Impact of the Eastern Mediterranean Transient on the distribution of anthropogenic CO2 and first estimate of acidification for the Mediterranean Sea

In the Mediterranean Sea the carbon chemistry is poorly known. However, the impact of the regional and large-scale anthropogenic pressures on this fragile environment rapidly modifies the distribution of the carbonate system key properties like C_T (total dissolved inorganic carbon), A_T (total alkalinity), C_ANT (anthropogenic CO₂), and pH. This leads inexorably to the acidification of its waters. In order to improve our knowledge, we first develop interpolation procedures to estimate C_T and A_T from oxygen, salinity, and temperature data using all available data from the EU/MEDAR/MEDATLAS II database. The acceptable levels of precision obtained for these estimates (6.11 ??mol-kg⁻¹ for C_T and 6.08 ??mol kg⁻¹ for A_T) allow us to draw the distribution of C_ANT (with an uncertainty of 6.75 ??mol kg⁻¹) using the Tracer combining Oxygen, inorganic Carbon, and total Alkalinity (TrOCA) approach. The results indicate that: 1) all Mediterranean water bodies are contaminated by anthropogenic carbon; 2) the lowest concentration of C_ANT is 37.5 ??mol kg⁻¹; and 3) the western basin is more contaminated than the Eastern basin. After reconstructing the distribution of key properties (C_T, A_T, C_ANT) for four periods of time (between 1986 and 2001) along a west-east section throughout the whole Mediterranean Sea, we analyze the impact of the Eastern Mediterranean Transient (EMT). Not only has the concentration of C_ANT increased (especially in the intermediate and the bottom layers of the eastern basin, during and after the EMT), but also the distribution of all properties has been considerably perturbed. This is discussed in detail. For the first time, the level of acidification is estimated for the Mediterranean Sea. Our results indicate that for the year 2001 all waters (even the deepest) have been acidified by values ranging from −0.14 to −0.05 pH unit since the beginning of the industrial era, which is clearly higher than elsewhere in the open ocean. Given that the pH of seawater may affect a very large number of chemical and biological processes, our results stress the necessity to develop new programs of research to understand and then predict the evolution of the carbonate system properties in the Mediterranean Sea.     

Transient Eastern Mediterranean deep waters in response to the massive dense-water output of the Aegean Sea in the 1990s

We present a detailed account of the changing hydrography and the large-scale circulation of the deep waters of the Eastern Mediterranean (EMed) that resulted from the unique, high-volume influx of dense waters from the Aegean Sea during the 1990s, and of the changes within the Aegean that initiated the event, the so-called ‘Eastern Mediterranean Transient’ (EMT). The analysis uses repeated hydrographic and transient tracer surveys of the EMed in 1987, 1991, 1995, 1999, and 2001/2002, hydrographic time series in the southern Aegean and southern Adriatic Seas, and further scattered data. Aegean outflow averaged nearly 3 × 10⁶ m³ s⁻¹ between mid-1992 and late 1994, and was largest during 1993, when south and west of Crete Aegean-influenced deep waters extended upwards to 400 m depth. EMT-related Aegean outflow prior to 1992, confined to the region around Crete and to 1800 m depth-wise, amounted to about 3% of the total outflow. Outflow after 1994 up to 2001/2002, derived from the increasing inventory of the tracer CFC-12, contributed 20% to the total, of 2.8 × 10¹⁴ m³. Densities in the southern Aegean Sea deep waters rose by 0.2 kg/m³ between 1987 and 1993, and decreased more slowly thereafter. The Aegean waters delivered via the principal exit pathway in Kasos Strait, east of Crete, propagated westward along the Cretan slope, such that in 1995 the highest densities were observed in the Hellenic Trench west of Crete. Aegean-influenced waters also crossed the East Mediterranean Ridge south of Crete and from there expanded eastward into the southeastern Levantine Sea. Transfer into the Ionian mostly followed the Hellenic Trench, largely up to the trench’s northern end at about 37°N. From there the waters spread further west while mixing with the resident waters. Additional transfer occurred through the Herodotus Trough in the south. Levantine waters after 1994 consistently showed temperature–salinity (T–S) inversions in roughly 1000–1700 m depth, with amplitudes decreasing in time. The T–S distributions in the Ionian Sea were more diverse, one cause being added Aegean outflow of relatively lower density through the Antikithira Strait west of Crete. Spreading of the Aegean-influenced waters was quite swift, such that by early 1995 the entire EMed was affected. and strong mixing is indicated by near-linear T–S relationships observed in various places. Referenced to 2000 and 3000 dbar, the highest Aegean-generated densities observed during the event equaled those generated by Adriatic Sea outflow in the northern Ionian Sea prior to the EMT. A precarious balance between the two dense-water source areas is thus indicated. A feedback is proposed which helped triggering the change from a dominating Adriatic source to the Aegean source, but at the same time supported the previous long-year dominance of the Adriatic. The EMed deep waters will remain transient for decades to come.     

