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A unique multilabeling at a single-site protocol of the Ru(bpy)32+electrochemiluminescence (ECL) system is proposed. Nanoparticles (NPs) were used as assembly substrates to enrich ECL co-reactants of Ru(bpy)32+to construct nanoscale-enhanced ECL labels. Two different kinds of NP substrates [including semiconductor NPs (CdTe) and noble metal NPs (gold)] capped with 2-(dimethylamino)ethanethiol (DMAET) [a tertiary amine derivative which is believed to be one of the most efficient of co-reactants of the Ru(bpy)32+system] were synthesized through a simple one-pot synthesis method in aqueous media. Although both CdTe and gold NPs realized the enrichment of ECL co-reactants, they presented entirely different ECL performances as nanoscale ECL co-reactants of Ru(bpy)32+. The different effects of these two NPs on the ECL of Ru(bpy)32+were studied. DMAET-capped CdTe NPs showed enormous signal amplification of Ru(bpy)32+ECL, whereas DMAET-capped gold NPs showed a slight quenching effect of the ECL signal. DMAET-capped CdTe NPs can be considered to be excellent nanoscale ECL labels of the Ru(bpy)32+system, as even a NP solution sample of 10−18M was still detectable after an electrostatic self-assembly concentration process. DMAET-capped CdTe NPs were further applied in the construction of aptamer-based biosensing system for proteins and encouraging results were obtained. [ABSTRACT FROM AUTHOR]

This study aims to assess the nanotribology research output at global level using scientometric tools. The SCOPUS database was used to retrieve records related to the nanotribology research for the period 1996–2010. Publications were counted on a fractional basis. The level of collaboration and its citation impact were examined. The performance of the most productive countries, institutes and most preferred journals is assessed. Various visualization tools such as the Sci2 tool and Ucinet were employed. The USA ranked top in terms of number of publications, citations per paper and h-index, while Switzerland published a higher percentage of international collaborative papers. The most productive institution was Tsinghua University followed by Ohio State University and Lanzhou Institute of Chemical Physics, CAS. The most preferred journals were Tribology Letters, Wear and Journal of Japanese Society of Tribologists. The result of author keywords analysis reveals that Molecular Dynamics, MEMS, Hard Disk and Diamond like Carbon are major research topics. [ABSTRACT FROM AUTHOR]

A two-dimensional model of sediment column geophysics and geochemistry has been adapted to the problem of an accretionary wedge formation, patterned after the margin of the Juan de Fuca plate as it subducts under the North American plate. Much of the model description was given in a companion paper about application of the model to a passive margin setting; here we build on that formulation to simulate the deformation of the sediment wedge as it approaches the subduction zone. The active margin configuration of the model shares sensitivities with the passive margin configuration, in that sensitivities to organic carbon deposition and respiration kinetics, and to vertical bubble transport and redissolution in the sediment, are stronger than the sensitivity to ocean temperature. The active margin simulation also shows a sensitivity to plate subduction velocity, with higher plate velocities producing less hydrate per meter of coastline than slower velocities or the passive margin configuration. However, the local hydrate concentrations, as pore volume saturation, are higher in the active setting than the passive, as generally observed in the field. [ABSTRACT FROM AUTHOR]

In this paper, wastepaper gasification with carbon dioxide or steam has been investigated in the presence of molten carbonate catalysts. The reactions of wastepaper with steam or carbon dioxide have been compared. Hydrogen was the main product on the condition of steam used as reactant gas, but in the case where carbon dioxide was used, the amount of carbon monoxide generated from wastepaper gasification greatly increased via the Boudouard reaction. Different ratios of mixtures of lithium, sodium and potassium carbonates as the catalysts have been tested; the lithium carbonate was found to play a critical role. The reaction rate of carbon conversion was approximately first order for low carbon conversions. Both the rate constants and the activation energies have been calculated at different temperatures (923–1023 K). In additions, the flexibility of this technique was examined with three different types of wastepaper. The results suggest that this process can promote effective use of wastepaper and recovery of carbon dioxide. At 1023 K, a high value of cold gas efficiency of about 95% was acquired. [Copyright &y& Elsevier]

A series of papers have suggested that freshwater discharge, including a large amount of dissolved organic matter (DOM), has increased since the middle of the 20th century. In this study, a semi-analytical algorithm for estimating light absorption coefficients of the colored fraction of DOM (CDOM) was developed for Southern Beaufort Sea waters using remote sensing reflectance at six wavelengths in the visible spectral domain corresponding to MODIS ocean color sensor. This algorithm allows to separate colored detrital matter (CDM) into CDOM and non-algal particles (NAP) by determining NAP absorption using an empirical relationship between NAP absorption and particle backscattering coefficients. Evaluation using independent datasets, that were not used for developing the algorithm, showed that CDOM absorption can be estimated accurately to within an uncertainty of 35% and 50% for oceanic and turbid waters, respectively. In situ measurements showed that dissolved organic carbon (DOC) concentrations were tightly correlated with CDOM absorption (r² = 0.97). By combining the CDOM absorption algorithm together with the DOC versus CDOM relationship, it is now possible to estimate DOC concentrations in the near-surface layer of the Southern Beaufort Sea using satellite ocean color data. DOC concentrations in the surface waters were estimated using MODIS ocean color data, and the estimates showed reasonable values compared to in situ measurements. We propose a routine and near real-time method for deriving DOC concentrations from space, which may open the way to an estimate of DOC budgets for Arctic coastal waters. [ABSTRACT FROM AUTHOR]

The effects of neodymium:yttrium-aluminium-garnet (Nd:YAG) laser and silicon carbide (SiC) paper on the surface micro-topography of titanium-6 aluminium-4 vanadium (Ti6Al4V) alloy were examined in relation to the response of bone cells. The study was performed in three distinct stages: (1) after surface treatment of samples by laser and SiC paper, the surface hardness, surface roughness, corrosion resistance and surface tension were evaluated; (2) the growth of mouse connective tissue fibroblast cells (L-929) on untreated and treated samples was assessed in vitro; (3) the response of goat osteoblast cells to untreated and treated implanted samples was assessed in vivo. The surface roughness varied between 7 +/- 0.02 for laser-treated samples (LTSs) at 140 J cm(-2) and 21.8 +/- 0.05 for mechanically treated samples (MTSs). The surface hardness was found to vary from 377 Vickers hardness number (VHN) for MTSs to 850 VHN for LTSs. A corrosion potential of -0.21V was achieved for the LTSs compared with -0.51V for the MTSs. The LTSs exhibited a more hydrophilic behaviour (i.e. wettability) than did the MTSs. No cytotoxicity effect, unlike for the MTSs, was observed for the LTSs. The results of in vivo tests indicated longitudinal growth of osteoblast cells along the grooves on the samples formed by the SiC paper, and multidirectional spreading of the cells on the LTSs. [ABSTRACT FROM AUTHOR]

