Dissolved organic carbon in rainwater: Glassware decontamination and sample preservation and volatile organic carbon

The efficiency of different methods for the decontamination of glassware used for the analysis of dissolved organic carbon (DOC) was tested using reported procedures as well as new ones proposed in this work. A Fenton solution bath (1.0 mmol L-1 Fe2+ and 100 mmol L-1 H2O2) for 1 h or for 30 min employing UV irradiation showed to combine simplicity, low cost and high efficiency. Using the optimized cleaning procedure, the DOC for stored UV-irradiated ultrapure water reached concentrations below the limit of detection (0.19 mu mol C L-1). Filtered (0.7 mu m) rain samples maintained the DOC integrity for at least 7 days when stored at 4 degrees C. The volatile organic carbon (VOC) fraction in the rain samples collected at two sites in São Paulo state (Brazil) ranged from 0% to 56% of their total DOC content. Although these high-VOC concentrations may be derived from the large use of ethanol fuel in Brazil, our results showed that when using the high-temperature catalytic oxidation technique, it is essential to measure DOC rather than non-purgeble organic carbon to estimate organic carbon, since rainwater composition can be quite variable, both geographically and temporally. (C) 2007 Elsevier Ltd. All rights reserved.

Development and application of an analytical method for the determination of total atmospheric biogenic non-methane organic carbon

Ein wesentlicher Anteil an organischem Kohlenstoff, der in der Atmosphäre vorhanden ist, wird als leichtflüchtige organische Verbindungen gefunden. Diese werden überwiegend durch die Biosphäre freigesetzt. Solche biogenen Emissionen haben einen großen Einfluss auf die chemischen und physikalischen Eigenschaften der Atmosphäre, indem sie zur Bildung von bodennahem Ozon und sekundären organischen Aerosolen beitragen. Um die Bildung von bodennahem Ozon und von sekundären organischen Aerosolen besser zu verstehen, ist die technische Fähigkeit zur genauen Messung der Summe dieser flüchtigen organischen Substanzen notwendig. Häufig verwendete Methoden sind nur auf den Nachweis von spezifischen Nicht-Methan-Kohlenwasserstoffverbindungen fokussiert. Die Summe dieser Einzelverbindungen könnte gegebenenfalls aber nur eine Untergrenze an atmosphärischen organischen Kohlenstoffkonzentrationen darstellen, da die verfügbaren Methoden nicht in der Lage sind, alle organischen Verbindungen in der Atmosphäre zu analysieren. Einige Studien sind bekannt, die sich mit der Gesamtkohlenstoffbestimmung von Nicht-Methan-Kohlenwasserstoffverbindung in Luft beschäftigt haben, aber Messungen des gesamten organischen Nicht-Methan-Verbindungsaustauschs zwischen Vegetation und Atmosphäre fehlen. Daher untersuchten wir die Gesamtkohlenstoffbestimmung organische Nicht-Methan-Verbindungen aus biogenen Quellen. Die Bestimmung des organischen Gesamtkohlenstoffs wurde durch Sammeln und Anreichern dieser Verbindungen auf einem festen Adsorptionsmaterial realisiert. Dieser erste Schritt war notwendig, um die stabilen Gase CO, CO2 und CH4 von der organischen Kohlenstofffraktion zu trennen. Die organischen Verbindungen wurden thermisch desorbiert und zu CO2 oxidiert. Das aus der Oxidation entstandene CO2 wurde auf einer weiteren Anreicherungseinheit gesammelt und durch thermische Desorption und anschließende Detektion mit einem Infrarot-Gasanalysator analysiert. Als große Schwierigkeiten identifizierten wir (i) die Abtrennung von CO2 aus der Umgebungsluft von der organischen Kohlenstoffverbindungsfaktion während der Anreicherung sowie (ii) die Widerfindungsraten der verschiedenen Nicht-Methan-Kohlenwasserstoff-verbindungen vom Adsorptionsmaterial, (iii) die Wahl des Katalysators sowie (iiii) auftretende Interferenzen am Detektor des Gesamtkohlenstoffanalysators. Die Wahl eines Pt-Rd Drahts als Katalysator führte zu einem bedeutenden Fortschritt in Bezug auf die korrekte Ermittlung des CO2-Hintergrund-Signals. Dies war notwendig, da CO2 auch in geringen Mengen auf der Adsorptionseinheit während der Anreicherung der leichtflüchtigen organischen Substanzen gesammelt wurde. Katalytische Materialien mit hohen Oberflächen stellten sich als unbrauchbar für diese Anwendung heraus, weil trotz hoher Temperaturen eine CO2-Aufnahme und eine spätere Abgabe durch das Katalysatormaterial beobachtet werden konnte. Die Methode wurde mit verschiedenen leichtflüchtigen organischen Einzelsubstanzen sowie in zwei Pflanzenkammer-Experimenten mit einer Auswahl an VOC-Spezies getestet, die von unterschiedlichen Pflanzen emittiert wurden. Die Pflanzenkammer-messungen wurden durch GC-MS und PTR-MS Messungen begleitet. Außerdem wurden Kalibrationstests mit verschiedenen Einzelsubstanzen aus Permeations-/Diffusionsquellen durchgeführt. Der Gesamtkohlenstoffanalysator konnte den tageszeitlichen Verlauf der Pflanzenemissionen bestätigen. Allerdings konnten Abweichungen für die Mischungsverhältnisse des organischen Gesamtkohlenstoffs von bis zu 50% im Vergleich zu den begleitenden Standardmethoden beobachtet werden.

