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.     

贵州红枫湖近10年来(2009-2018年)水质变化及影响因素

为更好地研究贵州红枫湖的水质变化情况,本文利用贵阳市两湖一库环境保护监测站2009-2018年对红枫湖7个代表性监测点的营养盐、叶绿素a（Chl.a）浓度和水温、气温、透明度、降雨量等水文气象条件逐月监测数据,分析红枫湖10年间水体营养盐和Chl.a浓度以及部分水文气象条件的变化趋势.运用综合营养状态指数（TLI）对红枫湖营养状态进行评价,采用Pearson相关系数法统计分析10年内Chl.a浓度与总磷（TP）、总氮（TN）等水化学组成及水位、气温等水文气象条件的相关性.结果表明,2009-2018年红枫湖水体逐月TN浓度有较大波动（0.56~2.80 mg/L）,春、夏季高于秋、冬季;水体逐月TP浓度为0.016~0.103 mg/L,夏季略高于冬季;逐月氨氮（NH₃-N）浓度为0.007~0.71 mg/L,春季 > 冬季 > 秋季 > 夏季;水体逐月Chl.a浓度呈季节性波动（0.8~38.9 mg/m³）,夏季 > 春季 > 秋季 > 冬季,年内先上升后下降.TP、NH₃-N、Chl.a浓度整体呈下降趋势,10年间水质有很大改善.经计算红枫湖在这10年间处于中营养状态至轻度富营养状态,且营养状态指数呈逐年下降趋势,夏季TLI明显高于其他季节.统计分析表明,红枫湖水体Chl.a浓度与高锰酸盐指数、NH₃-N、TP浓度均呈显著正相关,与氮磷比呈显著负相关,与水温、pH、降雨量、气温、日照时数呈显著正相关,与透明度、气压呈显著负相关,与水位、湿度、风速无显著相关关系.表明这10年来红枫湖水体Chl.a浓度不仅受营养盐浓度控制,很大程度上还受控于气象和水文条件.     

不同上覆水氟浓度对湖泊沉积物氟释放与微生物群落的影响

通过模拟沙湖沉积物-水系统,以沙湖原水氟离子（F^-）浓度为1倍浓度（0.69 mg/L）,设置0.5倍浓度、1倍浓度、1倍浓度灭菌、2倍浓度和4倍浓度共5个实验组,探究不同上覆水F^-浓度背景下沙湖沉积物中F^-的迁移.结果表明,沉积物F^-的释放量随上覆水F^-浓度的增加而呈下降的趋势,其中2倍和4倍浓度组的沉积物由释放F^-转变为吸附F^-.碱性水体有利于沉积物F^-的释放,即随着pH增大,F^-释放量也会增加.微生物的Beta多样性层次聚类分析表明,F^-会抑制Paenisporosarcina与Thiobacillus的相对丰度,但对Fusibacter的生命活动具有促进作用.根据各浓度组间优势菌属相对丰度与环境因子的冗余分析可得,Acinetobacter、Thiobacillus相对丰度与pH呈负相关;Fusibacter相对丰度与F^-浓度呈显著正相关,而Thiobacillus的相对丰度则与F^-表现出弱负相关.通过对各浓度组中重要离子的分析发现,0.5倍组和4倍组中F^-的迁移受Ca²⁺、HCO₃^-和SO₄^2-浓度影响较大;相关性分析表明0.5倍浓度组的Ca²⁺、HCO₃^-浓度与F^-浓度呈极显著正相关,而4倍组中F^-浓度和Ca²⁺、HCO₃^-浓度呈负相关,SO₄^2-浓度和F^-浓度的相关性则是0.5倍组呈负相关,4倍组呈极显著正相关.本文在不同上覆水F^-浓度背景下全面探究了沙湖沉积物中F^-释放和迁移机理,为沙湖及其他含氟地表水的氟污染防治提供理论支持.     

