Spatiotemporal variations of dissolved inorganic carbon and controlling factors in a small karstic catchment,Southwestern China

Dissolved inorganic carbon (DIC) is the most important carbon component in karst aquatic system where fluid is highly transmissive, but has rarely been examined in the subtropical karst critical zone (K-CZ). In this study, concentrations of dissolved solutes and isotopic compositions of DIC (δ¹³C_DIC) at 11 sites of a 73.4 km² karstic catchment in Southwestern China were analysed monthly in order to uncover the spatiotemporal variations of both DIC and its dominant sources, and to identify relevant controlling factors. Both DIC concentrations and δ¹³C_DIC were highly variable, ranging from 2.52 to 5.85 mmol l⁻¹ and from −15.7 to −4.5‰, respectively. DIC in underground water (UGW) was higher in concentration and more depleted in ¹³C compared to surface water (SFS). DIC concentrations showed an inconsistent seasonal trend with other solutes, with higher values in the wet season at some sites. δ¹³C_DIC values were lower in the wet season than in the dry season. The results of mixing model IsoSource revealed spatiotemporal patterns of DIC sources. During the dry season, carbonate weathering was the primary contributor to DIC in UGW (excluding in the middle reaches). However, during the wet season, soil CO₂ was the dominant source of DIC in both UGW and SFS, and it was higher than in the dry season. Overall, there are significant spatiotemporal disparities and highly transmissive characteristics of both DIC and its sources in the K-CZ, which are controlled by multiple factors. This study also highlights that rainfall may play a crucial role in accelerating carbon dynamics in the K-CZ. High-frequency sampling campaigns in high-flow periods and deep analyses are needed in future work to elucidate the related processes and mechanisms. © 2019 John Wiley & Sons, Ltd.     

Dissolved inorganic carbon isotopes of a typical alpine river on the Tibetan Plateau revealing carbon sources,wetland effect and river recharge

The Nyangqu River, the largest right bank tributary of the Yarlung Zangbo River in the Qinghai–Tibet Plateau, was representative of an alpine riverine carbon cycle experiencing climate change. In this study, dissolved inorganic carbon (DIC) spatial and seasonal variations, as well as their carbon isotopic compositions (δ¹³C_DIC) in river water and groundwater were systematically investigated to provide constraints on DIC sources, recharge and cycling. Significant changes in the δ¹³C_DIC values (from −2.9‰ to −23.4‰) of the water samples were considered to be the result of different contributions of two dominant DIC origins: soil CO₂ dissolution and carbonate weathering. Three types of rock weathering (dissolution of carbonate minerals by H₂CO₃ and H₂SO₄, and silicate dissolution by H₂CO₃) were found to control the DIC input into the riverine system. In DIC cycling, groundwater played a significant role in delivering DIC to the surface water, and DIC supply from tributaries to the main stream increased from the dry season to the wet season. Notably, the depleted δ¹³C_DIC ‘peak’ around the 88.9° longitude, especially in the September groundwater samples, indicated the presence of ‘special’ DIC, which was attributed to the oxidation of methane from the Jiangsa wetland located nearby. This wetland could provide large amounts of soil organic matter available for bacterial degradation, producing ¹³C-depleted methane. Our study provided insights regarding the role of wetlands in riverine carbon cycles and highlighted the contribution of groundwater to alpine riverine DIC cycles.     

Factors controlling carbon isotope ratios of dissolved inorganic carbon in two major tributaries of the Han River,Korea

Understanding the carbon cycle of the Han River system in Korea is of prime interest in managing and preserving this valuable water resource for more than 20 million residents in the area. As a part of a comprehensive carbon cycling study for the Han River system, this report focuses on the carbon isotope compositions of dissolved inorganic carbon (DIC) in its two major tributaries, the North and the South Han Rivers. The major difference in carbonate chemistry of the tributaries originates primarily from the lithology of the catchment areas. The South Han River, draining a carbonate‐dominant terrain, has much higher alkalinities and DIC concentrations, whereas the lower concentrations in the North Han River indicate little influence of carbonate weathering. Likewise, δ¹³C_DIC values in the South Han River indicate that the DIC input from the carbonate rocks is important in controlling carbon isotope ratios of DIC. For the North Han River, the oxidation of organic material influences the amount of riverine DIC and δ¹³C_DIC values to a greater extent. Overall, remarkable seasonal and spatial variations of river chemistry and carbon isotope compositions of DIC reflect the variability in geo‐hydrologic characteristics, in the water regime, and in metabolic activities in the river water and/or the drainage areas. Copyright © 2006 John Wiley & Sons, Ltd.     

