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16 pages, 2 tables, 5 figures.-- This article is licensed under a Creative Commons Attribution 4.0 International License, The processes of warming, anthropogenic CO2 (Canth) accumulation, decreasing pHT (increasing [H+]T; concentration in total scale) and calcium carbonate saturation in the subarctic zone of the North Atlantic are unequivocal in the time-series measurements of the Iceland (IS-TS, 1985–2003) and Irminger Sea (IRM-TS, 1983–2013) stations. Both stations show high rates of Canth accumulation with different rates of warming, salinification and stratification linked to regional circulation and dynamics. At the IS-TS, advected and stratified waters of Arctic origin drive a strong increase in [H+]T, in the surface layer, which is nearly halved in the deep layer (44.7 ± 3.6 and 25.5 ± 1.0 pmol kg−1 yr−1, respectively). In contrast, the weak stratification at the IRM-TS allows warming, salinification and Canth uptake to reach the deep layer. The acidification trends are even stronger in the deep layer than in the surface layer (44.2 ± 1.0 pmol kg−1 yr−1 and 32.6 ± 3.4 pmol kg−1 yr−1 of [H+]T, respectively). The driver analysis detects that warming contributes up to 50% to the increase in [H+]T at the IRM-TS but has a small positive effect on calcium carbonate saturation. The Canth increase is the main driver of the observed acidification, but it is partially dampened by the northward advection of water with a relatively low natural CO2 content, FFP was founded by the Ministerio Ciencia, Innovación y Universidades (Grant No. PRX18/00312) for visiting Dr. Taro Takahashi in LDEO in 2019. FFP were also supported by the BOCATS2 Project (PID2019-104279GB-C21) co-funded by the Spanish Government and the Fondo Europeo de Desarrollo Regional (FEDER). FFP and SRO were supported by the European Union’s Horizon 2020 research and innovation program under Grant Agreement No. 820989 (project COMFORT, Our common future ocean in the Earth system-quantifying coupled cycles of carbon, oxygen and nutrients for determining and achieving safe operating spaces with respect to tipping points

We estimated monthly air–sea CO2 fluxes in the Arctic Ocean and its adjacent seas north of 60 ∘ N from 1997 to 2014. This was done by mapping partial pressure of CO2 in the surface water ( p CO2w ) using a self-organizing map (SOM) technique incorporating chlorophyll a concentration (Chl a ), sea surface temperature, sea surface salinity, sea ice concentration, atmospheric CO2 mixing ratio, and geographical position. We applied new algorithms for extracting Chl a from satellite remote sensing reflectance with close examination of uncertainty of the obtained Chl a values. The overall relationship between p CO2w and Chl a was negative, whereas the relationship varied among seasons and regions. The addition of Chl a as a parameter in the SOM process enabled us to improve the estimate of p CO2w , particularly via better representation of its decline in spring, which resulted from biologically mediated p CO2w reduction. As a result of the inclusion of Chl a , the uncertainty in the CO2 flux estimate was reduced, with a net annual Arctic Ocean CO2 uptake of 180 ± 130 Tg C yr−1 . Seasonal to interannual variation in the CO2 influx was also calculated.

In the version of this Article originally published, ammonia and NO emissions (and associated N deposition), nitrate leaching, and the CO emitted during urea hydrolysis following application to land were all accidentally omitted in the comparison of the greenhouse gas impacts of using ammonium nitrate and urea to produce wheat grain.

The global ocean absorbs about 25% of the carbon dioxide (CO 2 ) emitted into the air by human activities including the fossil fuel combustion and land use changes, thus partially alleviating the climate change induced by the accumulation of this greenhouse gas in the air. The rate of ocean’s uptake of CO 2 from air depends on the wind speed and the vapor pressure of CO 2 (or partial pressure of CO 2 ) of seawater, which vary with temperature, biological activities and circulation of ocean water. The equatorial Pacific Ocean is a major source area, whereas the temperate and high-latitude areas are sinks for atmospheric CO 2 . In balance, the global ocean is presently a net sink for atmospheric CO 2 . The distribution of the source and sink areas and the net sea-air CO 2 flux is described, and the results of various independent methods used for estimating the sea-air CO 2 flux are discussed.

To learn the effect of CO2 leakage on shallow drinking water aquifers, laboratory experiments were conducted to measure the chemical changes of aquifer water, in which the fine fraction of sedimentary rock from the Triassic Newark Basin Series were immersed. Elevated CO2 concentrations caused a decrease in pH, an increase in the concentrations of major ions including Ca, Mg, Si, K, and alkalinity, an enhanced dissolution of carbonate minerals, and an increase in the concentrations of trace elements including Mn, Fe, Be, Cr, Co, Cu, Zn, Rb, Zr, Cd, Sb, Ba, Pb, and U in water under both continuous CO2 flow and one-time injection batch experiments. The magnitude of concentration increase was significantly lower in batch experiments with one-time CO2 injection than in experiments with continuous CO2 flow, although less rigorous agitation was maintained in the batch experiment. The logarithmic elemental release rates of Ca, Mg, Si, Mn, Fe and Zn normalized by reactive surface area, when plotted together with those from field injection experiments, decreased with the increase of pH (or the decrease of log (pCO2)) following linear trends. The laboratory elemental release rates were 1-3 orders of magnitude higher than field injection experiment rates extrapolated to incubation pH conditions. Hydrogeochemical parameters including pH, major and trace elements, particularly Fe, Mn, Cd, Tl, and sulfate, can be used as early indicators for leakage detection and need to be monitored in compliance with the U.S. Environmental Protection Agency (EPA) drinking water regulations.

We present a 13 year (2002–2015) semimonthly time series of the partial pressure of CO2 in surface water (pCO2surf) and other carbonate system parameters from the Drake Passage. This record shows a clear increase in the magnitude of the sea-air pCO2 gradient, indicating strengthening of the CO2 sink in agreement with recent large-scale analyses of the world oceans. The rate of increase in pCO2surf north of the Antarctic Polar Front (APF) is similar to the atmospheric pCO2 (pCO2atm) trend, whereas the pCO2surf increase south of the APF is slower than the pCO2atm trend. The high-frequency surface observations indicate that an absence of a winter increase in total CO2 (TCO2) and cooling summer sea surface temperatures are largely responsible for increasing CO2 uptake south of the APF. Muted winter trends in surface TCO2 also provide temporary stability to the carbonate system that is already close to undersaturation with respect to aragonite.

Uptake uptick Has global warming slowed the uptake of atmospheric CO 2 by the Southern Ocean? Landschützer et al. say no (see the Perspective by Fletcher). Previous work suggested that the strength of the Southern Ocean carbon sink fell during the 1990s. This raised concerns that such a decline would exacerbate the rise of atmospheric CO 2 and thereby increase global surface air temperatures and ocean acidity. The newer data show that the Southern Ocean carbon sink strengthened again over the past decade, which illustrates the dynamic nature of the process and alleviates some of the anxiety about its earlier weakening trend. Science , this issue p. 1221 ; see also p. 1165

In remote regions such as the open Southern Ocean, satellite observations often provide the only available tool with which to evaluate large-scale biogeochemical processes. However, these observations need to be carefully evaluated with in situ measurements. With an average of 20 crossings per year from 2002 to 2011, the Drake Passage Time-series (DPT) represents one of the most complete datasets of biogeochemical measurements in the open Southern Ocean. This dataset offers a unique opportunity to validate satellite-based productivity algorithms and to improve understanding of the role of this region in the global carbon cycle. Net community production (NCP) was estimated using discrete measurements of total dissolved inorganic carbon (TCO2) and phosphate ( PO 4 3 − ), and high-frequency underway measurements of the partial pressure of carbon dioxide in the surface ocean (pCO2surf) from the DPT, combined with estimates of gas exchange, Ekman transport, wind stress curl, and vertical entrainment. We estimate annual NCP using seasonal PO 4 3 − ( NCP PO 4 3 − ) and TCO2 ( NCP TCO 2 ) budgets of 1.2±0.7 and 1.6±0.4 mol C m−2 yr−1, respectively. Budget terms for gas exchange, entrainment, and advective supply indicate that a closed system seasonal-drawdown approach that does not consider additional terms may underestimate NCP in this region by nearly 35%. NCP estimates are compared to satellite algorithms commonly used to estimate both net primary production (NPP) and organic carbon export. Budget-based NCP approaches indicate high rates of NCP during austral spring with little additional NCP over austral summer. In contrast, satellite approaches suggest a more gradual increase and decline in NCP rates over the growing season with approximately 40% of NCP accumulating during austral summer.

