Dissolved Organic Carbon Pool Research Articles

Carbon dynamics and inconstant porewater input in a mangrove tidal creek over contrasting seasons and tidal amplitudes

Constraining the contribution of mangrove-derived carbon in tidal creeks is fundamental to understanding the fate of mangrove primary production and the role of mangroves as coastal carbon sinks. Porewater measurements and 24-h time series in a mangrove tidal creek were conducted during the dry and wet season, and over contrasting tidal ranges at the Can Gio Biosphere Reserve, Vietnam. Surface water carbon concentrations (dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), partial pressure of carbon dioxide (pCO2)) and their respective δ13C values were correlated with radon, suggesting that porewater input drives mangrove-derived carbon in the tidal creek. Based on three complementary mixing models, porewater input contributed to about 30% of the water volume and 46% to 100% of DOC and DIC pools in the tidal creek at low tide, with variabilities between seasons and tidal amplitudes. The creek carbon pool was 88% DIC, 6% DOC, and 6% particulate organic carbon (POC). The pCO2 values during the wet season (2973–16,495 μatm) were on average 5-fold higher than during the dry season (584–2946 μatm). This was explained by a potential greater mineralization attributed to higher organic matter availability and residual humidity that stimulate bacterial activity, and by a potential tidal dilution changing the pCO2/DIC ratio as suggested by the Revelle factor. Consequently, average CO2 evasion from the creek was estimated at 327–427 mmolC m−2 d−1 during the wet season and 92–213 mmolC m−2 d−1 during the dry season, using two independent approaches. Tidal amplitude seemed to influence porewater input and its carbon loads, with a higher contribution during frequent and high tidal amplitudes (symmetric). However, the highest input occurred in a tidal cycle which was preceded by tidal cycle of low amplitude (asymmetric). We explain this ambiguity by the influence of both, rapid water turnover intensifying porewater exchange, and long water residence time enhancing carbon load in porewater.

Effects of Landcover, Soil Property, and Temperature on Covariations of DOC and CDOM in Inland Waters

AbstractSignificant uncertainty exists in the estimation of dissolved organic carbon (DOC) concentration via remote sensing from colored dissolved organic matter (CDOM) absorption in inland waters pointing to a need for more process‐based understanding of the relationship between CDOM and DOC. In this study, we examine the factors affecting the covariations of DOC and CDOM using controlled experiments combined with field measurements at subbasin scale that have varying environmental and biological conditions. Our analysis reveals that the DOC:CDOM ratio is mainly related to landcover types. Higher DOC:CDOM linear regression slopes observed in evergreen leaf litter leachate suggest that CDOM comprises a smaller fraction of the DOC pool in evergreen sites in comparison to agricultural and deciduous leaf litter leachates. Given the same DOC concentrations, the range of CDOM levels from deciduous forest plant varied 3 times greater than that from other plant types. Results indicate that soil narrows the slope differences in the linear regressions of DOC from CDOM for all plant types (by 19% of evergreen, 18% of agriculture, and 77% of deciduous). Raising soil temperature by 5°C could double the range of DOC concentration and CDOM absorption for all scenarios. We present a mathematical model to estimate DOC concentration in freshwater environment via CDOM variations with reference to land cover and soil effects. The model was able to explain 95% of field measurements of multiple years in four subbasins. This improved understanding is critical for the remote sensing of DOC directly via observations of CDOM.

Minor contribution of small thaw ponds to the pools of carbon and methane in the inland waters of the permafrost-affected part of the Western Siberian Lowland

