In situ measurement of dissolved inorganic carbon speciation in natural waters, pH, pC02, TA, & TC02, Honolulu, Hawaii, February 16-18, 2005: workshop proceedings

The Alliance for Coastal Technology (ACT) convened a workshop on the in situ measurement of dissolved inorganic carbon species in natural waters in Honolulu, Hawaii, on February 16, 17, and 18, 2005. The workshop was designed to summarize existing technologies for measuring the abundance and speciation of dissolved inorganic carbon and to make strategic recommendations for future development and application of these technologies to coastal research and management. The workshop was not focused on any specific technology, however, most of the attention of the workshop was on in situ pC02 sensors given their recent development and use on moorings for the measurement of global carbon fluxes. In addition, the problems and limitations arising from the long-term deployment of systems designed for the measurement of pH, total dissolved inorganic carbon (DIC), and total alkalinity (TA) were discussed. Participants included researchers involved in carbon biogeochemistry, industry representatives, and coastal resource managers. The primary questions asked during the workshop were: I. What are the major impediments to transform presently used shipboard pC02 measurement systems for use on cost-eficient moorings? 2. What are the major technical hurdles for the in situ measurement of TA and DIC? 3. What specific information do we need to coordinate efforts for proof of concept' testing of existing and new technologies, inter-calibration of those technologies, better software development, and more precise knowledge quantzjjing the geochemistry of dissolved inoeanic carbon species in order to develop an observing system for dissolved inorganic carbon? Based on the discussion resulting from these three questions, the following statements were made: Statement No. 1 Cost-effective, self-contained technologies for making long-term, accurate measurements of the partial pressure of C02 gas in water already exist and at present are ready for deployment on moorings in coastal observing systems. Statement No. 2 Cost-effective, self-contained systems for the measurement of pH, TA, and DIC are still needed to both fully define the carbonate chemistry of coastal waters and the fluxes of carbon between major biogeochemical compartments (e.g., air-sea, shelf-slope, water column-sediment, etc.). (pdf contains 23 pages)

Photosynthetic inorganic carbon utilization of gametophytes and sporophytes of Undaria pinnatifida (Phaeophyceae)

The characteristics of inorganic carbon assimilation by photosynthesis were investigated in male and female gametophytes and juvenile sporophytes of Undaria pinnatifida. Gametophytes and sporophytes have detectable extracellular and intracellular carbonic anhydrase (CA) activity, and the CA inhibitor, acetazolamide (AZ), significantly inhibited their photosynthesis O-2 evolution. In pH-drift experiments, it was found that gametophytes did not raise the final pH of seawater above 9.00 (CO2 concentrations of about 2.2 mu M), indicating a low ability to utilize inorganic carbon. In contrast, sporophytes rapidly raised pH to over 9.53 and depleted the free CO2 Concentration to less than 0.16 mu M. The apparent photosynthetic affinity for CO2 was almost the same for gametophytes and sporophytes, whereas gametophytes had a much lower affinity for HCO3- than sporophytes. Two inhibitors of band 3 anion exchange protein (DIDS and SITS) inhibited the photosynthesis of gametophytes but not that of sporophytes. It was indicated that both gametophytes and sporophytes were capable of using HCO3-, which involved the external CA activity, and a direct HCO3- use also occurred in the former, but the latter showed a greater capacity of HCO3- use than the former. In addition, male and female gametophytes did not show great differences in the inorganic carbon uptake mechanism underlying photosynthesis.

