfate ions is identified in the calcite during growth. Solutions supersaturated with respect to calcite with solution concentration ratio of one and a constant pH of 10.2, were prepared and sulfate was added as Na₂SO₄ aqueous solution. The solution composition was readjusted in order to keep the supersaturation and pH constant. PHREEQC was used to determine relevant solution concentrations. In situ AFM experiments of calcite growth were performed using a fluid cell and flowing solutions passed over a freshly cleaved calcite surface. Growth rates were determined from the closure of the rhombohedral etch pits induced by initial dissolution with pure water. The spreading rate of 2-dimensional nuclei was also measured. At low concentrations of sulfate (≤ 0.5 mM), no effect on the growth rate of the calcite was observed. At higher concentrations (2 to 3 mM) of sulfate, the growth rate increased, possibly because a higher concentration of calcium and carbonate was necessary to maintain the supersaturation constant. At much higher concentrations of additional sulfate (up to 60 mM) the growth rate of the calcite was substantially decreased, despite the fact that a further increase of calcium and carbonate was required. The morphology of 2-dimensional growth nuclei became increasingly elongated with increasing sulfate content. Measurements of step height showed that newly grown steps were approximately 1 Å higher when grown in high sulfate concentrations, compared to steps grown in sulfate-free solutions. At sulfate concentrations above 5 mM the growth mechanism changes from layer growth to surface roughening. These observations suggest that the new growth has incorporated sulfate into the calcite surface.     

Rare Earth Element and yttrium compositions of Archean and Paleoproterozoic Fe formations revisited: New perspectives on the significance and mechanisms of deposition

The ocean and atmosphere were largely anoxic in the early Precambrian, resulting in an Fe cycle that was dramatically different than today’s. Extremely Fe-rich sedimentary deposits—i.e., Fe formations—are the most conspicuous manifestation of this distinct Fe cycle. Rare Earth Element (REE) systematics have long been used as a tool to understand the origin of Fe formations and the corresponding chemistry of the ancient ocean. However, many earlier REE studies of Fe formations have drawn ambiguous conclusions, partially due to analytical limitations and sampling from severely altered units. Here, we present new chemical analyses of Fe formation samples from 18 units, ranging in age from ca. 3.0 to 1.8 billion years old (Ga), which allow a reevaluation of the depositional mechanisms and significance of Precambrian Fe formations. There are several temporal trends in our REE and Y dataset that reflect shifts in marine redox conditions. In general, Archean Fe formations do not display significant shale-normalized negative Ce anomalies, and only Fe formations younger than 1.9 Ga display prominent positive Ce anomalies. Low Y/Ho ratios and high shale-normalized light to heavy REE (LREE/HREE) ratios are also present in ca. 1.9 Ga and younger Fe formations but are essentially absent in their Archean counterparts. These marked differences in Paleoproterozoic versus Archean REE + Y patterns can be explained in terms of varying REE cycling in the water column.Similar to modern redox-stratified basins, the REE + Y patterns in late Paleoproterozoic Fe formations record evidence of a shuttle of metal and Ce oxides across the redoxcline from oxic shallow seawater to deeper anoxic waters. Oxide dissolution—mainly of Mn oxides—in an anoxic water column lowers the dissolved Y/Ho ratio, raises the light to heavy REE ratio, and increases the concentration of Ce relative to the neighboring REE (La and Pr). Fe oxides precipitating at or near the chemocline will capture these REE anomalies and thus evidence for this oxide shuttle. In contrast, Archean Fe formations do not display REE + Y patterns indicative of an oxide shuttle, which implies an absence of a distinct Mn redoxcline prior to the rise of atmospheric oxygen in the early Paleoproterozoic. As further evidence for reducing conditions in shallow-water environments of the Archean ocean, REE data for carbonates deposited on shallow-water Archean carbonate platforms that stratigraphically underlie Fe formations also lack negative Ce anomalies. These results question classical models for deposition of Archean Fe formations that invoke oxidation by free oxygen at or above a redoxcline. In contrast, we add to growing evidence that metabolic Fe oxidation is a more likely oxidative mechanism for these Fe formations, implying that the Fe distribution in Archean oceans could have been controlled by microbial Fe uptake rather than the oxidative potential of shallow-marine environments.     

Dredging-induced nutrient release from sediments to the water column in a southeastern saltmarsh tidal creek

Dredging is a large-scale anthropogenic disturbance agent in coastal and estuarine habitats that can profoundly affect water quality. We examined the impact of a small-scale dredging operation in a salt marsh in South Carolina by comparing nutrient levels (NH(4)(+), NO(x), PO(4)(-)) and total suspended solid concentrations before and during dredging activities. Nutrient enrichment was evaluated within the context of tidal, seasonal, and inter-annual variability by using long-term water chemistry data provided by the North Inlet-Winyah Bay National Estuarine Research Reserve. The conditions of the dredging permit (i.e., its relatively small scale), the season chosen for the work (fall-winter), the nature of the sediments dredged (coarse-grained), and the amount of natural variability in the estuary's water chemistry (even on a daily time-scale) all minimized the impact of the dredging activities. Results of this study will add to the limited body of empirical data that should be considered in evaluating future dredging permit applications related to shallow estuarine waterways.     