Dissolved inorganic carbon sourcing using δ13CDIC from a karst influenced river system

Rivers, representing the primary conduits of dissolved inorganic carbon (DIC) from the continents to the oceans, are important components to the global carbon cycle. To better understand the complex carbon cycling dynamics within two nested, mixed lithology watersheds, two sites were studied along the karst influenced upper Green River in south‐central Kentucky, USA. Weekly samples were collected from June 2013 through May 2014 and analyzed for δ¹³C_DIC. The mixing model IsoSource was employed to better understand source partitioning differences over seasonal time spans and across the two nested basins. In both the lithologically mixed upstream basin (53% carbonate rocks, 47% siliciclastic) and carbonate rock dominated downstream basin (96% carbonate rocks in the drainage area between Greensburg and Munfordville, 78% in the total area upstream from Munfordville), DIC was primarily derived from soil respiration. The proportion of DIC from dissolved carbonate minerals derived from the downstream carbonate rock dominated basin was similar to the upstream basin, due to carbonate mineral dissolution having such a consistent effect on the overall DIC content of the river. Seasonally, soil respiration provided the most DIC from fall to winter. Early spring precipitation, combined with limited seasonal photosynthesis, shifted groundwater to be the primary source of DIC, bringing in a flush of carbonate mineral‐rich water during higher flows. This study provides insight into carbon dynamics across multiple lithologies and the important influence of seasonality using carbon isotope sourcing to determine carbonate mineral dissolution variability and aid in understanding its contribution to global carbon flux quantification. Copyright © 2015 John Wiley & Sons, Ltd.     

Alkalinity and dissolved inorganic carbon exports from tropical and subtropical river catchments discharging to the Great Barrier Reef,Australia

Dissolved inorganic carbon (DIC) transport by rivers is an important control on the pH and carbonate chemistry of the coastal ocean. Here, we combine DIC and total alkalinity (TAlk) concentrations from four tropical rivers of the Great Barrier Reef region in Australia with daily river discharge to quantify annual river loads and export rates. DIC in the four rivers ranged from 284 to 2,639 μmol kg⁻¹ and TAlk ranged from 220 to 2,612 μmol kg⁻¹. DIC:TAlk ratios were mostly greater than one suggesting elevated exports of free [CO₂*]. This was pronounced in the Johnstone and Herbert rivers of the tropical wet north. The largest annual loads were transported in the two large river catchments of the southern Great Barrier Reef region, the Fitzroy and Burdekin rivers. The carbon stable isotopic composition of DIC suggests that carbonate weathering was the dominant source of DIC in the southern rivers, and silicate weathering was likely a source of DIC in the northern Wet Tropics rivers. Annual loads and export rates were strongly driven by precipitation and discharge patterns, the occurrence of tropical cyclones, and associated flooding events, as well as distinct seasonal dry and wet periods. As such, short-lived hydrological events and long-term (seasonal and inter-annual) variation of DIC and TAlk that are pronounced in rivers of the tropical and subtropical wet and dry climate zone should be accounted for when assessing inorganic carbon loads to the coastal ocean and the potential to buffer against or accelerate ocean acidification.     

河库连续体中溶解性无机碳及其同位素的时空分异特征——以澜沧江云南段为例

河流及水库等水生态系统中的溶解性无机碳(DIC)是全球碳循环与大气、陆地和海洋之间碳相互作用的重要组成部分.以澜沧江云南段上游天然河段及下游梯级水库群形成的连续体为研究对象,分析了河库连续体表层水体中水化学特征、溶解性无机碳浓度及其碳同位素时空分布特征.研究结果表明:河库连续体水体中溶解无机碳(DIC)及其同位素(δ13 C DIC)组成特征总体表现为:DIC浓度丰水期较低,枯水期较高,平均值分别为2.59±0.44和3.30±0.37 mmol/L;δ13 C DIC值丰水期偏负、枯水期偏正,平均值分别为-8.52‰±0.38‰和-6.95‰±0.53‰,与自然河流的季节变化特征相似.水体DIC来源主要包括土壤及水体有机质分解生成的CO 2、碳酸盐风化和水气界面CO 2的交换过程.澜沧江河库连续体中DIC浓度及δ13 C DIC组成的时空异质性特征与流域岩性、土壤生物地球化学过程以及微生物活动强度等均有较大关系.当前,澜沧江梯级水库群建库时间短,梯级联合运行下调度复杂,水文条件多变,梯级水库对河流重要生源要素——碳累积影响方面的“水库效应”还不明显.     