Significance of non‐sinking particulate organic carbon and dark CO2 fixation to heterotrophic carbon demand in the mesopelagic northeast Atlantic

[EN] It is generally assumed that sinking particulate organic carbon (POC) constitutes the main source of organic carbon supply to the deep ocean's food webs. However, a major discrepancy between the rates of sinking POC supply (collected with sediment traps) and the prokaryotic organic carbon demand (the total amount of carbon required to sustain the heterotrophic metabolism of the prokaryotes; i.e., production plus respiration, PCD) of deep-water communities has been consistently reported for the dark realm of the global ocean. While the amount of sinking POC flux declines exponentially with depth, the concentration of suspended, buoyant non-sinking POC (nsPOC; obtained with oceanographic bottles) exhibits only small variations with depth in the (sub)tropical Northeast Atlantic. Based on available data for the North Atlantic we show here that the sinking POC flux would contribute only 4–12% of the PCD in the mesopelagic realm (depending on the primary production rate in surface waters). The amount of nsPOC potentially available to heterotrophic prokaryotes in the mesopelagic realm can be partly replenished by dark dissolved inorganic carbon fixation contributing between 12% to 72% to the PCD daily. Taken together, there is evidence that the mesopelagic microheterotrophic biota is more dependent on the nsPOC pool than on the sinking POC supply. Hence, the enigmatic major mismatch between the organic carbon demand of the deep-water heterotrophic microbiota and the POC supply rates might be substantially smaller by including the potentially available nsPOC and its autochthonous production in oceanic carbon cycling models.

Geochemistry and degree of organic carbon preservation in non-bioturbated, shaly sediments

Based on 13 published porewater H2S and sulphate profiles the amount of H2S escaping from non-bioturbated shales varies between some few % to 45% of the amount of bacterially generated H2S. This finding permits calculation of the original organic carbon (TOCor) content of immature nonbioturbated shales using TOC and sulphur content data. In two immature non-bioturbated sequences from Hungary (Toarcian and Oligocene) the first-order correlation between HI and TOC/TOCor was found to be stronger than that between HI and TOC, indicating that sulphate reduction was the leading process both in decrease in TOC content and degradation of kerogen source potential.

Reduction of functionalized graphite oxides by trioctylphosphine in non-polar organic solvents

Graphene, functionalized with oleylamine (OA) and soluble in non-polar organic solvents, was produced on a large scale with a high yield by combining the Hummers process for graphite oxidation, an amine-coupling process to make OA-functionalized graphite oxide (OA-GO), and a novel reduction process using trioctylphosphine (TOP). TOP acts as both a reducing agent and an aggregation-prevention surfactant in the reduction of OA-GO in 1,2-dichlorobenzene (DCB). The reduction of OA-GO is confirmed by X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, and Raman spectroscopy. The exfoliation of GO, OA GO, and OA-functionalized graphene (OA-G) is verified by atomic force microscopy. The conductivity of TOP-reduced OA G, which is deduced from the current–voltage characteristics of a vacuum-filtered thin film, shows that the reduction of functionalized GO by TOP is as effective as the reduction of GO by hydrazine.

