The role of organic haze in Titan's atmospheric chemistry: I. Laboratory investigation on heterogeneous reaction of atomic hydrogen with Titan tholin

In Titan's atmosphere consisting of N₂ and CH₄, large amounts of atomic hydrogen are produced by photochemical reactions during the formation of complex organics. This atomic hydrogen may undergo heterogeneous reactions with organic aerosol in the stratosphere and mesosphere of Titan. In order to investigate both the mechanisms and kinetics of the heterogeneous reactions, atomic deuterium is irradiated onto Titan tholin formed from N₂ and CH₄ gas mixtures at various surface-temperatures of the tholin ranging from 160 to 310 K. The combined analyses of the gas species and the exposed tholin indicate that the interaction mechanisms of atomic deuterium with the tholin are composed of three reactions; (a) abstraction of hydrogen from tholin resulting in gaseous HD formation (HD recombination), (b) addition of D atom into tholin (hydrogenation), and (c) removal of carbon and/or nitrogen (chemical erosion). The reaction probabilities of HD recombination and hydrogenation are obtained as ηabst=1.9(±0.6)×¹⁰⁻³×exp(−300/T) and ηhydro=2.08(±0.64)×exp(−1000/T), respectively. The chemical erosion process is very inefficient under the conditions of temperature range of Titan's stratosphere and mesosphere. Under Titan conditions, the rates of hydrogenation > HD recombination ? chemical erosion. Our measured HD recombination rate is about 10 times (with an uncertainty of a factor of 3-5) the prediction of previous theoretical model. These results imply that organic aerosol can remove atomic hydrogen efficiently from Titan's atmosphere through the heterogeneous reactions and that the presence of aerosol may affect the subsequent organic chemistry.     

Laboratory studies of methane and ethane adsorption and nucleation onto organic particles: Application to Titan's clouds

Titan, Saturn's largest moon, has a thick nitrogen/methane atmosphere. The temperature and pressure conditions in Titan's atmosphere are such that the methane vapor should condense near the tropopause to form clouds. Several ground-based measurements have observed sparse cloud-like features in Titan's atmosphere, while the Cassini mission to Saturn has provided large scale images of the clouds. However, Titan's cloud formation conditions remain poorly constrained. Heterogeneous nucleation (from the vapor phase onto a solid or liquid aerosol surface) greatly enhances cloud formation relative to homogeneous nucleation. In order to elucidate the cloud formation mechanism near the tropopause, we have performed laboratory measurements of the adsorption of methane and ethane onto solid organic particles (tholins) representative of Titan's photochemical haze. We find that monolayers of methane adsorb onto tholin particles at saturation ratios less than unity. We also find that solid methane nucleates onto the adsorbed methane at a saturation ratio of S=1.07±0.008. This implies that Titan's methane clouds should form easily. This is consistent with recent measurements of the column of methane ruling out excessive methane supersaturation. In addition, we find ethane adsorbs onto tholin particles in a metastable phase prior to nucleation. However, ethane nucleation onto the adsorbed ethane occurs at a relatively high saturation ratio of S=1.36±0.08. These findings are consistent with the recent report of polar ethane clouds in Titan's lower stratosphere.     

New experimental constraints on the composition and structure of tholins

Powdered samples of carbon-nitrogen-hydrogen “tholins” that mimic Titan's atmosphere aerosols were produced under levitation conditions in the laboratory with a dusty plasma (PAMPRE experiment) using different initial N₂:CH₄ gas mixtures and studied using UV Raman and infrared spectroscopy, X-ray diffraction and high resolution transmission electron microscopy (HRTEM). Comparison between the tholins produced in the PAMPRE experiments and samples prepared by other techniques reveal that they form a fairly homogeneous family of hydrogenated carbon nitride materials. Wall effects during the PAMPRE deposition experiments and other were found to have little effect on the chemical structure of tholins. The first-order UV Raman bands of the disordered carbonaceous materials point to a large contribution of sp² clusters present compared with olefinic CN or CC groupings, whereas features at 690 and 980 cm⁻¹ suggest C₃N₃ rings are present as a species inserted in the macromolecular network. Diffraction techniques do not indicate the presence of large polyaromatic species in any of the tholins studied, whatever their nitrogen concentration, in disagreement with certain previous observations. This precludes the idea that the nature and degree of absorption in the visible range is controlled by the size of polyaromatic species, as has been observed in series of carbon-based materials obtained via thermal processing. Infrared spectroscopy analysis of the tholins has confirmed earlier identifications of chemical groups present including primary amines, nitriles, and alkyl moieties such as CH₂/CH₃, but has ruled out CH₂/CH₃ branches appearing on secondary or tertiary amines. Similar analyses were also performed on a polymeric (HCN)_x material, which was found to present several similarities with the tholins, hence suggesting similar polymerization processes.     

