Carbon and nitrogen content of marine pore waters

We have developed sampling methods and an analytical system to determine the concentration of dissolved organic C (DOC) in marine pore waters. Our analytical approach is a modification of recently developed high-temperature, Pt-catalyzed oxidation methods; it uses Chromatographic trapping of the DOC-derived CO2 followed by reduction to CH4 and flame ionization detection. Sampling experiments with nearshore sediments indicate that pore-water separation by whole-core squeezing causes artificially elevated DOC concentrations, while pore-water recovery by sectioning and centrifugation does not appear to introduce DOC artifacts. Results from a set of northwestern Atlantic continental slope cores suggest that net DOC production accounts for >50% of the organic C that is recycled at the sediment-water interface.

(Table T1) Dissolved carbohydrate concentrations of interstitial waters from seven ODP Leg 201 sites

Total dissolved carbohydrates (DCHOs) were determined in interstitial waters collected at open-ocean and Peru margin sites cored during Ocean Drilling Program Leg 201. Concentrations of DCHOs ranged from 0 to ~1500 µM and showed no consistent trends between open-ocean and Peru margin sites either in the magnitude or direction of downhole interstitial water gradients. In contrast, relative DCHO concentrations (normalized to dissolved organic carbon concentrations) were higher in open-ocean vs. margin sediments. These trends are consistent with results from more shallow estuarine and nearshore continental margin sediments and may be related to changes in the overall controls on sediment organic matter remineralization with decreasing remineralization rates.

The North Pacific biological pump: Rates, efficiency and influence on ocean carbon uptake

Thesis (Ph.D.)--University of Washington, 2016-05

Controls on mangrove forest-atmosphere carbon dioxide exchanges in western Everglades National Park

We report on net ecosystem production (NEP) and key environmental controls on net ecosystem exchange (NEE) of carbon dioxide (CO2) between a mangrove forest and the atmosphere in the coastal Florida Everglades. An eddy covariance system deployed above the canopy was used to determine NEE during January 2004 through August 2005. Maximum daytime NEE ranged from −20 to −25 mmol (CO2) m−2 s−1 between March and May. Respiration (Rd) was highly variable (2.81 ± 2.41 mmol (CO2) m−2 s−1), reaching peak values during the summer wet season. During the winter dry season, forest CO2 assimilation increased with the proportion of diffuse solar irradiance in response to greater radiative transfer in the forest canopy. Surface water salinity and tidal activity were also important controls on NEE. Daily light use efficiency was reduced at high (>34 parts per thousand (ppt)) compared to low (ppt) salinity by 46%. Tidal inundation lowered daytime Rd by ∼0.9 mmol (CO2) m−2 s−1 and nighttime Rd by ∼0.5 mmol (CO2) m−2 s−1. The forest was a sink for atmospheric CO2, with an annual NEP of 1170 ± 127 g C m−2 during 2004. This unusually high NEP was attributed to year‐round productivity and low ecosystem respiration which reached a maximum of only 3 g C m−2 d−1. Tidal export of dissolved inorganic carbon derived from belowground respiration likely lowered the estimates of mangrove forest respiration. These results suggest that carbon balance in mangrove coastal systems will change in response to variable salinity and inundation patterns, possibly resulting from secular sea level rise and climate change. Citation: Barr, J. G., V. Engel, J. D. Fuentes,

Stream dissolved organic matter bioavailability and composition in watersheds underlain with discontinuous permafrost

We examined the impact of permafrost on dissolved organic matter (DOM) composition in Caribou-Poker Creeks Research Watershed (CPCRW), a watershed underlain with discontinuous permafrost, in interior Alaska. We analyzed long term data from watersheds underlain with varying degrees of permafrost, sampled springs and thermokarsts, used fluorescence spectroscopy, and measured the bioavailabity of dissolved organic carbon (DOC). Permafrost driven patterns in hydrology and vegetation influenced DOM patterns in streams, with the stream draining the high permafrost watershed having higher DOC and dissolved organic nitrogen (DON) concentrations, higher DOC:- DON and greater specific ultraviolet absorbance (SUVA) than the streams draining the low and medium permafrost watersheds. Streams, springs and thermokarsts exhibited a wide range of DOC and DON concentrations (1.5–37.5 mgC/L and 0.14–1.26 mgN/L, respectively), DOC:DON (7.1–42.8) and SUVA (1.5–4.7 L mgC-1 m-1). All sites had a high proportion of humic components, a low proportion of protein components, and a low fluorescence index value (1.3–1.4), generally consistent with terrestrially derivedDOM. Principal component analysis revealed distinct groups in our fluorescence data determined by diagenetic processing and DOM source. The proportion of bioavailable DOC ranged from 2 to 35%, with the proportion of tyrosine- and tryptophan-like fluorophores in the DOM being a major predictor of DOC loss (p\0.05, R2 = 0.99). Our results indicate that the degradation of permafrost in CPCRW will result in a decrease in DOC and DON concentrations, a decline in DOC:DON, and a reduction in SUVA, possibly accompanied by

