Carboxylic monoacids in the air of mayombe forest (Congo): Role of the forest as a source or sink

In the tropical rain forests of the Congo during the dry season, from June to September 1987, carboxylic acid partial pressures (P _gas) in the air above the canopy, at ground level, and at the boundary layer, were estimated from water samples such as fog and rainwater. The concentrations of these acids were also measured in the sap of tree leaves. Tree leaves act as a sink or as a source if the acid P _gas is greater of lower than the acid concentrations in molecular form in sap. For each of these soluble gases, there is a value of P _gas where the exchange is nul. This is called the compensation point. Values of the compensation point for some tree leaves were evaluated according to Henry's law. Henry's law coefficients at ppm levels were redetermined for formic (HCOOH), acetic (CH₃COOH), propionic (CH₃CH₂COOH), and isobutyric (CH₃CH(CH₃)COOH) acids.By comparison of P _gas and compensation points, it is concluded that the forest was a potential source for these acids. The soil-or the litter-acts as a significant source of a carboxylic acid of C₃ or C₄ atoms in the aliphatic chain. This carboxylic acid, not yet fully characterized, could play an important role in the rain acidity in forested zones of the equatorial areas.The direct emission of these carboxylic acids by vegetation was the main source in the boundary layer above the forest. The average emissions were 3.1×10⁹, 7.8×10⁹, and 8.4×10⁹ molecules cm^-2 s^-1 for HCOOH, CH₃COOH, and CH₃CH₂COOH, respectively. The savanna is an exogenous source of HCOOH and CH₃CH₂COOH during moderately rainy days for 30% of the time. The ozonolysis of isoprene seems to be a small source of HCOOH.     

Oxidation of the Kaapvaal lithospheric mantle driven by metasomatism

The oxidation state, reflected in the oxygen fugacity (fO₂), of the subcratonic lithospheric mantle is laterally and vertically heterogeneous. In the garnet stability field, the Kaapvaal lithospheric mantle becomes progressively more reducing with increasing depth from Δlog fO₂ FMQ-2 at 110 km to FMQ-4 at 210 km. Oxidation accompanying metasomatism has obscured this crystal-chemical controlled depth-fO₂ trend in the mantle beneath Kimberley, South Africa. Chondrite normalized REE patterns for garnets, preserve evidence of a range in metasomatic enrichment from mild metasomatism in harzburgites to extensive metasomatism by LREE-enriched fluids and melts with fairly unfractionated LREE/HREE ratios in phlogopite-bearing lherzolites. The metasomatized xenoliths record redox conditions extending up to Δlog fO₂ = FMQ, sufficiently oxidized that magnesite would be the stable host of carbon in the most metasomatized samples. The most oxidized lherzolites, those in or near the carbonate stability field, have the greatest modal abundance of phlogopite and clinopyroxene. Clinopyroxene is modally less abundant or absent in the most reduced peridotite samples. The infiltration of metasomatic fluids/melts into diamondiferous lithospheric mantle beneath the Kaapvaal craton converted reduced, anhydrous harzburgite into variably oxidized phlogopite-bearing lherzolite. Locally, portions of the lithospheric mantle were metasomatized and oxidized to an extent that conversion of diamond into carbonate should have occurred. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Determination of the REE in Geological Reference Materials DTS-1 (Dunite) and PCC-1 (Peridotite) by Ultrasonic and Microconcentric Desolvating Nebulisation ICP-MS

Inductively coupled plasma-mass spectrometry is well suited for the precise, accurate and rapid determination of rare earth elements in most geological samples. However, determination of rare earth elements in certain mantle-derived materials, without applying preconcentration techniques, remains problematical due to low natural concentrations (generally < 1 ng g⁻¹). Consequently, USGS reference materials DTS-1 (a dunite) and PCC-1 (a partially serpentinized harzburgite) have only suggested rather than recommended values for the rare earth elements in reference material compilations. We compared results obtained using two ICP-MS instruments: a U-5000AT ultrasonic nebuliser coupled to a PQ2+ quadrupole ICP-MS and an ELEMENT sector field ICP-MS equipped with a MCN-6000 microconcentric desolvating nebuliser, with the suggested literature values for these two reference materials. Precision and accuracy of analytical methods employed by both instruments were demonstrated by excellent relative standard deviations (< 2%) and inter-laboratory agreement (< 5%) for numerous analyses of BHVO-1 and BIR-1, which are well established with rare earth elements contents at the μg g⁻¹ level. Repeat analyses of DTS-1 and PCC-1 at each laboratory indicate that each method is generally precise to better than 5% at sub-g g⁻¹ levels. Furthermore, values from both instruments generally agree to within 10%. Our DTS-1 and PCC-1 values agree reasonably well with selected data reported in the literature (except for Ce and Sm in DTS-1) but exhibit poorer agreement with reported compilation values. With the demonstrated level of precision and accuracy, we contend that these new values for DTS-1 and PCC-1, generated by two different instruments, are the best estimates of the true whole-rock composition of these samples reported to date.     