Despite the potential importance of small (< 1000 m2) thaw ponds and thermokarst lakes in greenhouse gas (GHG) emissions from inland waters of high latitude and boreal regions, these features have not been fully inventoried and the volume of GHG and carbon in thermokarst lakes remains poorly constrained. This is especially true for the vast Western Siberia Lowland (WSL) which is subject to strong thermokarst activity. We assessed the number of thermokarst lakes and their size distribution for the permafrost-affected WSL territory based on a combination of medium-resolution Landsat-8 images and high-resolution Kanopus-V scenes on 78 test sites across the WSL in a wide range of lake sizes (from 20 to 2 × 108 m2). The results were in fair agreement with other published data for world lakes including those in circum-polar regions. Based on available measurements of CH4, CO2, and dissolved organic carbon (DOC) in thermokarst lakes and thaw ponds of the permafrost-affected part of the WSL, we found an inverse relationship between lake size and concentration, with concentrations of GHGs and DOC being highest in small thaw ponds. However, since these small ponds represent only a tiny fraction of the landscape (i.e. ~1.5% of the total lake area), their contribution to the total pool of GHG and DOC in inland lentic water of the permafrost-affected part of the WSL is less than 2%. As such, despite high concentrations of DOC and GHG in small ponds, their role in overall C storage can be negated. Ongoing lake drainage due to climate warming and permafrost thaw in the WSL may lead to a decrease in GHG emission potential from inland waters and DOC release from lakes to rivers.

Influences of organic carbon speciation on hyporheic corridor biogeochemistry and microbial ecology

The hyporheic corridor (HC) encompasses the river–groundwater continuum, where the mixing of groundwater (GW) with river water (RW) in the HC can stimulate biogeochemical activity. Here we propose a novel thermodynamic mechanism underlying this phenomenon and reveal broader impacts on dissolved organic carbon (DOC) and microbial ecology. We show that thermodynamically favorable DOC accumulates in GW despite lower DOC concentration, and that RW contains thermodynamically less-favorable DOC, but at higher concentrations. This indicates that GW DOC is protected from microbial oxidation by low total energy within the DOC pool, whereas RW DOC is protected by lower thermodynamic favorability of carbon species. We propose that GW–RW mixing overcomes these protections and stimulates respiration. Mixing models coupled with geophysical and molecular analyses further reveal tipping points in spatiotemporal dynamics of DOC and indicate important hydrology–biochemistry–microbial feedbacks. Previously unrecognized thermodynamic mechanisms regulated by GW–RW mixing may therefore strongly influence biogeochemical and microbial dynamics in riverine ecosystems.

Large Stimulation of Recalcitrant Dissolved Organic Carbon Degradation by Increasing Ocean Temperatures

More than 96% of organic carbon in the ocean is in the dissolved form, most of it with lifetimes of decades to millennia. Yet, we know very little about the temperature sensitivity of dissolved organic carbon (DOC) degradation in a warming ocean. Combining independent estimates from laboratory experiments, oceanographic cruises and a global ocean DOC cycling model, we assess the relationship between DOC decay constants and seawater temperatures. Our results show that the apparent activation energy of DOC decay (Ea) increases by 3-fold from the labile (lifetime of days) and semi-labile (lifetime of months) to the semi-refractory (lifetime of decades) DOC pools, with only minor differences between the world’s largest ocean basins. This translates into increasing temperature coefficients (Q10) from 1.7–1.8 to 4–8, showing that the generalised assumption of a constant Q10 of ~2 for biological rates is not universally applicable for the microbial degradation of DOC in the ocean. Therefore, rising ocean temperatures will preferentially impact the microbial degradation of the more recalcitrant and larger of the three studied pools. Assuming a uniform 1oC warming scenario throughout the ocean, our model predicts a global decrease of the DOC reservoir by 7 ± 1 Pg C. This represents a 15% reduction of the semi-labile + semi-refractory DOC pools.

Shifting DOC concentration and quality in the freshwater lakes of the Kangerlussuaq region: An experimental assessment of possible mechanisms

ABSTRACT Since 2003, concentrations of dissolved organic carbon (DOC) in lakes in the Kangerlussuaq region declined by 14–55 percent, with these decreasing DOC concentrations potentially altering lake ecology and reflecting changes in regional carbon (C) cycling. To evaluate possible mechanisms responsible for this shift, we performed experiments to test the effects of dust addition, bacterial activity, or photodegradation on DOC concentration and two DOC quality metrics: the specific ultraviolet absorbance (SUVA254) and the chromophoric DOC spectral slope coefficient (S275–295). Lake-water DOC concentrations did not decline in any treatments, but there were changes in DOC quality. Dust addition increased SUVA254 and decreased the magnitude of S275–295 in one lake, the impacts of bacterial activity were variable, and sunlight exposure elicited a decline in SUVA254 and an increase in the magnitude of S275–295 in all lakes. These results suggest that DOC pools in the study lakes are photoreactive, even though the lakes are characterized by long residence times, but that declining DOC concentration did not result from this mechanism. While the tested mechanisms did not explain the decline in DOC concentration observed in recent years, they did yield new information about how dust, bacterial activity, or light can influence DOC quality in the lakes of the Kangerlussuaq region.

