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Abstract. High-frequency continuous measurements of the partial pressure of CO2 (pCO2) are crucial for constraining the spatiotemporal dynamics of CO2 emissions from inland water systems. However, direct measurements of pCO2 are scarce, and no systematic comparisons have been conducted on the suitability of the widely used measurement systems for continuous underway or long-term deployment in various field conditions. We compared spray- and marble-type equilibrators and a membrane-enclosed CO2 sensor to assess their suitability for continuous long-term or underway pCO2 measurements in an urbanized river system in Korea. Both equilibrators had a shorter response time compared with the membrane-enclosed sensor, and could capture large spatial variations of pCO2 during a transect study along a highly urbanized river reach. The membrane-enclosed sensor based on passive equilibration provided comparable underway measurements along the river sections where pCO2 varied within the sensor detection range. When deployed in a eutrophic river site, the membrane-enclosed sensor was able to detect large diel variations in pCO2. However, biofouling on the membrane could reduce the accuracy of the measurement during long deployments exceeding several days. The overall results suggest that the fast response of the equilibrator systems facilitates capturing large spatial variations in pCO2 during short underway measurements. However, the attendant technical challenges of these systems, such as clogging and desiccant maintenance, have to be addressed carefully to enable their long-term deployment. The membrane-enclosed sensor would be suitable as an alternative tool for long-term continuous measurements if membrane biofouling could be overcome by appropriate antifouling measures such as copper mesh coverings.

Abstract.Forests play an important role in the global carbon (C) cycle, and the South Korean forests also contribute to this global C cycle. While the South Korean forest ecosystem was almost completely destroyed by exploitation and the Korean War, it has successfully recovered because of nationalscale reforestation programs since 1973. There have been several studies on the estimation of C stocks and balances over the past decades in the South Korean forests. However, a retrospective long-term study that includes biomass and dead organic matter C and validates dead organic matter C is still lacking. Accordingly, we estimated the C stocks and their changes of both biomass and dead organic matter C during the 1954-2012 period using a process-based model, the Korean Forest Soil Carbon model, and the 5th South Korean national forest inventory (NFI) report. Validation processes were also conducted based on the 5th NFI and statistical data. Simulation results showed that the biomass C stocks increased from 36.4 to 440.4 Tg C at a rate of 7.0 Tg C yr −1 during the period 1954-2012. The dead organic matter C stocks increased from 386.0 to 463.1 Tg C at a rate of 1.3 Tg C yr −1 during the same period. The estimates of biomass and dead organic matter C stocks agreed well with observed C stock data. The annual net biome production (NBP) during the period 1954-2012 was 141.3 g C m −2 yr −1 , which increased from −8.8 g C m −2 yr −1 in 1955 to 436.6 g C m −2 yr −1 in 2012. Because of the small forested area, the South Korean forests had a comparatively lower contribution to the annual C sequestration by global forests. In contrast, because of the extensive reforestation programs, the NBP of South Korean forests was much higher than those of other countries. Our results could provide the forest C dynamics in South Korean forests before and after the onset of reforestation programs.

Continuous underway measurements were combined with a basin-scale survey to examine human impacts on CO outgassing in a highly urbanized river system in Korea. While the partial pressure of CO (pCO) was measured at 15 sites using syringe equilibration, 3 cruises employing an equilibrator were done along a 30 km transect in the Seoul metropolitan area. The basin-scale survey revealed longitudinal increases in surface water pCO and dissolved organic carbon (DOC) in the downstream reach. Downstream increases in pCO, DOC, fluorescence index, and inorganic N and P reflected disproportionately large contributions from wastewater treatment plant (WWTP) effluents carried by major urban tributaries. Cruise transects exhibited strong localized peaks of pCO up to 13 000 μatm and CO enrichment along the confluences of tributaries at an average flow, whereas CO pulses were dampened by increased flow during the monsoon period. Fluctuations in pCO along the eutrophic reach downstream of the confluences reflected environmental controls on the balance between photosynthesis, biodegradation, and outgassing. The results underscore WWTP effluents as an anthropogenic source of nutrients, DOC, and CO and their influences on algal blooms and associated C dynamics in eutrophic urbanized river systems, warranting further research on urbanization-induced perturbations to riverine metabolic processes and carbon fluxes.

