INTERACTIVE CONTROLS OF WATER TABLE POSITION AND PLANT FUNCTIONAL TYPES ON PEAT POREWATER CHARACTER IN NORTHERN BOG ECOSYSTEMS: IMPLICATIONS FOR CARBON CYCLING DYNAMICS

Northern wetlands, and particularly peatlands, have been shown to store around 30% of the world's soil carbon and thus play a significant role in the carbon cycle of our planet. Changes in climate are altering peatland hydrology and vegetation communities. These changes are possibly resulting in declines in the ability of peatlands to sequester carbon because losses through carbon oxidation and mineralization are likely to increase relative to C inputs from net primary production in a warmer, drier climate. However, the consequences of interactive effects of altered hydrology and vegetation on carbon storage are not well understood. This research evaluated the importance of plant species, water table, and their interactive effects on porewater quality in a northern peatland with an average pH of 4.54, ranging from 4.15 to 4.8. We assessed the effects of plant functional group (ericaceous shrubs, sedges, and bryophytes) and water table position on biogeochemical processes. Specifically, we measured dissolved organic carbon (DOC), total dissolved nitrogen (TDN), potential enzyme activity, organic acids, anions and cations, spectral indexes of aromaticity, and phenolic content. Our results indicate that acetate and propionate concentrations in the sedge-dominated communities declined with depth and water table drawdown, relative to the control and ericaceous treatments. DOC increased in the lowered water table treatments in all vegetation community types, and the peat porewater C:N ratio declined in the sedge-dominated treatments when the water table was lowered. The relationship between DOC and ferrous iron showed significant responses to vegetation type; the exclusion of Ericaceae resulted in less ferrous iron per unit DOC compared to mixed species treatments and Ericaceae alone. This observation was corroborated with higher mean oxidation redox potential profiles (integrating 20, 40, and 70 cm) measured in the sedge treatments, compared with the mixed and Ericaceae species treatments over a growing season. Enzymatic activities did not show as strong of a response to treatments as expected; the oxidative enzyme peroxidase and the hydrolytic enzyme phosphatase were the only enzymes to respond to water table, where the potential activity of both enzymes increased with water table drawdown. Overall, there were significant interactive effects between changes in vegetation and water table position on peat porewater composition. These data suggest that vegetation effects on oxidation reduction potentials and peat porewater character can be as important as water table position in northern bog ecosystems.

Inverse modelling of the 14C bomb pulse in stalagmites to constrain the dynamics of soil carbon cycling at selected European cave sites

The decomposition of soil organic matter (SOM) is temperature dependent, but its response to a future warmer climate remains equivocal. Enhanced rates of decomposition of SOM under increased global temperatures might cause higher CO2 emissions to the atmosphere, and could therefore constitute a strong positive feedback. The magnitude of this feedback however remains poorly understood, primarily because of the difficulty in quantifying the temperature sensitivity of stored, recalcitrant carbon that comprises the bulk (>90%) of SOM in most soils. In this study we investigated the effects of climatic conditions on soil carbon dynamics using the attenuation of the 14C ‘bomb’ pulse as recorded in selected modern European speleothems. These new data were combined with published results to further examine soil carbon dynamics, and to explore the sensitivity of labile and recalcitrant organic matter decomposition to different climatic conditions. Temporal changes in 14C activity inferred from each speleothem was modelled using a three pool soil carbon inverse model (applying a Monte Carlo method) to constrain soil carbon turnover rates at each site. Speleothems from sites that are characterised by semi-arid conditions, sparse vegetation, thin soil cover and high mean annual air temperatures (MAATs), exhibit weak attenuation of atmospheric 14C ‘bomb’ peak (a low damping effect, D in the range: 55–77%) and low modelled mean respired carbon ages (MRCA), indicating that decomposition is dominated by young, recently fixed soil carbon. By contrast, humid and high MAAT sites that are characterised by a thick soil cover and dense, well developed vegetation, display the highest damping effect (D = c. 90%), and the highest MRCA values (in the range from 350 ± 126 years to 571 ± 128 years). This suggests that carbon incorporated into these stalagmites originates predominantly from decomposition of old, recalcitrant organic matter. SOM turnover rates cannot be ascribed to a single climate variable, e.g. (MAAT) but instead reflect a complex interplay of climate (e.g. MAAT and moisture budget) and vegetation development.

