Transfer of carbon dioxide and methane through the soil‐water‐atmosphere system at Mer Bleue peatland,Canada

Surface waters associated with peatlands, supersaturated with CO₂ and CH₄ with respect to the atmosphere, act as important pathways linking a large and potentially unstable global repository of C to the atmosphere. Understanding the drivers and mechanisms which control C release from peatland systems to the atmosphere will contribute to better management and modelling of terrestrial C pools. We used non‐dispersive infra‐red (NDIR) CO₂ sensors to continuously measure gas concentrations in a beaver pond at Mer Bleue peatland (Canada); measurements were made between July and August 2007. Concentrations of CO₂ in the surface water (10 cm) reached 13 mg C l^?1 (epCO₂ 72), and 26 mg C l^?1 (epCO₂ 133) at depth (60 cm). The study also showed large diurnal fluctuations in dissolved CO₂ which ranged in amplitude from ～1·6 mg C l^?1 at 10 cm to ～0·2 mg C l^?1 at 60 cm depth. CH₄ concentration and supersaturation (epCH₄) measured using headspace analysis averaged 1·47 mg C l^?1 and 3252, respectively; diurnal cycling was also evident in CH₄ concentrations. Mean estimated evasion rates of CO₂ and CH₄ over the summer period were 44·92 ± 7·86 and 0·44 ± 0·25 µg C m^?2s^?1, respectively. Open water at Mer Bleue is a significant summer hotspot for greenhouse gas emissions within the catchment. Our results suggest that CO₂ concentrations during the summer in beaver ponds at Mer Bleue are strongly influenced by biological processes within the water column involving aquatic plants and algae (in situ photosynthesis and respiration). In terms of carbon cycling, soil‐stream connectivity at this time of year is therefore relatively weak. Copyright © 2008 John Wiley & Sons, Ltd.     

Carbon dioxide,methane, and dissolved carbon dynamics in an urbanized river system

Estimates of greenhouse gas evasion from rivers have been refined over the past decades to constrain their role in global carbon cycle processes. However, despite 55% of the human population living in urban areas, urban rivers have had limited attention. We monitored carbon dynamics in an urbanized river (River Kelvin, 331 km², UK) to explore the drivers of dissolved carbon lateral and vertical export. Over a 2-year sampling period, riverine methane (CH₄) and carbon dioxide (CO₂) concentrations were consistently oversaturated with respect to atmospheric equilibria, leading to continual degassing to the atmosphere. Carbon stable isotopic compositions (δ¹³C) indicated that terrestrially derived carbon comprised most of the riverine CH₄ and dissolved CO₂ (CO₂*) load while dissolved inorganic carbon (DIC) from groundwater was the main form of riverine DIC. The dynamics of CH₄, CO₂*, and DIC in the river were primarily hydrology-controlled, that is, [CH₄] and [CO₂*] both increased with elevated discharge, total [DIC] decreased with elevated discharge while the proportion of biologically derived DIC increased with increasing discharge. The concentration of dissolved organic carbon (DOC) showed a weak relationship with river hydrology in summer and autumn and was likely influenced by the combined sewer overflows. Carbon emission to the atmosphere is estimated to be 3.10 ± 0.61 kg C·m⁻²·yr⁻¹ normalized to water surface area, with more than 99% emitted as CO₂. Annual carbon loss to the coastal estuary is approximately 4.69 ± 0.70 Gg C yr⁻¹, with annual DIC export approximately double that of DOC. Per unit area, the River Kelvin was a smaller carbon source to the atmosphere than natural rivers/streams but shows elevated fluxes of DIC and DOC under comparable conditions. This research illustrates the role urban systems may have on riverine carbon dynamics and demonstrates the potential tight link between urbanization and riverine carbon export.     