Sources and transport of dissolved and particulate organic carbon in the Mississippi River estuary and adjacent coastal waters of the northern Gulf of Mexico

Dissolved organic carbon (DOC), stable carbon isotopic (delta(13)C) compositions of DOC and particulate organic carbon (POC), and elemental C/N ratios of POC were measured for samples collected from the lower Mississippi and Atchafalaya rivers and adjacent coastal waters in the northern Gulf of Mexico during the low flow season in June 2000 and high flow season in April 2001. These isotopic and C/N results combined with DOC measurements were used to assess the sources and transport of terrestrial organic matter from the Mississippi and Atchafalaya rivers to the coastal region in the northern Gulf of Mexico. delta(13)C values of both POC (-23.8parts per thousand to -26.8parts per thousand) and DOC (-25.0parts per thousand to -29.0parts per thousand) carried by the two rivers were more depleted than the values measured for the samples collected in the offshore waters. Strong seasonal variations in delta(13)C distributions were observed for both POC and DOC in the surface waters of the region. Fresh water discharge and horizontal mixing played important roles in the distribution and transport of terrestrial POC and DOC offshore. Our results indicate that both POC and DOC exhibited non-conservative behavior during the mixing especially in the mid-salinity range. Based on a simple two end-member mixing model, the comparison of the measured DOC-delta(13)C with the calculated conservative isotopic mixing curve indicated that there was a significant in situ production of marine-derived DOC in the mid- to high-salinity waters consistent with our in situ chlorophyll-a measurements. Our DOC-delta(13)C data suggest that a removal of terrestrial DOC mainly occurred in the high-salinity (>25) waters during the mixing. Our study indicates that the mid- to high- (10-30) salinity range was the most dynamic zone for organic carbon transport and cycling in the Mississippi River estuary. Variability in isotopic and elemental compositions along with variability in DOC and POC concentrations suggest that autochthonous production, bacterial utilization, and photo-oxidation could all play important roles in regulating and removing terrestrial DOC in the northern Gulf of Mexico and further study of these individual processes is warranted. (C) 2004 Elsevier B.V. All rights reserved.

Capacity of soil to protect organic carbon and biochemical characteristics of density fractions in Ziwulin Haplic Greyxems soil

Physical protection is one of the important ways to stabilize organic carbon in soils. In order to understand the role of soils as a carbon sink or source in global climatic change and carbon cycles and properly manage soils as a carbon sink, we ought to know how many organic carbon (OC) in a given soil could be protected. By a density fractionation approach and ultrasonic technique, each soil sample was divided into three fractions: free light fraction (free-LF), occluded fraction (occluded-LF) and heavy fraction (HF). The obtained fractions were analyzed for total OC content, carbohydrate content and recalcitrant OC content. The results showed: (i) In the whole soil profile, dominance of OC consistently decreased in the following order: HF, free-LF, occluded-LF. This suggested that OC in soils were mostly protected. From 0-10 to 60-80 cm horizons, the OC in free-LF decreased from 25.27% to 3.72%, while OC in HF they were increased from 72.57% to 95.39%. The OC in occluded-LF was between 2.16% and 0.89%. (ii) Organic carbon recalcitrance in free-LF was similar to that in HF, and was even higher than that in HF below the surface horizon. This suggested that free-LF was not always the most fresh and non-decomposed fraction. OM quality of HF was higher than that of free-LF in the surface 10 cm below, namely the protected OM had higher quality than free OM in these horizons.