The Mediterranean Sea is one of the most oligotrophic regions of the oceans, and nutrients have been shown to limit both phytoplankton and bacterial activities. This has direct implications on the stock of dissolved organic carbon (DOC), whose high variability has already been well-documented even if measurements are still sparse and are associated with important uncertainties. We here propose a Mediterranean Basin-scale view of the export of organic carbon, under its dissolved and particulate forms. For this purpose, we have used a coupled model combining a mechanistic biogeochemical model (Eco3M-MED) and a high-resolution (eddy-resolving) hydrodynamic simulation (NEMO-MED12). This is the first Basin-scale application of the biogeochemical model Eco3M-MED and is shown to reproduce the main spatial and seasonal biogeochemical characteristics of the Mediterranean Sea. Model estimations of carbon export are of the same order of magnitude as estimations from in situ observations, and their respective spatial patterns are consistent with each other. As for surface chlorophyll, nutrient concentrations, and productivity, strong differences between the Western and Eastern Basins are evidenced by the model for organic carbon export, with only 39% of organic carbon (particulate and dissolved) export taking place in the Western Basin. The major result is that except for the Alboran Sea, dissolved organic carbon (DOC) contribution to organic carbon export is higher than that of particulate (POC) in the whole Basin, especially in the Eastern Basin. This paper also investigates the seasonality of DOC and POC exports as well as the differences in the processes involved in DOC and POC exports. [ABSTRACT FROM AUTHOR]

Thermal-optical analysis is currently under consideration by the European standardization body (CEN) as the reference method to quantitatively determine organic carbon (OC) and elemental carbon (EC) in ambient air. This paper presents an overview of the critical parameters related to the thermal-optical analysis including thermal protocols, critical factors and interferences of the methods examined, method inter-comparisons, inter-laboratory exercises, biases and artifacts, and reference materials. The most commonly used thermal protocols include NIOSH-like, IMPROVE_A and EUSAAR_2 protocols either with light transmittance or reflectance correction for charring. All thermal evolution protocols are comparable for total carbon (TC) concentrations but the results vary significantly concerning OC and especially EC concentrations. Thermal protocols with a rather low peak temperature in the inert mode like IMPROVE_A and EUSAAR_2 tend to classify more carbon as EC compared to NIOSH-like protocols, while charring correction based on transmittance usually leads to smaller EC values compared to re flectance. The difference between reflectance and transmittance correction tends to be larger than the difference between different thermal protocols. Nevertheless, thermal protocols seem to correlate better when reflectance is used as charring correction method. The difference between EC values as determined by the different protocols is not only dependent on the optical pyrolysis correction method, but also on the chemical properties of the samples due to different contributions from various sources. The overall conclusion from this literature review is that it is not possible to identify the "best" thermal-optical protocol based on literature data only, although differences attributed to the methods have been quantified when possible. [ABSTRACT FROM AUTHOR]

As Arctic regions warm, the large organic carbon pool stored in permafrost becomes increasingly vulnerable to thaw and decomposition. The transfer of newly mobilized carbon to the atmosphere and its potential influence upon climate change will largely depend on the reactivity and subsequent fate of carbon delivered to aquatic ecosystems. Dissolved organic carbon (DOC) is a key regulator of aquatic metabolism and its biodegradability will determine the extent and rate of carbon release from aquatic ecosystems to the atmosphere. Knowledge of the mechanistic controls on DOC biodegradability is however currently poor due to a scarcity of long-term data sets, limited spatial coverage of available data, and methodological diversity. Here, we performed parallel biodegradable DOC (BDOC) experiments at six Arctic sites (16 experiments) using a standardized incubation protocol to examine the effect of methodological differences used as common practice in the literature. We further synthesized results from 14 aquatic and soil leachate BDOC studies from across the circum-arctic permafrost region to examine pan-Arctic trends in BDOC. An increasing extent of permafrost across the landscape resulted in higher BDOC losses in both soil and aquatic systems. We hypothesize that the unique composition of permafrost-derived DOC combined with limited prior microbial processing due to low soil temperature and relatively shorter flow path lengths and transport times, resulted in higher overall terrestrial and freshwater BDOC loss. Additionally, we found that the fraction of BDOC decreased moving down the fluvial network in continuous permafrost regions, i.e. from streams to large rivers, suggesting that highly biodegradable DOC is lost in headwater streams. We also observed a seasonal (January-December) decrease in BDOC losses in large streams and rivers, but no apparent change in smaller streams and soil leachates. We attribute this seasonal change to a combination of factors including shifts in carbon source, changing DOC residence time related to increasing thaw-depth, increasing water temperatures later in the summer, as well as decreasing hydrologic connectivity between soils and surface water as the seasons progress. Our results suggest that future, climate warming-induced shifts of continuous permafrost into discontinuous permafrost regions could affect the degradation potential of thaw-released DOC as well as its variability throughout the Arctic summer. We lastly present a recommended standardized BDOC protocol to facilitate the comparison of future work and improve our knowledge of processing and transport of DOC in a changing Arctic. [ABSTRACT FROM AUTHOR]

Transformations of dissolved organic matter (DOM) in boreal lakes lead to large greenhouse gas emissions as well as substantial carbon storage in sediments. Using novel molecular characterization approaches and photochemical degradation experiments we studied how seasonal patterns in water column stratification affected the DOM in a Swedish lake under late winter and early summer conditions. Dissolved organic carbon (DOC) concentrations were consistently higher above the sediment when compared to surface waters. Solely photobleaching could not explain this difference in DOC because the lake was covered by 40 cm thick ice during late winter sampling and still showed the same DOC trend. The differences in the molecular diversity between surface water DOM in winter and summer were consistent with summertime photobleaching/decarboxylation reactions and a possible bacterial consumption of photo-products. Additional photodegradation experiments using simulated sunlight showed a production of highly oxidized organic molecules and low molecular weight compounds in all late winter samples and also in the deep water sample in summer. In the surface summer DOM sample, few such molecules were produced during the photodegradation experiments confirming that DOM was already photobleached prior to the experiments. This study suggests that photobleaching, and therefore also the ice cover during winter plays a central role in surface DOM structural dynamics with important differences in the molecular composition of DOM between surface and deep boreal lake waters. The release of DOC from boreal lake sediments likely also contribute to this pattern. Photochemical degradation of DOM may be more extensive following ice-out and water column turnover when non-light exposed and thereby photosensitive DOM is photo-mineralized. Hence, the yearly DOM photo-mineralization may be greater than inferred from studies of recently light exposed DOM. [ABSTRACT FROM AUTHOR]