Impact of Hurricane Irene and Tropical Storm Lee on riparian zone hydrology and biogeochemistry

Although riparian zones are well known to reduce nitrogen (N) and phosphorus (P) runoff to streams, they also have the potential to affect greenhouse gas (CO₂, N₂O, and CH₄) fluxes to the atmosphere. Following large storms, soil biogeochemical conditions often become more reduced, especially in oxbow depressions and side channels, which can lead to hot moments of greenhouse gas production. Here, we investigate the impact of the remnants of Hurricane Irene and Tropical Storm Lee on riparian zone hydrology (water table: WT), and biogeochemistry (oxidation‐reduction potential [ORP], dissolved oxygen [DO], NO₃^?, PO₄^3?, CO₂, N₂O, CH₄). Results indicate that large storms have the potential to reset WT levels for weeks to months. Overbank flooding at our site following Irene and Lee led to the infiltration of well‐oxygenated water at depth (higher DO and ORP) while promoting the development of anoxic conditions within soil aggregates near the soil surface (increased N₂O and CH₄ fluxes). A short‐term increase in CO₂ emission was observed following Irene at our site where aerobic respiration was water‐limited. Over a 2‐year period, an oxbow depression exhibited higher WT, higher N₂O and CH₄ fluxes (hot moment), higher CO₂ fluxes (seasonal), and lower NO₃^? concentrations (seasonal) than the rest of the riparian zone. However, neither Irene, nor Lee, nor the oxbow depression significantly impacted PO₄^3?. Dissolved organic carbon, ORP, and DO data illustrate the time‐lag (>20 years) between the creation of an oxbow depression and the development of reducing conditions despite clear differences in riparian zone and oxbow WT dynamics.     

城市景观湖泊不同时间尺度CH4通量特征及影响因素分析——以南京市莫愁湖为例

城市景观湖泊对温室气体的收支发挥着重要作用。本文以南京市莫愁湖为研究对象,采用静态箱—温室气体分析仪法实时监测湖泊水—气界面CH₄通量,分析湖泊主要温室气体CH₄在日尺度和季节尺度上因冒泡和扩散排放方式不同对其通量的影响,探究影响湖泊CH₄通量的因素。结果表明:(1)在日尺度上,四季24 h内CH₄均呈排放状态,受白天冒泡影响,四季CH₄总通量均存在白天高于夜间的日变化特征。(2)在季节尺度上,莫愁湖CH₄排放通量呈现显著的时空异质性,受冒泡通量的影响夏季CH₄通量明显高于春、秋、冬三季;B区的CH₄总通量(6.04 nmol/(m²·s))显著高于A区(3.82 nmol/(m²·s)),水体的营养化程度和离岸距离是空间变化的主要影响因素。A、B两区CH₄排放夏季以冒泡排放为主,春、秋、冬以扩散排放为主。(3)在日尺度上,CH₄     

The fluvial flux of particulate organic matter from the UK: the emission factor of soil erosion

Soil erosion has been identified as a potential global carbon sink since eroded organic matter is replaced at source and eroded material is readily buried. However, this argument has relied on poor estimates of the total fate of in‐transit particulates and could erroneously imply soil erosion could be encouraged to generate carbon stores. These previous estimates have not considered that organic matter can also be released to the atmosphere as a range of greenhouse gases, not only carbon dioxide (CO₂), but also the more powerful greenhouse gases methane (CH₄) and nitrous oxide (N₂O). As soil carbon lost by erosion is only replaced by uptake of CO₂, this could represent a considerable imbalance in greenhouse gas warming potential, even if it is not significant in terms of overall carbon flux. This work therefore considers the flux of particulate organic matter through UK rivers with respect to both carbon fluxes and greenhouse gas emissions. The results show that, although emissions to the atmosphere are dominated by CO₂, there are also considerable fluxes of CH₄ and N₂O. The results suggest that soil erosion is a net source of greenhouse gases with median emission factors of 5.5, 4.4 and 0.3 tonnes CO_2eq/yr for one tonne of fluvial carbon, gross carbon erosion and gross soil erosion, respectively. This study concludes that gross soil erosion would therefore only be a net sink of both carbon and greenhouse gases if all the following criteria are met: the gross soil erosion rate were very low (<91 tonnes/km²/yr); the eroded carbon were completely replaced by new soil organic matter; and if less than half of the gross erosion made it into the stream network. By establishing the emission factor for soil erosion, it becomes possible to properly account for the benefits of good soil management in minimizing losses of greenhouse gases to the atmosphere as a by‐product of soil erosion. Copyright © 2015 John Wiley & Sons, Ltd.     

