Equilibrium H/H fractionations in organic molecules: I. Experimental calibration of ab initio calculations     

Ying Wang  Alex L. Sessions  Robert J. Nielsen  William A. Goddard III 《Geochimica et cosmochimica acta》2009,73(23):7060-7075

Carbon-bound hydrogen in sedimentary organic matter can undergo exchange over geologic timescales, altering its isotopic composition. Studies investigating the natural abundance distribution of ¹H and ²H in such molecules must account for this exchange, which in turn requires quantitative knowledge regarding the endpoint of exchange, i.e., the equilibrium isotopic fractionation factor (α_eq). To date, relevant data have been lacking for molecules larger than methane. Here we describe an experimental method to measure α_eq for C-bound H positions adjacent to carbonyl group (H_α) in ketones. H at these positions equilibrates on a timescale of days as a result of keto-enol tautomerism, allowing equilibrium ²H/¹H distributions to be indirectly measured. Molecular vibrations for the same ketone molecules are then computed using Density Functional Theory at the B3LYP/6-311G** level and used to calculate α_eq values for H_α. Comparison of experimental and computational results for six different straight and branched ketones yields a temperature-dependent linear calibration curve with slope = 1.081−0.00376T and intercept = 8.404−0.387T, where T is temperature in degrees Celsius. Since the dominant systematic error in the calculation (omission of anharmonicity) is of the same size for ketones and C-bound H in most other linear compounds, we propose that this calibration can be applied to analogous calculations for a wide variety of organic molecules with linear carbon skeletons for temperatures below 100 °C. In a companion paper (Wang et al., 2009) we use this new calibration dataset to calculate the temperature-dependent equilibrium isotopic fractionation factors for a range of linear hydrocarbons, alcohols, ethers, ketones, esters and acids.  相似文献   

Raman spectroscopy and biomarker analysis reveal multiple carbon inputs to a Precambrian glacial sediment     

Alison Olcott Marshall  Frank A. Corsetti  Alex L. Sessions  Craig P. Marshall 《Organic Geochemistry》2009,40(11):1115-1123

Extractable biomarkers can help elucidate the environment and biota of ancient glaciations, although the method must be applied with care, as glacial sediments have a potential for incorporation of older detrital carbon. In Phanerozoic glacial sediments, the distinct elemental, molecular and isotopic compositions of the terrestrial and marine biomass allow discrimination between primary marine and redeposited terrestrial organic matter. However, as the Proterozoic biosphere was largely microbial and marine, biomarker and isotopic analyses are insufficient for distinguishing primary organic matter from secondary reworked organic matter. Here, we report the combined application of Raman spectroscopy and biomarker analysis to Precambrian glacial sediments, which, together, allows discrimination between mixed pools of organic carbon and provides a promising new approach for rapidly screening Precambrian sediments for immature organic matter amenable to biomarker analysis.  相似文献   

Soil erosion and sediment transport in Tanzania: Part I – sediment source tracing in three neighbouring river catchments     

Maarten Wynants  Linus Munishi  Kelvin Mtei  Samuel Bodé  Aloyce Patrick  Alex Taylor  David Gilvear  Patrick Ndakidemi  William H. Blake  Pascal Boeckx 《地球表面变化过程与地形》2021,46(15):3096-3111

Water bodies in Tanzania are experiencing increased siltation, which is threatening water quality, ecosystem health, and livelihood security in the region. This phenomenon is caused by increasing rates of upstream soil erosion and downstream sediment transport. However, a lack of knowledge on the contributions from different catchment zones, land-use types, and dominant erosion processes, to the transported sediment is undermining the mitigation of soil degradation at the source of the problem. In this context, complementary sediment source tracing techniques were applied in three Tanzanian river systems to further the understanding of the complex dynamics of soil erosion and sediment transport in the region. Analysis of the geochemical and biochemical fingerprints revealed a highly complex and variable soil system that could be grouped in distinct classes. These soil classes were unmixed against riverine sediment fingerprints using the Bayesian MixSIAR model, yielding proportionate source contributions for each catchment. This sediment source tracing indicated that hillslope erosion on the open rangelands and maize croplands in the mid-zone contributed over 75% of the transported sediment load in all three river systems during the sampling time-period. By integrating geochemical and biochemical fingerprints in sediment source tracing techniques, this study demonstrated links between land use, soil erosion and downstream sediment transport in Tanzania. This evidence can guide land managers in designing targeted interventions that safeguard both soil health and water quality.  相似文献   

Soil erosion and sediment transport in Tanzania: Part II – sedimentological evidence of phased land degradation     

Maarten Wynants  Aloyce Patrick  Linus Munishi  Kelvin Mtei  Samuel Bodé  Alex Taylor  Geoffrey Millward  Neil Roberts  David Gilvear  Patrick Ndakidemi  Pascal Boeckx  William H. Blake 《地球表面变化过程与地形》2021,46(15):3112-3126