蒙新高原岱海夏季叶绿素a浓度空间分布及影响因子

基于2019年夏季(8月)对岱海水样的实测数据分析,通过运用克里金插值、相关性分析、多元线性逐步回归、主成分分析方法,探究了叶绿素a(Chl.a)的空间分布特征及其与水环境因子的相关关系,并讨论了相应的防治措施。研究显示:Chl.a空间分布呈现由岸边向湖心递减的趋势,总氮(TN)、总磷(TP)、氨氮(NH₃-N)、硝态氮(NO^-₃-N)、正磷酸盐(PO^3-₄-P)空间分布特征与Chl.a空间分布特征相近,采样期内岱海湖局部区域水质状况已达到富营养状态;Chl.a与浊度(Turbidity)、TP、TN、悬浮物(SS)、pH、NO^-₃-N、NH₃-N、PO^3-₄-P、蓝绿藻丰度(CYANO)呈极显著正相关,与溶解氧(DO)呈显著负相关,与电导率(Cond.)呈正相关、与氮磷比(TN/TP)呈负相关;各湖区Chl.a与环境因子相关关系不同,全湖逐步线性回归方程为Y_Chl.a=-21.42+8.658X_pH-0.865X_DO+0.779X_NH3-N+0.699X_Turbidity+0.502X_CYANO;岱海不同湖区因子对Chl.a浓度的影响存在差异,各湖区Chl.a与环境因子相关关系不同,通过岱海与我国其他湖泊Chl.a与环境因子的相关性关系对比分析,湖泊地理属性差异及营养物质输入浓度是影响Chl.a变化的重要因素;本研究岱海的TN/TP平均值为12.23,说明夏季岱海湖Chl.a变化为氮磷共同限制。     

生态补水对白洋淀流域地表水和地下水水化学特征的影响

生态补水是维持和改善白洋淀生态环境的重要途径.为研究生态补水对白洋淀水环境的影响,分别在补水前与补水后采集淀水、河水及地下水样品,分析区域地表水和地下水水化学特征.结果表明：（1）白洋淀补水前、后地表水与地下水的水化学组成中Na⁺为主要阳离子,补水后阴离子以HCO₃^-为主,淀区南部地表水电导率高;补水后地表水与地下水Ca²⁺、Mg²⁺和HCO₃^-浓度显著增加,水体电导率降低.（2）补水前地下水为Na-HCO₃型水,地表水主要为Na-Cl·SO₄及Na-Cl·HCO₃类型;补水后地表水与浅层地下水向Ca·Mg-HCO₃型演化,深层地下水水化学类型基本保持不变.（3）生态补水使白洋淀水位升高,淀区水面积增大,缓解了水资源短缺的问题;同时也使浅层地下水水化学组成发生改变,而深层地下水暂未受到影响.生态补水后,受稀释和混合作用的影响,水体Na⁺、Cl^-和SO₄^2-浓度显著下降,Ca²⁺、Mg²⁺及HCO₃^-浓度增加.在白洋淀生态补水中应"先治污,后补水",以减少补水过程中污染物向淀区的运移,还应注意区域地下水位上升过程中的阳离子交换及水岩相互作用,为合理调配生态补水及改善白洋淀生态环境提供科学依据.     

秋季连续打捞蓝藻对水-气界面温室气体通量的影响

在巢湖西北半湖近岸带设置大型围隔研究秋季连续打捞蓝藻对湖泊温室气体通量的影响,应用YL-1000型大型仿生式水面蓝藻清除设备进行原位打捞蓝藻,通过便携式温室气体分析仪-静态箱法对大型围隔内水-气界面CH₄、CO₂通量特征及其影响因素进行观测.结果表明：对比未打捞区,蓝藻连续打捞下打捞区水体中叶绿素a（Chl.a）、悬浮物（SS）浓度不断下降,两者削减率分别为72%、85%,Chl.a、SS浓度分别下降到29.6±2.5 μg/L、12.5±1.2 mg/L,打捞对围隔内颗粒态物质去除效果十分明显;打捞过程中水体溶解性有机物（DOM）中微生物代谢类腐殖质（C1）、类蛋白（C3）显著下降趋势,打捞区C1、C3组分（0.18±0.02、0.06±0.01 RU）强度明显低于未打捞区（0.26±0.05、0.12±0.03 RU）,打捞能有效控制藻源性溶解性有机质释放.同时,打捞区水-气界面CH₄通量呈显著下降趋势,未打捞区CH₄通量平均值（17.473±1.514 nmol/（m²·s））为打捞区（7.004±4.163 nmol/（m²·s））近2倍,CH₄通量与Chl.a、C1、C3组分均呈显著正相关,水体中藻源性溶解态有机质对CH₄通量具有促进作用;打捞区CO₂释放通量呈显著上升趋势,打捞区CO₂吸收通量（-0.200±0.069 μmol/（m²·s））明显低于未打捞区（-0.344±0.017 μmol/（m²·s））,CO₂通量与Chl.a、温度均呈显著负相关.秋季打捞对CH₄、CO₂综合日平均通量减排量值为0.275±0.076 mol/（m²·d）（以CO₂当量计）.研究结果揭示了巢湖秋季连续打捞蓝藻过程对水-气界面温室气体具有显著减排作用,且能在一定程度上减缓蓝藻水华与湖泊富营养化、气候变暖之间的恶性循环,为湖泊碳循环和蓝藻水华灾害防控提供科学数据支撑和理论参考.     