The role of dissolved organic matter bioavailability in promoting phytoplankton blooms in Florida Bay

The clear, shallow, oligotrophic waters of Florida Bay are characterized by low phytoplankton biomass, yet periodic cyanobacteria and diatom blooms do occur. We hypothesized that allochthonous dissolved organic matter (DOM) was providing a subsidy to the system in the form of bound nutrients. Water from four bay sites was incubated under natural light and dark conditions with enrichments of either DOM ( > 1 kD, 2×DOM) or inorganic nutrients (N+P). Samples were analyzed for bacterial numbers, bacterial production, phytoplankton biomass, phytoplankton community structure, and production, nutrients, and alkaline phosphatase (AP) activity. The influence of 2×DOM enrichment on phytoplankton biomass developed slowly during the incubations and was relatively small compared to nutrient additions. Inorganic nutrient additions resulted in an ephemeral bloom characterized initially as cyanobacterial and brown algae but which changed to dinoflagellate and/or brown algae by day six. The DIN:TP ratio decreased 10-fold in the N+P treatments as the system progressed towards N limitation. This ratio did not change significantly for 2×DOM treatments. In addition, these experiments indicated that both autotrophic and heterotrophic microbial populations in Florida Bay may fluctuate in their limitation by organic and inorganic nutrient availability. Both N+P and 2×DOM enrichments revealed significant and positive response in bioavailability of dissolved organic carbon (BDOC). Potential BDOC ranged from 1.1 to 35.5%, with the most labile forms occurring in Whipray Basin. BDOC at all sites was stimulated by the 2×DOM addition. Except for Duck Key, BDOC at all sites was also stimulated by the addition of N+P. BDOC was lower in the dry season than in the wet season (5.56% vs. 16.86%). This may be explained by the distinct chemical characteristics of the DOM produced at different times of year. Thus, both the heterotrophic and autotrophic microbial communities in Florida Bay are modulated by bioavailability of DOM. This has ramifications for the fate of DOM from the Everglades inputs, implicating DOM bioavailability as a contributing factor in regulating the onset, persistence, and composition of phytoplankton blooms.

Mangrove production and carbon sinks: A revision of global budget estimates

Mangrove forests are highly productive but globally threatened coastal ecosystems, whose role in the carbon budget of the coastal zone has long been debated. Here we provide a comprehensive synthesis of the available data on carbon fluxes in mangrove ecosystems. A reassessment of global mangrove primary production from the literature results in a conservative estimate of ∼218 ± 72 Tg C a−1. When using the best available estimates of various carbon sinks (organic carbon export, sediment burial, and mineralization), it appears that >50% of the carbon fixed by mangrove vegetation is unaccounted for. This unaccounted carbon sink is conservatively estimated at ∼112 ± 85 Tg C a−1, equivalent in magnitude to ∼30–40% of the global riverine organic carbon input to the coastal zone. Our analysis suggests that mineralization is severely underestimated, and that the majority of carbon export from mangroves to adjacent waters occurs as dissolved inorganic carbon (DIC). CO2 efflux from sediments and creek waters and tidal export of DIC appear to be the major sinks. These processes are quantitatively comparable in magnitude to the unaccounted carbon sink in current budgets, but are not yet adequately constrained with the limited published data available so far.