Soil resources in parts of Tanzania are rapidly being depleted by increased rates of soil erosion and downstream sediment transport, threatening ecosystem health, water and livelihood security in the region. However, incomplete understanding to what effect the dynamics of soil erosion and sediment transport are responding to land-use changes and climatic variability are hindering the actions needed to future-proof Tanzanian land-use practices. Complementary environmental diagnostic tools were applied to reconstruct the rates and sources of sedimentation over time in three Tanzanian river systems that have experienced changing land use and climatic conditions. Detailed historical analysis of sediment deposits revealed drastic changes in sediment yield and source contributions. Quantitative sedimentation reconstruction using radionuclide dating showed a 20-fold increase in sediment yield over the past 120 years. The observed dramatic increase in sediment yield is most likely driven by increasing land-use pressures. Deforestation, cropland expansion and increasing grazing pressures resulted into accelerating rates of sheet erosion. A regime shift after years of progressive soil degradation and convergence of surface flows resulted into a highly incised landscape, where high amounts of eroded soil from throughout the catchment are rapidly transported downstream by strongly connected ephemeral drainage networks. By integrating complementary spatial and temporal evidence bases, this study demonstrated links between land-use change, increased soil erosion and downstream sedimentation. Such evidence can guide stakeholders and policy makers in the design of targeted management interventions to safeguard future soil health and water quality.  相似文献   

植物挥发性有机物的初步研究   总被引：1，自引：0，他引：1  

白建辉  王明星  胡非  James P.Greenberg  Alex B.Guenther 《气候与环境研究》2003,8(2):180-187

2000年1～6月期间,美国国家大气研究中心(NCAR)和中国科学院大气物理研究所的科学家发展了一套自动的气相色谱系统和分析方法,用于分析大气中的挥发性有机物.此系统性能稳定,重复性好,对美国大气研究中心附近的大气进行了采样分析.作者简单介绍了此自动系统以及采样分析结果.  相似文献   

In situ measurements of wind‐driven salt fluxes through constructed channels in a coastal wetland ecosystem          下载免费PDF全文

Alex K. Manda  Enrique Reyes  James M. Pitt 《水文研究》2018,32(5):636-643

A suite of instruments was deployed in a coastal wetland ecosystem in the Albemarle estuarine system, North Carolina (USA), to characterize wind‐driven transport of saltwater through a constructed (man‐made) channel. Flow velocity, electrical conductivity, and stage were measured in a representative channel over a 2‐month period from May to July 2014, during which 4 wind tides were observed. Collected data show that thousands of metric tons of salt were advected through the channel into coastal wetlands during each event, which lasted up to 4 days. The results reveal that as much as 36% of advected salts accumulated in the wetlands, suggesting that the cumulative effects of these events on the health of coastal wetlands in the Albemarle system may be substantial due to the abundance of constructed channels and the frequency of wind‐driven tidal events. This study is the first to quantify wind‐driven salt fluxes through constructed channels in coastal wetland settings.  相似文献   

Mesoscale and microscale shock effects in the LL6 S4 chondrites Saint‐Séverin and Elbert: A tale of two breccias     

Richard C. Hugo  Alex M. Ruzicka  Alan E. Rubin 《Meteoritics & planetary science》2020,55(6):1418-1438

Saint‐Séverin and Elbert, two LL6 chondrite breccias, were systematically studied to evaluate multiple deformation effects on spatial scales ranging from thin section (mesoscale) to micron‐submicron (microscale) using optical microscopy, electron backscatter diffraction (EBSD), and transmission electron microscopy (TEM). The different techniques provide consistent results but have complementary strengths, together providing a powerful approach to unravel even complex impact histories. Both meteorites have an S4 conventional shock stage, but interclast areas are more deformed, and clasts are more deformed in Elbert than in Saint‐Séverin. TEM and EBSD data provide compelling evidence that Saint‐Séverin experienced significant shock deformation while already hot, and cooled rapidly afterward, as a result of a major, possibly disruptive impact on the LL chondrite parent body ~4.4 Ga ago. In contrast, Elbert was shocked from a cold initial state but was heated significantly during shock, and cooled in a localized hot impact deposit on the LL asteroid. Both meteorites probably were shocked at least twice; data for Saint‐Séverin are best reconciled with a three‐impact model.  相似文献   

Long‐term temporal and spatial patterns in bioeroding sponge distribution at the Abrolhos Bank,Brazil, Southwestern Atlantic     

Fernando Coreixas de Moraes  Fernanda Cervi  Cludia S. Karez  Leonardo T. Salgado  Rodrigo L. Moura  Gabriella A. Leal  Alex C. Bastos  Gilberto M. Amado‐Filho 《Marine Ecology》2019,40(3)

