The Italian Apennines are among the most important sources of freshwater for several Italian regions. With evidences of deep CO2-rich fluids intruding into aquifers in the nearby central-southern Apennines, a thorough investigation into the geochemistry of groundwater became critical to ensure the water quality in the area. Here, we show the main hydrogeochemical processes occurring in the Matese Massif (MM) aquifer through the investigation of 98 water samples collected from springs and water wells. All waters were classified as HCO3 type with Ca dominance (from 50% up to 97%) and variable amount of Mg (from 1% up to 49%). A multivariate statistical approach through the application of the factor analysis (FA) highlighted three main hydrogeochemical processes: (i) water-carbonate rock interactions mostly enhanced in peripheral areas of the MM by CO2 deep degassing; (ii) addition of NaCl-rich components linked to recharging process and to water mixing processes of the groundwater with a thermal component relatively rich in Cl, Na, and CO2; (iii) anthropogenic activities influencing groundwater composition at the foothills of MM. Furthermore, the first detailed TDIC, pCO2, and δ13C-TDIC distribution maps of the MM area have been created, which track chemical and isotopic anomalies in several peripheral areas (Pratella, Ailano, and Telese) throughout the region. These maps systematically highlight that the greater the amount of dissolved carbon occurs the heavier the C isotope enrichment, especially in the peripheral areas. Conversely, spring waters emerging at higher altitudes within MM are only slightly mineralized and associated with δ13C-TDIC values mainly characterized by recharging processes with the addition of biogenic carbon during the infiltration process through the soil.

River is characterized by obvious spatial heterogeneity in catchment, which is exacerbated by special environment features of calcium-rich, alkaline and DIC-rich(dissolved inorganic carbon) in karst river. Thus, it also leads to significant spatial variation in the CO2 degassing across water-air interface. Main ions, physicochemical parameters, δ13CDIC value and two common approaches(floating chamber(FC) and thin boundary layer models(TBL) were used to analyze the CO2 degassing characteristics in Guijiang River, a karst river, China. The results were as follows:1 Hydrochemistry in Guijiang River basin showed a significant spatial change. All of HCO3-, Ca2+, specific conductivity, total dissolved solids(TDS), SIc and pCO2 showed similar distribution characteristics in the following order:tributaries in the middle reaches > middle reaches > Downstream > Upstream of Guijiang River. 2 During the monitoring period, CO2 degassing occurred in all the sampling sites and it was the CO2 source for the atmosphere. The mean CO2 evasion was 237 mg·(m2·h)-1 in Guijiang River, which located in the range of average CO2 evasion of global river. However, significant spatial variations also occurred along Guijiang River. The CO2 degassing flux in tributaries of the middle reaches and middle reaches of the mainstream were obviously larger than those in downstream and upstream of the mainstream. 3 CO2 degassing was mainly affected by carbonate equilibrium system in tributaries in the middle reaches and middle reaches in the mainstream of the Guijiang River basin, which resulted in obviously larger CO2 degassing than those in downstream and upstream of mainstream. However, the CO2 degassing flux in tributaries of the middle reaches was also simultaneously affected by biological photosynthesis, and the minimum CO2 degassing flux[6.38 mg·(m2·h)-1] appeared in tributaries of the middle reaches. In addition, the CO2 degassing flux in mainstream upstream was mainly affected by atmospheric environmental factors, while it was synergetically influenced by many factors in mainstream downstream.

CO2 cycle process or sources/sinks are not only the basis of understanding and responding to global climate change, but also the core of the current global climate change research. Gas exchange across water-air interface in terrestrial surface water is an important way of nutrient elements (carbon, nitrogen) exchange between aquatic ecosystems and ambient air. Escaping CO2 gas from surface water is also actively involved in the modern carbon cycle. In the material cycle in karst regions, CO2 plays a key role in karst processes, driving the formation of karst features. Karst groundwater with high water CO2 partial pressure (pCO2) often shows highly positive CO2 concentration gradient to atmosphere after it is discharged to surface, so the evaluation of CO2 exchange fluxes across karst water-air interface is important for karst carbon cycle research. This paper researched CO2 exchange fluxes across water-air interface in the karst surface stream in detail which was fed by Guancun subterranean stream in Liuzhou city, Guangxi province. Closed static chamber method and portable hand-holding CO2 sensor (GM70) were both employed in CO2 exchange fluxes monitoring. The results showed that CO2 degassing was the mainly form of CO2 exchange across the steam water-air interface. CO2 degassing flux in subterranean stream outlet (G1 site) ranged from 139.48 to 890.84 mg·(m2·h)-1 with an average of 445.72 mg·(m2·h)-1. CO2 degassing flux in stream downstream site (G2 site) ranged from 16.54 to 844.18 mg·(m2·h)-1 with an average of 159.81 mg·(m2·h)-1. The CO2 degassing flux in G1site was higher than that in G2 site. CO2 degassing fluxes in rainy season in both G1 and G2 site were higher than those in dry season. Stable carbon analysis of CO2 gas (δ13C-CO2) found that CO2 degassing from karst stream might influence air CO2 carbon isotope near water surface, which resulted in the more negative δ13C-CO2 value with the increase of CO2 degassing flux. Significant spatio-temporal variations of δ13C-CO2 were found, and the δ13C-CO2 in the rainy season was more negative than that in dry season and δ13C-CO2 in G1 site was more negative than that in G2 site. As a result of stream CO2 degassing, the hydrochemical characteristics of steam varied along stream running, which resulted in decrease of HCO3-, EC and pCO2 and increase of pH, SIc and δ13C-DIC in the stream.