Climatological mean monthly distributions of pH in the total H+ scale, total CO2 concentration (TCO2), and the degree of CaCO3 saturation for the global surface ocean waters (excluding coastal areas) are calculated using a data set for pCO(2), alkalinity and nutrient concentrations in surface waters (depths

Accurate assessment of anthropogenic carbon dioxide (CO2) emissions and their redistribution among the atmosphere, ocean, and terrestrial biosphere is important to better understand the global carbon cycle, support the development of climate policies, and project future climate change. Here we describe data sets and a methodology to quantify all major components of the global carbon budget, including their uncertainties, based on the combination of a range of data, algorithms, statistics and model estimates and their interpretation by a broad scientific community. We discuss changes compared to previous estimates, consistency within and among components, alongside methodology and data limitations. CO2 emissions from fossil-fuel combustion and cement production (EFF) are based on energy statistics, while emissions from land-use change (ELUC), mainly deforestation, are based on combined evidence from land-cover change data, fire activity associated with deforestation, and models. The global atmospheric CO2 concentration is measured directly and its rate of growth (G ATM) is computed from the annual changes in concentration. The mean ocean CO2 sink (SOCEAN) is based on observations from the 1990s, while the annual anomalies and trends are estimated with ocean models. The variability in SOCEAN is evaluated for the first time in this budget with data products based on surveys of ocean CO2 measurements. The global residual terrestrial CO2 sink (SLAND) is estimated by the difference of the other terms of the global carbon budget and compared to results of independent dynamic global vegetation models forced by observed climate, CO2 and land cover change (some including nitrogen-carbon interactions). All uncertainties are reported as ±1σ ,reflecting the current capacity to characterise the annual estimates of each component of the global carbon budget. For the last decade available (2003-2012), EFF was 8.6±0.4 GtC yr-1, ELUC 0.9±0.5 GtC yr-1, GATM 4.3±0.1 GtC yr-1, SOCEAN 2.5±0.5 GtC yr -1, and SLAND 2.8±0.8 GtC yr-1. For year 2012 alone, EFF grew to 9.7±0.5 GtC yr-1, 2.2% above 2011, reflecting a continued growing trend in these emissions, G ATM was 5.1±0.2 GtC yr-1, SOCEAN was 2.9±0.5 GtC yr-1, and assuming an ELUC of 1.0±0.5 GtC yr-1 (based on the 2001-2010 average), S LAND was 2.7±0.9 GtC yr-1. GATM was high in 2012 compared to the 2003-2012 average, almost entirely reflecting the high EFF. The global atmospheric CO2 concentration reached 392.52±0.10 ppm averaged over 2012. We estimate that EFF will increase by 2.1% (1.1- 3.1 %) to 9.9±0.5 GtC in 2013, 61% above emissions in 1990, based on projections of world gross domestic product and recent changes in the carbon intensity of the economy.With this projection, cumulative emissions ofCO2 will reach about 535±55 GtC for 1870-2013, about 70% from EFF (390±20 GtC) and 30% from ELUC (145±50 GtC). This paper also documents any changes in the methods and data sets used in this new carbon budget from previous budgets (Le Quéré et al. 2013). All observations presented here can be downloaded from the Carbon Dioxide Information Analysis Center (doi:10.3334/CDIAC/GCP-2013-V2.3). © 2014 Author(s) CC Attribution 3.0 License., 0, SCOPUS: ar.j, info:eu-repo/semantics/published

[1] The Chukchi Sea is thought to be a globally important sink of atmospheric CO2 due to the summertime drawdown of surface pCO2 by phytoplankton and subsequent shelf-to-basin transport of CO2-enriched subsurface waters into the upper halocline of the Arctic Ocean. Here we show that annually occurring storm-induced mixing events during autumn months disrupt water column stratification and stir up remineralized carbon from subsurface waters to the surface, leading to CO2 outgassing to the atmosphere. Our analysis provides a new understanding of the dynamics of carbon cycling in the region and suggests that late season wind events are strong and frequent enough to significantly decrease the carbon sink strength of the Chukchi Sea on a scale of relevance to the global carbon cycle. These results highlight the importance of obtaining data with more complete seasonal and spatial coverage in order to accurately constrain regional to basin-scale carbon flux budgets.

We investigated the yield, gelation and sugar composition of water-soluble polysaccharides that had been extracted from soybean cotyledons under acidic conditions. SSPS were easily extracted at several pHs. The highest yield was about twice that reported by Morita et al., after extraction in boiling water, or by Kawamura et al., after extraction in hot water (90°C) with the stepwise addition of ammonium oxalate and 0.5% NaOH. Our results show that the average molecular weight was relatively high for both SSPS extracted in the weakly acidic pH range of 4-6 at 100-120°C and in the strongly acidic pH range of 2-3 at 40-80°C. The water-soluble polysaccharide solutions which were extracted under the former conditions remained fluid, but those which were extracted under the latter conditions gelled. However, the molecular weight distribution and sugar composition were similar for SSPS isolated by using both sets of conditions. Furthermore, water-soluble soybean polysaccharides were found to consist of rhamnogalacturonans, which could endure hydrolysis, and arabinogalactans, which were easily hydrolyzed under acidic conditions.

Continental margin carbon cycling is complex, highly variable over a range of space and time scales, and forced by multiple physical and biogeochemical drivers. Predictions of globally significant air–sea CO2 fluxes in these regions have been extrapolated based on very sparse data sets. We present here a method for predicting coastal surface-water pCO2 from remote-sensing data, based on self organizing maps (SOMs) and a nonlinear semi-empirical model of surface water carbonate chemistry. The model used simple empirical relationships between carbonate chemistry (total dissolved carbon dioxide (TCO2) and alkalinity (TAlk)) and satellite data (sea surface temperature (SST) and chlorophyll (Chl)). Surface-water CO2 partial pressure (pCO2) was calculated from the empirically-predicted TCO2 and TAlk. This directly incorporated the inherent nonlinearities of the carbonate system, in a completely mechanistic manner. The model’s empirical coefficients were determined for a target study area of the central North American Pacific continental margin (22–50°N, within 370 km of the coastline), by optimally reproducing a set of historical observations paired with satellite data. The model-predicted pCO2 agreed with the highly variable observations with a root mean squared (RMS) deviation of 0.8 (r = 0.81; r2 = 0.66). This level of accuracy is a significant improvement relative to that of simpler models that did not resolve the biogeochemical sub-regions or that relied on linear dependences on input parameters. Air–sea fluxes based on these pCO2 predictions and satellite-based wind speed measurements suggest that the region is a ∼14 Tg C yr−1 sink for atmospheric CO2 over the 1997–2005 period, with an approximately equivalent uncertainty, compared with a ∼0.5 Tg C yr−1 source predicted by a recent bin-averaging and interpolation-based estimate for the same area. Fil: Hales, Burke. State University of Oregon; Estados Unidos Fil: Strutton, Peter G.. University Of Tasmania; Australia Fil: Saraceno, Martin. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones del Mar y la Atmosfera. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones del Mar y la Atmosfera; Argentina Fil: Letelier, Ricardo. State University of Oregon; Estados Unidos Fil: Takahashi, Taro. Lamont-Doherty Earth Observatory; Estados Unidos Fil: Feely, Richard. National Oceanic and Atmospheric Administration. Pacific Marine Environmental Laboratory; Estados Unidos Fil: Sabine, Christopher. National Oceanic and Atmospheric Administration. Pacific Marine Environmental Laboratory; Estados Unidos Fil: Chavez, Francisco. Monterey Bay Aquarium Research Institute; Estados Unidos

Estimates of the anthropogenic global-integrated sea-air carbon dioxide (CO2) flux from 1990 to 2009, based on different models and measurements, range from –1.4 to –2.6 Pg C yr–1. The median values of anthropogenic CO2 for each method show better agreement and are: −1.9 for Pg C yr−1 for numerical ocean general circulation hind cast models (OGCMs) with parameterized biogeochemistry; –2.1 Pg C yr–1 for atmospheric inverse models; –1.9 Pg C yr–1 for global atmospheric constraints based on O2 / N2 ratios for 1990–2000; and –2.4 Pg C yr–1 for oceanic inverse models. An updated estimate of this anthropogenic CO2 flux based on a climatology of sea-air partial pressure of CO2 differences (ΔpCO2) (Takahashi et al., 2009) and a bulk formulation of gas transfer with wind speed for year 2000 is –2.0 Pg C yr–1. Using this ΔpCO2 climatology and empirical relationships of pCO2 with sea-surface temperature (SST) anomalies (Park et al., 2010a), the interannual variability of the contemporary CO2 flux is estimated to be 0.20 Pg C yr–1 (1σ) from 1990 through 2009. This is similar to the variability estimated by the OGCMs of 0.16 Pg C yr–1 but smaller than the interannual variability from atmospheric inverse estimates of 0.40 Pg C yr–1. The variability is largely driven by large-scale climate re-organizations. The decadal trends for different methods range from –0.13 (Pg C yr–1) decade–1 to –0.50 (Pg C yr−1) decade−1. The OGCMs and the data based sea-air CO2 flux estimates show smaller uptakes and appreciably smaller decadal trends than estimates based on changes in carbon inventory suggesting that methods capable of resolving shorter timescales are showing a slowing of the rate of ocean CO2 uptake. It is not clear if this large difference in trend is a methodological issue or a real natural feedback.