溶解性有机碳耦合营养状态解析河流CO2动态及驱动因素

为全面探索河流溶解性有机碳(DOC)与二氧化碳(CO₂)动态及驱动因素的相关关系,以我国三峡库区河流——澎溪河为对象,于雨季和旱季采集表层水体水样,分别通过原位和室内测定,明确水文参数(水温、pH、碱度和流速)、DOC浓度和营养元素(总氮(TN)和总磷(TP))浓度,并计算水体CO₂分压(pCO₂)、水—气界面CO₂交换通量和营养元素化学计量比(DOC∶TN、DOC∶TP和TN∶TP)。以河流CO₂、DOC和营养状态动态变化为基础,通过对DOC、TN、TP、营养元素化学计量比和荧光峰(B、T、A、M、C、D和N)与河流pCO₂的多维分析建立及评估潜在的耦合关系,从而揭示特定区域河流CO₂的来源与驱动因素特征。结果显示,澎溪河水—气界面CO₂交换速率在3.75~22.9 m/d范围内,雨季((9.91±4.93)m/d) > 旱季((6.69±4.30)m/d),pCO₂在65.95~20642.41 μatm范围内,F平均值为(629.4±1426.8)mmol/(m²·d),河流总体表现为大气CO₂源。水体DOC总体在1.42~7.88 mg/L范围内,且旱季((4.50±0.17)mg/L)>雨季((2.87±0.18)mg/L),TN在0.176~1.917 mg/L范围内,旱季((1.205±0.353)mg/L)>雨季((0.665±0.306)mg/L),TP在0.0003~0.169 mg/L范围内。在该流域雨季,类酪氨酸、类色氨酸和土壤富里酸占比显著高于旱季,而类腐殖质、微生物衍生腐殖质和生物生产力占比显著低于旱季。旱季水体pCO₂与TP呈显著正相关,与营养元素化学计量比(TN∶TP和DOC∶TP)呈显著负相关,而雨季与生物生产力呈显著负相关,营养状态与pCO₂存在季节耦合关系。生物代谢过程是河流CO₂饱和的主要原因,而降雨能够促进这一内在联系。     