Leaky savannas: the significance of lateral carbon fluxes in the seasonal tropics

Globally, dissolved inorganic carbon (DIC) accounts for more than half the annual flux of carbon exported from terrestrial ecosystems via rivers. Here, we assess the relative influences of biogeochemical and hydrological processes on DIC fluxes exported from a tropical river catchment characterized by distinct land cover, climate and geology transition from the wet tropical mountains to the low‐lying savanna plains. Processes controlling changes in river DIC were investigated using dissolved organic carbon, particulate organic carbon and DIC concentrations and stable isotope ratios of DIC (δ¹³C_DIC) at two time scales: seasonal and diel. The recently developed Isotopic Continuous Dissolved Inorganic Carbon Analyser was used to measure diel DIC concentration and δ¹³C_DIC changes at a 15‐min temporal resolution. Results highlight the predominance of biologically mediated processes (photosynthesis and respiration) controlling diel changes in DIC. These resulted in DIC concentrations varying between 3.55 and 3.82 mg/l and δ¹³C_DIC values ranging from ?19.7 ± 0.31‰ to ?17.1 ± 0.08‰. In contrast, at the seasonal scale, we observed wet season DIC variations predominantly from mixing processes and dry season DIC variations due to both mixing processes and biological processes. The observed wet season increases in DIC concentrations (by 6.81 mg/l) and δ¹³C_DIC values of river water (by 5.4‰) largely result from proportional increases in subsurface inflows from the savanna plains (C₄ vegetation) region relative to inflows from the rainforest (C₃ vegetation) highlands. The high DIC river load during the wet season resulted in the transfer of 97% of the annual river carbon load. Therefore, in this gaining river, there are significant seasonal variations in both the hydrological and carbon cycles, and there is evidence of substantial coupling between the carbon cycles of the terrestrial and the fluvial environments. Recent identification of a substantial carbon sink in the savannas of northern Australia during wetter years in the recent past does not take into account the possibility of a substantial, rapid, lateral flux of carbon to rivers and back to the atmosphere. Copyright © 2015 John Wiley & Sons, Ltd.     

Hydrological regulation of chemical weathering and dissolved inorganic carbon biogeochemical processes in a monsoonal river

To better understand the mechanisms relating to hydrological regulations of chemical weathering processes and dissolved inorganic carbon (DIC) behaviours, high-frequency sampling campaigns and associated analyses were conducted in the Yu River, South China. Hydrological variability modifies the biogeochemical processes of dissolved solutes, so major ions display different behaviours in response to discharge change. Most ions become diluted with increasing discharge because of the shortened reactive time between rock and water under high-flow conditions. Carbonate weathering is the main source of major ions, which shows strong chemostatic behaviour in response to changes in discharge. Ions from silicate weathering exhibit a significant dilution effect relative to the carbonate-sourced ions. Under high temperatures, the increased soil CO₂ influx from the mineralisation of organic material shifts the negative carbon isotope ratios of DIC (δ¹³C_DIC) during the high-flow season. The δ¹³C_DIC values show a higher sensitivity than DIC contents in response to various hydrological conditions. Results from a modified isotope-mixing model (IsoSource) demonstrate that biological carbon is a dominant source of DIC and plays an important role in temporal carbon dynamics. Furthermore, this study provides insights into chemical weathering processes and carbon dynamics, highlighting the significant influence of hydrological variability to aid understanding of the global carbon cycle.     