In the soil-less culture, root zone environment can be easily modified to create stress conditions such as low and high temperatures, drought and high salinity by applying physical and chemical properties of water. Low temperature stress to plant body can induce adaptive functions in plant such as osmoregulation and antioxidation, which are expected to result in production of value-added vegetables enriched in sugars and antioxidants, etc. In this study, production of value-added vegetables was examined by applying low temperature stress only to roots in a soil-less culture. Spinach plants (Spinacia oleracea L. cv. Orai) were grown in a soil-less culture, where the root zone temperature was controlled at a normal temperature of 20°C. Two weeks before the harvest, the low temperature stress treatment with a root zone temperature of 5°C was applied for only one week. This low temperature stress to roots induced plant adaptive functions of osmoregulation and antioxidation, and healthful substances for human health such as sugars, ascorbic acid and Fe were significantly enriched in edible shoots. Furthermore, concentrations of nitrates and oxalic acid in shoots, which are harmful substances, were extremely decreased with depression in water and nutrient absorption by roots. These suggest that the only one week treatment with low temperature stress only to roots is applicable for production of value-added leafy vegetables.

This paper describes the ways and means of assembling and quality controling the Irminger Sea and Iceland Sea time-series biogeochemical data which are included in the CARINA data set. The Irminger Sea and the Iceland Sea are hydrographically different regions where measurements of sea water carbon and nutrient chemistry were started in 1983. The sampling is seasonal, four times a year. The carbon chemistry is studied with measurements of the partial pressure of carbon dioxide in seawater, pCO2, and total dissolved inorganic carbon, TCO2. The carbon chemistry data are for surface waters only until 1991 when water column sampling was initiated. Other measured parameters are salinity, dissolved oxygen and the inorganic nutrients nitrate, phosphate and silicate. Because of the CARINA criteria for secondary quality control, depth >1500 m, the IRM-TS could not be included in the routine QC and the IS-TS only in a limited way. However, with the information provided here, the quality of the data can be assessed, e.g. on the basis of the results obtained with the use of reference materials.

Accurate assessment of anthropogenic carbon dioxide (CO2) emissions and their redistribution among the atmosphere, ocean, and terrestrial biosphere is important to better understand the global carbon cycle, support the development of climate policies, and project future climate change. Here we describe data sets and a methodology to quantify all major components of the global carbon budget, including their uncertainties, based on the combination of a range of data, algorithms, statistics, and model estimates and their interpretation by a broad scientific community. We discuss changes compared to previous estimates, consistency within and among components, alongside methodology and data limitations. CO2 emissions from fossil fuel combustion and cement production (EFF) are based on energy statistics and cement production data, respectively, while emissions from land-use change (ELUC), mainly deforestation, are based on combined evidence from land-cover-change data, fire activity associated with deforestation, and models. The global atmospheric CO2 concentration is measured directly and its rate of growth (GATM) is computed from the annual changes in concentration. The mean ocean CO2 sink (SOCEAN) is based on observations from the 1990s, while the annual anomalies and trends are estimated with ocean models. The variability in SOCEAN is evaluated with data products based on surveys of ocean CO2 measurements. The global residual terrestrial CO2 sink (SLAND) is estimated by the difference of the other terms of the global carbon budget and compared to results of independent dynamic global vegetation models forced by observed climate, CO2, and land-cover-change (some including nitrogen-carbon interactions). We compare the mean land and ocean fluxes and their variability to estimates from three atmospheric inverse methods for three broad latitude bands. All uncertainties are reported as ±1σ, reflecting the current capacity to characterise the annual estimates of each component of the global carbon budget. For the last decade available (2004-2013) EFF was 8.9 ± 0.4 GtC yr-1, ELUC 0.9 ± 0.5 GtC yr-1, GATM 4.3 ± 0.1 GtC yr-1, SOCEAN 2.6 ± 0.5 GtC yr-1, and SLAND 2.9 ± 0.8 GtC yr-1. For year 2013 alone, EFF grew to 9.9 ± 0.5 GtC yr-1, 2.3% above 2012, continuing the growth trend in these emissions, ELUC was 0.9 ± 0.5 GtC yr-1, GATM was 5.4 ± 0.2 GtC yr-1, SOCEAN was 2.9 ± 0.5 GtC yr-1, and SLAND was 2.5 ± 0.9 GtC yr-1. GATM was high in 2013, reflecting a steady increase in EFF and smaller and opposite changes between SOCEAN and SLAND compared to the past decade (2004-2013). The global atmospheric CO2 concentration reached 395.31 ± 0.10 ppm averaged over 2013. We estimate that EFF will increase by 2.5% (1.3-3.5%) to 10.1 ± 0.6 GtC in 2014 (37.0 ± 2.2 GtCO2 yr-1), 65% above emissions in 1990, based on projections of world gross domestic product and recent changes in the carbon intensity of the global economy. From this projection of EFF and assumed constant ELUC for 2014, cumulative emissions of CO2 will reach about 545 ± 55 GtC (2000 ± 200 GtCO2) for 1870-2014, about 75% from EFF and 25% from ELUC. This paper documents changes in the methods and data sets used in this new carbon budget compared with previous publications of this living data set (Le Quéré et al. 2013, 2014). All observations presented here can be downloaded from the Carbon Dioxide Information Analysis Center (doi:10.3334/CDIAC/GCP-2014)., 0, SCOPUS: ar.j, info:eu-repo/semantics/published

We developed a system to accurately, precisely, and rapidly measure total dissolved carbon dioxide ( T CO 2 ) in a continuously flowing seawater stream. The system is based on a gas-permeable membrane contactor, through which CO 2 evolved from an acidified seawater stream is continuously and quantitatively stripped by a flowing gas stream. The CO 2 content of this strip-gas stream, which is proportional to the TCO 2 of the seawater stream via a simple mass balance, is then analyzed using a non-dispersive infra-red (NDIR) gas analyzer. Laboratory results have shown that the system has an e-folding response time of 6 s and is able to resolve changes in signal with better than ± 0.1% precision. Independent coulometric analyses of check samples collected in the field, analyses of internal check samples, and analyses of certified reference materials have shown the accuracy of the system to be reliable to ± 0.1%. Coupled with the Lamont Pumping SeaSoar system, the T CO 2 system has yielded high spatial resolution distributions of T CO 2 across the New England shelfbreak front. These T CO 2 data, in conjunction with collocated P CO 2 measurements of similar resolution, allowed us to calculate total alkalinity ( T ALK ) at the high spatial resolution of the T CO 2 and P CO 2 measurements. While we cannot rule out or fully constrain the effects of mixing or variations in fresh water input, distributions of T ALK relative to T CO 2 , in the context of several independent lines of reasoning, indicated that biogenic calcium carbonate production may play an important role in shaping the T ALK and T CO 2 distributions in waters across the New England shelfbreak front.

To investigate CO2 chemistry in ocean water with greater time-space resolutions, we developed measurement systems, which have state-of-the-art precision but an order of magnitude or better increase in the frequency of analysis, for carbon dioxide partial pressures (PCO2) and total carbon dioxide concentrations (TCO2) in seawater. The PCO2 system was based on equilibration of a CO2-free carrier gas stream with aqueous carbon dioxide in a flowing seawater sample stream using a commercially available membrane contactor unit normally employed in industrial applications followed by nondispersive infrared (NDIR) absorbance detection of the CO2 in the exit carrier gas. The TCO2 system was based on injection of a small-volume seawater sample loop (~1 mL) into an acid (0.1 N HCl) liquid carrier stream to convert all carbonate and bicarbonate ions to aqueous carbon dioxide; this acidified sample was then passed through a custom-made small-volume membrane contactor unit where the sample's PCO2 was determined by equilibration of a CO2-free carrier gas followed by NDIR detection. Results from lab tests and a field experiment in the Ross Sea polynya, Antarctica, are presented. The PCO2 system was determined to have a response time of about 3 s and precision of better than 1 µatm. The TCO2 system had a maximum analysis rate of one sample per 36 s, and reproducibility was determined to be better than 0.2% for a period of hours.

The availability of iron is known to exert a controlling influence on biological productivity in surface waters over large areas of the ocean and may have been an important factor in the variation of the concentration of atmospheric carbon dioxide over glacial cycles. The effect of iron in the Southern Ocean is particularly important because of its large area and abundant nitrate, yet iron-enhanced growth of phytoplankton may be differentially expressed between waters with high silicic acid in the south and low silicic acid in the north, where diatom growth may be limited by both silicic acid and iron. Two mesoscale experiments, designed to investigate the effects of iron enrichment in regions with high and low concentrations of silicic acid, were performed in the Southern Ocean. These experiments demonstrate iron's pivotal role in controlling carbon uptake and regulating atmospheric partial pressure of carbon dioxide.