Predicted soil organic carbon stocks and changes in Kenya between 1990 and 2030

Under the United Nations Framework Convention on Climate Change (UNFCCC), Non-Annex 1 countries such as Kenya are obliged to report green house gas (GHG) emissions from all sources where possible, including those from soils as a result of changes in land use or land management. At present, the convention encourages countries to estimate emissions using the most advanced methods possible, given the country circumstances and resources. Estimates of soil organic carbon (SOC) stocks and changes were made for Kenya using the Global Environment Facility Soil Organic Carbon (GEFSOC) Modelling System. The tool conducts analysis using three methods: (1) the Century general ecosystem model; (2) the RothC soil C decomposition model; and (3) the Intergovernmental Panel on Climate Change (IPCC) method for assessing soil C at regional scales. The required datasets included: land use history, monthly mean precipitation, monthly mean minimum and maximum temperatures for all the agro-climatic zones of Kenya and historical vegetation cover. Soil C stocks of 1.4-2.0 Pg (0-20 cm), compared well with a Soil and Terrain (SOTER) based approach that estimated similar to .8-2.0 Pg (0-30 cm). In 1990 48% of the country had SOC stocks of < 18 t C ha(-1) and 20% of the country had SOC stocks of 18-30 t C ha(-1), whereas in 2000 56% of the country had SOC stocks of < 18 t C ha(-1) and 31% of the country had SOC stocks of 18-30 t C ha(-1). Conversion of natural vegetation to annual crops led to the greatest soil C losses. Simulations suggest that soil C losses remain substantial throughout the modelling period of 1990-2030. All three methods involved in the GEFSOC System estimated that there would be a net loss of soil C between 2000 and 2030 in Kenya. The decline was more marked with RothC than with Century or the IPCC method. In non-hydric soils the SOC change rates were more pronounced in high sandy soils compared to high clay soils in most land use systems. (C) 2007 Elsevier B.V. All rights reserved.

Fine-scale temporal characterization of trends in soil water dissolved organic carbon and potential drivers

Long-term monitoring of surface water quality has shown increasing concentrations of Dissolved Organic Carbon (DOC) across a large part of the Northern Hemisphere. Several drivers have been implicated including climate change, land management change, nitrogen and sulphur deposition and CO2 enrichment. Analysis of stream water data, supported by evidence from laboratory studies, indicates that an effect of declining sulphur deposition on catchment soil chemistry is likely to be the primary mechanism, but there are relatively few long term soil water chemistry records in the UK with which to investigate this, and other, hypotheses directly. In this paper, we assess temporal relationships between soil solution chemistry and parameters that have been argued to regulate DOC production and, using a unique set of co-located measurements of weather and bulk deposition and soil solution chemistry provided by the UK Environmental Change Network and the Intensive Forest Monitoring Level II Network . We used statistical non-linear trend analysis to investigate these relationships at 5 forested and 4 non-forested sites from 1993 to 2011. Most trends in soil solution DOC concentration were found to be non-linear. Significant increases in DOC occurred mostly prior to 2005. The magnitude and sign of the trends was associated qualitatively with changes in acid deposition, the presence/absence of a forest canopy, soil depth and soil properties. The strongest increases in DOC were seen in acidic forest soils and were most clearly linked to declining anthropogenic acid deposition, while DOC trends at some sites with westerly locations appeared to have been influenced by shorter-term hydrological variation. The results indicate that widespread DOC increases in surface waters observed elsewhere, are most likely dominated by enhanced mobilization of DOC in surficial organic horizons, rather than changes in the soil water chemistry of deeper horizons. While trends in DOC concentrations in surface horizons have flattened out in recent years, further increases may be expected as soil chemistry continues to adjust to declining inputs of acidity.

Effect of natural organic compounds on the removal of organic carbon in coagulation and flocculation processes

Natural organic matter (NOM) in water contains organic compounds that are both hydrophobic and hydrophilic with a wide range of molecular weights. It is composed of non-homogeneous organic compounds such as humic substances, amino acids, sugars, aliphatic and aromatic acids, and other chemical synthetic organic matters. NOM in water is a major concern not only because of its contribution to the formation of disinfection by-products (DBPs) and taste and odor, but also its influence on the demand for coagulants and disinfectants, the removal efficiency of water treatment processes, etc. This research aims at identifying the influence of NOM in coagulation and flocculation processes in order to optimize the coagulation and flocculation conditions. In this study, pretreated pond water was used as the source water. It was observed from the experimental results that: (1) The optimum pH for coagulation to remove NOM is around 7. (2) The optimum alum dose at this pH can vary from 125-1,225 mgl-1 when the TOC is increased from 4 to 25 mgl-1. (3) The presence of secondary compounds such as Ca2+, Mg2+ divalent cations had no significant effect on the removal of organic matter. (4) The presence of clay increased the organic removal by 15%. (5) The organic compound with higher molecular weight has higher removal affinity in coagulation process. (6) Floc size and settling velocity of floc and sludge production all increased with the increase in NOM concentration. From the results of Capillary Suction Time (CST) tests, the floc formed with lower TOC readily released the water to make the dewatering process easier. (7) The organic removal efficiency was significantly different for natural water containing non-homogeneous organic compounds compared to the synthetic water containing humic acid only (homogeneous organic matter). For example, the NOM removal efficiency was 80% for the synthetic water containing humic acid with TOC of 7 mgl-1 at pH 7; but the NOM removal for the pretreated pond water was 60%.