Photo-dissolution of flocculent, detrital material in aquatic environments: Contributions to the dissolved organic matter pool

This study shows that light exposure of flocculent material (floc) from the Florida Coastal Everglades (FCE) results in significant dissolved organic matter (DOM) generation through photo-dissolution processes. Floc was collected at two sites along the Shark River Slough (SRS) and irradiated with artificial sunlight. The DOM generated was characterized using elemental analysis and excitation emission matrix fluorescence coupled with parallel factor analysis. To investigate the seasonal variations of DOM photo-generation from floc, this experiment was performed in typical dry (April) and wet (October) seasons for the FCE. Our results show that the dissolved organic carbon (DOC) for samples incubated under dark conditions displayed a relatively small increase, suggesting that microbial processes and/or leaching might be minor processes in comparison to photo-dissolution for the generation of DOM from floc. On the other hand, DOC increased substantially (as much as 259 mgC gC−1) for samples exposed to artificial sunlight, indicating the release of DOM through photo-induced alterations of floc. The fluorescence intensity of both humic-like and protein-like components also increased with light exposure. Terrestrial humic-like components were found to be the main contributors (up to 70%) to the chromophoric DOM (CDOM) pool, while protein-like components comprised a relatively small percentage (up to 16%) of the total CDOM. Simultaneously to the generation of DOC, both total dissolved nitrogen and soluble reactive phosphorus also increased substantially during the photo-incubation period. Thus, the photo-dissolution of floc can be an important source of DOM to the FCE environment, with the potential to influence nutrient dynamics in this system.

Early diagenesis of plant-derived dissolved organic matter along a wetland, mangrove, estuary ecotone

We studied the role of photochemical and microbial processes in contributing to the transformation of dissolved organic matter (DOM) derived from various plants that dominate the Florida Everglades. Plant-derived DOM leachate samples were exposed to photochemical and microbial degradation and the optical, chemical, and molecular weight characteristics measured over time. Optical parameters such as the synchronous fluorescence intensity between 270 and 290 nm (Fnpeak I), a strong indicator of protein and/or polyphenol content, decreased exponentially in all plant leachate samples, with microbial decay constants ranging from 21.0 d21 for seagrass to 20.11 d21 for mangrove (half-life [t1/2] 5 0.7–6.3 d). Similar decreases in polyphenol content and dissolved organic carbon (DOC) concentration also occurred but were generally an order of magnitude lower or did not change significantly over time. The initial molecular weight composition was reflected in the rate of Fnpeak I decay and suggests that plantderived DOM with a large proportion of high molecular weight structures, such as seagrass derived DOM, contain high concentrations of easily microbially degradable proteinaceous components. For samples exposed to extended simulated solar radiation, polyphenol and Fnpeak I photochemical decay constants were on average 20.7 d21 (t1/2 1.0 d). Our data suggest that polyphenol structures of plant-derived DOM are particularly sensitive to photolysis, whereas high molecular weight protein-like structures are degraded primarily through physical–chemical and microbial processes. Furthermore, microbial and physical processes initiated the formation of recalcitrant, highly colored high molecular weight polymeric structures in mangrove-derived DOM. Thus, partial, biogeochemical transformation of plant-derived DOM from coastal areas is rapid and is likely to influence carbon and nutrient cycling, especially in areas dominated by seagrass and mangrove forests.

Flux of organic carbon in a riverine mangrove wetland in the Florida Coastal Everglades

Short-term (daily) and seasonal variations in concentration and flux of dissolved organic carbon (DOC) were examined over 15 tidal cycles in a riverine mangrove wetland along Shark River, Florida in 2003. Due to the influence of seasonal rainfall and wind patterns on Shark River’s hydrology, samplings were made to include wet, dry and transitional (Norte) seasons. We used a flume extending from a tidal creek to a basin forest to measure vertical (vegetated soil/water column) and horizontal (mangrove forest/tidal creek) flux of DOC. We found significant (p < 0.05) variations in surface water temperature, salinity, conductivity, pH and mean concentration of DOC with season. Water temperature and salinity followed seasonal patterns of air temperature and rainfall, while mean DOC concentration was highest during the dry season (May), followed by the wet (October) and ‘Norte’ (December) seasons. This pattern of DOC concentration may be due to a combination of litter production and inundation pattern of the wetland. In contrast to daily (between tides) variation in DOC flux between the mangrove forest and tidal creek, daily variations of mean water quality were not significant. However, within-tide variation of DOC flux, dissolved oxygen content and salinity was observed. This indicated that the length of inundation and water source (freshwater vs. saltwater) variation across tidal cycles influenced water quality and DOC flux in the water column. Net DOC export was measured in October and December, suggesting the mangrove forest was a source of DOC to the adjacent tidal creek during these periods. Net annual export of DOC from the fringe mangrove to both the tidal creek and basin mangrove forest was 56 g C m−2 year−1. The seasonal pattern in our flux results indicates that DOC flux from this mangrove forest may be governed by both freshwater discharge and tidal range.