Mediterranean reservoirs receive frequent Saharan dust inputs with soil-derived organic compounds mostly during stratification periods, when run-off inputs are particularly limited. Here, we quantified and optically characterized the water-soluble organic carbon (WSOC) of the (dry and wet) atmospheric deposition in collectors located near three reservoirs from the Western Mediterranean Basin. In addition, we determined, during the stratification period, the WSOC contribution to the pool of dissolved organic carbon (DOC) and the influence of the chromophoric organic compounds from the dust on water transparency. We found synchrony both in the WSOC atmospheric inputs among collectors and in the DOC dynamics among the three reservoirs. DOC concentrations and WSOC atmospheric inputs were positive and significantly correlated in the two reservoirs more sensitive to atmospheric inputs: the most oligotrophic reservoir (Quentar) and the reservoir with the highest ratio of surface area to mixing water depth (Cubillas). Nevertheless, WSOC atmospheric inputs, during the stratification period, represented less than 10% of the total DOC pool, suggesting that indirect effects of dust inputs such as primary productivity stimulation may also induce these synchronic patterns. Chromophoric compounds from dust inputs can significantly reduce water transparency to ultraviolet radiation (UVR). The depths where UVR at λ = 320 nm is reduced to ten percent of surface intensity (Z10%) decreased 15 cm (about 24%) in Beznar, 17 cm (about 27%) in Cubillas, and 43 cm (about 39%) in Quéntar due to dust inputs. [ABSTRACT FROM AUTHOR]

We present a new geologic-time and basin-spatial scale model of the continental margin methane cycle. The model, SpongeBOB, is used to simulate evolution of the carbon cycle in a passive sedimentary continental margin in response to changing oceanographic and geologic forcing over a time scale of 140 million years. The model is somewhat less sensitive to temperature than our previous results with a one-dimensional model, but is more sensitive to reasonable changes in POC than it is to reasonable changes in temperature. This behavior could lead to higher inventories of hydrate during hothouse climate conditions, rather than lower as generally assumed, due to the enrichment of the sediments in organic carbon. The hydrate inventory in the model is extremely sensitive to the ability of methane bubbles to rise within the sediment column, and how far gas-phase methane can get through the sediment column before it redissolves when it reaches undersaturated conditions. Hydrate formation is also sensitive to deep respiration of migrating petroleum in the model. The geochemistry of the sediment column is altered by the addition of vertical high-permeability chimneys intended to mimic the effects of heterogeneity in the real sediment column due to faults and chimneys, and produces results consistent with measured pore-water tracers Due to image rights restrictions, multiple line equation(s) cannot be graphically displayed. and 129I. Pore water DIC concentrations are consistent with chemical weathering at depth within the sediment column. The carbon isotopic composition of the DIC is consistent with a methane production efficiency from POC of 50 %, which is somewhat lower than redox balance with the H/C of organic matter in the model. Other phenomena which we simulated had only small impact on the hydrate inventory, including thermogenic methane, dissolved organic carbon, and sediment transport characteristics. [ABSTRACT FROM AUTHOR]

The controls on stream dissolved organic carbon (DOC) concentrations were investigated in a 68 km² catchment by applying a landscape-mixing model to test if downstream concentrations could be predicted from contributing landscape elements. The landscape-mixing model reproduced the DOC concentration well throughout the stream network during times of high discharge, but was even more useful for providing a baseline for residual analysis, which highlighted areas for further conceptual model development. The landscape-mixing model approach is conceptually simple and easy to apply, requiring relatively few field measurements and minimal parameterization. The residual analysis highlighted areas of the stream network that were not well represented by simple mixing of headwaters, as well as flow conditions during which simple mixing based on headwater watershed characteristics did not apply. Specifically, we found that during periods of base flow the larger valley streams underlain by fine sorted sediments had much lower DOC concentrations than would be predicted by simple mixing; while peatland streams had higher DOC than predicted. During periods of intermediate and high flow the model made more accurate predictions of downstream DOC. Our interpretation is that the higher degree of hydrological connectivity during high flows, possibly combined with shorter stream residence times, increased the predictive power of this whole-watershed based mixing model. However, there was still a clear pattern during high discharge periods, with peatland streams having lower DOC than would be predicted by simple mixing while forested streams had higher DOC. These observations suggest several potential mechanisms to be further explored using more focused field and process-based modeling studies, especially on the role of changing hydrological pathways. [ABSTRACT FROM AUTHOR]

Rising atmospheric CO2 may stimulate future forest productivity, possibly increasing carbon storage in terrestrial ecosystems, but how tropospheric ozone will modify this response is unknown. Because of the importance of fine roots to the belowground C cycle, we monitored fine-root biomass and associated C fluxes in regenerating stands of trembling aspen, and mixed stands of trembling aspen and paper birch at FACTS-II, the Aspen FACE project in Rhinelander, Wisconsin. Free-air CO2 enrichment (FACE) was used to elevate concentrations of CO2 (average enrichment concentration 535 µl l–1) and O3 (53 nl l–1) in developing forest stands in 1998 and 1999. Soil respiration, soil pCO2, and dissolved organic carbon in soil solution (DOC) were monitored biweekly. Soil respiration was measured with a portable infrared gas analyzer. Soil pCO2 and DOC samples were collected from soil gas wells and tension lysimeters, respectively, at depths of 15, 30, and 125 cm. Fine-root biomass averaged 263 g m–2 in control plots and increased 96% under elevated CO2. The increased root biomass was accompanied by a 39% increase in soil respiration and a 27% increase in soil pCO2. Both soil respiration and pCO2 exhibited a strong seasonal signal, which was positively correlated with soil temperature. DOC concentrations in soil solution averaged ~12 mg l–1 in surface horizons, declined with depth, and were little affected by the treatments. A simplified belowground C budget for the site indicated that native soil organic matter still dominated the system, and that soil respiration was by far the largest flux. Ozone decreased the above responses to elevated CO2, but effects were rarely statistically significant. We conclude that regenerating stands of northern hardwoods have the potential for substantially greater C input to soil due to greater fine-root production under elevated CO2. Greater fine-root biomass will be accompanied by greater soil C efflux as soil respiration, but leaching losses of C will probably be unaffected. [ABSTRACT FROM AUTHOR]