We adapted a commercially available flow-injection autoanalyzer (Lachat Quik-Chem 8000) to measure seawater nitrate concentrations at a rate of nearly 0.1 Hz and phosphate and silicate concentrations at a rate half that. Several minor improvements, including reduced sample-loop size, high sample flushing rate, modified carrier chemistry, and use of peak height rather than peak area as a proxy for nutrient concentration aided in the increase in sampling rate. The most significant improvement, however, was the construction of a copperized cadmium NO 3 ‐ reduction column that had a high surface area to volume ratio and a stable packing geometry. Preliminary results from a cruise in the Ross Sea in austral spring of 1997 are shown. Precision of all three analyses is better than 1%. Comparison of the nutrient concentrations determined by the rapid analysis method described here with traditional discrete analyses shows that nitrate and silicate determined by the two approaches are within a few percent of each other, but that the phosphate concentrations determined by the rapid analysis are as much as 10% lower than those determined by the discrete analyses.

In addition to efforts aimed at reducing anthropogenic production of greenhouse gases, geological storage of CO2 is being explored as a strategy to reduce atmospheric greenhouse gas emission and mitigate climate change. Previous studies of the deep subsurface in North America have not fully considered the potential negative effects of CO2 leakage into shallow drinking water aquifers, especially from a microbiological perspective. A test well in the Newark Rift Basin was utilized in two field experiments to investigate patterns of microbial succession following injection of CO2-saturated water into an isolated aquifer interval, simulating a CO2 leakage scenario. A decrease in pH following injection of CO2 saturated aquifer water was accompanied by mobilization of trace elements (e.g. Fe and Mn), and increased bacterial cell concentrations in the recovered water. 16S ribosomal RNA gene sequence libraries from samples collected before and after the test well injection were compared to link variability in geochemistry to changes in aquifer microbiology. Significant changes in microbial composition, compared to background conditions, were found following the test well injections, including a decrease in Proteobacteria, and an increased presence of Firmicutes, Verrucomicrobia and microbial taxa often noted to be associated with iron and sulfate reduction. The concurrence of increased microbial cell concentrations and rapid microbial community succession indicate significant changes in aquifer microbial communities immediately following the experimental CO2 leakage event. Samples collected one year post-injection were similar in cell number to the original background condition and community composition, although not identical, began to revert toward the pre-injection condition, indicating microbial resilience following a leakage disturbance. This study provides a first glimpse into the in situ successional response of microbial communities to CO2 leakage after subsurface injection in the Newark Basin and the potential microbiological impact of CO2 leakage on drinking water resources.

48 pages, 9 figures, 10 tables.-- Proyecto Carbochange, Accurate assessment of anthropogenic carbon dioxide (CO2) emissions and their redistribution among the atmosphere, ocean, and terrestrial biosphere is important to better understand the global carbon cycle, support the development of climate policies, and project future climate change. Here we describe data sets and a methodology to quantify all major components of the global carbon budget, including their uncertainties, based on the combination of a range of data, algorithms, statistics, and model estimates and their interpretation by a broad scientific community. We discuss changes compared to previous estimates as well as consistency within and among components, alongside methodology and data limitations. CO2 emissions from fossil fuels and industry (EFF) are based on energy statistics and cement production data, while emissions from land-use change (ELUC), mainly deforestation, are based on combined evidence from land-cover-change data, fire activity associated with deforestation, and models. The global atmospheric CO2 concentration is measured directly and its rate of growth (GATM) is computed from the annual changes in concentration. The mean ocean CO2 sink (SOCEAN) is based on observations from the 1990s, while the annual anomalies and trends are estimated with ocean models. The variability in SOCEAN is evaluated with data products based on surveys of ocean CO2 measurements. The global residual terrestrial CO2 sink (SLAND) is estimated by the difference of the other terms of the global carbon budget and compared to results of independent dynamic global vegetation models forced by observed climate, CO2, and land-cover change (some including nitrogen–carbon interactions). We compare the mean land and ocean fluxes and their variability to estimates from three atmospheric inverse methods for three broad latitude bands. All uncertainties are reported as ±1σ, reflecting the current capacity to characterise the annual estimates of each component of the global carbon budget. For the last decade available (2005–2014), EFF was 9.0 ± 0.5 GtC yr−1, ELUC was 0.9 ± 0.5 GtC yr−1, GATM was 4.4 ± 0.1 GtC yr−1, SOCEAN was 2.6 ± 0.5 GtC yr−1, and SLAND was 3.0 ± 0.8 GtC yr−1. For the year 2014 alone, EFF grew to 9.8 ± 0.5 GtC yr−1, 0.6 % above 2013, continuing the growth trend in these emissions, albeit at a slower rate compared to the average growth of 2.2 % yr−1 that took place during 2005–2014. Also, for 2014, ELUC was 1.1 ± 0.5 GtC yr−1, GATM was 3.9 ± 0.2 GtC yr−1, SOCEAN was 2.9 ± 0.5 GtC yr−1, and SLAND was 4.1 ± 0.9 GtC yr−1. GATM was lower in 2014 compared to the past decade (2005–2014), reflecting a larger SLAND for that year. The global atmospheric CO2 concentration reached 397.15 ± 0.10 ppm averaged over 2014. For 2015, preliminary data indicate that the growth in EFF will be near or slightly below zero, with a projection of −0.6 [range of −1.6 to +0.5] %, based on national emissions projections for China and the USA, and projections of gross domestic product corrected for recent changes in the carbon intensity of the global economy for the rest of the world. From this projection of EFF and assumed constant ELUC for 2015, cumulative emissions of CO2 will reach about 555 ± 55 GtC (2035 ± 205 GtCO2) for 1870–2015, about 75 % from EFF and 25 % from ELUC. This living data update documents changes in the methods and data sets used in this new carbon budget compared with previous publications of this data set (Le Quéré et al., 2015, 2014, 2013). All observations presented here can be downloaded from the Carbon Dioxide Information Analysis Center (doi:10.3334/CDIAC/GCP_2015)., NERC provided funding to C. Le Quéré, R. Moriarty, and the GCP through their International Opportunities Fund specifically to support this publication (NE/103002X/1). G. P. Peters and R. M. Andrew were supported by the Norwegian Research Council (236296). J. G. Canadell was supported by the Australian Climate Change Science Programme. S. Sitch was supported by EU FP7 for funding through projects LUC4C (GA603542). R. J. Andres was supported by US Department of Energy, Office of Science, Biological and Environmental Research (BER) programmes under US Department of Energy contract DE-AC05- 00OR22725. T. A. Boden was supported by US Department of Energy, Office of Science, Biological and Environmental Research (BER) programmes under US Department of Energy contract DE-AC05-00OR22725.J. I. House was supported by the Leverhulme foundation and the EU FP7 through project LUC4C (GA603542). P. Friedlingstein was supported by the EU FP7 for funding through projects LUC4C (GA603542) and EMBRACE (GA282672). A. Arneth was supported by the EU FP7 for funding through LUC4C (603542), and the Helmholtz foundation and its ATMO programme. D. C. E. Bakker was supported by the EU FP7 for funding through project CARBOCHANGE (284879), the UK Ocean Acidification Research Programme (NE/H017046/1; funded by the Natural Environment Research Council, the Department for Energy and Climate Change and the Department for Environment, Food and Rural Affairs). L. Barbero was supported by NOAA’s Ocean Acidification Program and acknowledges support for this work from the National Aeronautics and Space Administration (NASA) ROSES Carbon Cycle Science under NASA grant 13-CARBON13_2-0080. P. Ciais acknowledges support from the European Research Council through Synergy grant ERC-2013-SyG-610028 “IMBALANCE-P”. M. Fader was supported by the EU FP7 for funding through project LUC4C (GA603542). J. Hauck was supported by the Helmholtz Postdoc Programme (Initiative and Networking Fund of the Helmholtz Association). R. A. Feely and A. J. Sutton were supported by the Climate Observation Division, Climate Program Office, NOAA, US Department of Commerce. A. K. Jain was supported by the US National Science Foundation (NSF AGS 12-43071) the US Department of Energy, Office of Science and BER programmes (DOE DE-SC0006706) and NASA LCLUC programme (NASA NNX14AD94G). E. Kato was supported by the ERTDF (S-10) from the Ministry of Environment, Japan. K. Klein Goldewijk was supported by the Dutch NWO VENI grant no. 863.14.022. S. K. Lauvset was supported by the project “Monitoring ocean acidification in Norwegian waters” from the Norwegian Ministry of Climate and Environment. V. Kitidis was supported by the EU FP7 for funding through project CARBOCHANGE (264879). C. Koven was supported by the Director, Office of Science, Office of Biological and Environmental Research of the US Department of Energy under contract no. DE-AC02-05CH11231 as part of their Regional and Global Climate Modeling Program. P. Landschützer was supported by GEOCarbon. I. T. van der Lann-Luijkx received financial support from OCW/NWO for ICOS-NL and computing time from NWO (SH-060-13). I. D. Lima was supported by the US National Science Foundation (NSF AGS-1048827). N. Metzl was supported by Institut National des Sciences de l’Univers (INSU) and Institut Paul Emile Victor (IPEV) for OISO cruises. D. R. Munro was supported by the US National Science Foundation (NSF PLR-1341647 and NSF AOAS-0944761). J. E. M. S. Nabel was supported by the German Research Foundation’s Emmy Noether Programme (PO1751/1-1) and acknowledges Julia Pongratz and Kim Naudts for their contributions. Y. Nojiri and S. Nakaoka were supported by the Global Environment Research Account for National Institutes (1432) by the Ministry of Environment of Japan. A. Olsen appreciates support from the Norwegian Research Council (SNACS, 229752). F. F. Pérez were supported by BOCATS (CTM2013-41048-P) project co-founded by the Spanish government and the Fondo Europeo de Desarrollo Regional (FEDER). B. Pfeil was supported through the European Union’s Horizon 2020 research and innovation programme AtlantOS under grant agreement no. 633211. D. Pierrot was supported by NOAA through the Climate Observation Division of the Climate Program Office. B. Poulter was supported by the EU FP7 for funding through GEOCarbon. G. Rehder was supported by BMBF (Bundesministerium für Bildung und Forschung) through project ICOS, grant no. 01LK1224D. U. Schuster was supported by NERC UKOARP (NE/H017046/1), NERC RAGANRoCC (NE/K002473/1), the European Space Agency (ESA) OceanFlux Evolution project, and EU FP7 CARBOCHANGE (264879). T. Steinhoff was supported by ICOS-D (BMBF FK 01LK1101C) and EU FP7 for funding through project CARBOCHANGE (264879). J. Schwinger was supported by the Research Council of Norway through project EVA (229771). T. Takahashi was supported by grants from NOAA and the Comer Education and Science Foundation. B. Tilbrook was supported by the Australian Department of Environment and the Integrated Marine Observing System. B. D. Stocker was supported by the Swiss National Science Foundation and FP7 funding through project EMBRACE (282672). S. van Heuven was supported by the EU FP7 for funding through project CARBOCHANGE (264879). G. R. van der Werf was supported by the European Research Council (280061). A. Wiltshire was supported by the Joint UK DECC/Defra Met Office Hadley Centre Climate Programme (GA01101) and EU FP7 Funding through project LUC4C (603542). S. Zaehle was supported by the European Research Council (ERC) under the Eu ropean Union’s Horizon 2020 research and innovation programme (QUINCY; grant agreement no. 647204). ISAM (PI: Atul K. Jain) simulations were carried out at the National Energy Research Scientific Computing Center (NERSC), which is supported by the US DOE under contract DE-AC02-05CH11231. Contributions from the Scripps Institution of Oceanography were supported under DoE grant DE-SC0012167 and by Schmidt Philanthropies. This is NOAA-PMEL contribution number 4400