Mechanisms of Bicarbonate Use Influence the Photosynthetic Carbon Dioxide Sensitivity of Tropical Seagrasses

The photosynthetic bicarbonate () use properties of three widely distributed tropical seagrasses were compared using a series of laboratory experiments. Photosynthetic rates of Thalassia testudinum, Halodule wrightii, and Syringodium filiforme were monitored in an enclosed chamber while being subjected to shifts in pH and dissolved inorganic carbon. Specific mechanisms of seagrass use were compared by examining the photosynthetic effects of the carbonic anhydrase inhibitor acetazolamide (AZ). All seagrasses increased photosynthetic rates with reduced pH, suggesting a large effect of dissolved aqueous carbon dioxide (CO2(aq)). However, there was considerable interspecific variation in pH response. T. testudinum was highly sensitive, increasing photosynthetic rates by 100% as the pH was reduced from 8.2 to 7.4, whereas rates in H. wrightii and S. filiforme increased by only 20% over a similar range, and displayed prominent photosynthetic plateaus, indicating an increased capacity for use. Additional incubations that manipulated [] under constant [CO2(aq)] support these findings, as only H. wrightii and S. filiforme increased photosynthetic rates with increasing []. T. testudinum responded to AZ addition, indicating that carbonic anhydrase enzymes facilitate limited use. H. wrightii and S. filiforme showed no response to AZ, suggesting alternate, more efficient mechanisms of use. Estimated kinetic parameters, Ks(CO2) and Vmax, revealed interspecific variation and further support these conclusions. Variation in photosynthetic pH responses and AZ sensitivity indicate distinctions in the carbon use properties of seagrasses exposed to similar environmental conditions. These results suggest that not all seagrasses will similarly respond to future increases in CO2(aq) availability. Attention towards potential shifts in competitive interactions within multispecific seagrass beds is warranted.

Using Optical Properties to Quantify Fringe Mangrove Inputs to the Dissolved Organic Matter (DOM) Pool in a Subtropical Estuary

Dissolved organic carbon (DOC) concentration and dissolved organic matter (DOM) optical properties were analyzed along two estuarine river transects during the wet and dry seasons to better understand DOM dynamics and quantify mangrove inputs. A tidal study was performed to assess the impacts of tidal pumping on DOM transport. DOM in the estuaries showed non-conservative mixing indicative of mangrove-derived inputs. Similarly, fluorescence data suggest that some terrestrial humic-like components showed non-conservative behavior. An Everglades freshwater-derived fluorescent component, which is associated with soil inputs from the Northern Everglades, behaved conservatively. During the dry season, a protein-like component behaved conservatively until the mid-salinity range when non-conservative behavior due to degradation and/or loss was observed. The tidal study data suggests mangrove porewater inputs to the rivers following low tide. The differences in quantity of DOM exported by the Shark and Harney Rivers imply that geomorphology and tidal hydrology may be a dominant factor controlling the amount of DOM exported from the mangrove ecotone, where up to 21 % of the DOC is mangrove-derived. Additionally, nutrient concentrations and other temporal factors may control DOM export from the mangroves, particularly for the microbially derived fluorescent components, contributing to the seasonal differences. The wet and dry season fluxes of mangrove DOM from the Shark River is estimated as 0.27 × 109 mg C d−1 and 0.075 × 109 mg C d−1, respectively, and the Harney River is estimated as 1.9 × 109 mg C d−1 and 0.20 × 109 mg C d−1.

Biogeochemical Effects of Simulated Sea Level Rise on Carbon Loss in an Everglades Mangrove Peat Soil

Saltwater intrusion and inundation can affect soil microbial activity, which regulates the carbon (C) balance in mangroves and helps to determine if these coastal forests can keep pace with sea level rise (SLR). This study evaluated the effects of increased salinity (+15 ppt), increased inundation (−8 cm), and their combination, on soil organic C loss from a mangrove peat soil (Everglades, Florida, USA) under simulated tides. Soil respiration (CO2 flux), methane (CH4) flux, dissolved organic carbon (DOC) production, and porewater nutrient concentrations were quantified. Soil respiration was the major pathway of soil organic C loss (94–98%) and was approximately 90% higher in the control water level than the inundated treatment under elevated salinity. Respiration rate increased with water temperature, but depended upon salinity and tidal range. CH4 flux was minimal, while porewater DOC increased with a concomitant, significant decline in soil bulk density under increased inundation. Porewater ammonium increased (73%) with inundation and soluble reactive phosphorus increased (32%) with salinity. Overall, the decline in soil organic C mineralization from combined saltwater intrusion and prolonged inundation was not significant, but results suggest SLR could increase this soil’s susceptibility to peat collapse and accelerate nutrient and DOC export to adjacent Florida Bay.