Changes in soil utilization significantly affect aggregate stability and aggregateassociated soil organic carbon (SOC). A field investigation and indoor analysis were conducted in order to study the soil aggregate stability and organic carbon distribution in the water-stable aggregates (WSA) of the bare land (BL), grassland (GL), shrubland (SL), and woodland (WL) in a typical karst gorge region. The results indicated that the BL, GL, SL, and WL were dominated by particles with sizes > 5mm under dry sieving treatment, and that the soil aggregate contents of various sizes decreased as the particle size decreased. In addition, the BL, GL, SL, and WL were predomi nantly comprised of WSA< 0.25mm under wet sieving treatment, and that the WSA contents initially increased, then decreased, and then increased again as the particle size decreased. Furthermore, at a soil depth of 0-60 cm, the mean weight diameter (MWD), geometrical mean diameter (GMD), and fractal dimensions (D) of the dry aggregates and water-stable aggregates in the different types of land were ranked, in descending order, as WL>GL>SL>BL. The contents of WSA> 0.25mm, MWD and GMD increased significantly, in that order, and the percentage of aggregate destruction (PAD) and fractal dimensions decreased significantly as the soil aggregate stability improved. The results of this study indicated that, as the SOC contents increased after vegetation restoration, the average SOC content of WL was 2.35, 1.37, and 1.26 times greater than that in the BL, GL, and SL, respectively. The total SOC and SOC associated in WSA of various sizes were the highest at a soil depth of 0-20 cm. In addition, the SOC contents of the WSA increased as the soil aggregate sizes decreased. The SOC contents of the WSA< 0.25mm were highest except in the bare land, and the SOC contents of the aggregates < 0.25 mm, which ranged from 18.85 to 41.08 %, com prised the majority of the total aggregate SOC contents. The woodland and grassland facilitated WSA stability and SOC protection, thus, promoting the natural restoration of vegetation by reducing artificial disturbances could effectively restore the ecology of and prevent soil erosion in karst regions. [ABSTRACT FROM AUTHOR]

Glacial runoff is an important source of dissolved organic carbon (DOC) for downstream heterotrophic activity, despite the low overall DOC concentrations. This is because of the abundance of bioavailable, low molecular weight (LMW) DOC species. However, the provenance and character of LMW-DOC is not fully understood. We investigated the abundance and composition of DOC in subglacial environments via a molecular level DOC analysis of basal ice, which forms by water/sediment freeze-on to the glacier sole. Spectrofluorometry and a novel ion chromatographic method, which has been little utilised in glacial science for LMW-DOC determinations, were employed to identify and quantify the major LMW fractions (free amino acids, carbohydrates and carboxylic acids) in basal ice from four glaciers, each with a different basal debris type. Basal ice from Joyce Glacier (Antarctica) was unique in that 98%of the LMW-DOC was derived from the extremely diverse FAA pool, comprising 14 FAAs. LMW-DOC concentrations in basal ice were dependent on the bioavailability of the overridden organic carbon (OC), which in turn, was influenced by the type of overridden material. Mean LMWDOC concentrations in basal ice from Russell Glacier (Greenland), Finsterwalderbreen (Svalbard) and Engabreen (Norway) were low (0-417nMC), attributed to the relatively refractory nature of the OC in the overridden paleosols and bedrock. In contrast, mean LMW-DOC concentrations were an order of magnitude higher (4430nMC) in basal ice from Joyce Glacier, a reflection of the high bioavailability of the overridden lacustrine material (> 17% of the sediment OC comprised extractable carbohydrates, a proxy for bioavailable OC). We find that the overridden material may act as a direct (via abiotic leaching) and indirect (via microbial cycling) source of DOC to the subglacial environment and provides a range of LMW-DOC compounds that may stimulate microbial activity in wet sediments in current subglacial environments. [ABSTRACT FROM AUTHOR]

Bogs can store large amounts of lead (Pb) and arsenic (As) attributed to atmospheric deposition of anthropogenic emissions. Pb and As are exported along with dissolved organic carbon (DOC) in these organic-rich systems, but it is not yet clear which hydrological (pre-)conditions favor their export. This study combines one year continuous monitoring of precipitation, bog water level and pore water concentration changes with bog discharge, DOC, As and Pb stream concentrations and fluxes. Concentrations ranged from 5 to 30mgL-1 for DOC, 0.2 to 1.9 μg L-1 for As and 1.3 to 12 μg L-1 for Pb with highest concentrations in late summer. As and Pb concentrations significantly correlated with DOC concentrations. Fluxes depended strongly on discharge, as 40% of As and 43% of Pb were exported by the upper 10% of discharge, pointing out the over-proportional contribution of heavy rain and high discharge events to annual As, Pb and DOC export. Exponential increase in element export from the bog is explained by connection of additional DOC, As and Pb pools in the acrotelm during water table rise, which is most pronounced after drought. Pb, As and DOC concentrations in pore water provide evidence of an increase of the soluble Pb pool as soon as the peat layer gets hydrologically connected, while DOC and As peak concentrations in runoff lag in comparison to Pb. Our data indicates a distinct bog-specific discharge threshold of 8 L s-1, which is thought to depend mainly on the bogs size and drainage conditions. Above this threshold element concentration do not further increase and discharge gets diluted. Combining pore water and discharge data shows that As and Pb exports are not only dependent on the amount of precipitation and discharge, but on the frequency and depth of water table fluctuations. Comparing the annual bog As and Pb export with element inventories indicates that As is much more mobilized than Pb, with annual fluxes accounting for 0.85 and 0.27‰ of total As and Pb inventory, respectively. [ABSTRACT FROM AUTHOR]

Optical measurements using ultra-violet/visible (UV/Vis) spectrophotometric sensors and fluorescent dissolved organic matter (FDOM) sensors have recently been used as proxies of dissolved organic carbon (DOC) concentrations of streams and rivers at high temporal resolution. Despite of the merits of the sensors, temperature changes and particulate matter in water can interfere the sensor readings, over-or under-estimating DOC concentrations. However, little efforts have been made to compare responses of the two types of the sensors in natural conditions. We conducted both laboratory ex¬periments and in situ monitoring with a UV/Vis sensor and a FDOM sensor during the three storm events in the fall of 2012 and the spring of 2013 in a forest stream in Korea in order to compare their performance. Laboratory experiments using the Suwannee River natural organic matter, humic acid, and fulvic acid demonstrated strong linear relationships between both the sensor signals and measured DOC concentrations with R² ≥ 0.98. Although temperature compensation might not be needed for the UV/Vis sensor, it was sensitive to relativley small changes in turbidity. In contrast, the FDOM sensor was insenstive to relatively low turbidity while the FDOM sensor outputs de¬creased significantly as temperature increased, requiring temperature compensated FDOM (e.g. FDOM20 for 20°C) for in situ monitoring of DOC. The results suggest that both sensors can be employed as a proxy for stream DOC concentrations after temperature and turbidity compensation in a forest stream where terrestrially derived humic-like materials are dominant components. [ABSTRACT FROM AUTHOR]