A number of workers have recently shown that the thermodynamic constants for the dissociation of carbonic acid in seawater of Mehrbach et al. are more reliable than measurements made on artificial seawater. These studies have largely been confined to looking at the internal consistency of measurements of total alkalinity (TA), total inorganic carbon dioxide (TCO2) and the fugacity of carbon dioxide (fCO2). In this paper, we have examined the field measurements of pH, fCO2, TCO2 and TA on surface and deep waters from the Atlantic, Indian, Southern and Pacific oceans to determine the pK1, pK2 and pK2−pK1. These calculations are possible due to the high precision and accuracy of the field measurements. The values of pK2 and pK2−pK1 over a wide range of temperatures (−1.6–38°C) are in good agreement (within ±0.005) with the results of Mehrbach et al. The measured values of pK1 at 4°C and 20°C are in reasonable agreement (within ±0.01) with all the constants determined in laboratory studies. These results indicate, as suggested by internal consistency tests, that the directly measured values of pK1+pK2 of Mehrbach et al. on real seawater are more reliable than the values determined for artificial seawater. It also indicates that the large differences of pK2−pK1 (0.05 at 20°C) in real and artificial seawater determined by different investigators are mainly due to differences in pK2. These differences may be related to the interactions of boric acid with the carbonate ion. The values of pK2−pK1 determined from the laboratory measurements of Lee et al. and Lueker et al. at low fCO2 agree with the field-derived data to ±0.016 from 5°C to 25°C. The values of pK2−pK1 decrease as the fCO2 or TCO2 increases. This effect is largely related to changes in the pK2 as a function of fCO2 or TCO2. The values of fCO2 calculated from an input of TA and TCO2, which require reliable values of pK2−pK1, also vary with fCO2. The field data at 20°C has been used to determine the effect of changes of TCO2 on pK2 giving an empirical relationship: which is valid at TCO2>2050 μmol kg−1. This assumes that the other dissociation constants such as KB for boric acid are not affected by changes in TCO2. The slope is in reasonable agreement with the laboratory studies of Lee et al. and Lueker et al. (−1.2×10−4 to −1.9×10−4). This equation eliminates the dependence of the calculated fCO2 on the level of fCO2 or TCO2 in ocean waters (σ=29.7 μatm in fCO2). An input of pH and TCO2 yields values of fCO2 and TA that are in good agreement with the measured values (±22.3 μatm in fCO2 and ±4.3 μmol kg−1 in TA). The cause of the decrease in pK2 at high fCO2 is presently unknown. The observed inconsistencies between the measured and computed fCO2 values may be accounted for by adding the effect of organic acid (∼8 μmol kg−1) to the interpretation of the TA. Further studies are needed to elucidate the chemical reactions responsible for this effect.

OBJECTIVE: Total gastrectomy produces calcium malabsorption and osteopenia. We examined the effects of feeding water-soluble soybean fiber (WSSF), a highly fermentable dietary fiber with low viscosity, on calcium absorption and bone characteristics in totally gastrectomized rats. METHODS: Male Sprague-Dawley rats were assigned to two groups: sham operation and gastrectomy. After the postoperative recovery period, rats of each group were fed diets with or without WSSF (50 g/kg diet) for 4 wk. RESULTS: Net calcium absorption and femoral dry weight and calcium content and maximum breaking force were lower in the gastrectomy groups than in the sham groups. In the gastrectomy groups, calcium absorption and these femoral parameters were higher in rats fed the WSSF diet than in rats fed the WSSF-free diet. Feeding WSSF increased the concentrations of short-chain fatty acids and soluble calcium and decreased the pH in cecal contents. Net calcium absorption in gastrectomized rats correlated positively with the concentration of total short-chain fatty acids (the sum of acetic, propionic, and butyric acids) in cecal contents ( r = 0.545, P r = −0.628, P CONCLUSIONS: These findings indicate that ingestion of WSSF partly prevents the diminished calcium absorption after total gastrectomy in rats, resulting in the improvement of postgastrectomy osteopenia. The increase of calcium absorption may be associated with cecal fermentation of WSSF.

Characteristics of an amperometric CO2 sensor have been investigated for the measurement of CO2 concentration in air and CO2 partial pressure in seawater. Use of RuO2 for the gas permeable pH-dependent electrode, in place of PtO, leads to improved sensitivity. The sensor showed good current response for a wide range of CO2 concentrations in air. For seawater, the partial pressure of CO2 can be measured continuously with the sensor. CO2 from the sample solution permeates into the sensor electrolyte through the membrane in a similar manner as with gas sensing. The CO2 concentration or partial pressure can be detected as a current of pH dependent RuO2 reduction induced by hydrogen ions supplied from CO2.

A new class of water-soluble redox reagents (1–4) that contain selenium as the active site was developed for the purpose of the redox control of protein structures. The X-ray crystallographic analyses revealed that trans-3,4-dihydroxy-1-selenolane (DHSred) (1) and its Se-oxide (DHSox) (2) have two axial hydroxy groups on the selenolane five-membered ring, whereas trans-1,2-diselenane-4,5-diol (DSTox) (3), a selenium analog of oxidized dithiothreitol (DTTox), has two equatorial hydroxy groups on the diselenane six-membered ring. According to the vicinal 3JHH coupling constants observed for 1–3, it was suggested that they adopt similar structures in solution to those in the solid state. Diselenothreitol (DSTred) (4), a selenium analog of dithiothreitol (DTTred), was also synthesized, but it was too air sensitive to be isolated. The reactions of 1–4 with DTTox and DTTred indicated that the oxidizing power of DHSox (2) exceeds by far that of DTTox, while the reducing power of DSTred (4) exceeds that of DTTred. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:293–299, 2001

The concentration of CO2 in the atmosphere is projected to reach twice the preindustrial level by the middle of the 21st century. This increase will reduce the concentration of CO32− of the surface ocean by 30% relative to the preindustrial level and will reduce the calcium carbonate saturation state of the surface ocean by an equal percentage. Using the large 2650 m3 coral reef mesocosm at the BIOSPHERE-2 facility near Tucson, Arizona, we investigated the effect of the projected changes in seawater carbonate chemistry on the calcification of coral reef organisms at the community scale. Our experimental design was to obtain a long (3.8 years) time series of the net calcification of the complete system and all relevant physical and chemical variables (temperature, salinity, light, nutrients, Ca2+,pCO2, TCO2, and total alkalinity). Periodic additions of NaHCO3, Na2CO3, and/or CaCl2 were made to change the calcium carbonate saturation state of the water. We found that there were consistent and reproducible changes in the rate of calcification in response to our manipulations of the saturation state. We show that the net community calcification rate responds to manipulations in the concentrations of both Ca2+ and CO32− and that the rate is well described as a linear function of the ion concentration product, [Ca2+]0.69[CO32−]. This suggests that saturation state or a closely related quantity is a primary environmental factor that influences calcification on coral reefs at the ecosystem level. We compare the sensitivity of calcification to short-term (days) and long-term (months to years) changes in saturation state and found that the response was not significantly different. This indicates that coral reef organisms do not seem to be able to acclimate to changing saturation state. The predicted decrease in coral reef calcification between the years 1880 and 2065 A.D. based on our long-term results is 40%. Previous small-scale, short-term organismal studies predicted a calcification reduction of 14-30%. This much longer, community-scale study suggests that the impact on coral reefs may be greater than previously suspected. In the next century coral reefs will be less able to cope with rising sea level and other anthropogenic stresses.