Radiocarbon Analysis of Elemental and Organic Carbon in Switzerland during Winter-Smog Episodes from 2008 to 2012 – Part I: Source Apportionment and Spatial Variability

While several studies have investigated winter-time air pollution with a wide range of concentration levels, hardly any results are available for longer time periods covering several winter-smog episodes at various locations; e.g., often only a few weeks from a single winter are investigated. Here, we present source apportionment results of winter-smog episodes from 16 air pollution monitoring stations across Switzerland from five consecutive winters. Radiocarbon (14C) analyses of the elemental (EC) and organic (OC) carbon fractions, as well as levoglucosan, major water-soluble ionic species and gas-phase pollutant measurements were used to characterize the different sources of PM10. The most important contributions to PM10 during winter-smog episodes in Switzerland were on average the secondary inorganic constituents (sum of nitrate, sulfate and ammonium = 41 ± 15%) followed by organic matter (OM) (34 ± 13%) and EC (5 ± 2%). The non-fossil fractions of OC (fNF,OC) ranged on average from 69 to 85 and 80 to 95% for stations north and south of the Alps, respectively, showing that traffic contributes on average only up to ~ 30% to OC. The non-fossil fraction of EC (fNF,EC), entirely attributable to primary wood burning, was on average 42 ± 13 and 49 ± 15% for north and south of the Alps, respectively. While a high correlation was observed between fossil EC and nitrogen oxides, both primarily emitted by traffic, these species did not significantly correlate with fossil OC (OCF), which seems to suggest that a considerable amount of OCF is secondary, from fossil precursors. Elevated fNF,EC and fNF,OC values and the high correlation of the latter with other wood burning markers, including levoglucosan and water soluble potassium (K+) indicate that residential wood burning is the major source of carbonaceous aerosols during winter-smog episodes in Switzerland. The inspection of the non-fossil OC and EC levels and the relation with levoglucosan and water-soluble K+ shows different ratios for stations north and south of the Alps (most likely because of differences in burning technologies) for these two regions in Switzerland.

Meta-Analysis of Long-Term Land Management Effect on Soil Organic Carbon (SOC) in Ethiopia

The role of Soil Organic Carbon (SOC) in mitigating climate change, indicating soil quality and ecosystem function has created research interested to know the nature of SOC at landscape level. The objective of this study was to examine variation and distribution of SOC in a long-term land management at a watershed and plot level. This study was based on meta-analysis of three case studies and 128 surface soil samples from Ethiopia. Three sites (Gununo, Anjeni and Maybar) were compared after considering two Land Management Categories (LMC) and three types of land uses (LUT) in quasi-experimental design. Shapiro-Wilk tests showed non-normal distribution (p = 0.002, a = 0.05) of the data. SOC median value showed the effect of long-term land management with values of 2.29 and 2.38 g kg-1 for less and better-managed watersheds, respectively. SOC values were 1.7, 2.8 and 2.6 g kg-1 for Crop (CLU), Grass (GLU) and Forest Land Use (FLU), respectively. The rank order for SOC variability was FLU>GLU>CLU. Mann-Whitney U and Kruskal-Wallis test showed a significant difference in the medians and distribution of SOC among the LUT, between soil profiles (p<0.05, confidence interval 95%, a = 0.05) while it is not significant (p>0.05) for LMC. The mean and sum rank of Mann Whitney U and Kruskal Wallis test also showed the difference at watershed and plot level. Using SOC as a predictor, cross-validated correct classification with discriminant analysis showed 46 and 49% for LUT and LMC, respectively. The study showed how to categorize landscapes using SOC with respect to land management for decision-makers.