Spatial and Temporal Variability of Dissolved Organic Matter Quantity and Composition in an Oilgotrophic Subtropical Coastal Wetland

Dissolved organic matter (DOM) is an essential component of the carbon cycle and a critical driver in controlling variety of biogeochemical and ecological processes in wetlands. The quality of this DOM as it relates to composition and reactivity is directly related to its sources and may vary on temporal and spatial scales. However, large scale, long-term studies of DOM dynamics in wetlands are still scarce in the literature. Here we present a multi-year DOM characterization study for monthly surface water samples collected at 14 sampling stations along two transects within the greater Everglades, a subtropical, oligotrophic, coastal freshwater wetland-mangrove-estuarine ecosystem. In an attempt to assess quantitative and qualitative variations of DOM on both spatial and temporal scales, we determined dissolved organic carbon (DOC) values and DOM optical properties, respectively. DOM quality was assessed using, excitation emission matrix (EEM) fluorescence coupled with parallel factor analysis (PARAFAC). Variations of the PARAFAC components abundance and composition were clearly observed on spatial and seasonal scales. Dry versus wet season DOC concentrations were affected by dry-down and re-wetting processes in the freshwater marshes, while DOM compositional features were controlled by soil and higher plant versus periphyton sources respectively. Peat-soil based freshwater marsh sites could be clearly differentiated from marl-soil based sites based on EEM–PARAFAC data. Freshwater marsh DOM was enriched in higher plant and soil-derived humic-like compounds, compared to estuarine sites which were more controlled by algae- and microbial-derived inputs. DOM from fringe mangrove sites could be differentiated between tidally influenced sites and sites exposed to long inundation periods. As such coastal estuarine sites were significantly controlled by hydrology, while DOM dynamics in Florida Bay were seasonally driven by both primary productivity and hydrology. This study exemplifies the application of long term optical properties monitoring as an effective technique to investigate DOM dynamics in aquatic ecosystems. The work presented here also serves as a pre-restoration condition dataset for DOM in the context of the Comprehensive Everglades Restoration Plan (CERP).

Effects of Land Use on Sources and Ages of Inorganic and Organic Carbon in Temperate Headwater Streams

The amounts, sources and relative ages of inorganic and organic carbon pools were assessed in eight headwater streams draining watersheds dominated by either forest, pasture, cropland or urban development in the lower Chesapeake Bay region (Virginia, USA). Streams were sampled at baseflow conditions six different times over 1 year. The sources and ages of the carbon pools were characterized by isotopic (δ13C and ∆14C) analyses and excitation emission matrix fluorescence with parallel factor analysis (EEM–PARAFAC). The findings from this study showed that human land use may alter aquatic carbon cycling in three primary ways. First, human land use affects the sources and ages of DIC by controlling different rates of weathering and erosion. Relative to dissolved inorganic carbon (DIC) in forested streams which originated primarily from respiration of young, 14C-enriched organic matter (OM; δ13C = −22.2 ± 3 ‰; ∆14C = 69 ± 14 ‰), DIC in urbanized streams was influenced more by sedimentary carbonate weathering (δ13C = −12.4 ± 1 ‰; ∆14C = −270 ± 37 ‰) and one of pasture streams showed a greater influence from young soil carbonates (δ13C = −5.7 ± 2.5 ‰; ∆14C = 69 ‰). Second, human land use alters the proportions of terrestrial versus autochthonous/microbial sources of stream water OM. Fluorescence properties of dissolved OM (DOM) and the C:N of particulate OM (POM) suggested that streams draining human-altered watersheds contained greater relative contributions of DOM and POM from autochthonous/microbial sources than forested streams. Third, human land uses can mobilize geologically aged inorganic carbon and enable its participation in contemporary carbon cycling. Aged DOM (∆14C = −248 to −202 ‰, equivalent14C ages of 1,811–2,284 years BP) and POM (∆14C = −90 to −88 ‰, 14C ages of 669–887 years BP) were observed exclusively in urbanized streams, presumably a result of autotrophic fixation of aged DIC (−297 to −244 ‰, 14C age = 2,251–2,833 years BP) from sedimentary shell dissolution and perhaps also watershed export of fossil fuel carbon. This study demonstrates that human land use may have significant impacts on the amounts, sources, ages and cycling of carbon in headwater streams and their associated watersheds.