喀斯特地区梯级水库建造对水化学分布的影响

为深入了解河流梯级筑坝对喀斯特地区河流水化学分布的影响,于2017年1、4、7和10月别对乌江干流洪家渡水库(多年调节)、乌江渡水库(季调节)和索风营水库(日调节) 3个具有不同滞留时间的水库进行水样采集,分析入库水、坝前剖面水和下泄水的水化学特征,探讨河流梯级筑坝对水化学分布及风化速率估算的影响.研究结果表明:3个水库深层水比表层水HCO3-浓度分别高12.9%、5.5%和8.0%,Ca~(2+)浓度分别高15.9%、2.4%和8.5%.河流梯级筑坝一定程度上改变了水体水化学组成,从而影响碳酸盐岩风化速率估算.整体上,洪家渡水库、索风营水库和乌江渡水库的全年风化速率变化范围分别为:-1.7%～15.4%、-5.6%～1.1%和-0.3%～3.4%.河流筑坝作用对风化速率估算及主量离子浓度的影响:HCO_3~-与Ca~(2+)浓度分布均为:洪家水库乌江渡水库索风营水库,这与水体滞留时间长短规律一致,表明水体滞留时间影响着水化学的组成分布.同时水体离子浓度表现出明显的季节性差异,丰水期各水库变化率明显大于枯水期.上述结论表明喀斯特地区河流连续筑坝后水化学组成及分布特征发生了一定程度改变,影响流域化学风化速率的估算,且影响程度随水体滞留时间延长而增大,并受气温影响.因此,今后在估算流域风化速率及探究水化学空间变化时应对筑坝作用加以考虑,以便更加准确地评估喀斯特流域岩石风化在全球碳循环中的作用.     

Carbon flux and landscape evolution in epigenic karst aquifers modeled from geochemical mass balance

This paper considers the contributions of epigenic karst processes as a major element of the carbon cycle and a significant agent of landscape evolution. Geochemical models developed from monitoring data and water samples are used to estimate the variation and magnitude of dissolved inorganic carbon (DIC) flux in karst landscapes at several scales, from local to global. At the local scale, the Cumberland River watershed of southeast Kentucky, these geochemical models are also used to evaluate the potential role of sulfur in the production of DIC and to compute an estimated rate of landscape erosion. Geochemical modeling using ionic species and modeled discharge reveal a variable rate of DIC flux driven by large fluctuations in calcite saturation and discharge. Ratios of reaction products and principal component analyses (PCA) suggest that some bedrock dissolution may be driven by the oxidation of reduced sulfur derived from brines entrained into the karst aquifers. Over the 3730 km² of carbonate exposure in the Cumberland River, 25.8–62.4 Gg/yr of carbon dioxide (CO₂) is conveyed from the atmosphere through the dissolution of carbonate. At the global scale, this translates to 123–296 Tg/yr of CO₂ delivered by karst processes into the aqueous system. The bedrock portion of DIC equates to a flux of 32.6 ± 2.6 m³ – 35.2 ± 2.8 m³ of bedrock during the period of study of which 29% was dolomite. This translates to a landscape erosion rate of 13.1–17.9 mm/ka in the 3.45–4.32 km² of carbonate exposure in the studied watershed. Based upon 16+ km of cave survey data spanning a vertical range of 72 to 75 m above base level, this suggests that cave development in the watershed spans the Plio‐Pleistocene. Using the modeled erosion rates, the ages of cave levels, 4.03–5.71, 3.08–4.56, 1.57–2.43, 1.01–1.67, 0.45–0.91, and < 0.45 Ma, are in good agreement with regional studies of Plio‐Pleistocene landscape evolution in the Appalachian Lowland Plateaus. Copyright © 2015 John Wiley & Sons, Ltd.     

Carbon isotopes in the rivers from the Lesser Antilles: origin of the carbonic acid consumed by weathering reactions in the Lesser Antilles