Reconstructing long‐term records of dissolved CO2

The dissolved CO₂ concentration of stream waters is an important component of the terrestrial carbon cycle. This study reconstructs long‐term records of dissolved CO₂ concentration for the outlets of two large catchments (818 and 586 km²) in northern England. The study shows that:

• 1. The flux of dissolved CO₂ from the catchments (as carbon per catchment area), when adjusted for that which would be carried by the river water at equilibrium with the atmosphere, is between 0 and 0·39 t km⁻² year⁻¹ for the River Tees and between 0 and 0·65 t km⁻² year⁻¹ for the River Coquet.
• 2. The flux of dissolved CO₂ is closely correlated with dissolved organic carbon (DOC) export and is unrelated to dissolved CO₂ export from the headwaters of the study catchments.
• 3. The evasion rate of CO₂ from the rivers (as carbon per stream area) is between 0·0 and 1·49 kg m⁻² year⁻¹, and calculated in‐stream productions of CO₂ are estimated as between 0·5 and 2·5% of the stream evasion rate.
• 4. By mass balance, it is estimated that 8% of the annual flux of DOC is lost within the streams of the catchment.

The study shows that the loss of CO₂ from the streams of the Tees catchment is between 3·1 and 7·5 kt year⁻¹ (as carbon) for the River Tees, which is the same order as annual CH₄ flux from peats within the catchment and approximately 50% of the net CO₂ exchange to the peats of the catchment. Copyright © 2005 John Wiley & Sons, Ltd.     

大型水库分层期和混合期溶存温室气体空间变化及排放通量

水库作为温室气体的重要来源,对区域气候变化有不可忽略的影响。然而,目前对水库溶存温室气体的空间异质性及垂向特征的认知仍然欠缺。为了揭示水库分层期和混合期溶存温室气体空间特征及排放通量,也为厘清水库温室气体产生和排放的关键过程提供重要支撑。研究选择东北地区大型水库——汤河水库为对象,于2021年7—9月和10月(分别代表水库分层期和混合期)对水库不同位置(坝前、库中和库尾)开展溶存温室气体垂向分层监测。研究结果显示,水库CH₄排放通量变化范围为0.018～0.174 mmol/(m²·d),是大气CH₄的源,空间分布为库尾>库中>坝前;CO₂通量为-4.91～58.77 mmol/(m²·d),除分层期东支库尾,其余点位均表现为大气CO₂的源,空间分布为坝前>库中>库尾。时间上,分层期CH₄排放通量(0.071±0.044 mmol/(m²·d))高于混合期((0.027±0.008) mm...     

亚热带城市湖泊与河流CO2气体通量特征及其影响因素

湖泊、河流等内陆水体是连接陆地生态系统和海洋的“长程碳环路”的重要节点,也是温室气体二氧化碳(CO₂)排放源,在调节陆地、海洋间的碳迁移转换中发挥着重要作用。相对于自然水体,城市水体因面积小、水深浅且受监测方法限制,水-气界面碳通量经常被忽略。为探讨我国亚热带城市水体温室气体排放特征,本研究以湖南省长沙市典型城市水体,包括洋湖、西湖、松雅湖、月湖4个湖泊和湘江长沙段为研究对象,分别于2022年4和10月采用光化学反馈-腔增强吸收光谱法(OF-CEAS)和扩散模型法对水-气界面CO₂通量进行对比测定。结果表明,长沙城市湖泊与河流春季为CO₂排放源,秋季为吸收汇,河流水-气界面CO₂通量呈显著季节差异。河湖之间CO₂通量在春季表现为显著差异,秋季差异不显著。CO₂通量与水体溶解氧、水体总氮浓度等呈显著正相关。2种方法的CO₂通量对比测定在湖泊上显著相关,但对河流而言相关性不显著。研究揭示的城市湖泊与河流CO₂气体的排放特征有利于深入探究城市水体碳的迁移转化,可对全面了解全球气候变化过程和河湖湿地温室气体减排和调控提供科学支撑。     

Simulation of crop growth and energy and carbon dioxide fluxes at different time steps from hourly to daily