Extracellular release (ER) by phytoplankton is the major source of fresh dissolved organic carbon (DOC) in marine ecosystems and accompanies primary production during all growth phases. Little is known, so far, on size and composition of released molecules, and to which extent ER occurs passively, by leakage, or actively, by exudation. Here, we report on ER by the widespread and bloom-forming coccolithophore Emiliania huxleyi grown under steady state conditions in phosphorus controlled chemostats (N: P=29, growth rate of µ=0.2 d-1). 14C incubations were accomplished to determine primary production (PP), comprised by particulate (PO 14C) and dissolved organic carbon (DO 14C), and the concentration and composition of particulate combined carbohydrates (pCCHO), and of high molecular weight (> 1 kDa, HMW) dissolved combined carbohydrates (dCCHO) as major components of ER. Information on size distribution of ER products was obtained by investigating distinct size classes (< 0.40 µm, < 1000 kDa, < 100 kDa and < 10 kDa) of DO 14C and HMW-dCCHO. Our results revealed relatively low ER during steady state growth, corresponding to ~ 4.5% of primary production, and similar ER rates for all size classes. Acidic sugars had a significant share on freshly produced pCCHO as well as on HMW-dCCHO. While pCCHO and the smallest size (< 10 kDa) fraction of HMW-dCCHO exhibited a similar sugar composition, dominated by high percentages of glucose (74-80 Mol %), the composition of HMW-dCCHO size-classes > 10 kDa was significantly different with higher Mol % of arabinose. Mol % of acidic sugars increased and Mol % glucose decreased with increasing size of HMW-dCCHO. We conclude that larger polysaccharides follow different production and release pathways than smaller molecules, potentially serving distinct ecological and biogeochemical functions. [ABSTRACT FROM AUTHOR]

Dissolved organic carbon (DOC) concentrations -- mainly of terrestrial origin -- are increasing worldwide in inland waters. The biodegradability of the DOC varies depending on quantity and chemical quality. Heterotrophic bacteria are the main consumers of DOC and thus determine DOC temporal dynamics and availability for higher trophic levels. It is therefore crucial to understand the processes controlling the bacterial turnover of additional allochthonous and autochthonous DOC in aquatic systems. Our aim was to study bacterial carbon (C) turnover with respect to DOC quantity and chemical quality using both allochthonous and autochthonous DOC sources. We incubated a natural bacterial community with allochthonous C (13C-labeled beech leachate) and increased concentrations and pulses (intermittent occurrence of organic matter input) of autochthonous C (algae lysate). We then determined bacterial carbon consumption, activities, and community composition together with the carbon flow through bacteria using stable C isotopes. The chemical analysis of single sources revealed differences in aromaticity and fractions of low and high molecular weight substances (LMWS and HMWS, respectively) between allochthonous and autochthonous C sources. In parallel to these differences in chemical composition, we observed a higher availability of allochthonous C as evidenced by increased DOC consumption and bacterial growth efficiencies (BGE) when solely allochthonous C was provided. In treatments with mixed sources, rising concentrations of added autochthonous DOC resulted in a further, significant increase in bacterial DOC consumption from 52 to 68% when nutrients were not limiting. This rise was accompanied by a decrease in the humic substances (HS) fraction and an increase in bacterial biomass. Stable C isotope analyses of phospholipid fatty acids (PLFA) and respired dissolved inorganic carbon (DIC) supported a preferential assimilation of autochthonous C and respiration of the allochthonous C. Changes in DOC concentration and consumption in mixed treatments did not affect bacterial community composition (BCC), but BCC differed in single vs. mixed incubations. Our study highlights that DOC quantity affects bacterial C consumption but not BCC in nutrient-rich aquatic systems. BCC shifted when a mixture of allochthonous and autochthonous C was provided simultaneously to the bacterial community. Our results indicate that chemical quality rather than source of DOC per se (allochthonous vs. autochthonous) determines bacterial DOC turnover. [ABSTRACT FROM AUTHOR]

During the anomalous hot summer in 2012, surface air temperatures in Western Siberia were 5 to 10°C higher than those observed during the previous period of >30 yr. This unusual climate phenomenon provided an opportunity to examine the effects of short-term natural heating of water in thermokarst ponds and lakes in discontinuous permafrost zones and compare these observations to previous field results obtained when the temperature was normal during the summer of 2010 in the same region. Thermokarst bodies of water shrank significantly, water levels dropped approximately 50 cm in large lakes and small (<10-100m²) ponds, and shallow soil depressions disappeared. Based on samples from ~40 bodies of water collected previously and in 2012, first-order features of changes in chemical composition in response to increased water temperatures (from 14.1±2.2 to 23.8±2.3°C in 2010 and 2012, respectively) were established. In these thermokarst bodies of water that covered a full range of surface areas, the average conductivity and pH were almost unchanged, whereas dissolved organic carbon (DOC), Cl- and SO4- concentrations were higher by a factor of ~2 during summer 2012 compared to periods with normal temperatures. Similarly, most divalent metals and insoluble trivalent and tetravalent elements were more concentrated by a factor of 1.7-2.4 in the summer of 2012 than normal periods. The average concentrations of dissolved CO2 and CH4 during the hot summer of 2012 increased by factors of 1.4 and 4.9, respectively. For most of the trace elements bound to colloids, the degree of colloidal binding decreased by a factor of 1.44±0.33 (for an average of 40 elements) during the hot summer of 2012 compared to normal periods. Increases in CO2 and CH4 concentrations with the decreasing size of the body of water were well-pronounced during the hot summer of 2012. The concentrations of CO2 and CH4 significantly increased by factors of 5 and 150, respectively, in small (≤10² m²) from thaw lake surfaces; (2) decrease of molecular sizes of TE complexes and increase of potential bioavailability of metal micronutrients in water columns; and (3) relatively conservative responses by CO2, DOC and trace element concentrations. compared to large (≥104 m²) thermokarst (thaw) lakes. Taken together, these trends suggest that, for a conservative scenario of lake size distribution, lake water warming at high latitudes will produce (1) a significant increase in methane emission capacity. [ABSTRACT FROM AUTHOR]