城镇化流域氮、磷污染特征及影响因素——以宁波北仑区小浃江为例

我国快速的城镇化过程造成了河流氮、磷等营养盐的污染和潜在的水体富营养化问题.对城镇流域水体氮、磷污染特征及其演变趋势的识别具有重要意义.本研究选取长三角典型城镇地区宁波市北仑区小浃江流域为研究对象,在流域内根据空间分布、土地利用类型、人类活动强度等情况布设样点,于2017年夏季和冬季采集水样,研究流域水体氮、磷污染的时空分布特征并分析其污染来源和评估其富营养化水平.结果表明：流域内铵态氮（NH₄⁺-N）、;硝态氮（NO₃^--N）、亚硝态氮（NO₂^--N）、总氮（TN）、总磷（TP）和叶绿素a（Chl.a）浓度范围分别为0.63~3.25 mg/L、0.52~3.75 mg/L、0.02~0.22 mg/L、1.61~12.86 mg/L、0.02~0.74 mg/L和0.6~60.57 μg/L.各个采样点氮、磷分布具有较大的空间异质性和季节变化规律.富营养化综合指数EI评估结果显示,整个流域富营养化程度属于贫至中营养级.氮、磷浓度与土地类型面积占比的Spearman相关性统计表明,100 m缓冲区建设用地面积占比与NH₄⁺-N、NO₂^--N、TN、溶解氧（DO）浓度具有显著相关性,湿地面积占比与DO浓度呈显著正相关.汇水区域内林地面积占比与NH₄⁺-N、NO₂^--N、TP、PO₄^3--P、COD、Chl.a浓度呈显著负相关,与DO浓度呈显著正相关.相关性分析和冗余分析表明城镇化的面源污染及可能存在的点源污染是小浃江流域氮、磷污染的主要来源.因此,在小浃江流域100 m范围内,控制建设用地的规模和污染排放是减轻流域氮、磷污染的主要途径.在汇水区域内,增加林地植被的面积对减少氮、磷污染具有重要影响.     

青藏盐湖卤水演化及资源

本文通过揭示宵蔵盐湖卤水在浓缩过程中成盐元素的行为以及卤水水化学炎型与PH值等的变化,得出结论如下：1.卤水中主要离子的演化方向是按Ca²⁺→Na⁺→K⁺→Mg²⁺→Ca²⁺（阳离子）和CO₃^2-→HCO₃^-→SO₄^2-→Cl^-（阴离子）顺序进行。2.除了析出固体外,微量元素一般在最后的浓缩卤水和析盐后的残余卤水中髙度富集。已査明盐湖卤水中有63种元素,其中钾、镁、硼、锂、铷、铯、铀、钍、稀土、氘已构成可以综合利用的宝贵资源。     

粤东五华河流域的化学风化与CO2吸收

基于对粤东五华河干流和支流水体的物理、化学组成测试数据,应用质量平衡法和相关分析法探讨湿热山地丘陵地区岩石化学风化过程对大气CO₂的吸收.结果表明:五华河水体的总溶解性固体含量(77.11 mg/L)接近于世界河流的平均值(65 mg/L);离子组成以Ca²⁺、Na⁺和HCO₃^-为主,可溶性Si次之.五华河流域化学径流组成主要源自硅酸盐矿物化学风化过程的贡献,碳酸盐矿物的贡献较少;大气和土壤CO₂是流域内岩石化学风化的主要侵蚀介质.与同一气候带其他河流相比较,五华河流域岩石化学风化过程对大气CO₂的吸收通量(2.14×105mol/(km²·a))较低,这主要是由于流域内缺乏碳酸盐岩所导致.     

Dynamics and sources of dissolved organic carbon during phytoplankton bloom in hypereutrophic Lake Taihu (China)

To establish the influence of phytoplankton blooms on the dynamics and sources of dissolved organic carbon (DOC) in Lake Taihu, the concentrations and stable carbon isotope values (δ¹³C) of DOC and particulate organic carbon (POC) were analyzed, along with environmental factors, including water temperature, chlorophyll a (Chl a) concentration, phytoplankton community and total bacterial abundance, from March to August 2013 at five sites in Lake Taihu. Significant differences were observed in the DOC concentrations and δ¹³C_DOC values at the sampling sites. On average, the proportion of DOC in the total organic carbon (TOC) pool ranged from 30% ± 10% to 81% ± 7%. POC was positively associated with both Chl a concentration and cyanobacteria biomass, suggesting that cyanobacteria blooms contribute to the POC pool in Lake Taihu. Depleted ¹³C in DOC relative to POC was observed in August, indicating that DOC was partially derived from POC in August. However, Chl a explained only 40% of the variation in DOC in the entirety of Lake Taihu, and at two sites far from the estuary, the contribution of allochthonous carbon was less than 50% in August. These results suggested a greater influence of allochthonous sources on the DOC pool. Moreover, the biodegradability of DOC was further determined by the total dissolved carbohydrates to DOC ratio (TCHO/DOC), specific UV absorbance (SUVA₂₅₄), and the concentrations of bioavailable DOC (BDOC). On average, 17% of the variation in DOC was attributable to the BDOC pool, and the BDOC concentration correlated positively with Chl a, cyanobacteria biomass, and total bacterial abundance, suggesting that cyanobacteria–derived DOC is biodegradable and is preferentially utilized by bacteria.     