A review of paired catchment studies for determining changes in water yield resulting from alterations in vegetation

Paired catchment studies have been widely used as a means of determining the magnitude of water yield changes resulting from changes in vegetation. This review focuses on the use of paired catchment studies for determining the changes in water yield at various time scales resulting from permanent changes in vegetation. The review considers long term annual changes, adjustment time scales, the seasonal pattern of flows and changes in both annual and seasonal flow duration curves. The paired catchment studies reported in the literature have been divided into four broad categories: afforestation experiments, deforestation experiments, regrowth experiments and forest conversion experiments. Comparisons between paired catchment results and a mean annual water balance model are presented and show good agreement between the two methodologies. The results highlight the potential underestimation of water yield changes if regrowth experiments are used to predict the likely impact of permanent alterations to a catchment's vegetation. An analysis of annual water yield changes from afforestation, deforestation and regrowth experiments demonstrates that the time taken to reach a new equilibrium under permanent land use change varies considerably. Deforestation experiments reach a new equilibrium more quickly than afforestation experiments. The review of papers reporting seasonal changes in water yield highlights the proportionally larger impact on low flows. Flow duration curve comparison provides a potential means of gaining a greater understanding of the impact of vegetation on the distribution of daily flows.     

The effect of El Niño Southern Oscillation cycles on the decadal scale suspended sediment behavior of a coastal dry‐summer subtropical catchment

Rivers display temporal dependence in suspended sediment–water discharge relationships. Although most work has focused on multi‐decadal trends, river sediment behavior often displays sub‐decadal scale fluctuations that have received little attention. The objectives of this study were to identify inter‐annual to decadal scale fluctuations in the suspended sediment–discharge relationship of a dry‐summer subtropical river, infer the mechanisms behind these fluctuations, and examine the role of El Niño Southern Oscillation climate cycles. The Salinas River (California) is a moderate sized (11 000 km²), coastal dry‐summer subtropical catchment with a mean discharge (Q_mean) of 11.6 m³ s^?1. This watershed is located at the northern most extent of the Pacific coastal North America region that experiences increased storm frequency during El Niño years. Event to inter‐annual scale suspended sediment behavior in this system was known to be influenced by antecedent hydrologic conditions, whereby previous hydrologic activity regulates the suspended sediment concentration–water discharge relationship. Fine and sand suspended sediment in the lower Salinas River exhibited persistent, decadal scale periods of positive and negative discharge corrected concentrations. The decadal scale variability in suspended sediment behavior was influenced by inter‐annual to decadal scale fluctuations in hydrologic characteristics, including: elapsed time since small (~0.1 × Q_mean), and moderate (~10 × Q_mean) threshold discharge values, the number of preceding days that low/no flow occurred, and annual water yield. El Niño climatic activity was found to have little effect on decadal‐scale fluctuations in the fine suspended sediment–discharge relationship due to low or no effect on the frequency of moderate to low discharge magnitudes, annual precipitation, and water yield. However, sand concentrations generally increased in El Niño years due to the increased frequency of moderate to high magnitude discharge events, which generally increase sand supply. Copyright © 2014 John Wiley & Sons, Ltd.     

Heterogeneous effects of warming and drought on selected wheat variety yields

Climate change is likely to significantly impact agricultural production in the Great Plains region of the Central United States. This study estimated the impact of changes in temperature and precipitation on wheat (triticum aestivum) variety yield distributions using the moment-based maximum entropy (MBME) model. This approach allows for quantification of potential weather impacts on the yield distribution, and allows these effects to vary across varieties. The unique data set matches wheat variety trial data for 1985 to 2011 with weather data from the exact trial site for 11 locations throughout Kansas. Ten widely-planted varieties with a range of biotic and abiotic characteristics were included for comparison. Weather scenarios were simulated for baseline, increased temperature (one-degree Celsius warming), decreased precipitation (tenth-percentile rainfall outcome), and a combination warming and drought scenario. Warming resulted in an 11 % yield reduction, drought a 22 % reduction, and warming and drought a cumulative 33 % reduction. These effects vary across varieties. Alternative measures of yield risk (e.g. yield variance and coefficient of variation) were also constructed under each scenario and a similar pattern of heterogeneous impacts emerges. The key findings are that (i) exposure to warming and drought lead to mean yield reductions coupled with increased yield risk for all varieties, and (ii) newer (post 2005) seed varieties have a yield advantage over older varieties, however this advantage is reduced under warming and drought conditions.     