In this paper, we use carbon isotopes in the dissolved load of rivers from the Lesser Antilles volcanic arc (Guadeloupe, Martinique and Dominica islands) to constrain the source of the carbon dioxide (CO₂) involved in the neutralization reactions during water–rock interactions. The δ¹³C data span a large range of variations, from –19‰ to –5 · 2‰ for DIC (dissolved inorganic carbon) concentrations ranging from 11 μM to 2000 μM. Coupled with major element concentrations, carbon isotopic ratios are interpreted as reflecting a mixture of magmatic CO₂ (enriched in heavy carbon (δ¹³C ≈ –3 · 5‰) and biogenic CO₂ produced in soils (enriched in light carbon (δ¹³C < –17‰)). Carbon isotopes show that, at the regional scale, 23 to 40% of CO₂ consumed by weathering reactions is of magmatic origin and is transferred to the river system through aquifers under various thermal regimes. These numbers remain first‐order estimates as the major uncertainty in using carbon isotopes as a source tracer is that carbon isotopes can be fractionated by a number of processes, including soil and river degassing. Chemical weathering is clearly, at least, partly controlled by the input of magmatic CO₂, either under hydrothermal (hot) or surficial (cold) weathering regimes. This study shows that the contribution of magmatic CO₂ to chemical weathering is an additional parameter that could explain the high weathering rates of volcanic rocks. The study also shows that a significant part of the carbon degassed from the Earth's interior is not released as CO₂ to the atmosphere, but as DIC to the ocean because it interacts with the groundwater system. This study calls for a better understanding of the contributions of deep carbon to the hydrosphere and its influence on the development of the Critical Zone. Copyright © 2013 John Wiley & Sons, Ltd.     

Annual fossil organic carbon delivery due to mechanical and chemical weathering of marly badlands areas

A key issue in the study of the carbon cycle is constraining the stocks and fluxes in and between C‐reservoirs. Among these, the role and importance of fossil organic carbon (FOC) release by weathering of outcropping sedimentary rocks on continental surfaces is still debated and remains poorly constrained. Our work focuses on FOC fluxes due to chemical and mechanical weathering of marls in two experimental watersheds with typical badlands geomorphology (Draix watersheds, Laval and Moulin, Alpes de Haute Provence, France). Organic matter from bedrock, soil litter and riverine particles are characterized by Rock‐Eval 6 pyrolysis. FOC fluxes due to mechanical weathering are then estimated by monitoring the annual particulate solid exports at the outlets of the watersheds (1985–2005 period). FOC fluxes from chemical weathering were calculated using Ca²⁺ concentrations in dissolved loads (year 2002) to assess the amount of FOC released by the dissolution of the carbonate matrix. Results show that FOC delivery is mainly driven by mechanical weathering, with a yield ranging from 30 to 59 t km^‐2 yr^‐1 in the Moulin (0.08 km²) and Laval (0.86 km²) catchments, respectively, (1985–2005 average). The release of FOC attributed to chemical weathering was 2.2 to 4.2 t km^‐2 for the year 2002. These high FOC fluxes from badlands are similar to those observed in tectonically active mountain catchments. At a regional scale, badland outcropping within the Durance watershed does not exceed 0.25% in area of the Rhône catchment, but could annually deliver 12 000 t yr^‐1 of FOC. This flux could correspond to 27% of the total particulate organic carbon (POC) load exported by the Rhône River to the Mediterranean Sea. At a global scale, our findings suggest that erosion of badlands may contribute significantly to the transfer of FOC from continental surfaces to depositional environments. Copyright © 2012 John Wiley & Sons, Ltd.     

Seasonal variations in the inorganic carbon system in the Pearl River (Zhujiang) estuary

Seasonal variations in the inorganic carbon system in the Pearl River estuary are examined based on data from five surveys during the spring, summer, fall, and winter seasons. Both total dissolved inorganic carbon (DIC) and total alkalinity (TAlk) values in the freshwater end-members are high in the dry season (>2700 μmol kg⁻¹ for DIC and >2400 μmol kg⁻¹ for TAlk) and substantially lower in the wet season (DIC and TAlk were ∼1000 and 700 μmol kg⁻¹, respectively). Riverine DIC flux and drainage basin weathering rates, however, are significantly higher in the wet season (611×10⁹ mol yr⁻¹ and 13.6×10⁵ mol km⁻² yr⁻¹) than in the dry season (237×10⁹ mol yr⁻¹ and 5.3×10⁵ mol km⁻² yr⁻¹).     

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.     