The dating of dipterocarp tree rings: establishing a record of carbon cycling and climatic change in the tropics

In a first step to obtain a proxy record of past climatic events (including the El Ni (n) over tildeo-Southern Oscillation) in the normally aseasonal tropical environment of Sabah, a radial segment from a recently fallen dipterocarp (Shorea Superba) was radiocarbon dated and subjected to carbon isotope analysis. The high-precision radiocarbon results fell into the ambiguous modern plateau where several calibrated dates can exist for each sample. Dating was achieved by wiggle matching using a Bayesian approach to calibration. Using the defined growth characteristics of Shorea superba, probability density distributions were calculated and improbable dates rejected. It was found that the tree most likely started growing around AD 1660-1685. A total of 173 apparent growth increments were measured and, therefore, it could be determined that the tree formed one ring approximately every two years. Stable carbon isotope values were obtained from resin-extracted wholewood from each ring. Carbon cycling is evident in the `juvenile effect', resulting from the assimilation of respired carbon dioxide and lower light levels below the canopy, and in the `anthropogenic effect' caused by increased industrial activity in the late-nineteenth and twentieth centuries. This study demonstrates that palaeoenvironmental information can be obtained from trees growing in aseasonal environments, where climatic conditions prevent the formation of well-defined annual rings.

Relative significance of pelagic, benthic and allochthonous organic matter to microbial carbon cycling in a phosphorus-depleted subtropical estuary (Florida Bay)

Heterotrophic bacteria are important decomposers and transformers of primary production and provide an important link between detritus and the aquatic food web. In seagrass ecosystems, much of seagrass primary production is unavailable through direct grazing and must undergo microbial reworking before seagrass production can enter the aquatic food web. The goal of my dissertation research is to understand better the role heterotrophic bacteria play in carbon cycling in seagrass estuaries. My dissertation research focuses on Florida Bay, a seagrass estuary that has experienced recent changes in carbon source availability, which may have altered ecosystem function. My dissertation research investigates the importance of seagrass, algal and/or cyanobacterial, and allochthonous-derived organic matter to heterotrophic bacteria in Florida Bay and helps establish the carbon base of the estuarine food web. ^ A three tiered approach to the study of heterotrophic bacterial carbon cycling and trophic influences in Florida Bay was used: (1) Spatiotemporal observations of environmental parameters (hydrology, nutrients, extracellular enzymes, and microbial abundance, biomass, and production); (2) Microbial grazing experiments under different levels of top-down and bottom-up influence; and (3) Bulk and compound-specific (bacteria-biomarker fatty acid analysis) stable carbon isotope analysis. ^ In Florida Bay, spatiotemporal patterns in microbial extracellular enzyme (also called ectoenzyme) activities indicate that microorganisms hydrolyzed selectively fractions of the estuarine organic matter pool. The microbial community hydrolyzed organic acids, peptides, and phosphate esters and did not use storage and structural carbohydrates. Organic matter use by heterotrophic bacterioplankton in Florida Bay was co-regulated by bottom-up (resource availability) and top-down (grazer mediated) processes. A bacterial carbon budget based on bacterial, epiphytic, and seagrass production indicates that heterotrophic bacterial carbon cycles are supported primarily through epiphytic production with mixing from seagrass production. Stable carbon isotope analysis of bacteria biomarkers and carbon sources in Florida Bay corroborate the results of the bacterial carbon budget. These results support previous studies of aquatic consumers in Florida Bay, indicating that epiphytic/benthic algal and/or cyanobacterial production with mixing from seagrass-derived organic matter is the carbon base of the seagrass estuarine food web. ^

Seawater carbonate chemistry and processes during experiments with Emiliania huxleyi (PML B93/11A)

The formation of calcareous skeletons by marine planktonic organisms and their subsequent sinking to depth generates a continuous rain of calcium carbonate to the deep ocean and underlying sediments. This is important in regulating marine carbon cycling and ocean-atmosphere CO2 exchange. The present rise in atmospheric CO2 levels causes significant changes in surface ocean pH and carbonate chemistry. Such changes have been shown to slow down calcification in corals and coralline macroalgae, but the majority of marine calcification occurs in planktonic organisms. Here we report reduced calcite production at increased CO2 concentrations in monospecific cultures of two dominant marine calcifying phytoplankton species, the coccolithophorids Emiliania huxleyi and Gephyrocapsa oceanica . This was accompanied by an increased proportion of malformed coccoliths and incomplete coccospheres. Diminished calcification led to a reduction in the ratio of calcite precipitation to organic matter production. Similar results were obtained in incubations of natural plankton assemblages from the north Pacific ocean when exposed to experimentally elevated CO2 levels. We suggest that the progressive increase in atmospheric CO2 concentrations may therefore slow down the production of calcium carbonate in the surface ocean. As the process of calcification releases CO2 to the atmosphere, the response observed here could potentially act as a negative feedback on atmospheric CO2 levels.