Understanding the exchange processes of energy and carbon dioxide (CO₂) in the soil–vegetation–atmosphere system is important for assessing the role of the terrestrial ecosystem in the global water and carbon cycle and in climate change. We present a soil–vegetation–atmosphere integrated model (ChinaAgrosys) for simulating energy, water and CO₂ fluxes, crop growth and development, with ample supply of nutrients and in the absence of pests, diseases and weed damage. Furthermore, we test the hypotheses of whether there is any significant difference between simulations over different time steps. CO₂, water and heat fluxes were estimated by the improving parameterization method of the coupled photosynthesis–stomatal conductance–transpiration model. Soil water evaporation and plant transpiration were calculated using a multilayer water and heat‐transfer model. Field experiments were conducted in the Yucheng Integrated Agricultural Experimental Station on the North China Plain. Daily weather and crop growth variables were observed during 1998–2001, and hourly weather variables and water and heat fluxes were measured using the eddy covariance method during 2002–2003. The results showed that the model could effectively simulate diurnal and seasonal changes of net radiation, sensible and latent heat flux, soil heat flux and CO₂ fluxes. The processes of evapotranspiration, soil temperature and leaf area index agree well with the measured values. Midday depression of canopy photosynthesis could be simulated by assessing the diurnal change in canopy water potential. Moreover, the comparisons of simulated daily evapotranspiration and net ecosystem exchange (NEE) under different time steps indicated that time steps used by a model affect the simulated results. There is no significant difference between simulated evapotranspiration using the model under different time steps. However, simulated NEE produces large differences in the response to different time steps. Therefore, the accurate calculation of average absorbed photosynthetic active radiation is important for the scaling of the model from hourly steps to daily steps in simulating energy and CO₂ flux exchanges between winter wheat and the atmosphere. Copyright © 2007 John Wiley & Sons, Ltd.     

Groundwater impact on methane emissions from flooded paddy fields

High methane (CH₄) fluxes emitted from paddy fields strongly contribute to the accumulation of greenhouse gases into the atmosphere, compromising the eco-compatibility of one of the most important world foods. A strong link exists between infiltration rates of irrigation water and CH₄ emissions. Since depth to the groundwater table affects infiltration rates, a relevant groundwater impact is expected on CH₄ emissions from paddy fields. In this work, a theoretical approach is adopted to investigate the aquifer effect on CH₄ dynamics in paddies. Infiltration rates are strongly affected by the development of different connection states between aquifer and irrigation ponded water. A strong reduction in infiltration rates results from a water table near to the soil surface, when the system is hydraulically connected. When the groundwater level increases, the infiltration rate reduction due to the switch from disconnected to connected state promotes a relevant increase of CH₄ emissions. This is due to a strong reduction of dissolved organic carbon (DOC) percolation, which leads to higher DOC availability for microbial CH₄ production and, consequently, higher CH₄ emissions. Our simulations show that CH₄ fluxes can be reduced by up to 24% when groundwater level is decreased and the aquifer is disconnected from ponding water. In paddies with shallow aquifers, lowering the water table with a drainage system could thus represent a promising CH₄ mitigation option.     

Sources and variability of CO2 in a prealpine stream gravel bar

Gravel bars (GBs) contribute to carbon dioxide (CO₂) emissions from stream corridors, with CO₂ concentrations and emissions dependent on prevailing hydraulic, biochemical, and physicochemical conditions. We investigated CO₂ concentrations and fluxes across a GB in a prealpine stream over three different discharge‐temperature conditions. By combining field data with a reactive transport groundwater model, we were able to differentiate the most relevant hydrological and biogeochemical processes contributing to CO₂ dynamics. GB CO₂ concentrations showed significant spatial and temporal variability and were highest under the lowest flow and highest temperature conditions. Further, observed GB surface CO₂ evasion fluxes, measured CO₂ concentrations, and modelled aerobic respiration were highest at the tail of the GB over all conditions. Modelled CO₂ transport via streamwater downwelling contributed the largest fraction of the measured GB CO₂ concentrations (31% to 48%). This contribution increased its relative share at higher discharges as a result of a decrease in other sources. Also, it decreased from the GB head to tail across all discharge‐temperature conditions. Aerobic respiration accounted for 17% to 36% of measured surface CO₂ concentrations. Zoobenthic respiration was estimated to contribute between 4% and 8%, and direct groundwater CO₂ inputs 1% to 23%. Unexplained residuals accounted for 6% to 37% of the observed CO₂ concentrations at the GB surface. Overall, we highlight the dynamic role of subsurface aerobic respiration as a driver of spatial and temporal variability of CO₂ concentrations and evasion fluxes from a GB. As hydrological regimes in prealpine streams are predicted to change following climatic change, we propose that warming temperatures combined with extended periods of low flow will lead to increased CO₂ release via enhanced aerobic respiration in newly exposed GBs in prealpine stream corridors.     