Effects of agricultural land use on dissolved organic carbon and nitrogen in surface runoff and subsurface drainage

Dissolved organic carbon (DOC) load in discharges from cultivated soils may have negative impacts on surface waters. The magnitude of the load may vary according to soil properties or agricultural management practices. This study quantifies the DOC load of cultivated mineral soils and investigates whether the load is affected by agricultural practices. Discharge volumes and concentrations of DOC and dissolved organic nitrogen (DON) were continually measured at three sites from surface runoff and artificial subsurface drainage or from combined total discharge over a two-year period (2012–2014). Two experimental sites in South-West Finland had clayey soils (with soil carbon contents of 2.7–5.9% in the topmost soil layer), and the third site in West-Central Finland had sandy soil (soil carbon contents of 4.3–6.2%). Permanent grassland, organic manure application, mineral fertilization, and conventional ploughing or no-till activities were studied. Furthermore, the biodegradable DOC pool of surface runoff and subsurface drainage water from no-till and ploughed fields was estimated in a 2-month incubation experiment with natural bacterial communities collected from the Baltic Sea seawater.The annual DOC and DON loads were affected by discharge volume and seasonal weather conditions. The loads varied between 25–52kgha−1 and 0.8–3.2kgha−1, respectively, and were comparable to those from boreal forests with similar soil types. The DOC load increased with increasing topsoil carbon content at all sites. There were slightly higher DOC concentrations and DOC load from permanent grassland, but otherwise we could not distinguish any clear management-induced differences in the total DOC loads. While only 6–17% of the DOC in discharge water was biologically degraded during the 2-month incubation, the proportion of biodegradable (labile) DOC in surface runoff appeared to increase when soil was ploughed compared to no-till.

Atmospheric fluxes of soluble organic C, N, and P to the Mediterranean Sea: Potential biogeochemical implications in the surface layer

Linking atmospheric deposition to marine carbon and nutrient cycle is hampered by the lack of data on atmospheric fluxes of organic matter. To fill this gap, this study reports the first quantification of atmospheric fluxes of soluble organic carbon (SOC), nitrogen (SON) and phosphate (SOP) to the NW Mediterranean Sea. Simultaneous measurements of dissolved organic carbon (DOC), dissolved organic nitrogen (DON) and dissolved organic phosphate (DOP) in the surface mixed layer (SML) allowed estimating the potential contribution of atmospheric fluxes to marine DOC, DON and DOP inventories. We found an annual atmospheric flux of 59mmolCm−2year−1 for SOC, 16.4mmolNm−2year−1 for SON and 23.6µmolPm−2year−1 for SOP, with proportions of SON and SOP to total soluble nitrogen and phosphate of 40% and 25%, respectively. Assuming these annual fluxes valid for the entire western Mediterranean basin, atmospheric fluxes would be higher than DOC, DON and DOP fluxes from the Rhône River by a factor of 6, 17 and 2, for C, N and P, respectively. Inventories of DOC, DON and DOP in the surface mixed layer displayed similar trends over the study period with maximum values at the end of the stratification period. DOP contributed by 85±11% to total dissolved phosphate (TDP) pool and exhibited a labile fraction (LDOP) of 27±19%. The contribution of atmospheric deposition to the DOC, DON and DOP pools in the SML, estimated for the stratification period, was low for C (3%) and P (4.5%) and moderate for N (12%). The labile fraction of atmospheric SOP (LSOP) was quantified throughout the sampling period and showed a high variability ranging from 0 to 97%. Atmospheric fluxes of LSOP contributed by 7% to marine LDOP pool and could sustain up to 8% of the heterotrophic prokaryotic phosphate demand in the SML of the NW Mediterranean Sea during the stratification period. The results obtained in this study stress the need to include atmospheric fluxes of organic matter in marine biogeochemical models to achieve a more complete picture of carbon and nutrient cycle in the Mediterranean Sea.

