Photoelectrochemical reduction of CO2 mediated with methylviologen at roughened silver electrodes

The photoelectrocatalytic effect for the reduction of CO2 mediated with methylviologen (MV) was studied at mercury, polished silver and roughened silver electrodes using electrochemical and surface-enhanced Raman scattering (SERS) techniques. A large photoelectrocatalytic effect for the reduction of CO2 in the presence of MV was observed at the roughened silver electrode, whereas there was only a very small photoelectrocatalytic current at a more negative potential on mercury and polished silver electrodes. The SERS spectra of MV in the presence and absence of CO2, along with the electrochemical results, demonstrate that the surface adsorbed complexes, MV+ -Ag and MV0-Ag, played a role as the mediator for photoinduced electron transfer to CO2 in the solution. The results also suggest that the surface plasmon resonance of the nanoscale silver particle contributes to the overall photoelectrocatalytic effect on a roughened silver electrode.

Synthesis, crystal structure and magnetic properties of a series of polymeric lanthanoid-copper complexes [Ln(2)Cu(3){O(CH2-CO2)(2)}(6)].nH(2)O (Ln=La, Nd, n=9; Ln=Er, n=6)

The reaction of diglycolic acid, O(CH2CO2H)(2), with Cu(NO3)(2) . H2O and lanthanoid nitrate hydrate produces a series of novel Ln-Cu mixed metal complexes, [Ln(2)CU(3){O(CH2CO2)(2)}(6)]. nH(2)O (Ln = La, Nd, n = 9; Ln = Er, n = 6), which have been characterized by elemental analysis, i.r. spectroscopy, magnetic measurements and X-ray crystallography. The Ln(3+) and Cu2+ ions are connected by the carboxylate groups of the ligands, resulting in the formation of a complicated network.

Analysis of the sea-level variability along the Chinese coast and estimation of the impact of a CO2-perturbed atmospheric circulation

The relationship between monthly sea-level data measured at stations located along the Chinese coast and concurrent large-scale atmospheric forcing in the period 1960-1990 is examined. It is found that sea-level varies quite coherently along the whole coast, despite the geographical extension of the station set. A canonical correlation analysis between sea-level and sea-level pressure (SLP) indicates that a great part of the sea-level variability can be explained by the action of the wind stress on the ocean surface. The relationship between sea-level and sea-level pressure is analyzed separately for the summer and winter half-years. In winter, one factor affecting sea-level variability at all stations is the SLP contrast between the continent and the Pacific Ocean, hence the intensity of the winter Monsoon circulation. Another factor that affects coherently all stations is the intensity of the zonal circulation at mid-latitudes. In the summer half year, on the other hand, the influence of SLP on sea-level is spatially less coherent: the stations in the Yellow Sea are affected by a more localized circulation anomaly pattern, whereas the rest of the stations is more directly connected to the intensity of the zonal circulation. Based on this analysis, statistical models (different for summer and winter) to hindcast coastal sealevel anomalies from the large-scale SLP field are formulated. These models have been tested by fitting their internal parameters in a test period and reproducing reasonably the sea-level evolution in an independent period. These statistical models are also used to estimate the contribution of the changes of the atmospheric circulation on sea-level along the Chinese coast in an altered climate. For this purpose the ouput of 150 year-long experiment with the coupled ocean-atmosphere model ECHAM1-LSG has been analyzed, in which the atmospheric concentration of greenhouse gases was continuously increased from 1940 until 2090, according to the Scenario A projection of the Intergovermental Panel on Climate Change. In this experiment the meridional (zonal) circulation relevant for sea-level tends to become weaker (stronger) in the winter half year and stronger (weaker) in summer. The estimated contribution of this atmospheric circulation changes to coastal sea-level is of the order of a few centimeters at the end of the integration, being in winter negative in the Yellow Sea and positive in the China Sea with opposite signs in the summer half-year.

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.