三峡水库澎溪河消落区土-气界面CO2和CH4通量初探

水库近岸湿地(消落区)温室气体(CO₂、CH₄)产汇是水库温室气体效应问题的重要组成部分.本文以三峡水库支流澎溪河的白家溪、养鹿两处大面积消落区为研究对象,于2010年6 9月水库低水位运行期间,对近岸消落区土-气界面CO₂、CH₄通量进行监测.白家溪消落区土-气界面CO₂通量均值为12.38±2.42 mmol/(m²·h);CH₄通量均值为0.0112±0.0064 mmol/(m²·h).养鹿消落区CO₂、CH₄通量均值分别为10.54±5.17、0.14±0.16 mmol/(m²·h).总体上,6 9月土-气界面CO₂通量呈增加趋势,而CH₄通量水平呈现显著的递减趋势.消落区土地出露后植被恢复,在一定程度上促进了土壤有机质含量的增加,使得6 9月CO₂释放通量的总体趋势有所增加.消落区退耕后,其甲烷氧化菌的活性得到恢复,加之在土地出露曝晒过程中土壤透气性增强,使得消落区土壤对大气中CH₄吸收氧化潜势增强.尽管如此,仍需进一步的研究以明晰消落区土-气界面CO₂、CH₄产汇的主要影响因素.     

Seasonal variation of fluxes and distributions of dissolved methane in the North Yellow Sea

The concentrations and sea-to-air fluxes of dissolved methane (CH₄) were investigated in the North Yellow Sea during August 2006, January, April and October 2007. Dissolved CH₄ concentrations showed obvious seasonal variation, with maximum values occurring in summer and lowest values occurring in winter. The saturations of dissolved CH₄ in surface waters ranged from 78.7% to 1679.7% with an average of 252.4%. The estimated atmospheric CH₄ fluxes using the Liss and Merlivat (LM86), and Wanninkhof formulae (W92) were (4.2±4.7), (11.6±10.3), (8.5±12.7) and (0.2±1.0), and (6.9±7.3), (14.6±22.3), (13.8±14.3) and (0.4±1.7) μmol·(m² d)⁻¹, respectively, for spring, summer, autumn and winter. Based on the average annual atmospheric CH₄ flux and the area of the North Yellow Sea, the annual CH₄ emission was estimated to be (2.4×10⁻²–4.2×10⁻²) Tg a⁻¹, which suggests that the North Yellow Sea was a net source of atmospheric CH₄.     

三峡水库澎溪河水-气界面CO2、CH4扩散通量昼夜动态初探

三峡水库温室气体效应近年来备受关注.为揭示三峡水库典型支流澎溪河水-气界面CO₂和CH₄通量的昼夜动态规律,明晰短时间尺度下该水域温室气体释放的影响因素,在2010年6月至2011年5月的一个完整水文周年内,选择4个具有代表性的时段(2010年8、11月和2011年2、5月)对澎溪河高阳平湖水域开展昼夜跟踪观测.结果表明:2010年8、11月和2011年2、5月4次采样的CO₂日总通量值分别为-8.34、73.94、28.13和-20.12 mmol/(m²·d),相应的CH₄日总通量值分别为2.22、0.11、0.32和7.16 mmol/(m²·d),不同时期昼夜变化明显.研究水域CO₂和CH₄通量过程不具同步性:CO₂昼夜通量变化可能更显著地受到水柱光合/呼吸过程的影响,但瞬时气象过程(水汽温差、瞬时风速等)在高水位时期亦可对CO₂通量产生显著影响;CH₄昼夜通量变化与水温条件改变更为密切.     