Occurrence of α, ω-dicarboxylic acids and ω-oxoacids in surface waters of the Rhone River and fluxes into the Mediterranean Sea

The Mediterranean Sea is a semi-enclosed marine environment surrounded by densely populated areas. This ecosystem is under strong anthropogenic pressure at present. Riverine waters are important input pathways of water-soluble organic compounds that potentially contribute to the dissolved organic carbon (DOC) pool. Here, we report the first ever measurements of bi-functional carboxylic acids such as α, ω -dicarboxylic acids (or diacids) and related polar compounds ω -oxoacids (or ketoacids) (BCAs=α, ω-dicarboxylic acids+ω -oxoacids), along with the DOC levels in Rhone River waters. Surface water samples were collected from February 2006 to June 2009 approximately 50km above the Rhone River mouth, which is the main supplier of freshwater to the Mediterranean Sea. The BCA concentrations averaged 32.4±15.3µgl−1, and exhibited a wide range of values from 13.2µgl−1 (Spring 2008) to 71.2µgl−1 (winter 2007). The contribution of carbon from BCAs to the DOC pool (BCA-C) accounted for 0.28 to 1.42% of the DOC. Although no seasonal trend was evident in the studied period, our results showed that the highest BCA concentrations did not always follow high water discharges. α,ω -dicarboxylic acids are the most abundant compound class (20.7±10.6µgl−1), which is followed by ω -oxoacids (11.7±6.2µgl−1). The Rhone River was estimated to deliver between 1.37 and 16.4 t d−1 of BCA to the Gulf of Lions. Assuming a mean water discharge of ∼1790m3s−1, a broad estimate suggests a loading of 750–4000 t yr−1 BCAs to the northwestern Mediterranean Sea. Our results indicated that glyoxylic acid (ωC2) was the most abundant BCA followed by oxalic acid (C2di) and fumaric acid (trans configuration of unsaturated C4 diacid). This result indicates that there is a different molecular distribution between the aquatic and atmospheric compartments, including rainwaters and aerosols, for which previous studies highlighted a predominance of oxalic acid, which was followed by malonic and/or succinic acid. Runoff and riverine biological process (rather than photochemical oxidation reactions) are hypothesized to control the BCA occurrence and molecular distribution in the Rhone River and thus their inputs to the coastal NW Mediterranean Sea, although the environmental implications of this stock of BCA are still unknown.

Redox and temperature-sensitive changes in microbial communities and soil chemistry dictate greenhouse gas loss from thawed permafrost

Greenhouse gas (GHG) emissions from thawed permafrost are difficult to predict because they result from complex interactions between abiotic drivers and multiple, often competing, microbial metabolic processes. Our objective was to characterize mechanisms controlling methane (CH4) and carbon dioxide (CO2) production from permafrost. We simulated permafrost thaw for the length of one growing season (90 days) in oxic and anoxic treatments at 1 and 15 °C to stimulate aerobic and anaerobic respiration. We measured headspace CH4 and CO2 concentrations, as well as soil chemical and biological parameters (e.g. dissolved organic carbon (DOC) chemistry, microbial enzyme activity, N2O production, bacterial community structure), and applied an information theoretic approach and the Akaike information criterion to find the best explanation for mechanisms controlling GHG flux. In addition to temperature and redox status, CH4 production was explained by the relative abundance of methanogens, activity of non-methanogenic anaerobes, and substrate chemistry. Carbon dioxide production was explained by microbial community structure and chemistry of the DOC pool. We suggest that models of permafrost CO2 production are refined by a holistic view of the system, where the prokaryote community structure and detailed chemistry are considered. In contrast, although CH4 production is the result of many syntrophic interactions, these actions can be aggregated into a linear approach, where there is a single path of organic matter degradation and multiple conditions must be satisfied in order for methanogenesis to occur. This concept advances our mechanistic understanding of the processes governing anaerobic GHG flux, which is critical to understanding the impact the release of permafrost C will have on the global C cycle.