Photosynthetic utilization of inorganic carbon in the economic brown alga, Hizikia Fusiforme (Sargassaceae) from the South China Sea

The mechanism of inorganic carbon (C-i) acquisition by the economic brown macroalga, Hizikia fusiforme (Harv.) Okamura (Sargassaceae), was investigated to characterize its photosynthetic physiology. Both intracellular and extracellular carbonic anhydrase (CA) were detected, with the external CA activity accounting for about 5% of the total. Hizikia fusiforme showed higher rates of photosynthetic oxygen evolution at alkaline pH than those theoretically derived from the rates of uncatalyzed CO2 production from bicarbonate and exhibited a high pH compensation point (pH 9.66). The external CA inhibitor, acetazolamide, significantly depressed the photosynthetic oxygen evolution, whereas the anion-exchanger inhibitor 4,4'-diisothiocyano-stilbene-2,2'-disulfonate had no inhibitory effect on it, implying the alga was capable of using HCO3- as a source of C-i for its photosynthesis via the mediation of the external CA. CO2 concentrations in the culture media affected its photosynthetic properties. A high level of CO2 (10,000 ppmv) resulted in a decrease in the external CA activity; however, a low CO2 level (20 ppmv) led to no changes in the external CA activity but raised the intracellular CA activity. Parallel to the reduction in the external CA activity at the high CO2 was a reduction in the photosynthetic CO2 affinity. Decreased activity of the external CA in the high CO2 grown samples led to reduced sensitiveness of photosynthesis to the addition of acetazolamide at alkaline pH. It was clearly indicated that H. fusiforme, which showed CO2-limited photosynthesis with the half-saturating concentration of C-i exceeding that of seawater, did not operate active HCO3- uptake but used it via the extracellular CA for its photosynthetic carbon fixation.

Photosynthetic responses to inorganic carbon in Ulva lactuca under aquatic and aerial states

Intertidal macroalgae experience continual alternation of photosynthesis between aquatic state at high tide and aerial state at low tide. The comparative photosynthetic responses to inorganic carbon were investigated in the common intertidal macroalga Ulva lactuca L. along the coast of Shantou between aquatic and aerial state. The inorganic carbon dissolved in seawater at present could fully (at 10 degreesC or 20 degreesC) or nearly (at 30 degreesC) saturate the aquatic photosynthesis of U. lactuca. However, the aerial photosynthesis was limited by current ambient atmospheric CO2 level, and such a limitation was more severe at higher temperature (20degrees - 30degrees T) than at lower temperature (10 T). The carbon-saturated maximal photosynthesis of U. lactuca under aerial state was much greater than that under aquatic state at 10 degreesC and 20 degreesC, while the maximal photosynthesis under both states was similar at 30 degreesC. The aerial values of K-m (CO2) for photosynthesis were higher than the aquatic values. On the contrary, the values of apparent photosynthetic CO2 conductance under aerial state were considerably lower than that under aquatic state. It was concluded that the increase of atmospheric CO2 would enhance the primary productivity of U. lactuca through stimulating the photosynthesis under aerial state during low tide.

Effects of CO2 enrichment on the bloom-forming cyanobacterium Microcystis aeruginosa (Cyanophyceae): Physiological responses and relationships with the availability of dissolved inorganic carbon

Microcystis aeruginosa Kutz. 7820 was cultured at 350 and 700 muL.L-1 CO2 to assess the impacts of doubled atmospheric CO2 concentration on this bloom-forming cyanobacterium. Doubling Of CO2 concentration in the airflow enhanced its growth by 52%-77%, with pH values decreased and dissolved inorganic carbon (DIC) increased in the medium. Photosynthetic efficiencies and dark respiratory rates expressed per unit chl a tended to increase with the doubling of CO2. However, saturating irradiances for photosynthesis and light-saturated photosynthetic rates normalized to cell number tended to decrease with the increase of DIC in the medium. Doubling of CO2 concentration in the airflow had less effect on DIC-saturated photosynthetic rates and apparent photosynthetic affinities for DIC. In the exponential phase, CO2 and HCO3- levels in the medium were higher than those required to saturate photosynthesis. Cultures with surface aeration were DIC limited in the stationary phase. The rate of CO2 dissolution into the liquid increased proportionally when CO2 in air was raised from 350 to 700 muL.L-1, thus increasing the availability of DIC in the medium and enhancing the rate of photosynthesis. Doubled CO2 could enhance CO2 dissolution, lower pH values, and influence the ionization fractions of various DIC species even when the photosynthesis was not DIC limited. Consequently, HCO3- concentrations in cultures were significantly higher than in controls, and the photosynthetic energy cost for the operation of CO2 concentrating mechanism might decrease.