Seasonal controls on DOC dynamics in nested upland catchments in NE Scotland

Spatial and temporal variability of hydrological responses affecting surface water dissolved organic carbon (DOC) concentrations are important for determining upscaling patterns of DOC export within larger catchments. Annual and intra‐annual variations in DOC concentrations and fluxes were assessed over 2 years at 12 sites (3·40–1837 km²) within the River Dee basin in NE Scotland. Mean annual DOC fluxes, primarily correlated with catchment soil coverage, ranged from 3·41 to 9·48 g m^?2 yr^?1. Periods of seasonal (summer–autumn and winter–spring) DOC concentrations (production) were delineated and related to discharge. Although antecedent temperature mainly determined the timing of switchover between periods of high DOC in the summer‐autumn and low DOC in winter‐spring, inter‐annual variability of export within the same season was largely dependent on its associated water flux. DOC fluxes ranged from 1·39 to 4·80 g m^?2 season^?1 during summer–autumn and 1·43 to 4·15 g m^?2 season^?1 in winter–spring.Relationships between DOC areal fluxes and catchment scale indicated that mainstem fluxes reflect the averaging of highly heterogeneous inputs from contrasting headwater catchments, leading to convergent DOC fluxes at catchment sizes of ca 100 km². However, during summer–autumn periods, in contrast to winter–spring, longitudinal mainstem DOC fluxes continue to decrease, most likely because of increasing biological processes. This highlights the importance of considering seasonal as well as annual changes in DOC fluxes with catchment scale. This study increases our understanding of the temporal variability of DOC upscaling patterns reflecting cumulative changes across different catchment scales and aids modelling of carbon budgets at different stages of riverine systems. Copyright © 2010 John Wiley & Sons, Ltd.     

Fluvial carbon export and CO2 efflux in representative nested headwater catchments of the eastern La Plata River Basin

This study involved a baseline evaluation of fluvial carbon export and degas rates in three nested rural catchments (1 to 80 km²) in Taboão, a representative experimental catchment of the Upper Uruguay River Basin. Analyses of the carbon content in stream waters and the catchment carbon yield were based on 4‐year monthly in situ data and statistical modeling using the United States Geological Survey load estimator model. We also estimated p CO₂ and degas fluxes using carbonate equilibrium and gas‐exchange formulas. Our results indicated that the water was consistently p CO₂ saturated (~90% of the cases) and that the steep terrain favors high gas evasion rates. The mean calculated fluvial export was 5.4 tC·km^?2·year^?1 with inorganic carbon dominating (dissolved inorganic carbon:dissolved organic carbon ratio >4), and degas rates (~40 tC km^?2·year^?1) were nearly sevenfold higher than the downstream export. The homogeneous land use in this nested catchment system results in similar water‐quality characteristics, and therefore, export rates are expected to be closely related to the rainfall–runoff relationships at each scale. Although the sampling campaigns did not fully reproduce storm‐event conditions and related effects such as flushing or dilution of in‐stream carbon, our results indicated a potential link between dissolved inorganic carbon and slower hydrological pathways related to subsurface water storage and movement.     

三峡水库CO2、CH4通量监测分析研究

自成库以来,三峡水库CO₂、CH₄等温室气体通量较蓄水前发生明显改变。如何科学认识和客观评估三峡水库修建及运行对其CO₂、CH₄等温室气体通量的影响备受关注。本文简要回顾了自2009年以来在三峡水库开展CO₂、CH₄等温室气体通量监测与分析工作,综述认为,现阶段三峡水库温室气体排放以水-气界面扩散释放为主要途径。陆源输入的有机碳是主导三峡水库CO₂、CH₄产生的主要碳源,但在局部区段或时段自源性有机碳的贡献亦十分显著。同蓄水前相比,三峡水库碳排放量呈现为净增加,淹没效应约占水库C净增量的20%,库区内点面源污染负荷并未对CO₂排放的净增量产生显著贡献,阻隔效应和生态系统重建效应对三峡水库碳排放的净增量产生显著贡献。近10年来,监测方法比对、监测点位优化等工作在一定程度上完善了三峡水库温室气体通量监测体系。新方法、新技术的引入也为三峡水库温室气体通量监测分析提供了有利支撑和保障,但复杂水文环境...     