Phytoplankton biomass size structure and its regulation in the Southern Yellow Sea (China): Seasonal variability

Phytoplankton size structure plays a significant role in controlling the carbon flux of marine pelagic ecosystems. The mesoscale distribution and seasonal variation of total and size-fractionated phytoplankton biomass in surface waters, as measured by chlorophyll a (Chl a), was studied in the Southern Yellow Sea using data from four cruises during 2006–2007. The distribution of Chl a showed a high degree of spatial and temporal variation in the study area. Chl a concentrations were relatively high in the summer and autumn, with a mean of 1.42 and 1.27 mg m⁻³, respectively. Conversely, in the winter and spring, the average Chl a levels were only 0.98 and 0.99 mg m⁻³. Total Chl a showed a clear decreasing gradient from coastal areas to the open sea in the summer, autumn and winter cruises. Patches of high Chl a were observed in the central part of the Southern Yellow Sea in the spring due to the onset of the phytoplankton bloom. The eutrophic coastal waters contributed at least 68% of the total phytoplankton biomass in the surface layer. Picophytoplankton showed a consistent and absolute dominance in the central region of the Southern Yellow Sea (>40%) in all of the cruises, while the proportion of microphytoplankton was the highest in coastal waters. The relative proportions of pico- and nanophytoplankton decreased with total biomass, whereas the proportion of the micro-fraction increased with total biomass. Relationships between phytoplankton biomass and environmental factors were also analysed. The results showed that the onset of the spring bloom was highly dependent on water column stability. Phytoplankton growth was limited by nutrient availability in the summer due to the strong thermocline. The combined effects of P-limitation and vertical mixing in the autumn restrained the further increase of phytoplankton biomass in the surface layer. The low phytoplankton biomass in winter was caused by vertical dispersion due to intense mixing. Compared with the availability of nutrients, temperature did not seem to cause direct effects on phytoplankton biomass and its size structure. Although interactions of many different environmental factors affected phytoplankton distributions, hydrodynamic conditions seemed to be the dominant factor. Phytoplankton size structure was determined mainly by the size-differential capacity in acquiring resource. Short time scale events, such as the spring bloom and the extension of Yangtze River plume, can have substantial influences, both on the total Chl a concentration and on the size structure of the phytoplankton.     

Low carbon dioxide partial pressure in a productive subtropical lake

The purposes of this study were to assess if Lake Apopka (FL, USA) was autotrophic or heterotrophic based on the partial pressure of dissolved carbon dioxide (pCO₂) in the surface water and to evaluate factors that influence the long-term changes in pCO₂. Monthly average pH, alkalinity and other limnological variables collected between 1987 and 2006 were used to estimate dissolved inorganic carbon (DIC), pCO₂ and CO₂ flux between surface water and atmosphere. Results indicated that average pCO₂ in the surface water was 196 μatm, well below the atmospheric pCO₂. Direct measurements of DIC concentration on three sampling dates in 2009 also supported pCO₂ undersaturation in Lake Apopka. Supersaturation in CO₂ occurred in this lake in only 13% of the samples from the 20-year record. The surface-water pCO₂ was inversely related to Chl a concentrations. Average annual CO₂ flux was 28.2 g C m⁻² year⁻¹ from the atmosphere to the lake water and correlated significantly with Chl a concentration, indicating that biological carbon sequestration led to the low dissolved CO₂ concentration. Low pCO₂ and high invasion rates of atmospheric CO₂ in Lake Apopka indicated persistent autotrophy. High rates of nutrient loading and primary production, a high buffering capacity, a lack of allochthonous loading of organic matter, and the dominance of a planktivorous–benthivorous fish food web have supported long-term net autotrophy in this shallow subtropical eutrophic lake. Our results also showed that lake restoration by the means of nutrient reduction resulted in significantly lower total phosphorus (TP) and Chl a concentrations, and higher pCO₂.     

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.     

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.     

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.