Iron and inorganic carbon in Liaodong Gulf sediments of Bohai Sea in China

Iron in seawater is an essential trace metal for phytoplankton that plays an important role in the marine carbon cycle. But most studies focused on oceanic iron fertilization in high nutrient low chlorophyll (HNLC) seawaters. A study of inorganic carbon (IC) forms and its influencing factors was presented in Liaodong Gulf sediments, and especially the influence of iron was discussed in detail. Inorganic carbon in Liaodong Gulf sediments was divided into five forms: NaCl, NH3·H2O, NaOH, NH2OH·HCl and HCl. The concentration of NaCl and NaOH forms were similar and they only occupied the minority of total inorganic carbon (TIC). However, NH3·H2O, NH2OH·HCl and HCl forms were the principal forms of TIC and accounted for more than 80% of TIC. Especially, the percentage of NH3·H2O form was much higher than that in the Changjiang River Estuary and Jiaozhou Bay sediments. All forms of inorganic carbon were influenced by organic carbon,pore water, iron, pH, redox potential(Eh) and sulfur potential(Es) in sediments, moreover, the influences had different characteristics for different IC forms. However, the redox reactions of iron affected mainly active IC forms. Iron had little effect on NH2OH·HCl and HCl forms of IC which were influenced mainly by pH. Iron had a stronger influence on NaCl, NaOH and NH3·H2O forms of IC; the influence of Fe2+ was higher than Fe3+ and its effect on NH3·H2O form was stronger than on NaCl and NaOH forms.

Forms and functions of inorganic carbon in the Jiaozhou Bay sediments

Inorganic carbon forms and their influencing factors, mutual transformation and contribution to carbon cycling in the Jiaozhou Bay sediments were discussed. The results show that inorganic carbon in sediments could be divided into five forms: NaCl form, NH3 center dot H2O form, NaOH form, NH2OH center dot HCl form and HCl form. Thereinto, NH2OH center dot HCl form and HCl form account for more than 70% of total inorganic carbon. There was close relationship among every form of inorganic carbon and their correlativity was clearly different with different sedimentary environment except the similar strong positive correlation among NH2OH center dot HCl form, HCl form and total inorganic carbon in all regions of the Jiaozhou Bay. All forms of inorganic carbon were influenced by organic carbon, pH, Eh, Es, nitrogen and phosphorus in sediments, but their influence had different characteristics in different regions. Every farm of inorganic carbon transformed into each other continuously during early diagenesis of sediments and the common phenomenon was that NaCl form, NH3 center dot H2O form, NaOH form and NH2OH center dot HCl form might transform into steady HCl form. NaCl form, NH3 center dot H2O form, NaOH form and NH2OH center dot HCl form could participate in carbon recycle and they are potential carbon source; HCl form may be buried for a long time in sediments, and it may be one of the final resting places of atmospheric CO2. Inorganic carbon which entered into sediments was about 4.98 x 10(10) g in the Jiaozhou Bay every year, in which about 1.47x10(10) g of inorganic carbon might be buried for a long time and about 3.51. x 10(10) g of inorganic carbon might return into seawater and take part in carbon recycling.

Determination for the different combined-form inorganic carbon in marine sediments

Marine sediment is the important sources and sinks of carbon. The inorganic carbon(IC) in marine sediments plays an important role in carbon cycling. In order to understand IC function in carbon cycling, sequential extraction method based on IC combined chemical strength difference were established to get five phases: NaCl phase (step I), NH3 - H2O phase (step II), NaOH phase (step III), NH2OH . HCl phase (step IV) and HCl phase(step V). The best extraction conditions were obtained by a series of experiments. Extractants were added into plastic centrifuge tubes in Step I - M, the capped tube were placed on a shaker table to keep the solids suspended for two hours. The suspended solution was separated by centrifugal, the residues were washed with water. The two supernatant were combined and the CO, was finally determined by volumetric analysis. The residues were transferred into conical flask in step IV and V, and then the extractants were added. The produced CO2 was adsorbed by saturated Ba(OH)(2) solution, and determined by volumetric analysis. This method for IC has a good precision in the analysis sediment samples.