Anthropogenic CO2 fluxes in the Otranto Strait (E. Mediterranean) in February 1995

This study presents the distribution and fluxes of dissolved inorganic carbon (C_T), total alkalinity (A_T) and anthropogenic carbon (C_ant) along the Otranto strait, during February 1995. Based on a limited number of properties (temperature, dissolved oxygen, total alkalinity and dissolved inorganic carbon), the composite tracer TrOCA was used to estimate the concentration of anthropogenic CO₂ in the Otranto strait.Total alkalinity exhibits high values and weak variability throughout the water column of the strait, probably associated with the dense water formation processes in the Adriatic basin that induce a rapid transport of the coastal alkalinity to the deep waters. Elevated C_ant concentrations and high anthropogenic pH variations are observed in the bottom layer of the strait, associated with the presence of Adriatic Deep Water (ADW). The study shows that large amounts of C_ant have penetrated the highly alkaline Eastern Mediterranean waters, thereby causing a significant pH reduction since the pre-industrial era.Estimates of the transports of C_T and C_ant through the strait indicate that during February 1995, the Adriatic Sea imports through the Otranto strait natural and anthropogenic carbon and acts as a net sink of carbon for the Ionian Sea. The anthropogenic carbon that is imported to the Adriatic Sea represents less than 1% of the net C_T inflow. The Levantine Intermediate Water (LIW) contributes to about one-third of the total C_T and C_ant inflow. Although the amounts of C_ant annually transported by LIW and ADW are almost equal, the contribution of C_ant to the C_T transported by each water mass is slightly higher in ADW (3.1%) than in LIW (2.6%), as a result of its higher mean C_ant concentration. The ADW, despite its weak contribution to the total outflow of C_ant, has a vital role for the sequestration and storage of the anthropogenic carbon, as this water mass is the main component of the Eastern Mediterranean Deep Waters and, thus, the anthropogenic CO₂ is transferred in the deep horizons of the Eastern Mediterranean, where it remains isolated for many years.     

Assessments of anthropogenic CO2 distribution in the tropical Atlantic Ocean

With a limited number of properties (salinity, temperature, total dissolved inorganic carbon, total alkalinity, and oxygen) from a recent cruise in the tropical Atlantic Ocean, we use the simple and recent approach TrOCA (Tracer combining Oxygen, inorganic Carbon, and total Alkalinity) to estimate the distribution of anthropogenic CO₂ along three latitudinal sections. In order to assess the quality of the anthropogenic CO₂ distribution, results from the method are compared to the CFC-11 measurements. We discuss the large-scale distribution of the main water masses of the tropical Atlantic Ocean in the light of the anthropogenic CO₂ and the CFC-11 distributions. Keeping in mind that the anthropogenic CO₂ emission began 60 years earlier than that of CFC-11, the former provides new insight on the local circulation and efficiency of the tropical waters to store the atmospheric carbon.     