Spatial and temporal variations of pCO2, dissolved inorganic carbon and stable isotopes along a temperate karstic watercourse

This study investigated CO₂ degassing and related carbon isotope fractionation effects in the Wiesent River that drains a catchment in the karst terrain of the Franconian Alb, Southern Germany. The river was investigated by physico‐chemical and stable isotope analyses of water and dissolved inorganic carbon during all seasons along 65‐km long downstream transects between source and mouth. Calculated pCO₂ values at the source were 21 400 ± 2400 µatm. The pCO₂ rapidly decreased in the river water and dropped to an average of 1240 ± 330 µatm near the mouth. About 90% of this decrease occurred within the first 6 km of the river. The river was supersaturated with respect to CO₂ over its entire course and must have acted as a continuous year‐round CO₂ source to the atmosphere. The average CO₂ flux from the karst river was estimated with 450 mmol m^?2 day^?1 with higher fluxes up to 5680 mmol m^?2 day^?1 at the source. At the source, δ¹³C_DIC values showed no seasonal variations with an average of ?14.2 ± 0.2‰. This indicated that groundwater retained high pCO₂ mainly from soil CO₂. The contribution of soil CO₂ to dissolved inorganic carbon was estimated at 65% to 72%. The downstream CO₂ loss caused a positive shift in δ¹³C_DIC values of 2‰ between source and mouth because of the preferential loss of the ¹²C isotope during degassing. Considering the findings of this study and the fact that carbonate lithology covers a significant part of the earth's surface, CO₂ evasion from karst regions might contribute notably to the annual carbon dioxide release from global freshwater systems. Copyright © 2015 John Wiley & Sons, Ltd.     

Impacts of Methane on Carbon Dioxide Storage in Brine Formations

In the context of geological carbon sequestration (GCS), carbon dioxide (CO₂) is often injected into deep formations saturated with a brine that may contain dissolved light hydrocarbons, such as methane (CH₄). In this multicomponent multiphase displacement process, CO₂ competes with CH₄ in terms of dissolution, and CH₄ tends to exsolve from the aqueous into a gaseous phase. Because CH₄ has a lower viscosity than injected CO₂, CH₄ is swept up into a ‘bank’ of CH₄‐rich gas ahead of the CO₂ displacement front. On the one hand, this may provide a useful tracer signal of an approaching CO₂ front. On the other hand, the emergence of gaseous CH₄ is undesirable because it poses a leakage risk of a far more potent greenhouse gas than CO₂ if the cap rock is compromised. Open fractures or faults and wells could result in CH₄ contamination of overlying groundwater aquifers as well as surface emissions. We investigate this process through detailed numerical simulations for a large‐scale GCS pilot project (near Cranfield, Mississippi) for which a rich set of field data is available. An accurate cubic‐plus‐association equation‐of‐state is used to describe the non‐linear phase behavior of multiphase brine‐CH₄‐CO₂ mixtures, and breakthrough curves in two observation wells are used to constrain transport processes. Both field data and simulations indeed show the development of an extensive plume of CH₄‐rich (up to 90 mol%) gas as a consequence of CO₂ injection, with important implications for the risk assessment of future GCS projects.     

Distribution of the surface partial pressure of CO2 in the southern Yellow Sea and its controls

Surface partial pressure of CO₂ (pCO₂), dissolved inorganic carbon (DIC), temperature, salinity and chlorophyll a (Chl a) at grid stations were measured in the southern Yellow Sea (SYS; 32–37°N to 120–125°E) during four cruises conducted in March 2005 (winter), April 2006 (spring), May 2005 (late spring), and July 2001 (summer). Factors influencing pCO₂ spatial and seasonal variations are explored.Surface seawater pCO₂ during winter was oversaturated with respect to the atmosphere in the entire study area (380–606 μatm), primarily due to the complete mixing of the water column in winter which brought CO₂-enriched bottom water to the surface. However, during spring, surface pCO₂ in the central SYS was undersaturated relative to the atmosphere with a low range between 274 and 408 μatm. The net CO₂ sink in the central SYS was mainly due to the consumption of CO₂ by the strong phytoplankton activity and to the weak water stratification, whereas surface pCO₂ in the nearshore area was oversaturated for the atmosphere owing to vertical mixing and terrestrial inputs. During summer, surface pCO₂ varied between 125 and 599 μatm over the entire sampling area. In the Changjiang (Yangtze River) Diluted Water (CDW) area, surface pCO₂ was undersaturated because of the nutrient inputs via the Changjiang, triggering strong phytoplankton activity, whereas surface pCO₂ was oversaturated in other areas. We conclude that the nearshore area behaves as a source of atmospheric CO₂ during the entire investigated periods owing to vertical mixing and terrestrial inputs as well as upwelling, whereas the central region generally shifts from a source of CO₂ in March to a sink in the remaining time of the investigation.