Origin and chemical and isotopic evolution of dissolved inorganic carbon (DIC) in groundwater of the Okavango Delta,Botswana

The origin and the chemical and isotopic evolution of dissolved inorganic carbon (DIC) in groundwater of the Okavango Delta in semi-arid Botswana were investigated using DIC and major ion concentrations and stable oxygen, hydrogen and carbon isotopes (δD, δ¹⁸O and δ¹³C_DIC). The δD and δ¹⁸O indicated that groundwater was recharged by evaporated river water and unevaporated rain. The river water and shallow (<10 m) groundwater are Ca–Na–HCO₃ type and the deep (≥10 m) groundwater is Na–K–HCO₃ to HCO₃–Cl–SO₄ to Cl–SO₄–HCO₃. Compared to river water, the mean DIC concentrations were 2 times higher in shallow groundwater, 7 times higher in deep groundwater and 24 times higher in island groundwater. The δ¹³C_DIC indicate that DIC production in groundwater is from organic matter oxidation and in island groundwater from organic matter oxidation and dissolution of sodium carbonate salts. The ionic and isotopic evolution of the groundwater relative to evaporated river water indicates two independent pools of DIC.     

Carbon biogeochemistry of ground water, Guiyang, southwest China

Variations in the concentrations and isotopic compositions (delta13C(DIC)) of dissolved inorganic carbon (DIC) reflect contamination and biogeochemical cycling of the carbon in ground water. In order to understand contamination and biogeochemical cycling of DIC, we carried out research on the geochemistry of ground water of Guiyang, the capital city of Guizhou Province, China. Results show that ground water is mainly characterized by SO4.HCO3-Ca.Mg and HCO3-Ca.Mg chemical compositions. The hydrochemical characteristics of these types of water are mainly controlled by lithology of the aquifers. HCO3- is the dominant species of DIC in ground water and has lower concentrations and more negative values of delta13C(DIC) in the high-flow (summer monsoon) season, as compared to the low-flow season. This indicates that DIC is relatively enriched in carbon of biological origin in the high-flow season as compared to the low-flow season and that biological activities are the predominant control on shifts of stable carbon isotope values. The evidence that the delta13C(DIC) values of ground water decrease with increasing concentrations of anthropogenic species shows that the carbon isotopic composition of DIC can be a useful tracer of contamination, in addition to biogeochemical cycling of inorganic carbon in ground water. Results from this study show that ground water is impacted by significant levels of contamination from human activities, especially in the urban areas, as well as the northeast and west suburbs, in Guiyang city, southwest China.     

Catchment‐scale conceptual modelling of water and solute transport in the dual flow system of the karst critical zone

Hydrological and hydrochemical processes in the critical zone of karst environments are controlled by the fracture‐conduit network. Modelling hydrological and hydrochemical dynamics in such heterogeneous hydrogeological settings remains a research challenge. In this study, water and solute transport in the dual flow system of the karst critical zone were investigated in a 73.5‐km² catchment in southwest China. We developed a dual reservoir conceptual run‐off model combined with an autoregressive and moving average model with algorithms to assess dissolution rates in the “fast flow” and “slow flow” systems. This model was applied to 3 catchments with typical karst critical zone architectures, to show how flow exchange between fracture and conduit networks changes in relation to catchment storage dynamics. The flux of bidirectional water and solute exchange between the fissure and conduit system increases from the headwaters to the outfall due to the large area of the developed conduits and low hydraulic gradient in the lower catchment. Rainfall amounts have a significant influence on partitioning the relative proportions of flow and solutes derived from different sources reaching the underground outlet. The effect of rainfall on catchment function is modulated by the structure of the karst critical zone (e.g., epikarst and sinkholes). Thin epikarst and well‐developed sinkholes in the headwaters divert more surface water (younger water) into the underground channel network, leading to a higher fraction of rainfall recharge into the fast flow system and total outflow. Also, the contribution of carbonate weathering to mass export is also higher in the headwaters due to the infiltration of younger water with low solute concentrations through sinkholes.     

Dissolved inorganic carbon evolution in neutral discharge from mine tailings piles