Assessing regression‐based statistical approaches for downscaling precipitation over North America

This paper assesses linear regression‐based methods in downscaling daily precipitation from the general circulation model (GCM) scale to a regional climate model (RCM) scale (45‐ and 15‐km grids) and down to a station scale across North America. Traditional downscaling experiments (linking reanalysis/dynamical model predictors to station precipitation) as well as nontraditional experiments such as predicting dynamic model precipitation from larger‐scale dynamic model predictors or downscaling dynamic model precipitation from predictors at the same scale are conducted. The latter experiments were performed to address predictability limit and scale issues. The results showed that the downscaling of daily precipitation occurrence was rarely successful at all scales, although results did constantly improve with the increased resolution of climate models. The explained variances for downscaled precipitation amounts at the station scales were low, and they became progressively better when using predictors from a higher‐resolution climate model, thus showing a clear advantage in using predictors from RCMs driven by reanalysis at its boundaries, instead of directly using reanalysis data. The low percentage of explained variances resulted in considerable underestimation of daily precipitation mean and standard deviation. Although downscaling GCM precipitation from GCM predictors (or RCM precipitation from RCM predictors) cannot really be considered downscaling, as there is no change in scale, the exercise yields interesting information as to the limit in predictive ability at the station scale. This was especially clear at the GCM scale, where the inability of downscaling GCM precipitation from GCM predictors demonstrates that GCM precipitation‐generating processes are largely at the subgrid scale (especially so for convective events), thus indicating that downscaling precipitation at the station scale from GCM scale is unlikely to be successful. Although results became better at the RCM scale, the results indicate that, overall, regression‐based approaches did not perform well in downscaling precipitation over North America. Copyright © 2013 John Wiley & Sons, Ltd.     

Structure and dynamics of the Bok globule B335

CO maps of the Bok globule B335 are presented and used to derive its density profile, mass distribution, and rotational velocity structure. It is found that the cloud is in nearly hydrostatic equilibrium with a density profile that varies roughly as r^?1 in the core and r^?3 in the envelope. The observed rotation is unimportant in the force balance at the present stage of evolution.     

Extreme value estimates for arbitrary bandwidth Gaussian processes using the analytic envelope

A procedure is presented for the estimation of extreme values of stationary Gaussian random processes with arbitrary bandwidths. This approach is based on the analytic envelope defined by the Hilbert Transform; this envelope is Rayleigh distributed regardless of bandwidth. For experimentally derived data that has been converted into digital form, the Hilbert Transform is approximated using algorithms implemented on a digital computer to produce samples of the envelope's time history. Next, the degree of correlation between these envelope samples is taken into account using a method developed from simulation studies of a series of synthetic Gaussian time histories with varying bandwidths. Once this correlation effect has been estimated, the standard methods of order statistics are applied to these samples using the Rayleigh probability density function. Examples of applying this procedure to experimentally derived data are presented.     

Mn-oxides and sequestration of heavy metals in a suburban catchment basin of the Chesapeake Bay watershed

The Chesapeake Bay is greatly impacted by numerous pollutants including heavy metals and understanding the controls on the distribution of heavy metals in the watershed is critical to mitigation and remediation efforts in controlling this type of pollution. Clasts from a stormwater catchment basin draining a subdivision near George Mason University, Fairfax VA (38°50.090°N 78°19.204°W) were investigated using X-ray diffraction (XRD), Scanning electron microcopy (SEM) and energy dispersive spectroscopy (EDS) to determine the nature of Mn-oxide coatings and relationship to bound heavy metals. Mn-oxides are poorly crystalline and occur as subhedral to anhedral platy particles and more rarely as euhedral plates. Micronodules are a commonly observed texture. Chemical compositions of coatings are variable with average major constituent concentrations being Mn (33.38 wt%), Fe (11.88 wt%), Si (7.33 wt%), Al (5.03 wt%), and Ba (0.90 wt%). Heavy metals are found in the coatings with Zn being most prevalent, occurring in approximately 58% of analyses with an average concentration of (0.66 wt%). Minor amounts of Co, Ni, Pb, and Cl are observed. Heavy metals and Cl are interpreted as being derived from road pollution. Mn-oxides can serve as a sequestration mechanism for pollution but may also release heavy metals. Field and laboratory observations indicate Mn-oxides occurring on the surface of the clasts can be mechanically mobilized. This is a mechanism for transporting heavy metals into the Chesapeake Bay watershed. Deicing agents may serve as a mechanism to release heavy metals through cation exchange and increased ionic strength. This is the first detailed mineralogical investigation of Mn-oxides and the roles they may play in pollution in the Chesapeake Bay.     