Downstream mineralization and sedimentation of terrestrial dissolved organic carbon (DOC) render lakes important for landscape carbon cycling in the boreal region, with regulating processes potentially sensitive to perturbations associated with climate change including increased occurrence of wildfire. In this study we assessed chemical composition and reactivity (during both dark and UV incubations) of DOC from lakes and terrestrial sources within a peatland-rich western boreal plains region partially affected by a recent wildfire. While wildfire was found to increase aromaticity of DOC in peat pore-water above the water table, it had no effect on concentrations or composition of DOC from peatland wells and neither affected mineral well or lake DOC characteristics. Lake DOC composition reflected a mixing of peatland and mineral groundwater, with a greater influence of mineral sources to lakes in coarse- than fine-textured settings. Peatland DOC was less biodegradable than mineral DOC, but both mineralization and sedimentation of peatland DOC increased substantially during UV incubations through selective removal of aromatic humic and fulvic acids. DOC composition in lakes with longer residence times had characteristics consistent with increased UV-mediated processing. We estimate that about half of terrestrial DOC inputs had been lost within lakes, mostly due to UV-mediated processes. The importance of within-lake losses of aromatic DOC from peatland sources through UV-mediated processes indicate that terrestrial-aquatic C linkages in the study region are largely disconnected from recent terrestrial primary productivity. Together, our results suggest that characteristics of the study region (climate, surface geology and lake morphometry) render linkages between terrestrial and aquatic C cycling insensitive to the effects of wildfire by determining dominant terrestrial sources and within-lake processes of DOC removal [ABSTRACT FROM AUTHOR]

The dynamics of dissolved organic carbon (DOC) have been intensively studied in mature ecosystems, but little is known about DOC dynamics and the significance of DOC as a substrate for microbial activity in early-successional catchments. We determined the concentration, chemical composition, source, radiocarbon age, and bioavailability of DOC along the hydrological flow path from soil solution to a downstream pond in a recently constructed catchment (Chicken Creek Catchment, Germany). Soil solution, upwelling ground water, subsurface water in an alluvial fan, and pond water all had high DOC concentrations (averages of 6.0-11.6mgDOCL-1), despite small carbon stocks in either vegetation or soil of the early-successional catchment. The mean 14C age of DOC in upwelling ground water was 2600 to 2800 yr. Solid-state CPMAS 13C NMR revealed a higher proportion of aromatic compounds (32%) and a lower proportion of carbohydrates (33%) in upwelling ground water than in pond water (18% and 45%, respectively). The 14C age and 13C NMR spectra suggest that DOC was partly mobilized from charred organic matter of the Quaternary substrate. In an experimental 70-days incubation experiment, 20% of the total DOC was found to be bioavailable, irrespective of the water type. Origin of microbial communities (enriched from soil, stream sediment or pond water) had only marginal effects on overall DOC utilization. Overall, these data suggest that the old DOC can support microbial activity during early ecosystem succession to some extent, although the largest fraction is recalcitrant DOC that is exported from the catchment once it has been mobilized. [ABSTRACT FROM AUTHOR]

The Lena River Delta, which is the largest delta in the Arctic, extends over an area of 32 000 km² and likely holds more than half of the entire soil organic carbon mass stored in the seven major deltas in the northern permafrost regions. The geomorphic units of the Lena River Delta which were formed by true deltaic sedimentation processes are a Holocene river terrace and the active floodplains. Their mean soil organic carbon stocks for the upper 1m of soils were estimated at 29 kgm-2 ± 10 kgm-2 and at 14 kgm-2 ± 7 kgm-2, respectively. For the depth of 1m, the total soil organic carbon pool of the Holocene river terrace was estimated at 121 Tg± 43 Tg, and the soil organic carbon pool of the active floodplains was estimated at 120 Tg± 66 Tg. The mass of soil organic carbon stored within the observed seasonally thawed active layer was estimated at about 127 Tg assuming an average maximum active layer depth of 50 cm. The soil organic carbon mass which is stored in the perennially frozen ground below 50 cm soil depth, which is excluded from intense biogeochemical exchange with the atmosphere, was estimated at 113 Tg. The mean nitrogen (N) stocks for the upper 1m of soils were estimated at 1.2 kgm-2 ± 0.4 kgm-2 for the Holocene river terrace and at 0.9 kgm-2 ± 0.4 kgm-2 for the active floodplain levels, respectively. For the depth of 1m, the total N pool of the river terrace was estimated at 4.8 Tg± 1.5 Tg, and the total N pool of the floodplains was estimated at 7.7 Tg± 3.6 Tg. Considering the projections for deepening of the seasonally thawed active layer up to 120 cm in the Lena River Delta region within the 21st century, these large carbon and nitrogen stocks could become increasingly available for decomposition and mineralization processes. [ABSTRACT FROM AUTHOR]

Chemosynthetic communities in the deep-sea can be found at hydrothermal vents, cold seeps, whale falls and wood falls. While these communities have been suggested to exist in isolation from solar energy, much of the life associated with them relies either directly or indirectly on photosynthesis in the surface waters of the oceans. The sun indirectly provides oxygen, a byproduct of photosynthesis, which aerobic chemosynthetic microorganisms require to synthesize organic carbon from CO2. Planktonic life stages of many vent and cold seep invertebrates also directly feed on photosynthetically produced organic matter as they disperse to new vent and seep systems. While a large portion of the life at deep-sea chemosynthetic habitats can be linked to the sun and so could not survive without it, a small portion of anaerobically chemosynthetic microorganisms can persist in its absence. These small and exotic organisms have developed a way of life in the deep-sea which involves the use of resources originating in their entirety from terrestrial sources. [ABSTRACT FROM AUTHOR]

Based on four field investigations during 2003 and 2009 along the Yellow River mainstream, we examined the distributions, seasonal variations and transport features of organic carbon, with a focus on the impacts of human activities (reservoir construction and regulation scheme). The results showed that organic carbon transport processes in the Yellow River were different from other major rivers. Particulate organic carbon (POC) dominated in the Yellow River and it mainly originated from the Loess Plateau. POC levels in suspended sediment (POC %) ranged between 0.25% and 2.20% and more than 80%of POC concentrated in the particles with grain size smaller than 16 µm. On time scale, dissolved organic carbon (DOC) correlated negatively with discharges, indicating the influence of dilution effect. Along the river on spatial scales, DOC in the Qinghai-Tibet Plateau was closely related with temperature while DOC in the Loess Plateau showed the concentration effect, due to the abundant human input and the high ratio of evaporation to precipitation. Organic carbon in the Yellow River was very refractory and about 90% of POC and 70% of DOC cannot be degraded. Due to the high turbidity, the Yellow River suffers more impacts from the reservoirs in the transport of total suspended solids (TSS) and organic carbon. Ratios of DOC/POC ranged between 2.0 and 12 in the reservoirs and organic carbon was mainly in the dissolved from. POC deposited in the reservoirs of the Yellow River achieved 0.0033 Gta-1, about 8 times its annual POC flux discharged to the ocean. During the 2008 Water and Sediment Regulation (WSR) period, DOC and POC fluxes was as high as 1.1x1010 g and 2.2x1011 g respectively, accounting for 35% of annual DOC flux and 56% of the annual POC flux to the ocean. Discharges and material fluxes to the ocean decline sharply due to the reservoir construction while large amounts of water and sediment are transported to the ocean in such a short WSR period. These two human disturbances totally altered the processes of substance transport in the Yellow River, and may change the water chemical characteristics in the coastal zones. [ABSTRACT FROM AUTHOR]