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Abstract. Surface water concentrations of CO2, CH4, and N2O have rarely been measured simultaneously in river systems modified by human activities, contributing to large uncertainties in estimating global riverine emissions of greenhouse gases (GHGs). Basin-wide surveys of the three GHGs were combined with a small number of measurements of C isotope ratios in dissolved organic matter (DOM), CO2, and CH4 in the Han River basin, South Korea, to examine how longitudinal patterns of the three gases and DOM are affected by four cascade dams along a middle section of the North Han River (hereafter termed “middle reach”) and treated wastewater discharged to the lower Han River (“lower reach”) traversing the Seoul metropolitan area. Monthly monitoring and two-season comparison were conducted at 6 and 15 sites, respectively, to measure surface water gas concentrations and ancillary water quality parameters including concentrations of dissolved organic carbon (DOC) and optical properties of DOM. The basin-wide surveys were complemented with a sampling cruise along the lower reach and synoptic samplings along an urban tributary delivering effluents from a large wastewater treatment plant (WWTP) to the lower reach. The levels of pCO2 were relatively low in the middle reach (51–2465 µatm), particularly at the four dam sites (51–761 µatm), compared with those found in the largely forested upper basin with scattered patches of croplands (163–2539 µatm), the lower reach (78–11298 µatm), and three urban tributaries (2120–11970 µatm). The upper and middle reaches displayed generally low concentration ranges of CH4 and N2O, with some local peaks influenced by agricultural runoff and impoundments. By comparison, the lower reach exhibited exceptionally high concentrations of CH4 (1.2–15766 nmol L−1) and N2O (7.5–1396 nmol L−1), which were significantly correlated with different sets of variables such as DO and PO43- for CH4 and NH4+ and NO3- for N2O. Downriver increases in the levels of DOC and optical properties such as fluorescence index (FI) and protein-like fluorescence indicated an increasing DOM fraction of anthropogenic and microbial origin. The concentrations of the three GHGs and DOC were similar in magnitude and temporal variation at a WWTP discharge and the receiving tributary, indicating a disproportionate contribution of the WWTP effluents to the tributary gas and DOC exports to the lower reach. The values of δ13C in surface water CO2 and CH4 measured during the sampling cruise along the lower reach, combined with δ13C and Δ14C in DOM sampled across the basin, implied a strong influence of the wastewater-derived gases and aged DOM delivered by the urban tributaries. The downstream enrichment of 13C in CO2 and CH4 suggested that the spatial distribution of these gases across the eutrophic lower reach may also be constrained by multiple concomitant processes including outgassing, photosynthesis, and CH4 oxidation. The overall results suggest that dams and urban wastewater may create longitudinal discontinuities in riverine metabolic processes leading to large spatial variations in the three GHGs correlating with different combinations of DOM properties and nutrients. Further research is required to evaluate the relative contributions of anthropogenic and in-stream sources of the three gases and DOM in eutrophic urbanized river systems and constrain key factors for the contrasting impoundment effects such as autotrophy-driven decreases in pCO2 and in-lake production of CH4 and N2O.

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We investigated the influence of stand density [938 tree ha(-1) for high stand density (HD), 600 tree ha(-1) for medium stand density (MD), and 375 tree ha(-1) for low stand density (LD)] on soil CO(2) efflux (R (S)) in a 70-year-old natural Pinus densiflora S. et Z. forest in central Korea. Concurrent with R (S) measurements, we measured litterfall, total belowground carbon allocation (TBCA), leaf area index (LAI), soil temperature (ST), soil water content (SWC), and soil nitrogen (N) concentration over a 2-year period. The R (S) (t C ha(-1) year(-1)) and leaf litterfall (t C ha(-1) year(-1)) values varied with stand density: 6.21 and 2.03 for HD, 7.45 and 2.37 for MD, and 6.96 and 2.23 for LD, respectively. In addition, R (S) was correlated with ST (R (2) = 0.77-0.80, P < 0.001) and SWC (R (2) = 0.31-0.35, P < 0.001). It appeared that stand density influenced R (S) via changes in leaf litterfall, LAI and SWC. Leaf litterfall (R (2) = 0.71), TBCA (R (2) = 0.64-0.87), and total soil N contents in 2007 (R (2) = 0.94) explained a significant amount of the variance in R (S) (P < 0.01). The current study showed that stand density is one of the key factors influencing R (S) due to the changing biophysical and environmental factors in P. densiflora.