Effect of water excess on soil carbon dioxide,seepage water chemistry,and calcite speleothem growth: An experimental and modelling approach

The effect of the water excess in soil on soil gaseous carbon dioxide concentrations (c_CO2) was studied based on field experiments. The gradual water addition of 15 and 30 L m⁻² to leptosols and anthrosols, simulating 15 and 30 mm precipitation, respectively, caused the overall c_CO2 increase of 1.53 × 10⁻¹ mol m⁻³ (increase by 60%) and 1.61 × 10⁻¹ mol m⁻³ (increase by 112%) in the soil airs. The effect of the c_CO2 increment on seepage water, cave dripwater chemistry, and calcite speleothem overgrowths was deduced from geochemical modelling. It showed that the c_CO2 increments may lead to the increments in total dissolved carbon, aqueous calcium, and dissolved solids of 1.10 × 10⁻³ mol L⁻¹ (increase by 35%), 4.45 × 10⁻⁴ mol L⁻¹ (increase by 30%), and 1.55 × 10⁻³ mol L⁻¹ (increase by 34%), respectively. After the total degassing of CO₂ in the cave, the increment in the saturation index of dripwater, SI, could reach up to ΔSI = 0.31, which means an increase by hundreds of percent. The water excess of 5 L m⁻² following a dry period would cause the increment in saturation index ΔSI = 0.17. The modelling further showed that the c_CO2 increase associated with the 30 L m⁻² water excess could induce the calcite overgrowth up to 1 μm thick per 1 m² surface area. The effect of water excess with additional water supplies gradually weakens, probably due to reduced CO₂ diffusivity and soil microorganism activity. It can be assumed that the most contrasting peaks in dripwater chemistry are associated with the individual precipitation events after short dry periods. The increased supersaturation of dripwater is expected to lead to faster growth of speleothem and changes in calcite textures.     

Relative contributions of stream concentration,stream discharge and shoreline load to base cation trends in Red Chalk and Harp lakes,south‐central Ontario,Canada

We evaluated the importance and contributions of changes in stream base cation concentration, stream discharge and lake shoreline load to changes in base cation concentrations in two small inland lakes in south‐central Ontario. The shoreline load from ungauged drainage areas was calculated with a mass balance equation. An evaluation method based on the partial Mann–Kendall test quantified the relative contributions of these three explanatory drivers to the observed trends in lake concentration of Ca, K, Mg and Na. Over a 29‐year period (1978–2006) at Red Chalk and Harp lakes, declines in stream concentration and discharge were correlated with the declines in lake concentrations of all base cations (except for Na in Harp Lake), with contributions of 21–81% from stream concentration and 12–58% from discharge, whereas the shoreline load had little contribution to observed trends. The observed unusual increase in Na concentration at Harp Lake was correlated with the increase in stream Na concentration and additional load from road salts, with the shoreline load contributing a substantial 37%. These results may be applicable to numerous inland lakes with similar site conditions, including lakes found on the Canadian Shield. Copyright © 2015 John Wiley & Sons, Ltd.     

Use of soil‐streamwater relationships to assess regional patterns of acidic deposition effects in the northeastern USA

Declines of acidic deposition levels by as much as 50% since 1990 have led to partial recovery of surface waters in the northeastern USA but continued depletion of soil calcium through this same period suggests a disconnection between soil and surface water chemistry. To investigate the role of soil‐surface water interactions in recovery from acidification, the first regional survey to directly relate soil chemistry to stream chemistry during high flow was implemented in a 4144‐km² area of the Catskill region of New York, where acidic deposition levels are among the highest in the East. More than 40% of 95 streams sampled in the southern Catskill Mountains were determined to be acidified and had inorganic monomeric aluminum concentrations that exceeded a threshold that is toxic to aquatic biota. More than 80% likely exceeded this threshold during the highest flows, but less than 10% of more than 100 streams sampled were acidified in the northwestern portion of the region. Median Oa horizon soil base saturation ranged from 50% to 80% at 200 sites across the region, but median base saturation in the upper 10 cm of the B horizon was less than 20% across the region and was only 2% in the southern area. Aluminum is likely to be interfering with root uptake of calcium in the mineral horizon in approximately half the sampled watersheds. Stream chemistry was highly variable over the Catskill region and, therefore, did not always reflect the calcium depletion of the B horizon that our sampling suggested was nearly ubiquitous throughout the region. Published 2013. This article is a U.S. Government work and is in the public domain in the USA.     

Total mercury in sediments and in Brazilian Ariidae catfish from two estuaries under different anthropogenic influence

Santos-São Vicente estuary, located in São Paulo State, Brazil, has a history of contamination by inorganic chemicals such as mercury (Hg). In the 1980s the Cubatão was considered one of the most polluted sites in the world as a consequence of the intense industrial activities located in the city close to the estuary. To provide data and evaluate the local biota, total mercury (THg) contents were determined in sediments and in fish, Cathorops spixii, from different areas of the Santos-São Vicente estuary. For comparison, samples were also collected in a non-polluted system with similar hydrochemistry characteristics, the Cananeia estuary. The water characteristics and THg levels in sediment and fish samples confirmed a high human influence in the Santos-São Vicente estuary. The lowest THg values, observed in Cananeia, were evidence of low anthropogenic influence. High values observed in Santos-São Vicente show the necessity for a monitoring program.     

Formative pre-Hispanic agricultural soils in northwest Argentina

Our study area is from an early agricultural archaeological site named “El Tolar” (1st to 9th century AD), located in Tafí Valley (Tucumán, northwest Argentina). The objective was to identify geochemical signatures generated by the sustained agrarian use of soils. Chemical and pedological studies were made in different archaeological contexts. Physical and chemical features, such as bulk density, pH, organic and inorganic phosphorus, and available copper, manganese and iron, were taken into account. The results suggested that a buried paleosol identified was contemporary with the occupation of the site. It also showed characteristics clearly related to pre-Hispanic agrarian production. The concentrations of organic phosphorus and iron in agricultural soils probably reflect the use of fertilizers. The application of geoscience techniques allowed us to obtain important information on their behaviour and socio-economic development. This paper constitutes the first pedogeochemical approach to the study of Argentinean pre-Hispanic agricultural soils.     

青海西部祁漫塔格地区矽卡岩铁铜多金属矿床的矽卡岩类型和矿物学特征

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氧同位素质量依赖分馏线的精确确定

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