Modeling 400–500-kyr Pleistocene carbon isotope cyclicity through variations in the dissolved organic carbon pool

The carbon isotope (δ13C) record from the Plio-Pleistocene shows prominent 400-kyr cycles with maximum values at eccentricity minima during the Pliocene. The period extends to 500kyr in the Pleistocene after ~1.6Ma. Five δ13C maxima occurred at ~0.2, 0.5, 1.0, 1.5 and 1.9Ma over the last 2Ma. Although several hypotheses have been suggested to explain why the 400–500-kyr cycles are so strong in δ13C records and how they may have originated, the mechanism is still not clear. The aim of this study was to test the dissolved organic carbon (DOC) hypothesis, which was proposed recently to explain this 400–500-kyr cycle in deeper time. We used an intermediate complexity box model that is computationally efficient for studies involving longer timescales. The model incorporates sophisticated microbial processes, dividing the oceanic carbon cycle into a rapid and a slow cycle. The model result suggests that when more nutrients enter the surface ocean, the rapid carbon cycle is more active, and less refractory DOC (RDOC) is produced. The opposite sequence occurs when fewer nutrients enter the ocean. The modeled RDOC concentration and the δ13C of dissolved inorganic carbon (DIC) are anti-correlated with riverine nutrient input. According to mass conservation, the release of isotopically lighter carbon from the RDOC pool leads to lighter DIC δ13C while an increase in the RDOC pool enriches it. The transient simulations produced a one-to-one correspondence between modeled and measured δ13C. This study supports the hypothesis that chemical weathering-induced variations in the DOC pool act as a pacemaker for δ13C changes over 400–500-kyr cycles.

Degradation potentials of dissolved organic carbon (DOC) from thawed permafrost peat

Global warming can substantially affect the export of dissolved organic carbon (DOC) from peat-permafrost to aquatic systems. The direct degradability of such peat-derived DOC, however, is poorly constrained because previous permafrost thaw studies have mainly addressed mineral soil catchments or DOC pools that have already been processed in surface waters. We incubated peat cores from a palsa mire to compare an active layer and an experimentally thawed permafrost layer with regard to DOC composition and degradation potentials of pore water DOC. Our results show that DOC from the thawed permafrost layer had high initial degradation potentials compared with DOC from the active layer. In fact, the DOC that showed the highest bio- and photo-degradability, respectively, originated in the thawed permafrost layer. Our study sheds new light on the DOC composition of peat-permafrost directly upon thaw and suggests that past estimates of carbon-dioxide emissions from thawed peat permafrost may be biased as they have overlooked the initial mineralization potential of the exported DOC.

MoDIE: Moderate dissolved inorganic carbon (DI13C) isotope enrichment for improved evaluation of DIC photochemical production in natural waters

Photochemical reactions in natural waters are a sink for dissolved organic carbon (DOC) and a source of dissolved inorganic carbon (DIC). Although considered significant to the carbon budget of the oceans, DIC photoproduction rates remain poorly constrained due to the analytical challenge involved in accurately measuring very low production rates (likely sub-μM h− 1 for blue ocean waters) relative to high background DIC concentrations (~ 2 mM). In an attempt to overcome this analytical limitation, almost all previous DIC photoproduction studies in marine systems have relied on the stripping of background DIC prior to irradiation, with unknown consequences for the integrity of the DOC pool and its photoreactivity, and none have resulted in a satisfactory determination of photoproduced DIC in open ocean waters. Here, we use small additions of NaH13CO3 (< 10% of background DIC concentrations) to achieve moderate DI13C isotope enrichment (MoDIE) of river, estuarine, and seawater samples. We then quantify the shift in δ13C of DIC in irradiated samples via liquid chromatography - isotope ratio mass spectrometry (LC-IRMS) and use these shifts to calculate photoproduced DIC. MoDIE provides a new method to more precisely (± 56 to ± 340 nM DIC) and more rapidly quantify DIC photoproduction compared to previous methods. MoDIE was evaluated by determining initial DIC photoproduction rates, along with associated broadband photochemical efficiency data (ranging from 144 to 280 μmol DIC per mol photons absorbed), in riverine to offshore waters, and produced the earliest time point and most precise measurement of DIC photoproduction in unmodified, low-CDOM, blue water (ag(325) = 0.30 m− 1) reported to date. In addition to measuring small DIC changes from photochemistry, the use of MoDIE could provide a major advance for other ocean carbon cycling studies, including examination of oceanic respiration, carbonate mineral precipitation/dissolution, and assessment of ocean acidification.