Seawater carbonate chemistry and processes during experiments with coccolithophores (Emiliania huxleyi and Gephyrocapsa oceanica), 2000

The formation of calcareous skeletons by marine planktonic organisms and their subsequent sinking to depth generates a continuous rain of calcium carbonate to the deep ocean and underlying sediments1. This is important in regulating marine carbon cycling and ocean-atmosphere CO2 exchange2. The present rise in atmospheric CO2 levels3 causes significant changes in surface ocean pH and carbonate chemistry4. Such changes have been shown to slow down calcification in corals and coralline macroalgae5,6, but the majority of marine calcification occurs in planktonic organisms. Here we report reduced calcite production at increased CO2 concentrations in monospecific cultures of two dominant marine calcifying phytoplankton species, the coccolithophorids Emiliania huxleyi and Gephyrocapsa oceanica . This was accompanied by an increased proportion of malformed coccoliths and incomplete coccospheres. Diminished calcification led to a reduction in the ratio of calcite precipitation to organic matter production. Similar results were obtained in incubations of natural plankton assemblages from the north Pacific ocean when exposed to experimentally elevated CO2 levels. We suggest that the progressive increase in atmospheric CO2 concentrations may therefore slow down the production of calcium carbonate in the surface ocean. As the process of calcification releases CO2 to the atmosphere, the response observed here could potentially act as a negative feedback on atmospheric CO2 levels.

Sand fraction, organic carbon and nitrogen data, and calculated marine and terrestrial organic carbon fractions of surface sediments in the western Barents Sea

There is generally a lack of knowledge on how marine organic carbon accumulation is linked to vertical export and primary productivity patterns. In this study, a multi-proxy geochemical and organic-sedimentological approach is coupled with organic facies modelling focusing on regional calculations of carbon cycling and carbon burial on the western Barents Shelf between northern Scandinavia and Svalbard. OF-Mod 3D, an organic facies modelling software tool, is used to reconstruct the marine and terrestrial organic carbon fractions and to make inferences about marine primary productivity in this region. The model is calibrated with an extensive sample dataset and reproduces the present-day regional distribution of the organic carbon fractions well. Based on this new organic facies model, we present regional carbon mass accumulation rate calculations for the western Barents Sea. The calibration dataset includes location and water depth, sand fraction, organic carbon and nitrogen data and calculated marine and terrestrial organic carbon fractions.

The Toarcian in the Subbetic basin (southern Spain): Bio-events (ammonite and calcareous nannofossils) and carbon-isotope stratigraphy

A detailed carbon-isotope stratigraphic study for the uppermost Pliensbachian lowermost Aalenian interval in the Median Subbetic palaeogeographic domain (External zones of the Betic Cordillera, southern Spain) has been carried out. During the Early Jurassic, the Median Subbetic, which represents a typical basin of the Hispanic Corridor connecting the Tethys and the Eastern Pacific, was located in the westernmost Tethys. The analyzed sections encompass the entire Toarcian stage as represented in the southern Iberian palaeomargin. Rocks are mainly rhythmic sequences of grey marls and marly limestones containing a rich ammonite fauna, nannofossils, and benthic foraminifers-all these provide an accurate biostratigraphic control. The lower and upper Toarcian boundaries are well represented in some of these sections and therefore represent optimal sites to link the carbon-isotope curves to ammonite zones, and to nannofossil events. delta C-13 values of bulk carbonates from the different localities of the Subbetic basin have similar variations from the uppermost Pliensbachian to the lowermost Aalenian, suggesting changes in the original DIC carbon isotope composition along the Hispanic corridor. The transition from Pliensbachian to Toarcian is marked by increasing delta C-13 values from similar to 12 to 2.0 parts per thousand, interrupted in the Serpentinum Zone by a negative shift concomitant with the Toarcian oceanic anoxic event (T-OAE), with the major ammonite extinction event of the Toarcian, and an important turnover of calcareous nannoplankton. The negative shift observed in the Serpentinum Zone confirms the global perturbation of the carbon cycling documented along the Tethys and the palaeo-Pacific in organic material and in marine carbonates. However, the amplitude of the negative excursion (similar to - 1.5 parts per thousand) is not compatible with an isotopic homogeneous seawater DIC and/or CO2 atmospheric reservoirs. The interval from the middle to the top of the Toarcian delta C-13 shows relatively constant values, minor ammonite turnovers, and is associated with increasing diversity of calcareous nannoplankton. (c) 2012 Elsevier B.V. All rights reserved.