Oceanic iron fertilization: one of strategies for sequestration atmospheric CO2

Carbon cycle is connected with the most important environmental issue of Global Change. As one of the major carbon reservoirs, oceans play an important part in the carbon cycle. In recent years, iron seems to give us a good news that oceanic iron fertilization could stimulate biological productivity as CO2 sink of human-produced CO2. Oceanic iron fertilization experiments have verified that adding iron into high nutrient low chlorophyll (HNLC) seawaters can increase phytoplankton production and export organic carbon, and hence increase carbon sink of anthropogenic CO2, to reduce global warming. In sixty days, the export organic carbon could reach 10 000 times for adding iron by model prediction and in situ experiment, i.e. the atmospheric CO2 uptake and inorganic carbon drawdown in upper seawaters also have the same magnitude. Therefore, oceanic iron fertilization is one of the strategies for increasing carbon sink of anthropogenic CO2. The paper is focused on the iron fertilization, especially in situ ocean iron experiments in order that the future research is more efficient.

A comparison of future increased CO2 and temperature effects on sympatric Heterosigma akashiwo and Prorocentrum minimum

Very little is known about how global anthropogenic changes will affect major harmful algal bloom groups. Shifts in the growth and physiology of HAB species like the raphidophyte Heterosigma akashiwo and the dinoflagellate Prorocentrum minimum due to rising CO2 and temperature could alter their relative abundance and environmental impacts in estuaries where both form blooms, such as the Delaware Inland Bays (DIB). We grew semi-continuous cultures of sympatric DIB isolates of these two species under four conditions: (1) 20 degrees C and 375 ppm CO2 (ambient control), (2)20 degrees C and 750 ppm CO2 (high CO2),(3) 24 degrees C and 375 ppm CO2 (high temperature), and (4) 24 degrees C and 750 ppm CO2 (combined). Elevated CO2 alone or in concert with temperature stimulated Heterosigma growth, but had no significant effect on Prorocentrum growth. P-Bmax (the maximum biomass-normalized light-saturated carbon fixation rate) in Heterosigma was increased only by simultaneous CO2 and temperature increases, whereas P-Bmax in Prorocentrum responded significantly to CO2 enrichment, with or without increased temperature. CO2 and temperature affected photosynthetic parameters alpha, Phi(max), E-k, and Delta F/F'(m) in both species. Increased temperature decreased and increased the Chl a content of Heterosigma and M Prorocentrum, respectively. CO2 availability and temperature had pronounced effects on cellular quotas of C and N in Heterosigma, but not in Prorocentrum. Ratios of C:P and N:P increased with elevated carbon dioxide in Heterosigma but not in Prorocentrum. These changes in cellular nutrient quotas and ratios imply that Heterosigma could be more vulnerable to N limitation but less vulnerable to P-limitation than Prorocentrum under future environmental conditions. In general, Heterosigma growth and physiology showed a much greater positive response to elevated CO2 and temperature compared to Prorocentrum, consistent with what is known about their respective carbon acquisition mechanisms. Hence, rising temperature and CO2 either alone or in combination with other limiting factors could significantly alter the relative dominance of these two co-existing HAB species over the next century. (c) 2007 Elsevier B.V. All rights reserved.