Net community production (NCP) and nutrient deficits (Def( X )) were calculated using decreases in dissolved CO 2 and nutrient concentrations due to biological removal in the upper 200 m of the water column during four cruises in the Ross Sea, Antarctica along 76°30′S in 1996 and 1997. A comparison to excess dissolved and particulate organic carbon showed close agreement between surplus total organic carbon (TOC) and NCP during bloom initiation and productivity maximum; however, when TOC values had returned to low wintertime values NCP was still significantly above zero. This seasonal NCP, 3.9±1 mol C m −2 , must be equivalent to the particle export to depths greater than 200 m over the whole productive season. We estimate that the annual export was 55±22% of the seasonal maximum in NCP. The fraction of the seasonal maximum NCP that is exported through 200 m is significantly higher than that measured by moored sediment traps at a depth of 206 m. The removal of carbon, nitrate and phosphate (based on nutrient disappearance since early spring) and their ratios showed significant differences between regions dominated by diatoms and regions dominated by the haptophyte Phaeocystis antarctica . While the ΔC/ΔN removal ratio was similar (7.8±0.2 for diatoms and 7.2±0.1 for P. antarctica ), the ΔN/ΔP and ΔC/ΔP removal ratios for diatoms (10.1±0.3 and 80.5±2.3) were significantly smaller than those of P. antarctica (18.6±0.4 and 134.0±4.7). The similarity in ΔC/ΔN removal ratios of the two assemblages suggests that preferential uptake of phosphate by diatoms caused the dramatic differences in ΔC/ΔP and ΔN/ΔP removal ratios. In contrast to low ΔC/ΔP and ΔN/ΔP removal ratio in diatom-dominated areas early in the growing season, deficit N/P and C/P ratios in late autumn indicate that the elemental stochiometry of exported organic matter did not deviate significantly from traditional Redfield ratios. Changes in biologically utilized nutrient and carbon ratios over the course of the growing season indicated either a substantial remineralization of phosphate or a decrease in phosphate removal relative to carbon and total inorganic nitrogen over the bloom period. The species dependence in C/P ratios, and the relative constancy in the C/N ratios, makes N a better proxy of biological utilization of CO 2 .

The equatorial oceans are the dominant oceanic source of CO2 to the atmosphere, annually amounting to a net flux of 0.7–1.5 Pg (1015 g) of carbon, up to 72% of which emanates from the equatorial Pacific Ocean1,2,3. Limited observations indicate that the size of the equatorial Pacific source is significantly influenced by El Nino events4,5,6,7,8,9,10, but the effect has not been well quantified. Here we report spring and autumn multiannual measurements of the partial pressure of CO2 in the surface ocean and atmosphere in the equatorial Pacific region. During the 1991–94 El Nino period, the derived net annual sea-to-air flux of CO2 was 0.3 Pg C from autumn 1991 to autumn 1992, 0.6 Pg C in 1993, and 0.7 Pg C in 1994. These annual fluxes are 30–80% of that of 1996, a non-El-Nino year. The total reduction of the regional sea-to-air CO2 flux during the 1991–94 El Nino period is estimated to account for up to one-third of the atmospheric anomaly (the difference between the annual and long-term-average increases in global atmospheric CO2 content) observed over the same period.

An improved understanding of the partitioning of carbon between the atmosphere, terrestrial biosphere, and ocean allows for more accurate predictions of future atmospheric CO2 concentrations under various fossil-fuel CO2-emission scenarios. One of the more poorly quantified relevant processes is the interannual variability in the uptake of fossil-fuel CO2 from the atmosphere by the terrestrial biosphere and ocean. Existing estimates, based on atmospheric measurements, indicate that the oceanic variability is large1,2,3. Here we estimate the interannual variability in global net air–sea CO2 flux using changes in the observed wind speeds and the partial pressure of CO2 ( ) in surface sea water and the overlying air. Changes in seawater are deduced from interannual anomalies in sea surface temperature and the regionally and seasonally varying temperature-dependence of seawater , assuming that variations in sea surface temperature reflect seawater changes caused by thermodynamics, biological processes and water mixing. The calculated interannual variability in oceanic CO2 uptake of 0.4 Gt C yr−1 (2σ) is much less than that inferred from the analysis of atmospheric measurements1,2,3. Our results suggest that variable sequestration of carbon by the terrestrial biosphere is the main cause of observed year-to-year variations in the rate of atmospheric CO2 accumulation.

In the austral winter (September–October) of 1994, a hydrographic cruise in the Pacific sector of the Southern Ocean (NBP94-5) was completed, complementing two austral summer cruises (February–March) in 1992 (WOCE S4-P) and 1994 (NBP94-2) in the same area. During all three cruises, the partial pressure of carbon dioxide and concentration of total carbon dioxide dissolved in seawater were determined throughout the water column, accompanied by oxygen and nutrient measurements. Seasonal changes in CO 2 and nutrients observed in the mixed layer above the remnant winter water were used to estimate utilization ratios, primary productivity, and new production. The mean rate of primary production over 120 days ranged from 6 to 24 mmol C m -2 d -1 , consistent with the notion of the Southern Ocean as a low productivity area. Primary production was highest in the northern limb of the Ross Sea Gyre, where the wintertime vertical stability of the upper water column was lower. The circulation patterns and nutrient distributions in the region studied appear to influence the primary production rates observed. The ratio of biogenic silica to carbon was found to be 0.66±0.02. The observed N/P utilization ratio of 13.0±1.2 and C/P utilization ratio of 91.4±7.9 are both significantly lower than the traditional Redfield ratios of 16 and 106, respectively. The former is, however, consistent with the ΔN/ΔP regeneration ratio of 14.0±0.3 discerned for deep waters south of the Polar Front. Hence, the classical C/P and N/P Redfield ratios do not appear to hold in Antarctic waters. On the other hand, the C/N utilization ratio of 6.9±0.6 does agree with the Redfield ratio of 6.6 (106/16). This C/N ratio also agrees with the ratio obtained for surface particulate organic matter (POM) taken during the WOCE S4-P cruise along 67°S. Accordingly, the biological cycles of carbon and nitrogen in the Southern Ocean appear to be “Redfieldian”.

Continuous underway measurements of atmospheric and surface seawater pCO 2 were collected on numerous cruises in the Sargasso Sea (32°N, 64°W) near Bermuda from June 1994 to November 1995. We observed that seawater pCO 2 was highly variable on different timescales, ranging from diel to seasonal. On diel timescales, pCO 2 changes of 5-25 μatm occurred in response to diurnal warming and cooling associated with solar heat fluxes. Over longer timescales, pCO 2 was influenced by atmospheric forcing and tropical cyclones. For example, a surface cooling of 3°C and decrease in pCO 2 of 45-50 μatm occurred after Hurricane Felix passed near Bermuda in August 1995. The decrease in pCO 2 was significant considering the annual change was 90-100 μatm. Over all timescales, temperature was the dominant control on pCO 2 variability. We found that surface pCO 2 conditions were accurately predicted from temperatures with small errors (4-9 μatm) if seasonal pCO 2 -temperature relationships were established. In future synthesis of regional pCO 2 data it should be feasible to use surface temperature, remotely sensed from space, as a tool for extrapolation over wider spatial scales in the North Atlantic subtropical gyre. Net annual fluxes of CO 2 for 1994 and 1995 (-0.25 to -0.6 mol CO 2 m -2 yr ') were directed from atmosphere to ocean and were similar to values reported for 1989-1993 by Bates et al. [1996b]. We found that short-term variability of pCO 2 (diel warming and cooling or atmospheric forcing), frequency of sampling (every 3-4 days or monthly), or use of temperature-derived pCO 2 did not affect estimates of net yearly CO 2 fluxes by more than 10-20%. However, strong winds associated with hurricanes decreased the net annual flux of CO 2 into the ocean by 19-28% in 1995. The major sources of error for air-sea gas exchange was uncertainty associated with gas transfer-wind speed relationships and differences in the types of wind speed data used (daily averaged versus climatological). Such uncertainties make it difficult to quantify the contribution of gas exchange to the carbon cycle and the balance of carbon import and export terms in the upper ocean of the Sargasso Sea.