CO2 exchange at air-sea interface in the Huanghai Sea

INTRODUCTIONTheroleoftheoceaniscrucialintheoverallcycleofCOZ,withitsspecialpumpingmechanismssuchassolubilitypumpingattheair-seainterfacewithcarbonatechemistry,biologicalpumpinginsurfacewatersandalsointhewatercolumn,anddynamicpumpingassociatedwithoceancirculation(BroeckerandPeng,1982).Inordertounderstandthesevariouspumpingprocessesintheocean,muchresearchhasbeencarriedoutonaglobalscaleasapartofeffortstounderstandtheglobalgeochemicalcycleofCOZ.TheHuanghaiSea,atypicalmid-latitudeepicontine…     

Carbonate chemistry and the anthropogenic CO2 in the South China Sea

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Accumulation of total CO2 during stagnation in the Baltic Sea deep water and its relationship to nutrient and oxygen concentrations

Accumulation of total CO₂ (C_T) was investigated in the sub-halocline deep water of the Gotland Sea (Baltic Sea) during a period of stagnation from 1995 to 1999. Depth profiles for C_T, nitrate, phosphate, and oxygen were measured during seven cruises in a grid consisting of 26 stations. The mean C_T increased by more than 60 μmol/kg from October 1995 to July 1999 corresponding to a mean accumulation rate of 1.1 mol/m² year. Taking into account vertical mixing, the vertical distribution of the C_T accumulation was used to determine mineralization rates at different depths. High rates immediately below the halocline indicated the existence of a fraction of organic matter, which is rapidly mineralized during sinking through the water column. A second fraction is more refractive and accumulates at the sediment surface in the deep center of the basin where it is slowly mineralized and partly buried. Phosphate release rates in anoxic waters and especially at the redoxcline were substantially higher than those estimated on the basis of the carbon mineralization and the Redfield C/P ratio. This is attributed to non-Redfield mineralization ratios and the dissolution of iron oxide/phosphate associates. The formation of nitrate by mineralization under oxic conditions was almost completely compensated by denitrification. Using the carbon mineralization rates and a C/N ratio of 8.4, a denitrification rate of 280 mmol/m² year was obtained, which approximately balances the input of nitrate/ammonia into the surface water. Relating the apparent oxygen utilization (AOU) to the C_T fraction that was generated by mineralization yielded a carbon mineralization/O₂ consumption ratio of 0.83.     

Long-term numerical evolution of the nitrogen bulk content in the Mediterranean Sea

The behavior of the Mediterranean ecosystem in response to realistic riverine inputs and dissolved matter exchange is investigated. The strategy is to evaluate the stability of the ecosystem subjected to various atmospheric inputs.     

东海陆架盆地CO2地质封存适宜性评价

温室气体过量排放引起了明显的全球气候变化及诸多次生灾害,CO2捕集与地质封存技术应运而生。中国东海沿岸CO2排放源众多,但陆上盆地面积狭小,无法满足巨量CO2封存的需求。根据相关学者做出的中国全海域级碳封存适宜性评价,东海陆架盆地在中国近海盆地中碳封存适宜性排名第3,面积宽广且封闭性好,因此,在此基础上对东海陆架盆地开展了盆地级碳封存适宜性评价。结合专家意见和相关学者研究成果,利用模糊综合评价法和层级分析法确立了适宜性评价指标体系及指标权重,再根据盆地内各二级构造单元的相关地质资料,按照评价指标分级赋分表对各单元的每个评价指标进行评分,结合权重计算出综合适宜性评分。综合考虑碳封存容量、封闭性及可操作性的评价结果认为,台北坳陷为盆地中碳封存综合适宜性最好的单元,可作为优先实验性封存区。     

Long-term comparison of macrobenthos within the soft bottoms of the Bay of Banyuls-sur-mer (northwestern Mediterranean Sea)

The macrofauna present at seven of the stations within the Bay of Banyuls-sur-mer (northwestern Mediterranean) initially sampled by Guille during the late 1960s was reassessed in 1994, using the same gear and techniques as those used during the reference study. Results showed an increase both in the number of species and of individuals (all species pooled) per unit of surface area at nearly all stations. This trend was not significant for total biomass. The most important changes were linked to the increase of the polychaete Ditrupa arietina (both within the Spisula subtruncata and the Nephtys hombergii community) and the decrease of the polychaetes Scoloplos armiger and Notomastus latericeus within the Scoloplos armiger community. The possible causes underlying these changes are discussed. The most probable cause is considered to be a slight modification of sediment composition (decrease of fine material in the sediment) within the Spisula subtruncata, the Nephtys hombergii and the Scoloplos armiger communities. Temporal changes in (1) Rhone river input, (2) small coastal river inputs, and (3) frequency of easterly storms may all have contributed to such a decrease.     