Nonlinear and threshold‐dominated runoff generation controls DOC export in a small peat catchment

AbstractWe used a relatively simple two‐layer, coupled hydrology‐biogeochemistry model to simultaneously simulate streamflow and stream dissolved organic carbon (DOC) concentrations in a small lead and arsenic contaminated upland peat catchment in northwestern Germany. The model procedure was informed by an initial data mining analysis, in combination with regression relationships of discharge, DOC, and element export. We assessed the internal model DOC processing based on stream DOC hysteresis patterns and 3‐hourly time step groundwater level and soil DOC data for two consecutive summer periods in 2013 and 2014. The parsimonious model (i.e., few calibrated parameters) showed the importance of nonlinear and rapid near‐surface runoff generation mechanisms that caused around 60% of simulated DOC load. The total load was high even though these pathways were only activated during storm events on average 30% of the monitoring time—as also shown by the experimental data. Overall, the drier period 2013 resulted in increased nonlinearity but exported less DOC (115 kg C ha−1 yr−1 ± 11 kg C ha−1 yr−1) compared to the equivalent but wetter period in 2014 (189 kg C ha−1 yr−1 ± 38 kg C ha−1 yr−1). The exceedance of a critical water table threshold (−10 cm) triggered a rapid near‐surface runoff response with associated higher DOC transport connecting all available DOC pools and subsequent dilution. We conclude that the combination of detailed experimental work with relatively simple, coupled hydrology‐biogeochemistry models not only allowed the model to be internally constrained but also provided important insight into how DOC and tightly coupled pollutants or trace elements are mobilized.

Abundant carbon substrates drive extremely high sulfate reduction rates and methane fluxes in Prairie Pothole Wetlands.

Inland waters are increasingly recognized as critical sites of methane emissions to the atmosphere, but the biogeochemical reactions driving such fluxes are less well understood. The Prairie Pothole Region (PPR) of North America is one of the largest wetland complexes in the world, containing millions of small, shallow wetlands. The sediment pore waters of PPR wetlands contain some of the highest concentrations of dissolved organic carbon (DOC) and sulfur species ever recorded in terrestrial aquatic environments. Using a suite of geochemical and microbiological analyses, we measured the impact of sedimentary carbon and sulfur transformations in these wetlands on methane fluxes to the atmosphere. This research represents the first study of coupled geochemistry and microbiology within the PPR and demonstrates how the conversion of abundant labile DOC pools into methane results in some of the highest fluxes of this greenhouse gas to the atmosphere ever reported. Abundant DOC and sulfate additionally supported some of the highest sulfate reduction rates ever measured in terrestrial aquatic environments, which we infer to account for a large fraction of carbon mineralization in this system. Methane accumulations in zones of active sulfate reduction may be due to either the transport of free methane gas from deeper locations or the co-occurrence of methanogenesis and sulfate reduction. If both respiratory processes are concurrent, any competitive inhibition of methanogenesis by sulfate-reducing bacteria may be lessened by the presence of large labile DOC pools that yield noncompetitive substrates such as methanol. Our results reveal some of the underlying mechanisms that make PPR wetlands biogeochemical hotspots, which ultimately leads to their critical, but poorly recognized role in regional greenhouse gas emissions.