Measurement of Kodaikanal white-light images – IV. Axial Tilt Angles of Sunspot Groups

The Kodaikanal sunspot data set, covering the interval 1906–1987, is used in conjunction with the similar Mount Wilson sunspot data set, covering the interval 1917–1985, to examine characteristics of sunspot group axial tilt angles. Good agreement is demonstrated between various results derived from the two independent data sets. In particular, the tendency for sunspot groups near the average tilt angle to be larger than those far from the average tilt angle is confirmed. Similarly the faster residual rotation rate for groups near the average tilt angle is also confirmed. Other confirmations are made for the relationships between latitude drift of sunspot groups and tilt angle, polarity separations, and axial expansion. Evidence is presented that tilt angles averaged over these long time intervals differ between the north and south hemispheres by about 1.4 deg. It is suggested that residual tilt angles show a slight systematic variation with phase in the activity cycle.     

Occurence of abundant diradicaloid moieties in the insoluble organic matter from the Orgueil and Murchison meteorites: a fingerprint of its extraterrestrial origin?

The highly aromatic structure of the macromolecular organic matter (OM) of the Murchison and Orgueil meteorites was recently shown to contain free organic radicals which are concentrated in micro-regions in contrast with terrestrial samples which always show an homogeneous distribution of radicals. An additional signature is revealed, in the present study, by the evolution of the radical concentration with temperature. Whereas in terrestrial samples, this concentration is independent of temperature (Curie magnetism), a significant increase is observed above 150 K in the two meteorites. Based on the electronic structure of organic radicals, calculated by Extended Hückel and Density Functional methods, this behavior was assigned to the occurrence of diradicaloid moieties hosted by aromatic structures of 10 to 15 rings and having a quinoidal structure. They represent 40 and 25% of the total radicals in Orgueil and Murchison, respectively. The search for the cosmochemical interpretation of this unique observation should open a new field of experimental investigations.     

Quantification of river water infiltration in shallow aquifers using acesulfame and anthropogenic gadolinium

This study has investigated the use of the artificial sweetener acesulfame and the magnetic resonance imaging contrast agent gadolinium as quantitative tracers for river water infiltration into shallow groundwater. The influence of a river on alluvial groundwater in a subalpine catchment in western Europe has been assessed using the ‘classical’ hydrochemical tracer chloride and the trace contaminants acesulfame and anthropogenic gadolinium. Mixing ratios for riverine bank filtrate with ambient groundwater and the uncertainties associated with the temporal and spatial tracer variability were calculated using acesulfame and gadolinium and compared with those obtained using chloride. The temporal variability of tracer concentrations in river water of gadolinium (standard deviation SD: 63%) and acesulfame (SD: 71%) both exceeded that of chloride (SD: 27%), and this was identified as the main source of uncertainty in the mixing analysis. Similar spatial distributions were detected in the groundwater for chloride and gadolinium, but not for acesulfame. Mixing analyses using acesulfame resulted in calculated mixing ratios that differed from those obtained using gadolinium and chloride by up to 83% and 92%, respectively. At the investigated site, which had oxic conditions and moderate temperatures, acesulfame was found to be a less reliable tracer than either gadolinium or chloride, probably because of natural attenuation and input from other sources. There was no statistically significant difference between the mixing ratios obtained using chloride or gadolinium, the mixing ratios obtained using gadolinium were 40–50% lower than those obtained using chloride. This is mainly due to a bias of the mean gadolinium concentration in river water towards higher values. In view of the uncertainties of the two tracers, neither could be preferred over the other for the quantification of bank filtrate in groundwater. At this specific site gadolinium was able to reliably identify river water infiltration and was a more precise tracer than chloride at low mixing ratios (<20%), because of the exclusive occurrence of gadolinium in river water and its high dynamic range. Copyright © 2015 John Wiley & Sons, Ltd.