Seasonal and interannual variability of the air–sea CO2 flux in the Atlantic sector of the Barents Sea

The seasonal and interannual variability of the air–sea CO₂ flux (F) in the Atlantic sector of the Barents Sea have been investigated. Data for seawater fugacity of CO₂ (fCO₂^sw) acquired during five cruises in the region were used to identify and validate an empirical procedure to compute fCO₂^sw from phosphate (PO₄), seawater temperature (T), and salinity (S). This procedure was then applied to time series data of T, S, and PO₄ collected in the Barents Sea Opening during the period 1990–1999, and the resulting fCO₂^sw estimates were combined with data for the atmospheric mole fraction of CO₂, sea level pressure, and wind speed to evaluate F.The results show that the Atlantic sector of the Barents Sea is an annual sink of atmospheric CO₂. The monthly mean uptake increases nearly monotonically from 0.101 mol C m^− 2 in midwinter to 0.656 mol C m^− 2 in midfall before it gradually decreases to the winter value. Interannual variability in the monthly mean flux was evaluated for the winter, summer, and fall seasons and was found to be ± 0.071 mol C m^− 2 month^− 1. The variability is controlled mainly through combined variation of fCO₂^sw and wind speed. The annual mean uptake of atmospheric CO₂ in the region was estimated to 4.27 ± 0.68 mol C m^− 2.     

Distributions and air-sea fluxes of CO2 in the summer Bering Sea

The 3rd Chinese National Arctic Research Expedition(CHINARE–Arctic III) was carried out from July to September in 2008. The partial pressure of CO2(pCO2) in the atmosphere and in surface seawater were determined in the Bering Sea during July 11–27, 2008, and a large number of seawater samples were taken for total alkalinity(TA) and total dissolved inorganic carbon(DIC) analysis. The distributions of CO2 parameters in the Bering Sea and their controlling factors were discussed. The pCO2 values in surface seawater presented a drastic variation from 148 to 563 μatm(1 μatm = 1.013 25×10-1 Pa). The lowest pCO2 values were observed near the Bering Sea shelf break while the highest pCO2 existed at the western Bering Strait. The Bering Sea generally acts as a net sink for atmospheric CO2 in summer. The air-sea CO2 fluxes in the Bering Sea shelf, slope, and basin were estimated at-9.4,-16.3, and-5.1 mmol/(m2·d), respectively. The annual uptake of CO2 was about 34 Tg C in the Bering Sea.     

Time-series of surface water CO2 and oxygen measurements on a platform in the central Arkona Sea (Baltic Sea): Seasonality of uptake and release

High resolution measurements of carbon dioxide and oxygen were made in surface waters of the central Arkona Sea (Baltic Sea) from May 2003 to September 2004. Sensors for CO₂ partial pressure (pCO₂^w) and oxygen (O₂) concentration were mounted in 7 m depth on a moored platform which is used for hydrographic and meteorological monitoring. The pCO₂^w data were obtained in half hour intervals and O₂ was measured each hour as an average of a 10 min measurement. To check the performance of the sensors, pCO₂^w and O₂ were determined by shipboard measurements on a research vessel which visited the site in 1–2 month intervals. In addition, pCO₂^w was measured on a “volunteer observing ship” (VOS) passing the platform each second day at a distance of about 25 km. Minima of 220 to 250 μatm of pCO₂^w were observed at the time of the spring bloom and a cyanobacteria bloom in mid-summer. During winter the pCO₂^w was mostly close to equilibrium with the atmosphere but maxima of 430 to 530 μatm were also observed. The seasonality of oxygen and pCO₂^w showed an opposing pattern. From a multiple regression analysis, we concluded that two processes primarily controlled pCO₂^w during our study: biological turnover and mixing. A parameterization, based on apparent oxygen utilisation (AOU) and salinity (S) only (pCO₂^w = 1.23 AOU + 43 S), reproduced the seasonality of pCO₂^w in surface water reasonably well. Based on our pCO₂, salinity, and temperature data set, we attempted to separate processes changing total inorganic carbon concentrations (C_T) by using an alkalinity–salinity relation for the area. The contribution of CO₂ gas exchange and mixing were calculated and from this the biological turnover was deduced to reveal the calculated C_T changes.The net annual uptake of CO₂ in the central Arkona Sea was estimated to be about 1.5 Tg (1.5·10¹² g) which was approximately balanced by a net oxygen release considering the uncertainties of the flux calculations. Near-coast CO₂ emission due to episodic upwelling partly compensated the uptake of the central part of the Arkona Sea reducing the overall magnitude of the CO₂ uptake.     