Effect of long-term phosphorus addition on the quantity and quality of dissolved organic carbon in a freshwater wetland of Northeast China

Understanding how P enrichment alters the quantity and quality of dissolved organic carbon (DOC) is important, because of their role in regulating the C cycle. Here, we established a four-level P addition experiment (0, 1.2, 4.8, and 9.6gPm−2year−1) in a N-limited freshwater wetland in the Sanjiang Plain, Northeast China. The aim of this study was to examine the effects of eight years of P addition on DOC concentration, SUVA254 (Abs254/DOC concentration, indicating the aromaticity of DOC), C:C ratio (Abs400/DOC concentration, indicating the proportion of colored humic substances in DOC), and E4:E6 ratio (Abs465/Abs665, indicating the molecular size of humic substances) in surface water and soil pore water (0–15cm depth) during the growing season (June through September). Our results showed similar changing trends in concentration and optical properties of DOC following eight years of P addition in the both surface water and soil pore water across the sampling dates. Generally, P addition decreased DOC concentration, SUVA254, and C:C ratio, and increased E4:E6 ratio, irrespective of P addition levels. These altered optical properties of DOC indicated that P addition decreased the molecular weight and aromaticity of DOC, and thus increased the quality of DOC. These results suggest P enrichment substantially reduces the quantity of DOC in N-limited temperate freshwater wetlands, and imply that increased DOC quality following P addition can further provide a positive feedback to decreased DOC pool.

Short-Term Dissolved Organic Carbon Dynamics Reflect Tidal, Water Management, and Precipitation Patterns in a Subtropical Estuary

Estuaries significantly impact the global carbon cycle by regulating the exchange of organic matter, primarily in the form of dissolved organic carbon (DOC), between terrestrial and marine carbon pools. Estuarine DOC dynamics are complex as tides and other hydrological and climatic drivers can affect carbon fluxes on short and long time scales. While estuarine and coastal DOC dynamics have been well studied, variations on short time scales are less well constrained. Recent advancements in sonde technology enable autonomous in situ collection of high frequency DOC data using fluorescent dissolved organic matter (fDOM) as a proxy, dramatically improving our capacity to characterize rapid changes in DOC, even in remote ecosystems. This study utilizes high-frequency fDOM measurements to untangle rapid and complex hydrologic drivers of DOC in the Shark River estuary, the main drainage of Everglades National Park, Florida. Non-conservative mixing of fDOM along the salinity gradient suggested mangrove inputs accounted for 6% of the total DOC pool. Average changes in fDOM concentrations through individual tidal cycles ranged from less than 10% to greater than 50% and multi-day trends greater than 100% change in fDOM concentration were observed. Salinity and water level both inversely correlated to fDOM at sub-hourly and daily resolutions, while freshwater controls via precipitation and water management were observed at diel to monthly time-scales. In particular, the role of water management in rapidly shifting estuarine salinity gradients and DOC export regimes at sub-weekly time-scales was evident. Additionally, sub-hourly spikes in ebb-tide fDOM indicated rapid exchange of DOC between mangrove sediments and the river channel. DOC fluxes calculated from high-resolution fDOM measurements were compared to monthly DOC measurements with high-resolution fluxes considerably improving accuracy of fluxes (thereby constraining carbon budgets). This study provides a better understanding of short-term DOC dynamics and associated hydrological drivers and indicates the importance of high-frequency measurements to accurately constraining coastal carbon processes and budgets, particularly in coastal systems increasingly altered by hydrologic restoration and climate change.

Impact of low pH/high pCO2 on the physiological response and fatty acid content in diatom Skeletonema pseudocostatum

pCO2/pH perturbation experiments were carried out under two different pCO2 levels to evaluate effects of CO2-driven ocean acidification on semi-continuous cultures of the marine diatom Skeletonema pseudocostatum CSA48. Under higher pCO2/lowered pH conditions, our results showed that CO2-driven acidification had no significant impact on growth rate, chlorophyll-a, cellular abundance, gross photosynthesis, dark respiration, particulate organic carbon and particulate organic nitrogen between CO2-treatments, suggesting that S. pseudocostatum is adapted to tolerate changes of ~0.5 units of pH under high pCO2 conditions. However, dissolved organic carbon (DOC) concentration and DOC/POC ratio were significantly higher at high pCO2, indicating that a greater partitioning of organic carbon into the DOC pool was stimulated by high CO2/low pH conditions. Total fatty acids (FAs) were significantly higher under low pCO2 conditions. The composition of FAs changed from low to high pCO2, with an increase in the concentration of saturated and a reduction of monounsaturated FAs. Polyunsaturated FAs did not show significant differences between pCO2 treatments. Our results lead to the conclusion that the balance between negative or null effect on S. pseudocostatum ecophysiology upon low pH/high pCO2 conditions constitute an important factor to be considered in order to evaluate the global effect of rising atmospheric CO2 on primary productivity in coastal ocean. We found a significant decrease in total FAs, however no indications were found for a detrimental effect of ocean acidification on the nutritional quality in terms of essential fatty acids.