[1] During the Southern Ocean Iron Experiment (SOFeX), January–February 2002, two iron fertilization experiments were conducted at the south (66.45°S, 171.8°W) and north (56.23°S, 172°W) patches. The south patch was replete with all macronutrients, whereas the north patch was nearly depleted of silicate. Using a towed water sampling/ measurement system, high resolution three-dimensional observations of temperature, salinity, CO2 partial pressure (pCO2) and the concentrations of total CO2 (TCO2), nitrate, phosphate and silicate in the upper 100 m were obtained 10 and 28 days after initial iron additions in the south and north patches, respectively. TCO2 and nutrient drawdowns observed in the south patch were small due to wind events that limited biological response in the early postfertilization period. At the north patch, drawdown signals were stronger, resulting from the longer time since fertilization. The north patch was dispersed along a frontal zone between two distinct waters, with the denser subducted under the lighter. Subduction limited CO2 uptake from the air, but provided alternative mechanisms for vertical carbon export. Based on the biogeochemical drawdowns and published estimates of the rate of the entrainment of nonfertilized waters into the patch, the mean net community productivity over 28 days was estimated to be 94 � 12 mmol carbon m � 2 day � 1 , to which the air-to-sea flux contributed only 2%. Despite low silicate concentrations and potential limitation of growth of silicifying plankton in the north patch, our estimates of the enhanced carbon uptake are similar to estimates from higher silicate environments. Citation: Hales, B., and T. Takahashi (2012), Mesoscale biogeochemical responses to iron fertilization in the upper layers of the Southern Ocean Iron Experiment areas, J. Geophys. Res., 117, C01018, doi:10.1029/2011JC006956.

International audience; Oceanic uptake of carbon dioxide substantially reduces the rate at which anthropogenic carbon accumulates in the atmosphere, slowing global climate change. Some studies suggest that the rate at which the oceans take up carbon has significantly decreased in recent years. Others suggest that decadal variability confounds the detection of long-term trends. Here, we examine trends in the partial pressure of carbon dioxide in the surface waters of three large biogeographic regions in the North Atlantic, using observational data collected between 1981 and 2009. We compare these oceanic observations with trends in atmospheric carbon dioxide levels, taken from a global observational network. We show that trends in oceanic carbon dioxide concentrations are variable on a decadal timescale, often diverging from trends in atmospheric carbon dioxide. However, when the entire 29-year period is considered, oceanic trends converge with atmospheric trends in all three regions; it takes 25 years for this long-term trend to emerge and overcome the influence of decadal-scale variability. Furthermore, in the southernmost biome, the data suggest that warming--driven by a multidecadal climate oscillation and anthropogenic forcing--has started to reduce oceanic uptake of carbon in recent years.

[1] Recent studies based on ocean and atmospheric carbon dioxide (CO2) observations, suggesting that the ocean carbon uptake has been reduced, may help explain the increase in the fraction of anthropogenic CO2 emissions that remain in the atmosphere. Is it a response to climate change or a signal of ocean natural variability or both? Regional process analyses are needed to follow the ocean carbon uptake and to enable better attributions of the observed changes. Here, we describe the evolution of the surface ocean CO2 fugacity (fCO2oc) over the period 1993–2008 in the North Atlantic subpolar gyre (NASPG). This analysis is based primarily on observations of dissolved inorganic carbon (DIC) and total alkalinity (TA) conducted at different seasons in the NASPG between Iceland and Canada. The fCO2oc trends based on DIC and TA data are also compared with direct fCO2 measurements obtained between 2003 and 2007 in the same region. During winters 1993–2003, the fCO2oc growth rate was 3.7 (±0.6) μatm yr−1, higher than in the atmosphere, 1.8 (±0.1) μatm yr−1. This translates to a reduction of the ocean carbon uptake primarily explained by sea surface warming, up to 0.24 (±0.04) °C yr−1. This warming is a consequence of advection of warm water northward from the North Atlantic into the Irminger basin, which occurred as the North Atlantic Oscillation (NAO) index moved into a negative phase in winter 1995/1996. In winter 2001–2008, the fCO2oc rise was particularly fast, between 5.8 (±1.1) and 7.2 (±1.3) μatm yr−1 depending on the region, more than twice the atmospheric growth rate of 2.1 (±0.2) μatm yr−1, and in the winter of 2007–2008 the area was supersaturated with CO2. As opposed to the 1990s, this appears to be almost entirely due to changes in seawater carbonate chemistry, the combination of increasing DIC and decreasing of TA. The rapid fCO2oc increase was not only driven by regional uptake of anthropogenic CO2 but was also likely controlled by a recent increase in convective processes-vertical mixing in the NASPG and cannot be directly associated with NAO variability. The fCO2oc increase observed in 2001–2008 leads to a significant drop in pH of −0.069 (±0.007) decade−1.

A new class of water-soluble redox reagents (1–4) that contain selenium as the active site was developed for the purpose of the redox control of protein structures. The X-ray crystallographic analyses revealed that trans-3,4-dihydroxy-1-selenolane (DHSred) (1) and its Se-oxide (DHSox) (2) have two axial hydroxy groups on the selenolane five-membered ring, whereas trans-1,2-diselenane-4,5-diol (DSTox) (3), a selenium analog of oxidized dithiothreitol (DTTox), has two equatorial hydroxy groups on the diselenane six-membered ring. According to the vicinal 3JHH coupling constants observed for 1–3, it was suggested that they adopt similar structures in solution to those in the solid state. Diselenothreitol (DSTred) (4), a selenium analog of dithiothreitol (DTTred), was also synthesized, but it was too air sensitive to be isolated. The reactions of 1–4 with DTTox and DTTred indicated that the oxidizing power of DHSox (2) exceeds by far that of DTTox, while the reducing power of DSTred (4) exceeds that of DTTred. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:293–299, 2001

International audience; Efforts to control climate change require the stabilization of atmospheric CO2 concentrations. This can only be achieved through a drastic reduction of global CO2 emissions. Yet fossil fuel emissions increased by 29% between 2000 and 2008, in conjunction with increased contributions from emerging economies, from the production and international trade of goods and services, and from the use of coal as a fuel source. In contrast, emissions from land-use changes were nearly constant. Between 1959 and 2008, 43% of each year's CO2 emissions remained in the atmosphere on average; the rest was absorbed by carbon sinks on land and in the oceans. In the past 50 years, the fraction of CO2 emissions that remains in the atmosphere each year has likely increased, from about 40% to 45%, and models suggest that this trend was caused by a decrease in the uptake of CO2 by the carbon sinks in response to climate change and variability. Changes in the CO2 sinks are highly uncertain, but they could have a significant influence on future atmospheric CO2 levels. It is therefore crucial to reduce the uncertainties.

The Iceland Sea is one part of the Nordic Seas. Cold Arctic Water prevails there and the deep-water is an important source of North Atlantic Deep Water. We have evaluated time series observations of measured pCO2 and total CO2 concentration from discrete seawater samples during 1985–2008 for the surface and 1994–2008 for deep-water, and following changes in response to increasing atmospheric carbon dioxide. The surface pH in winter decreases at a rate of 0.0024 yr−1, which is 50% faster than average yearly rates at two subtropical time series stations, BATS and ESTOC. In the deep-water regime (>1500 m), the rate of pH decline is a quarter of that observed in surface waters. The surface seawater carbonate saturation states (Ω) are about 1.5 for aragonite and 2.5 for calcite, about half of levels found in subtropical surface waters. During 1985–2008, the degree of saturation (Ω) decreased at an average rate of 0.0072 yr−1 for aragonite and 0.012 yr−1 for calcite. The aragonite saturation horizon is currently at 1710 m and shoaling at 4 m yr−1. Based on this rate of shoaling and on the local hypsography, each year another 800 km2 of seafloor becomes exposed to waters that have become undersaturated with respect to aragonite.

We synthesize estimates of the contemporary net air-sea CO2 flux on the basis of an inversion of interior ocean carbon observations using a suite of 10 ocean general circulation models (Mikaloff Fletcher et al., 2006, 2007) and compare them to estimates based on a new climatology of the air-sea difference of the partial pressure of CO2 (pCO2) (Takahashi et al., 2008). These two independent flux estimates reveal a consistent description of the regional distribution of annual mean sources and sinks of atmospheric CO2 for the decade of the 1990s and the early 2000s with differences at the regional level of generally less than 0.1 Pg C a−1. This distribution is characterized by outgassing in the tropics, uptake in midlatitudes, and comparatively small fluxes in thehigh latitudes. Both estimates point toward a small (∼ −0.3 Pg C a−1) contemporary CO2 sink in the Southern Ocean (south of 44°S), a result of the near cancellation between a substantial outgassing of natural CO2 and a strong uptake of anthropogenic CO2. A notable exception in the generally good agreement between the two estimates exists within the Southern Ocean: the ocean inversion suggests a relatively uniform uptake, while the pCO2-based estimate suggests strong uptake in the region between 58°S and 44°S, and a source in the region south of 58°S. Globally and for a nominal period between 1995 and 2000, the contemporary net air-sea flux of CO2 is estimated to be −1.7 ± 0.4 Pg C a−1 (inversion) and −1.4 ± 0.7 Pg C a−1 (pCO2-climatology), respectively, consisting of an outgassing flux of river-derived carbon of ∼+0.5 Pg C a−1, and an uptake flux of anthropogenic carbon of −2.2 ± 0.3 Pg C a−1 (inversion) and −1.9 ± 0.7 Pg C a−1 (pCO2-climatology). The two flux estimates also imply a consistent description of the contemporary meridional transport of carbon with southward ocean transport throughout most of the Atlantic basin, and strong equatorward convergence in the Indo-Pacific basins. Both transport estimates suggest a small hemispheric asymmetry with a southward transport of between −0.2 and −0.3 Pg C a−1 across the equator. While the convergence of these two independent estimates is encouraging and suggests that it is now possible to provide relatively tight constraints for the net air-sea CO2 fluxes at the regional basis, both studies are limited by their lack of consideration of long-term changes in the ocean carbon cycle, such as the recent possible stalling in the expected growth of the Southern Ocean carbon sink.