Carbon-Based Ocean Productivity and Phytoplankton Physiology from Space

Ocean biogeochemical and ecosystem processes are linked by net primary production (NPP) in the ocean's surface layer, where inorganic carbon is fixed by photosynthetic processes. Determinations of NPP are necessarily a function of phytoplankton biomass and its physiological status, but the estimation of these two terms from space has remained an elusive target. Here we present new satellite ocean color observations of phytoplankton carbon (C) and chlorophyll (Chl) biomass and show that derived Chl:C ratios closely follow anticipated physiological dependencies on light, nutrients, and temperature. With this new information, global estimates of phytoplankton growth rates (mu) and carbon-based NPP are made for the first time. Compared to an earlier chlorophyll-based approach, our carbon-based values are considerably higher in tropical oceans, show greater seasonality at middle and high latitudes, and illustrate important differences in the formation and demise of regional algal blooms. This fusion of emerging concepts from the phycological and remote sensing disciplines has the potential to fundamentally change how we model and observe carbon cycling in the global oceans.

(Figure 2) Organic carbon content, stable isotope ratios, TEX86 index and sea surface temperature reconstruction for the early Aptian of ODP Hole 198-1207B

The Cretaceous has long been recognized as a time when greenhouse conditions were fueled by elevated atmospheric CO2 and accompanied by perturbations of the global carbon cycle described as oceanic anoxic events (OAEs). Yet, the magnitude and frequency of temperature change during this interval of warm and equable climate are poorly constrained. Here we present a high-resolution record of sea-surface temperatures (SSTs) reconstructed using the TEX86 paleothermometer for a sequence of early Aptian organic-rich sediments deposited during the first Cretaceous OAE (OAE1a) at Shatsky Rise in the tropical Pacific. SSTs range from ~30 to ~36 °C and include two prominent cooling episodes of ~4 °C. The cooler temperatures reflect significant temperature instability in the tropics likely triggered by changes in carbon cycling induced by enhanced burial of organic matter. SST instability recorded during the early Aptian in the Pacific is comparable to that reported for the late Albian-early Cenomanian in the Atlantic, suggesting that such climate perturbations may have recurred during the Cretaceous with concomitant consequences for biota and the marine environment.

Stable carbon isotopes, Methane Index, and distributions of different GDGTs

Gas hydrates represent one of the largest pools of readily exchangeable carbon on Earth's surface. Releases of the greenhouse gas methane from hydrates are proposed to be responsible for climate change at numerous events in geological history. Many of these inferred events, however, were based on carbonate carbon isotopes which are susceptible to diagenetic alterations. Here we propose a molecular fossil proxy, i.e., the "Methane Index (MI)", to detect and document the destabilization and dissociation of marine gas hydrates. MI consists of the relative distribution of glycerol dibiphytanyl glycerol tetraethers (GDGTs), the core membrane lipids of archaea. The rational behind MI is that in hydrate-impacted environments, the pool of archaeal tetraether lipids is dominated by GDGT-1, -2 and -3 due to the large contribution of signals from the methanotrophic archaeal community. Our study in the Gulf of Mexico cold-seep sediments demonstrates a correlation between MI and the compound-specific carbon isotope of GDGTs, which is strong evidence supporting the MI-methane consumption relationship. Preliminary applications of MI in a number of hydrate-impacted and/or methane-rich environments show diagnostic MI values, corroborating the idea that MI may serve as a robust indicator for hydrate dissociation that is useful for studies of global carbon cycling and paleoclimate change.