Effects of ocean acidification on pelagic carbon fluxes in a mesocosm experiment

Abstract. About a quarter of anthropogenic CO2 emissions are currently taken up by the oceans, decreasing seawater pH. We performed a mesocosm experiment in the Baltic Sea in order to investigate the consequences of increasing CO2 levels on pelagic carbon fluxes. A gradient of different CO2 scenarios, ranging from ambient ( ∼ 370 µatm) to high ( ∼ 1200 µatm), were set up in mesocosm bags ( ∼ 55 m3). We determined standing stocks and temporal changes of total particulate carbon (TPC), dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), and particulate organic carbon (POC) of specific plankton groups. We also measured carbon flux via CO2 exchange with the atmosphere and sedimentation (export), and biological rate measurements of primary production, bacterial production, and total respiration. The experiment lasted for 44 days and was divided into three different phases (I: t0–t16; II: t17–t30; III: t31–t43). Pools of TPC, DOC, and DIC were approximately 420, 7200, and 25 200 mmol C m−2 at the start of the experiment, and the initial CO2 additions increased the DIC pool by ∼ 7 % in the highest CO2 treatment. Overall, there was a decrease in TPC and increase of DOC over the course of the experiment. The decrease in TPC was lower, and increase in DOC higher, in treatments with added CO2. During phase I the estimated gross primary production (GPP) was ∼ 100 mmol C m−2 day−1, from which 75–95 % was respired, ∼ 1 % ended up in the TPC (including export), and 5–25 % was added to the DOC pool. During phase II, the respiration loss increased to ∼ 100 % of GPP at the ambient CO2 concentration, whereas respiration was lower (85–95 % of GPP) in the highest CO2 treatment. Bacterial production was ∼ 30 % lower, on average, at the highest CO2 concentration than in the controls during phases II and III. This resulted in a higher accumulation of DOC and lower reduction in the TPC pool in the elevated CO2 treatments at the end of phase II extending throughout phase III. The “extra” organic carbon at high CO2 remained fixed in an increasing biomass of small-sized plankton and in the DOC pool, and did not transfer into large, sinking aggregates. Our results revealed a clear effect of increasing CO2 on the carbon budget and mineralization, in particular under nutrient limited conditions. Lower carbon loss processes (respiration and bacterial remineralization) at elevated CO2 levels resulted in higher TPC and DOC pools than ambient CO2 concentration. These results highlight the importance of addressing not only net changes in carbon standing stocks but also carbon fluxes and budgets to better disentangle the effects of ocean acidification.

New nutrients exert fundamental control on dissolved organic carbon accumulation in the surface Atlantic Ocean

The inventories of carbon residing in organic matter dissolved in the ocean [dissolved organic carbon (DOC)] and in the atmosphere as CO2 are of the same order of magnitude, such that small changes in the DOC pool could have important consequences in atmospheric carbon and thus climate. DOC in the global ocean is largely formed in the sunlit euphotic zone, but identifying predictable controls on that production is an important yet unrealized goal. Here, we use a testable and causative correlation between the net production of DOC and the consumption of new nutrients in the euphotic zone of the Atlantic Ocean. We demonstrate that new nutrients introduced to the euphotic zone by upwelling in divergence zones and by winter convective overturn of the water column, and the primary production associated with those nutrients, are the ultimate driver of DOC distributions across the Atlantic basins. As new nutrient input will change with a changing climate, the role of DOC in the ocean's biological pump should likewise be impacted.