A Method for Estimating the Cost of CO2 Mitigation through Afforestation

The Kyoto Protocol allows Annex I countries to use afforestation (theconversion of non-forest landto forest) to meet emissions reduction targets. We present a new method forestimating the cost of CO₂mitigation through afforestation based on econometric models of land use. Landuse models are developed from dataon observed land allocation decisions and quantify the relationship betweenthe share of land in forest and the netreturns to forestry, among other land use determinants. The econometricapproach measures the actual responsesby landowners to observed changes in net returns, in contrast to earlierstudies in which landowner responses aredictated by the researcher. Models are estimated for Maine, South Carolina,and Wisconsin. The estimated modelsare used to simulate subsidies for afforestation, which imply increases inforest area and net reductions inatmospheric CO₂ concentrations. Average cost measures – totalsubsidies divided by total carbon sequestered –are derived for afforestation programs with and without timber harvesting. Theuse of econometric land use modelsin integrated assessments of climate change is explored. We model the effectson land use patterns and the costsof CO₂ mitigation of changes in the net returns to agricultureinduced by climate change.     

High spatial resolution hyperspectral mapping of in-stream habitats, depths, and woody debris in mountain streams

This article evaluates the potential of 1-m resolution, 128-band hyperspectral imagery for mapping in-stream habitats, depths, and woody debris in third- to fifth-order streams in the northern Yellowstone region. Maximum likelihood supervised classification using principal component images provided overall classification accuracies for in-stream habitats (glides, riffles, pools, and eddy drop zones) ranging from 69% for third-order streams to 86% for fifth-order streams. This scale dependency of classification accuracy was probably driven by the greater proportion of transitional boundary areas in the smaller streams. Multiple regressions of measured depths (y) versus principal component scores (x₁, x₂,…, x_n) generated R² values ranging from 67% for high-gradient riffles to 99% for glides in a fifth-order reach. R² values were lower in third-order reaches, ranging from 28% for runs and glides to 94% for pools. The less accurate depth estimates obtained for smaller streams probably resulted from the relative increase in the number of mixed pixels, where a wide range of depths and surface turbulence occurred within a single pixel. Matched filter (MF) mapping of woody debris generated overall accuracies of 83% in the fifth-order Lamar River. Accuracy figures for the in-stream habitat and wood mapping may have been misleadingly low because the fine-resolution imagery captured fine-scale variations not mapped by field teams, which in turn generated false “misclassifications” when the image and field maps were compared.The use of high spatial resolution hyperspectral (HSRH) imagery for stream mapping is limited by the need for clear water to measure depth, by any tree cover obscuring the stream, and by the limited availability of airborne hyperspectral sensors. Nonetheless, the high accuracies achieved in northern Yellowstone streams indicate that HSRH imagery can be a powerful tool for watershed-wide mapping, monitoring, and modeling of streams.     

Masses for free-floating planets and dwarf planets

The mass and distance functions of free-floating planets(FFPs) would give major insights into the formation and evolution of planetary systems, including any systematic differences between those in the disk and bulge. We show that the only way to measure the mass and distance of individual FFPs over a broad range of distances is to observe them simultaneously from two observatories separated by D ～ O(0.01 au)(to measure their microlens parallax π_E) and to focus on the finite-source point-lens(FSPL) events(which yield the Einstein radius θ_E). By combining the existing KMTNet 3-telescope observatory with a 0.3 m 4 deg~2 telescope at L2, of order 130 such measurements could be made over four years, down to about M ～ 6 M_⊕for bulge FFPs and M ～ 0.7 M_⊕for disk FFPs. The same experiment would return masses and distances for many bound planetary systems. A more ambitious experiment, with two 0.5 m satellites(one at L2 and the other nearer Earth) and similar camera layout but in the infrared, could measure masses and distances of sub-Moon mass objects, and thereby probe(and distinguish between) genuine sub-Moon FFPs and sub-Moon "dwarf planets" in exo-Kuiper Belts and exo-Oort Clouds.     

碧口群火山岩的时代——SHRIMP锆石U—Pb测年结果

碧口群火山岩系是从原碧口系(叶连俊等,1944,后称碧口群)中解体出来的一个岩石单元(陶洪祥等,1993)。虽经过近60年的研究,但对某些关键问题,特别是碧口群火山岩系的时代,仍存在不同认识。在早期研究阶段(20世纪40～50年代)和60～70年代的区域地质调查工作中,碧口群和横丹群被视做一个整体,并通过地层层序关系探讨其时代。如,叶连俊等(1944)提出碧口系形成于志留—泥盆纪,黄振辉(1959)则认为碧口群属寒武—志留系。80年代以来对碧口群火山岩系进行的同位素年代学和地古生物学研究给出了从新元古代(赵祥生等,1990;胡正东,1990;李耀敏,1991;秦…