Dissolved inorganic carbon and CO2 fluxes across Jiaozhou Bay air-water interface

On the basis of data collected in the Jiaozhou Bay in June and July 2003, the DIC distribution in seawater is studied, and an average air-sea flux of CO2 is estimated. The results show that the content of DIC inside the bay is markedly higher than outside the bay in June, but the content of DIC outside the bay is markedly higher than inside the bay in July. The trend of DIC distribution inside the bay is similar, viz. the content is the maximum in the northeast, then decreases gradually toward the west, and the content is the minimum in the west. The total trend of vertical distribution is to increase gradually from surface to bottom. This characteristic of DIC distribution is determined by Jiaozhou Bay hydrology and there is a close relation between DIC and particulate N,P. Average CO2 flux across the air-sea interface is 0.55 mol/(m(2.)a) in June and 0.72 mol/(m(2.)a) in July. Jiaozhou Bay is considered as a net annual source for atmospheric CO2 in June and July, and the total CO2 flux from seawater into atmosphere is about 740 t in June and 969 t in July.

A simple and accurate method for determining accurately dissolved inorganic carbon in seawaters

Dissolved inorganic carbon (DIC) account for more than 95% of total carbon in seawater, so it is necessary to make reliable and precise measurements of DIC to study marine carbon cycling. In order to establish a simple and speed method, an airproof device of gas extraction-absorption was designed. Finally a simple method was developed for the determination of DIC in seawater through a large mount of experiments. The determination procedure is as follows: 100 similar to 150 mL seawater was put into conical flask, then add 10% H3PO4, the DIC in seawater sample was dissolved to form CO2 gas and carried by pure N-2, then the CO2 gas was absorbed by two grades 0.1 mol/L NaOH solution. Finally the absorbed solution was titrated by HCl standard solution of 0.01000 mol/L with the end points detected with the indicator phenolphthalein and bromocresol green-methyl red mixture. The precision and accuracy of the method were satisfied. This method was used to analyse seawater samples from Jiaozhou bay in June, 2003. The result shows that the average DIC in surface seawater is 2066 mumol/L, DIC in bottom seawater is 2075 mumol/L inside bay, but the average DIC in surface seawater is 1949 mumol/L, DIC in bottom seawater is 2147 mumol/L outside bay.

Inorganic carbon of sediments in the Yangtze River Estuary and Jiaozhou Bay

JGOFS results showed that the ocean is a major sink for the increasing atmospheric carbon dioxide resulting from human activity. However, the role of the coastal seas in the global carbon cycling is poorly understood. In the present work, the inorganic carbon (IC) in the Yangtze River Estuary and Jiaozhou Bay are studied as examples of offshore sediments. Sequential extraction was used to divide inorganic carbon in the sediments into five forms, NaCl form, NH3 H2O form, NaOH form, NH2OH HCl form and HCl form. Studied of their content and influencing factors were also showed that NaCl form < NH3 H2O form < NaOH form < NH2OH HCl form < HCl form, and that their influencing factors of pH, Eh, Es, water content, organic carbon, organic nitrogen, inorganic nitrogen, organic phosphorus and inorganic phosphorus on inorganic carbon can be divided into two groups, and that every factor has different influence on different form or on the same form in different environment. Different IC form may transform into each other in the early diagenetic process of sediment, but NaCl form, NH3 H2O form, NaOH form and NH2OH HCl form may convert to HCl form ultimately. So every IC form has different contribution to carbon cycling. This study showed that the contribution of various form of IC to the carbon cycle is in the order of NaOH form > NH2OH HCl form > NH3 H2O form > NaCl form > HCl form, and that the contribution of HCl form contributes little to carbon cycling, HCl form may be one of end-result of atmospheric CO2. So Yangtze River estuary sediment may absorb at least about 40.96x10(11) g atmospheric CO2 every year, which indicated that offshore sediment play an important role in absorbing atmospheric CO2.