Role of the Jiaozhon Bay as a source/sink of CO2 over a seasonal cycle

The seasonal evolution of dissolved inorganic carbon (DIC) and CO2 air-sea fluxes in the Jiaozhou Bay was investigated by means of a data set from four cruises covering a seasonal cycle during 2003 and 2004. The results revealed that DIC had no obvious seasonal variation, with an average concentration of 2035 mu mol kg(-1) C in surface water. However, the sea surface partial pressure of CO2 changed with the season. pCO(2) was 695 mu atm in July and 317 mu atm in February. Using the gas exchange coefficient calculated with Wanninkhof's model, it was concluded that the Jiaozhou Bay was a source of atmospheric CO, in spring, summer, and autumn, whereas it was a sink in winter. The Jiaozhou Bay released 2.60 x 10(11) mmol C to the atmosphere in spring, 6.18 x 10(11) mmol C in summer, and 3.01 x 10(11) mmol C in autumn, whereas it absorbed 5.32 x 10(10) mmol C from the atmosphere in winter. A total of 1.13 x 10(11) mmol C was released to the atmosphere over one year. The behaviour as a carbon source/sink obviously varied in the different regions of the Jiaozhou Bay. In February, the inner bay was a carbon sink, while the bay mouth and the Outer bay were carbon sources. In June and July, the inner and Outer bay were carbon sources, but the strength was different, increasing from the inner to the outer bay. In November, the inner bay was a carbon source, but the bay Mouth was a carbon sink. The outer bay was a weaker CO2 Source. These changes are controlled by many factors, the most important being temperature and phytoplankton. Water temperature in particular was the main factor controlling the carbon dioxide system and the behaviour of the Jiaozhou Bay as a carbon source/sink. The Jiaozhou Bay is a carbon dioxide source when the water temperature is higher than 6.6 degrees C. Otherwise, it is a carbon sink. Phytoplankton is another controlling factor that may play an important role in behaviour as a carbon source or sink in regions where the source or sink nature is weaker.

青藏高原高寒灌丛暖季CO2地-气交换特征

利用涡度相关技术对青藏高原高寒灌丛CO2通量进行连续观测,并以2003年7、8月份为例,对高寒灌丛暖季CO2通量变化模式及其主要气候影响因子进行了分析.结果表明,7、8月青藏高原高寒灌丛日平均净生态系统CO2交换(NEE)分别为-7.17,-7.26g/(m2•d);最高日NEE分别为-11.00,-12.09g/(m2•d).暖季高寒灌丛生态系统NEE日变化波动极为明显,8:00～19:00为CO2净吸收阶段,峰值一般出现在12:00左右,最大值为-1.72g/(m2•h)(7月份)、-1.63g/(m2•h)(8月份).19:00～次日8:00为CO2净释放,最大值为0.69g/(m2•h)(7月份)、0.86g/(m2•h)(8月份).在主要气候因子中,光合有效辐射(PAR)与NEE变化呈显著正相关,但PAR达到1000μmol/(m2•s)以后,随着PAR进一步升高,NEE有下降趋势.就温度而言,白昼(7:00～20:00)NEE变化与温度无显著关联,而夜间(21:00～次日6:00)温度与NEE变化呈显著正相关.

高寒草甸土壤有机碳储量和CO2通量

选择青藏高原东北隅海北站区的4种高寒草甸土壤进行高分辨率采样，测定土壤有机碳及其^14C信号；应用^14C示踪技术探讨高寒草甸土壤有机碳更新周期和CO2通量．研究得出海北站高寒草甸生态系统土壤有机碳储量在22．12×10^4～30．75×10^4kgC•hm^-2之间，平均为26．86×10^4kgC•hm^2．高寒草甸土壤有机碳的更新周期从表层的45～73a随深度增加到数百年甚至数千年或更长．高寒草甸生态系统土壤呼吸的CO2通量变化于103．24—254．93gC•m^-2•a^-1之间，平均为191．23gC•m^-2•a^-1．土壤有机质分解产生的CO2通量变化于73．3～181gC•m^-2•a^-1之间．矮嵩草草甸土壤30％以上的有机碳贮存在土壤表层（0～10cm）的活动碳库中，土壤有机质更新产生的CO2占整个剖面有机质更新产生的CO2通量的72．8％～81．23％．响应于全球变暖，青藏高原高寒草甸生态系统土壤有机碳的储量、流量、归宿变化等问题有待进一步研究．

草毡寒冻雏形土有机质补给、分解及大气CO2通量交换

调查草毡寒冻雏形土生物量及土壤有机质,利用涡度相关技术观测该区域作用层与大气CO2通量.结果表明：地下90%生物量集中于0～10 cm的表土层,年总净初级生产量约935.0 g/m2;土壤有机质含量在6.401～7.060%之间;净CO2通量呈明显的日变化和季节变化规律;5月中旬到9月底为CO2的净吸收（780 g CO2/m2）,其中以7月最高,净吸收量明显高于非生长季的,10月到翌年5月初CO2的净排放量（383 g CO2/m2）;全年固定碳高达397 g/m2.