CO2 in the Weddell Gyre and Antarctic Circumpolar Current: austral autumn and early winter

Quasi-continuous fugacity of CO₂ (fCO₂) data were collected in the eastern Weddell Gyre and southern Antarctic Circumpolar Current (ACC) of the Southern Ocean during austral autumn 1996. Full depth Total CO₂ (TCO₂) sections are presented for austral autumn and winter (1992) cruises. Pronounced fCO₂ gradients were observed at the Southern Ocean fronts. In the Weddell Gyre, fCO₂ regimes appeared to coincide with surface and subsurface hydrographic regimes. The southern ACC was supersaturated with respect to CO₂, as was part of the northern Weddell Gyre. The southern Weddell Gyre was markedly undersaturated. The great potential of autumn cooling for generating undersaturation and CO₂ uptake from the atmosphere was demonstrated. In the northeastern Weddell Gyre, upwelling of CO₂- and salt-rich deep water was shown to play a role as the horizontal fCO₂ distribution closely resembled that of the surface salinity. The total uptake of atmospheric CO₂ by the Weddell Gyre in autumn (45 days) was calculated to be 7·10¹² g C. The deep TCO₂ distribution noticeably reflected the different water masses in the region. A new deep TCO₂ maximum was detected in the ACC, which apparently characterizes the boundary between the equatorward flowing Antarctic Bottom Water (AABW) and the Circumpolar Deep Water (CDW). East of the Weddell Gyre, the AABW stratum is much thicker (>2000 m) than more to the west, on the prime meridian (<300 m).     

1990s年代际转型前后南海季风系统的季节变化

利用多变量经验正交分解(MV-EOF)等方法,研究了在季节变化尺度上南海季风系统的时空分布特征。结果表明:南海夏季风的爆发时间在1993—1994年前后存在显著的年代际转型,由爆发偏晚转变成爆发偏早。第一模态表现为冬夏反位相的年周期变化,但爆发早年夏季风持续时间略长于爆发晚年,空间上都反映了南海中央海盆区的夏季强降水和850 hPa上南海北部的气旋性环流异常,但夏季风爆发早年中国华南沿海降水加强而南海南部降水偏少。相应的大范围环流场上主要反映了南海夏季风爆发后进入盛夏时节亚太地区大范围的环流特征,南海夏季风爆发偏早年索马里越赤道气流偏强,东亚季风槽位置偏北,爆发偏晚年则相反。第二模态反映了南海季风系统春秋反位相的季节变化,且秋季的振幅更强,空间降水场上对应着秋季华南沿海和南海北部与南海中南部北旱南涝的跷跷板式分布,850 hPa风场上则主要表现为异常的东北季风,该模态时空特征表明南海夏季风爆发偏早年的秋季,冬季风建立也偏早,越南及周边地区的降水偏多。相应的大范围环流场上则主要反映了冬季风的环流特征,在南海夏季风爆发偏早年的秋季,菲律宾以东的热带对流减弱,PJ波列增强,爆发晚年则相反。     