We measured the concentrations of dissolved inorganic carbon (DIC) and major ions and the stable carbon isotope ratios of DIC (δ¹³C_DIC) in two creeks discharging from carbonate‐rich sulphide‐containing mine tailings piles. Our aim was to assess downstream carbon evolution of the tailings discharge as it interacted with the atmosphere. The discharge had pH of 6.5–8.1 and was saturated with respect to carbonates. Over the reach of one creek, the DIC concentrations decreased by 1.1 mmol C/l and δ¹³C_DIC increased by ~4.0‰ 200 m from the seep source. The decrease in the DIC concentrations was concomitant with decreases in the partial pressure of CO_2(aq) because of the loss of excess CO_2(aq) from the discharge. The corresponding enrichment in the δ¹³C_DIC is because of kinetic isotope fractionation accompanying the loss of CO_2(g). Over the reach of the other creek, there was no significant decrease in the DIC concentrations or notable changes in the δ¹³C_DIC. The insignificant change in the DIC concentrations and the δ¹³C_DIC is because the first water sample was collected 160 m away from the discharge seep, not accessible during this research. In this case, most of the excess CO_2(aq) was lost before our first sampling station. Our results indicate that neutral discharges from tailings piles quickly lose excess CO_2(aq) to the atmosphere and the DIC becomes enrich in ¹³C. We suggest that a significant amount of carbon cycling in neutral discharges from tailings piles occur close to the locations where the discharge seeps to the surface. Copyright © 2015 John Wiley & Sons, Ltd.     

Tidal-induced inorganic carbon dynamics in the Strait of Gibraltar

This study presents the distribution of dissolved inorganic carbon (DIC) along the Strait of Gibraltar, its tidal-induced variability, as well as the inorganic carbon exchange between the Atlantic Ocean and Mediterranean Sea. During November 2003, water column samples were collected at nine stations to measure total alkalinity (TA), pH, and dissolved oxygen (DO) for the spatial characterization of the carbonate system. At the same time, anchored samplings were carried out, above the Camarinal Sill and in the Eastern Section of the Strait, in order to assess the tidal mixing effects for oxygen and DIC distribution on the water column. Three distinct water masses can be discerned in this area: the Surface Atlantic Water (SAW), the Mediterranean Water (MW), and the less abundant North Atlantic Central Water (NACW). The observations show an increase in the DIC and a decrease in oxygen concentration with depth, related to the different physico-chemical features of each water mass. The results show the high time-dependence of the vertical distribution of DIC with the interface oscillation, affected by the intense mixing processes taking place in the Strait. Intense mixing episodes over the Camarinal Sill are responsible for an increase in the DIC concentrations in the upper layer of the Eastern Section of the Strait. Higher DIC concentrations in the Mediterranean than in the Atlantic waters are responsible for a net DIC transport of 1.47×10¹² mol C yr⁻¹ to the Atlantic Ocean. Nevertheless, the net exchange is highly sensitive to the interface definition, as well as to the estimate of water volume transport used.     

喀斯特水库水化学特征及对无机碳沉积通量的指示

为探究筑坝后不同水库物理、化学、生物过程对水化学和碳循环的影响,本研究对贵州三岔河流域的平寨水库、普定水库以及猫跳河流域的红枫湖水库进行研究,于2018年3月2019年1月分别在入库河流和库区采集了分层水样和沉降颗粒物,并探究水中主要离子及颗粒物通量的时空变化特征及其控制因素.结果表明,水体主要离子的主要来源受碳酸盐溶解影响,并且离子浓度受光合作用控制.红枫湖水库水体水化学类型为Ca-Mg-HCO₃-SO₄型,普定水库、平寨水库水化学类型均为Ca-HCO₃-SO₄.夏季藻类光合作用诱导碳酸盐沉淀导致水体表层Ca²⁺、HCO₃^-及溶解态Si浓度降低,其降低幅度分别为20.87%~44.25%、33.12%~51.18%、48.55%~96.34%.此外,藻类光合作用也影响C、N、Si等生源要素间的化学计量关系.Mg²⁺/Ca²⁺比值在水体垂向剖面上主要受碳酸钙沉淀的控制,而在不同水库之间则主要受流域岩性的控制.根据沉积物捕获器通量计算的平寨水库、普定水库、红枫湖水库夏季颗粒无机碳沉积通量分别为0.74、1.36、0.27 t/（km²·d）,而根据水体Ca²⁺浓度降低计算的通量分别为0.31~0.64、0.35~0.99、0.09~0.29 t/（km²·d）,根据水体HCO₃^-浓度降低计算的通量分别为0.30~0.65、0.29~1.26、0.12~0.33 t/（km²·d）.其红枫湖水库无机碳沉降通量的实测值与计算值接近,而平寨、普定水库实际沉降通量高于计算值,这可能是有外源输入导致.因此,利用水化学分层数据能对喀斯特水库中的无机碳沉降通量进行合理估算,并且能够得到较好的估算结果,从而指示碳循环的过程.