Methanol and ethanol analysis in marine sediment pore water

Low-molecular-weight (LMW) alcohols are produced during the microbial degradation of organic matter from precursors such as lignin, pectin, and carbohydrates. The biogeochemical behavior of these alcohols in marine sediment is poorly constrained but potentially central to carbon cycling. Little is known about LMW alcohols in sediment pore waters because of their low concentrations and high water miscibility, both of which pose substantial analytical challenges. In this study, three alternative methods were adapted for the analysis of trace amounts of methanol and ethanol in small volumes of saline pore waters: direct aqueous injection (DAI), solid-phase microextraction (SPME), and purge and trap (P&T) in combination with gas chromatography (GC) coupled to either a flame ionization detector (FID) or a mass spectrometer (MS). Key modifications included the desalination of samples prior to DAI, the use of a threaded midget bubbler to purge small-volume samples under heated conditions and the addition of salt during P&T. All three methods were validated for LMW alcohol analysis, and the lowest detection limit (60 nM and 40 nM for methanol and ethanol, respectively) was achieved with the P&T technique. With these methods, ambient concentrations of volatile alcohols were determined for the first time in marine sediment pore waters of the Black Sea and the Gulf of Mexico. A strong correlation between the two compounds was observed and tentatively interpreted as being controlled by similar sources and sinks at the examined stations.

Stable carbon and oxygen isotope record of diagenetic carbonates from the New Jersey shelf

Carbon cycling is an important but poorly understood process on passive continental margins. In this study, we use the ionic and stable isotopic composition of interstitial waters and the petrology, mineralogy, and stable isotopic composition of authigenic carbonates collected from Ocean Drilling Program (ODP) Leg 174A (Sites 1071 and 1072) to constrain the origin of the carbonates and the evolution of methane on the outer New Jersey shelf. The pore fluids of the New Jersey continental shelf are characterized by (1) a fresh-brackish water plume, and (2) organic matter degradation reactions, which proceed through sulfate reduction. However, only minor methanogenesis occurs. The oxygen isotopic composition of the pore fluids supports a meteoric origin of the low salinity fluids. Authigenic carbonates are found in nodules, thin (~1-cm) layers, and carbonate cemented pavements. Siderite is the most common authigenic carbonate, followed by dolomite and calcite. The oxygen isotopic composition of the authigenic carbonates, i.e. 1.3-6.5 per mil PeeDee Belemnite (PDB), indicates an origin in marine pore fluids. The carbon isotopic composition of dolomite cements range from -16.4 to -8.8 per mil PDB, consistent with formation within the zone of sulfate reduction. Siderite d13C values show a greater range (-17.67-16.4 per mil), but are largely positive (mean=2.8 per mil) and are interpreted to have formed throughout the zone of methanogenesis. In contrast, calcite d13C values are highly negative (as low as -41.7 per mil)and must have formed from waters with a large component of dissolved inorganic carbon derived from methane oxidation. Pore water data show that despite complete sulfate reduction, methanogenesis appears not to be an important process presently occurring in the upper 400 m of the outer New Jersey shelf. In contrast, the carbon isotopic composition of the siderites and calcites document an active methanogenic zone during their formation. The methane may have been either oxidized or vented from shelf sediments, perhaps during sea-level fluctuations. If this unaccounted and variable methane flux is an areally important process during Neogene sea-level fluctuations, then it likely plays an important role in long-term carbon cycling on passive continental margins

A long marine history of carbon cycle modulation by orbital-climatic changes

Pacing of the marine carbon cycle by orbital forcing during the Pliocene and Pleistocene Ice Ages [past 2.5 million years (Myr)] is well known. As older deep-sea sediment records are being studied at greater temporal resolution, it is becoming clear that similar fluctuations in the marine carbon system have occurred throughout the late Mesozoic and Tertiary, despite the absence of large continental ice sheets over much of this time. Variations in both the organic and the calcium carbonate components of the marine carbon system seem to have varied cyclically in response to climate forcing, and carbon and carbonate time series appear to accurately characterize the frequency spectrum of ancient climatic change. For the past 35 Myr, much of the variance in carbonate content carries the “polar” signal of obliquity [41,000 years (41 kyr)] forcing. Over the past 125 Myr, there is evidence from marine sediments of the continued role of precessional (≈21 kyr) climatic cycles. Repeat patterns of sedimentation at about 100, 400, and 2,400 kyr, the modulation periods of precession, persistently enter into marine carbon cycle records as well. These patterns suggest a nonlinear response of climate and/or the sedimentation of organic carbon and carbonates to precessional orbital perturbations. Nonlinear responses of the carbon system may help to amplify relatively weak orbital insolation anomalies into more significant climatic perturbations through positive feedback effects. Nonlinearities in the carbon cycle may have transformed orbital-climatic cycles into long-wavelength features on time scales comparable to the residence times of carbon and nutrient elements in the ocean.