Bioeroding sponges belong to the most dominant bioeroders, significantly contributing to the erosion of coral reefs. Some species are tolerant or even benefit from environmental conditions such as ocean warming, acidification, and eutrophication. In consequence, increases in sponge bioerosion have been observed on some coral reefs over the last decades. The Abrolhos Bank is the largest coral reef system in the South Atlantic. It has been affected by sedimentation, eutrophication, overfishing, and climate change, mainly affecting coastal reefs, and at lesser intensity outer ones as well. This study aimed to describe spatial and temporal patterns in bioeroding sponge distribution in carbonate substrates in the Abrolhos Bank. Photo‐quadrats were used to compare bioeroding sponge abundance between two shallow reefs: a coastal, Pedra de Leste (PL), and an outer reef, Parcel dos Abrolhos (PAB). Each individual was delimitated over the substrate by determining the sponge surface through a line connecting the outermost papillae. The study was conducted over 6 years in 2008–2009 and 2013–2016. Four species of bioeroding sponges were identified: Cliona carteri Ridley, 1881, C. delitrix Pang, 1973, C. cf. schmidtii Ridley, 1881, and Siphonodictyon coralliphagum Rützler, 1971. The distribution and abundance of species varied between the inner and outer reefs and across the years, and displayed certain selectivity for the calcareous substrates recorded. Crustose coralline algae (CCA) were the main substrate excavated by the most abundant bioeroding species, C. carteri, and represented 70% of the substrate types occupied by this sponge (CCA, coral overgrown by CCA and plain coral). The highest abundance of bioeroding sponges observed in photo‐quadrats was 21.3 individuals/m² at the outer reefs (PAB) in 2014. The abundances or areal extents of bioeroding sponges were up to 10 times greater on the outer reefs than on the coastal ones, where sedimentation is higher and more strongly influenced by siliciclastic material. Moreover, a higher herbivorous fish biomass has been reported on outer reefs which could also influence the higher abundance of bioeroding sponges in outer reefs. During the study period of 6 years, an increase in bioeroding sponge abundance was observed at the outer reefs (PAB), with the sea surface temperature increase. As CCA have an important role in reefal cementation and carbonate production in the Abrolhos reefs, a bioerosion impact might be expected, in particular, on the outer reefs.  相似文献   

Combining pixel and object based image analysis of ultra-high resolution multibeam bathymetry and backscatter for habitat mapping in shallow marine waters     

Daniel Ierodiaconou  Alexandre C. G. Schimel  David Kennedy  Jacquomo Monk  Grace Gaylard  Mary Young  Markus Diesing  Alex Rattray 《Marine Geophysical Researches》2018,39(1-2):271-288

Habitat mapping data are increasingly being recognised for their importance in underpinning marine spatial planning. The ability to collect ultra-high resolution (cm) multibeam echosounder (MBES) data in shallow waters has facilitated understanding of the fine-scale distribution of benthic habitats in these areas that are often prone to human disturbance. Developing quantitative and objective approaches to integrate MBES data with ground observations for predictive modelling is essential for ensuring repeatability and providing confidence measures for habitat mapping products. Whilst supervised classification approaches are becoming more common, users are often faced with a decision whether to implement a pixel based (PB) or an object based (OB) image analysis approach, with often limited understanding of the potential influence of that decision on final map products and relative importance of data inputs to patterns observed. In this study, we apply an ensemble learning approach capable of integrating PB and OB Image Analysis from ultra-high resolution MBES bathymetry and backscatter data for mapping benthic habitats in Refuge Cove, a temperate coastal embayment in south-east Australia. We demonstrate the relative importance of PB and OB seafloor derivatives for the five broad benthic habitats that dominate the site. We found that OB and PB approaches performed well with differences in classification accuracy but not discernible statistically. However, a model incorporating elements of both approaches proved to be significantly more accurate than OB or PB methods alone and demonstrate the benefits of using MBES bathymetry and backscatter combined for class discrimination.  相似文献   

Effects of the peat acid digestion protocol on geochemically and morphologically diverse tephra deposits     

Alistair J. Monteath  Alex E. Teuten  Paul D. M. Hughes  Stefan Wastegrd 《第四纪科学杂志》2019,34(4-5):269-274

Tephra shards for electron probe microanalysis are most efficiently extracted from peat using acid digestion, which removes organic material that hinders density separation methods. However, strong acids are known to alter glass chemical compositions, and several studies have examined how acid digestion affects rhyolitic volcanic glass. The focus on rhyolitic tephra in these studies leaves considerable uncertainty, as the dissolution rates of natural glasses (including tephra) are determined by the chemical composition and surface area/volume ratio, both of which vary in tephra deposits. Here, we use duplicate samples of basaltic, trachydacitic and rhyolitic tephra to examine physical and geochemical alteration following acid digestion. Scanning electron microscope imagery reveals no discernible degradation of glass surfaces, and electron probe microanalysis results from duplicate samples are statistically indistinguishable. These findings suggest the acid digestion protocol for organic peats does not significantly alter glass geochemistry regardless of shard morphologies or geochemical compositions.  相似文献