[1] Deep aquifers are potential long-term storage sites for anthropogenic CO2 emissions. The retention time and environmental safety of the injected CO2 depend on geologic and physical factors and on the chemical reactions between the CO2, the aquifer water, and the host rocks. The pH buffer capacity of the aquifer water and the acid neutralization potential of the host rocks are important factors for the permanent stabilization of the injected CO2. Mafic rocks, such as basalt, which primarily consists of Ca, Mg silicate minerals, have a high acid neutralization capacity by providing alkaline earth elements that form stable carbonate minerals. The carbonate minerals formed thus sequester CO2 in a chemically stable and environmentally benign form. In this study, we present results from a small-scale CO2 injection test in mafic and metasedimentary rocks. The injection test was conducted using a single-well push-pull test strategy. CO2 saturated water (pH = 3.5) was injected into a hydraulically isolated and permeable aquifer interval to study the acid neutralization capacity of Ca, Mg silicate rocks and to estimate in situ cation release rates. Release rates for Ca, Mg, and Na were calculated by use of solute compositions of water samples retrieved after the CO2 injection, the incubation time of the injected solution within the aquifer, and geometric estimates of the reactive surface area of the host rocks. Our results confirm rapid acid neutralization rates and water-rock reactions sufficient for safe and permanent storage of CO2. Carbonic acid was neutralized within hours of injection into a permeable mafic aquifer by two processes: mixing between the injected solution and the aquifer water, and water-rock reactions. Calculated cation release rates decrease with increasing pH that is confirmed by laboratory-based experiments. Large differences between release rates obtained from the field and laboratory experiments may be mainly due to uncertainties in the estimation of the reactive surface area in the field experiment and in hydrological and geological factors. Our results underscore the importance of defining bulk rock dissolution rates under in situ conditions in order to evaluate target formations for permanent mineral sequestration of carbon dioxide.

The condensation reaction of angiotensin II and tartaric acid in water at 100-140 degrees C proceeded without any added catalytic agent. One of the products, N-CO-tartarylangiotensin II, was confirmed by LC-MS, positive-ion MALDI-MS, and the fluorescamine method as a condensation product. The initial concentration of the substrates, temperatures, and initial pH affected the yield of the product. The higher concentrations and temperatures increased the concentration of the condensation product. The optimal pH for the condensation reaction was 3.0. The other C4 saturated dicarboxylic acids, malic and succinic acids, were also condensed by angiotensin II.

UPTAKE of atmospheric CO2 by the ocean's 'biological pump' is driven by export of carbon from the euphotic zone to deeper waters1,2. As nitrate is a limiting nutrient in large regions of the ocean, measurements of nitrate uptake are often used to estimate the amount of carbon exported in this way3–6. This presupposes knowledge of the molar C: N ratio in the organic material exported from the upper waters, which is usually taken to be 6.6 (the Redfield ratio7,8). Recent studies have suggested, however, that the consumption ratio of C:N may deviate from this value in coastal waters9–11. Here we present time-series from both coastal waters and open-ocean sites which demonstrate that net organic carbon production greatly exceeded that predicted from nitrate consumption and the Redfield C:N ratio. We found a similar discrepancy in sections across broad regions of the North Atlantic during eutrophic periods. Our results suggest that extrapolating from nitrate consumption using the Redfield ratio leads to significant underestimates of organic carbon export from the euphotic zone.

Four-week-old rats were fed on diets containing either no dietary fiber (DF) or a DF source (WSSF, ISF or cellulose) for 4 weeks. The DF level was adjusted to 5%. The WSSF diet contained 3% and 2%, respectively, of WSSF and cellulose. No rat in any group experienced diarrhea, and none of the experimental diets suppressed the growth of rats, the apparent absorption of major nutrients being almost 100%. However, the rate of degradation of DF during the digestive process was significantly different (p0.05, cellulose, 23.6%; WSSF with cellulose, 64.5% (WSSF degradation only was 91.8%); and ISF, 77.6%). The plasma and liver lipid levels were within normal ranges, although the liver cholesterol level in those rats fed on WSSF and ISF was significantly lower (p0.05) than in those fed on cellulose. The cecal organic acid contents were in the order of WSSFISFcelluloseDF-free. Furthermore, WSSF was effective in shortening the gastrointestinal transit time. The results indicate that WSSF seems to have favorable effects on the intestinal functions.

Atmospheric carbon dioxide increased at a rate of 2.8 petagrams of carbon per year (Pg C year −1 ) during 1988 to 1992 (1 Pg = 10 15 grams). Given estimates of fossil carbon dioxide emissions, and net oceanic uptake, this implies a global terrestrial uptake of 1.0 to 2.2 Pg C year −1 . The spatial distribution of the terrestrial carbon dioxide uptake is estimated by means of the observed spatial patterns of the greatly increased atmospheric carbon dioxide data set available from 1988 onward, together with two atmospheric transport models, two estimates of the sea-air flux, and an estimate of the spatial distribution of fossil carbon dioxide emissions. North America is the best constrained continent, with a mean uptake of 1.7 ± 0.5 Pg C year −1 , mostly south of 51 degrees north. Eurasia–North Africa is relatively weakly constrained, with a mean uptake of 0.1 ± 0.6 Pg C year −1 . The rest of the world's land surface is poorly constrained, with a mean source of 0.2 ± 0.9 Pg C year −1 .

This data documentation discusses the procedures and methods used to measure total carbon dioxide concentration (TCO{sub 2}) and partial pressure of CO{sub 2} (pCO{sub 2}) in discrete water samples collected during three expeditions of the Research Vessel (R/V) Knorr in the South Pacific Ocean. Conducted as part of the World Ocean Circulation Experiment (WOCE), the first cruise (WOCE Section P16A/P17A) began in Papeete, Tahiti, French Polynesia, on October 6, 1992, and returned to Papeete on November 25, 1992. The second cruise (WOCE Section P17E/P19S) began in Papeete on December 4, 1992, and finished in Punta Arenas, Chile, on January 22, 1993. The third expedition (WOCE Section P19C) started in Punta Arenas, on February 22 and finished in Panama City, Panama, on April 13, 1993. During the three expeditions, 422 hydrographic stations were occupied. Hydrographic and chemical measurements made along WOCE Sections P16A/P17A, P17E/P19S, and P19C included pressure, temperature, salinity, and oxygen [measured by conductivity, temperature, and depth (CTD) sensor], as well as discrete measurements of salinity, oxygen, phosphate, nitrate, nitrite, silicate, chlorofluorocarbons (CFC-11, CFC-12), TCO{sub 2}, and pCO{sub 2} measured at 4 and 20 C. In addition, potential temperatures were calculated from the measured variables.

Not all of the carbon dioxide produced by humans ends up in the atmosphere, but exactly where it all ends up and how much is captured by the oceans have been longstanding mysteries. In his Perspective, Takahashi discusses results reported in the same issue by Sabine et al. and Feely et al. that address these questions. Sabine et al. used an extensive data set to estimate the amount of carbon dioxide taken up by the oceans. Feely et al. studied what happens to calcium carbonate shell material from ocean organisms and the impact of industrial carbon dioxide on organism growth and dissolution of the shells. Such improvements in understanding the sources and sinks of carbon should provide information needed to make decisions about how to constrain the increase in atmospheric carbon dioxide.

This report summarizes the results of carbon dioxide and associated hydrographic measurements made during the oceanographic expedition, TUNES/2, aboard the R/V Thomas Washington in the central South Pacific Ocean. During the 40 day expedition, the total carbon dioxide concentration in 1000 seawater samples were determined using a coulometer system and the pCO(sub 2) in 940 seawater samples were determined using an equilibrator/gas chromatograph system. The alkalinity values in 900 water samples were computed using these measurements. In addition, 156 coulometric measurements were made for the Certified Reference Solutions (Batch No. 6) and yielded a mean value of 2303.2 +or- 1.5umol/kg. The chemical characteristics for the major water masses have been determined.