中国南海、东海及黄海海域海气二氧化碳通量与生产力的物理生物地球化学模拟研究

Marginal seas play important roles in regulating the global carbon budget, but there are great uncertainties in estimating carbon sources and sinks in the continental margins. A Pacific basin-wide physical-biogeochemical model is used to estimate primary productivity and air-sea CO_2 flux in the South China Sea(SCS), the East China Sea(ECS), and the Yellow Sea(YS). The model is forced with daily air-sea fluxes which are derived from the NCEP2 reanalysis from 1982 to 2005. During the period of time, the modeled monthly-mean air-sea CO_2 fluxes in these three marginal seas altered from an atmospheric carbon sink in winter to a source in summer. On annualmean basis, the SCS acts as a source of carbon to the atmosphere(16 Tg/a, calculated by carbon, released to the atmosphere), and the ECS and the YS are sinks for atmospheric carbon(–6.73 Tg/a and –5.23 Tg/a, respectively,absorbed by the ocean). The model results suggest that the sea surface temperature(SST) controls the spatial and temporal variations of the oceanic pCO_2 in the SCS and ECS, and biological removal of carbon plays a compensating role in modulating the variability of the oceanic pCO_2 and determining its strength in each sea,especially in the ECS and the SCS. However, the biological activity is the dominating factor for controlling the oceanic pCO_2 in the YS. The modeled depth-integrated primary production(IPP) over the euphotic zone shows seasonal variation features with annual-mean values of 293, 297, and 315 mg/(m~2·d) in the SCS, the ECS, and the YS, respectively. The model-integrated annual-mean new production(uptake of nitrate) values, as in carbon units, are 103, 109, and 139 mg/(m~2·d), which yield the f-ratios of 0.35, 0.37, and 0.45 for the SCS, the ECS, and the YS, respectively. Compared to the productivity in the ECS and the YS, the seasonal variation of biological productivity in the SCS is rather weak. The atmospheric pCO_2 increases from 1982 to 2005, which is consistent with the anthropogenic CO_2 input to the atmosphere. The oceanic pCO_2 increases in responses to the atmospheric pCO_2 that drives air-sea CO_2 flux in the model. The modeled increase rate of oceanic pCO_2 is0.91 μatm/a in the YS, 1.04 μatm/a in the ECS, and 1.66 μatm/a in the SCS, respectively.     

Increase of anthropogenic CO2 in the Pacific Ocean over the last two decades

The multiple-parameter linear regression method (Monitoring global ocean carbon inventories. Ocean Observing System Development Panel, Texas A&M University, College Station, TX, 1995, 54pp; Global Biogeochem. Cycles 13 (1999) 179) is used to compare inorganic carbon data from the GEOSECS CO₂ survey in the Pacific Ocean in 1973 to the WOCE/JGOFS global CO₂ survey in the 1990s. A model of total dissolved inorganic carbon (DIC) as a function of five variables (AOU, θ, S, Si, and PO₄) has been developed from the recent CO₂ survey data (namely CGC91 and CGC96) in the Pacific Ocean. After correcting for a systematic DIC offset of −30.3±7 μmol kg⁻¹ from the GEOSECS data, the residual DIC based on this model as computed from GEOSECS data has been used to estimate the anthropogenic CO₂ penetration in the Pacific Ocean. In the Northeast Pacific, we obtained an increase of CO₂ of 21.3±7.9 mol m⁻² over the period from GEOSECS in 1973 to CGC91 in 1991. This gives a mean anthropogenic CO₂ uptake rate of 1.3±0.5 mol m⁻² yr⁻¹ over this 17 year time period. In the South Pacific, north of 50°S between 180° and 120°W region, the integrated anthropogenic CO₂ inventory is estimated to be 19.7±5.7 mol m⁻² over the period from GEOSECS in 1974 to CGC96 in 1996. The equivalent mean CO₂ uptake rate is estimated to be 0.9±0.3 mol m⁻² yr⁻¹ over the 22 years. These results are compared with the isopycnal method (Nature 396 (1998) 560) to estimate the anthropogenic CO₂ signal in the Northeast Pacific (30°N, 152°W) at the crossover region between CGC91 and GEOSECS. The results of the isopycnal method are consistent with those derived from the MLR method. Both methods show an increase in anthropogenic CO₂ inventory in the ocean over two decades that is consistent with the increase expected if the ocean uptake has kept pace with the atmospheric CO₂ increase.     

南海东北部春季海表pCO_2分布及海-气CO_2通量

2013年南海东北部春季共享航次采用走航观测方式,现场测定了表层海水和大气的二氧化碳分压(pCO2)及相应参数。结合水文、化学等同步观测要素资料,对该海域pCO2的分布变化进行了探讨。结果表明,陆架区受珠江冲淡水、沿岸上升流及生物活动的影响,呈现CO2的强汇特征;吕宋海峡附近及吕宋岛西北附近海域受海表高温、黑潮分支"西伸"、吕宋岛西北海域上升流等因素影响,呈现强源特征。根据Wanninkhof的通量模式,春季整个南海东北部海域共向大气释放约4.25×104 t碳。