Carbon use efficiency (CUE) is a functional parameter that could possibly link the current increasingly accurate global estimates of gross primary production with those of net ecosystem exchange, for which global predictors are still unavailable. Nevertheless, CUE estimates are actually available for only a few ecosystem types, while information regarding agro-ecosystems is scarce, in spite of the simplified spatial structure of these ecosystems that facilitates studies on allocation patterns and temporal growth dynamics. We combined three largely deployed methods, eddy covariance, soil respiration and biometric measurements, to assess monthly values of CUE, net primary production (NPP) and allocation patterns in different plant organs in an apple orchard during a complete year (2010). We applied a measurement protocol optimized for quantifying monthly values of carbon fluxes in this ecosystem type, which allows for a cross-check between estimates obtained from different methods. We also attributed NPP components to standing biomass increments, detritus cycle feeding and lateral exports. We found that in the apple orchard both net ecosystem production and gross primary production on yearly basis, 380±30gCm-2 and 1263±189gCm-2 respectively, were of a magnitude comparable to those of natural forests growing in similar climate conditions. The largest differences with respect to forests are in the allocation pattern and in the fate of produced biomass. The carbon sequestered from the atmosphere was largely allocated to production of fruits: 49% of annual NPP was taken away from the ecosystem through apple production. Organic material (leaves, fine root litter, pruned wood and early fruit falls) contributing to the detritus cycle was 46% of the NPP. Only 5% was attributable to standing biomass increment, while this NPP component is generally the largest in forests. The CUE, with an annual average of 0.71±0.09, was higher than the previously suggested constant values of 0.47-0.50. Low nitrogen investment in fruits, the limited root-apparatus, and the optimal growth temperature and nutritional condition observed at the site are suggested to be explanatory variables for the high CUE observed. [ABSTRACT FROM AUTHOR]

Santos et al. (2012) address the important issue that 14C dating of the carbon occluded in silica phytoliths (PhytOC) isolated from contemporary plant materials can produce ages that are incompatible, being often several kyr older, with both their known recent origin and the 14C age of the bulk plant material. In their article, Santos et al. (2012) propose that the anomalously old 14C carbon dates of PhytOC from harvested plant materials are based on plants taking up "old" dissolved soil carbon to the plant by roots during nutrient uptake. They then propose that this old soil-derived carbon is subsequently partitioned from the general plant biomass into either the silica phytoliths they produce, or as recalcitrant organic matter elsewhere in the plant. We suggest that the full data available for PhytOC 14C dating does not support this hypothesis. Santos et al. (2012) also address the important issue of contamination of PhytOC by general plant biomass material that can occur with procedures that incompletely extract phytoliths. Whilst we agree that such contamination needs to be avoided when examining the nature of PhytOC, we also point out that the converse problem, i.e. removal of PhytOC by over-vigorous extraction procedures, can also have important adverse consequences. [ABSTRACT FROM AUTHOR]

Rising water temperatures due to climate and land-use change can accelerate biogeochemical fluxes from sediments to streams. We investigated impacts of increased stream water temperatures on sediment fluxes of dissolved organic carbon (DOC), nitrate, soluble reactive phosphorus (SRP) and sulfate. Experiments were conducted at 8 long-term monitoring sites across land use (forest, agricultural, suburban, and urban) at the Baltimore Ecosystem Study Long-Term Ecological Research (LTER) site in the Chesapeake Bay watershed. Over 20 yr of routine water temperature data showed substantial variation across seasons and years, and lab incubations were conducted at 4 temperatures (4°C, 15°C, 25°C and 35°C) for 48 h. Results indicated: (1) warming consistently increased sediment DOC fluxes to overlying water across land use but decreased DOC quality via increases in the humic-like to protein-like fractions (2) warming consistently increased SRP fluxes from sediments to overlying water across land use (3) warming increased sulfate fluxes from sediments to overlying water at rural/suburban sites but decreased sulfate fluxes at urban sites likely due to sulfate reduction (4) nitrate fluxes showed an increasing trend with temperature but with larger variability than SRP. Sediment fluxes of nitrate, SRP and sulfate were strongly related to watershed urbanization and organic matter content. Using relationships of sediment fluxes with temperature, we estimate a 5°C warming would increase the annual sediment release by 1.0-3.9 times. In addition to hydrologic variability, understanding warming impacts on coupled biogeochemical cycles in streams (e.g., organic matter mineralization, P sorption, nitrification, denitrification, and sulfate reduction) is critical for forecasting changes in carbon and nutrient exports across watershed land use. [ABSTRACT FROM AUTHOR]

The article focuses on a study which depicts a comparison between satellite-derived column-averaged dry air mole fractions of carbon dioxide retrieved from SCIAMACHY/ENVISAT using the WFM-DOAS algorithm and output from NOAA's global carbon dioxide modelling and assimilation system Carbon-Tracker. It examines the difference between SCIAMACHY and Carbon-Tracker dry air mole fractions of carbon dioxide. The sensitivity of the WFM-DOAS cloud detection algorithm is discussed.

Estimates of dissolved organic carbon (DOC) release by marine macrophyte communities (seagrass meadows and macroalgal beds) were obtained experimentally using in situ benthic chambers. The effect of light availability on DOC release by macrophyte communities was examined in two communities both by comparing net DOC release under light and dark, and by examining the response of net DOC release to longerterm (days) experimental shading of the communities. All most 85% of the seagrass communities and almost all of macroalgal communities examined acted as net sources of DOC. There was a weak tendency for higher DOC fluxes under light than under dark conditions in seagrass meadow. There is no relationship between net DOC fluxes and gross primary production (GPP) and net community production (NCP), however, this relationship is positive between net DOC fluxes and community respiration. Net DOC fluxes were not affected by shading of a T. testudinum community in Florida for 5 days, however, shading of a mixed seagrass meadow in the Philippines led to a significant reduction on the net DOC release when shading was maintained for 6 days compared to only 2 days of shading. Based on published and unpublished results we also estimate the global net DOC production by marine macrophytes. The estimated global net DOC flux, and hence export, from marine macrophyte is about 0.197±0.015 PgCyr-1 or 0.212±0.016 PgCyr-1 depending if net DOC flux by seagrass meadows was estimated by taking into account the low or high global seagrass area, respectively. [ABSTRACT FROM AUTHOR]

There has been increased salinization of fresh water over decades due to the use of road salt deicers, wastewater discharges, human-accelerated weathering, and groundwater irrigation. The effects of increased salinization on biogeochemical cycles in fresh- water ecosystems are still not well understood. We investigated potential impacts of increased salinization on fluxes of bioreactive elements from stream sediments and riparian soils to overlying stream water. Two-day incubations of sediments and soils with stream and deionized water across 3 salt levels were conducted at 8 routine monitoring stations at the Baltimore Ecosystem Study Long-Term Ecological Research (LTER) site in the Chesapeake Bay watershed. Ambient stream chemistry was also monitored before and after a snow event coinciding with road salt additions. Results indicated: (1) salinization typically increased sediment releases of labile dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), total dissolved Kjeldahl nitrogen (TKN) (ammonium+ammonia+dissolved organic nitrogen), and sediment transformations of nitrate, (2) salinization generally decreased DOC aromaticity and fluxes of soluble reactive phosphorus (SRP) from both sediments and soils, (3) the effects of increased salinization on sediment releases of DOC and TKN and DOC quality increased with percentage watershed urbanization. The differential responses of riparian soils and sediments to increased salinization were likely due to differences in organic matter amounts and composition. Results of the sediment and soil incubations were used to interpret changes in ambient stream chemistry before and after a snow event. Our results suggest that short-term increases in salinization can cause releases of significant amounts of labile organic carbon and nitrogen from stream substrates and organic transformations of nitrogen and phosphorus. Given that salinization of fresh water will increase in the future, potential impacts on coupled biogeochemical cycles and water quality should be expected. [ABSTRACT FROM AUTHOR]

Marine organic aerosols (MOA) have been shown to play an important role in tropospheric chemistry by impacting surface mass, cloud condensation nuclei, and ice nuclei concentrations over remote marine and coastal regions. In this work, an online marine primary organic aerosol emission parameterization, designed to be used for both global and regional models, was implemented into the GEOS-Chem model. The implemented emission scheme improved the large underprediction of organic aerosol concentrations in clean marine regions (normalized mean bias decreases from −79% when using the default settings to −12% when marine organic aerosols are added). Model predictions were also in good agreement (correlation coefficient of 0.62 and normalized mean bias of −36 %) with hourly surface concentrations of MOA observed during the summertime at an inland site near Paris, France. Our study shows that MOA have weaker coastalto-inland concentration gradients than sea-salt aerosols, leading to several inland European cities having > 10% of their surface submicron organic aerosol mass concen tration with a marine source. The addition of MOA tracers to GEOS-Chem enabled us to identify the regions with large contributions of freshly-emitted or aged aerosol having distinct physicochemical properties, potentially indicating optimal locations for future field studies. [ABSTRACT FROM AUTHOR]

Observation Package (ObsPack) is a framework designed to bring together atmospheric greenhouse gas observations from a variety of sampling platforms, prepare them with specific applications in mind, and package and distribute them in a self-consistent and well-documented product. Data products created using the ObsPack framework (called "ObsPack products") are intended to support carbon cycle modeling studies and represent the next generation of value-added greenhouse gas observation products modeled after the cooperative GLOBALVIEW products introduced in 1996. Depending on intended use, ObsPack products may include data in their original form reformatted using the ObsPack framework or may contain derived data consisting of averages, subsets or smoothed representations of original data. All products include extensive ancillary information (metadata) intended to help ensure the data are used appropriately, their calibration and quality assurance history are clearly described, and that individuals responsible for the measurements (data providers or principal investigators (PIs)) are properly acknowledged for their work. ObsPack products are made freely available using a distribution strategy designed to improve communication between data providers and product users. The strategy includes a data usage policy that requires users to directly communicate with data providers and an automated email notification system triggered when a product is accessed. ObsPack products will be assigned a unique Digital Object Identifier (DOI) to ensure each product can be unambiguously identified in scientific literature. Here we describe the ObsPack framework and its potential role in supporting the evolving needs of both data providers and product users. [ABSTRACT FROM AUTHOR]

We present an evaluation of aircraft observations of the carbon and greenhouse gases (CO2, CH4, N2O, and CO) using a direct-absorption pulsed quantum cascade laser spectrometer (QCLS) operated during the HIPPO and CalNex airborne experiments. The QCLS made continuous 1Hz measurements with 1-sigma Allan precisions of 20, 0.5, 0.09, and 0.15 ppb for CO2, CH4, N2O, and CO, respectively, over >500 flight hours on 79 research flights. The QCLS measurements are compared to two vacuum ultraviolet (VUV) CO instruments (CalNex and HIPPO), a cavity ring-down spectrometer (CRDS) measuring CO2 and CH4 (CalNex), two broadband non-dispersive infrared spectrometers (NDIR) measuring CO2 (HIPPO), two onboard gas chromatographs measuring a variety of chemical species including CH4, N2O, and CO (HIPPO), and various flask-based measurements of all four species. QCLS measurements are tied to NOAA and WMO standards using an in-flight calibration system and mean differences when compared to NOAA CCG flask data over the 59 HIPPO research flights were 100, 1, 1, and 2 ppb for CO2, CH4, N2O, and CO, respectively. The details of the end-to-end calibration procedures and the data quality-assurance and quality-control (QA/QC) are presented. Specifically, we discuss our practices for the traceability of standards given uncertainties in calibration cylinders, isotopic and surface effects for the long-lived greenhouse gas tracers, interpolation techniques for in-flight calibrations, and the effects of instrument linearity on retrieved mole fractions. [ABSTRACT FROM AUTHOR]

Monitoring the isotopic composition (δ13CDOC) of dissolved organic carbon (DOC) during flood events can be helpful for locating DOC sources in catchments and quantifying their relative contribution to DOC stream flux. High-resolution (13CDOC data were obtained on six successive storm events occurring during the highflow period in a small headwater catchment from western France. Intra-storm δ13CDOC values exhibit a marked temporal variability, with some storms showing large variations (> 2 ‰), and others yielding a very restricted range of values (< 1 ‰). Comparison of these results with previously published data shows that the range of intra-storm δ13CDOC values closely reflects the temporal and spatial variation in δ13CDOC observed in the riparian soils of this catchment during the same period. Using δ13C data in conjunction with hydrometric monitoring and an end-member mixing approach, we show that (i) > 80% of the stream DOC flux flows through the most superficial soil horizons of the riparian domain and (ii) the soil DOC flux is comprised of DOC coming ultimately from both riparian and upland domains. Based on its δ13C fingerprint, we find that the upland DOC contribution decreases from ca. 30% of the stream DOC flux at the beginning of the high-flow period to < 10% later in this period. Overall, upland domains contribute significantly to stream DOC export, but act as a size-limited reservoir, whereas soils in the wetland domains act as a near-infinite reservoir. Through this study, we show that δ13CDOC provides a powerful tool for tracing DOC sources and DOC transport mechanisms in headwater catchments. [ABSTRACT FROM AUTHOR]