Christopher L. Osburn

Fluorescence tracking of dissolved and particulate organic matter quality in a river-dominated estuary.

Excitation-emission matrix (EEM) fluorescence was combined with parallel factor analysis (PARAFAC) to model base-extracted particulate (POM) and dissolved (DOM) organic matter quality in the Neuse River Estuary (NRE), North Carolina, before and after passage of Hurricane Irene in August 2011. Principle components analysis was used to determine that four of the PARAFAC components (C1-C3 and C6) were terrestrial sources to the NRE. One component (C4), prevalent in DOM of nutrient-impacted streams and estuaries and produced in phytoplankton cultures, was enriched in the POM and in surface sediment pore water DOM. One component (C5) was related to recent autochthonous production. Photoexposure of unfiltered Neuse River water caused an increase in slope ratio values (S(R)) which corresponded to an increase in the ratio C2:C3 for DOM, and the production of C4 fluorescence in both POM and DOM. Changes to the relative abundance of C4 in POM and DOM indicated that advection of pore water DOM from surface sediments into overlying waters could increase the autochthonous quality of DOM in shallow microtidal estuaries. Modeling POM and DOM simultaneously with PARAFAC is an informative technique that is applicable to assessments of estuarine water quality.

Microbial activities and dissolved organic matter dynamics in oil-contaminated surface seawater from the Deepwater Horizon oil spill site.

The Deepwater Horizon oil spill triggered a complex cascade of microbial responses that reshaped the dynamics of heterotrophic carbon degradation and the turnover of dissolved organic carbon (DOC) in oil contaminated waters. Our results from 21-day laboratory incubations in rotating glass bottles (roller bottles) demonstrate that microbial dynamics and carbon flux in oil-contaminated surface water sampled near the spill site two weeks after the onset of the blowout were greatly affected by activities of microbes associated with macroscopic oil aggregates. Roller bottles with oil-amended water showed rapid formation of oil aggregates that were similar in size and appearance compared to oil aggregates observed in surface waters near the spill site. Oil aggregates that formed in roller bottles were densely colonized by heterotrophic bacteria, exhibiting high rates of enzymatic activity (lipase hydrolysis) indicative of oil degradation. Ambient waters surrounding aggregates also showed enhanced microbial activities not directly associated with primary oil-degradation (β-glucosidase; peptidase), as well as a twofold increase in DOC. Concurrent changes in fluorescence properties of colored dissolved organic matter (CDOM) suggest an increase in oil-derived, aromatic hydrocarbons in the DOC pool. Thus our data indicate that oil aggregates mediate, by two distinct mechanisms, the transfer of hydrocarbons to the deep sea: a microbially-derived flux of oil-derived DOC from sinking oil aggregates into the ambient water column, and rapid sedimentation of the oil aggregates themselves, serving as vehicles for oily particulate matter as well as oil aggregate-associated microbial communities.

Photobleaching of dissolved organic material from a tidal marsh-estuarine system of the Chesapeake Bay.

Wetlands and tidal marshes in the Rhode River estuary of the Chesapeake Bay act as important sources of dissolved organic carbon and strongly absorbing dissolved organic matter (DOM) for adjacent estuarine waters. The effects of solar exposure on the photochemical degradation of colored DOM (CDOM) were examined for material derived from different sources (estuarine and freshwater parts of the Rhode River, sub‐watershed stream, marshes) in this estuarine ecosystem. Consistent with changes in fluorescence emission, absorption loss upon exposure to different portions of the solar spectrum (i.e. different long‐pass cut‐off filters) occurred across the entire spectrum but the wavelength of maximum photobleaching decreased as the cut‐off wavelength of the filter decreased. Our results illustrate that solar exposure can cause either an increase or a decrease in the CDOM absorption spectral slope, SCDOM, depending on the spectral quality of irradiation and, thus, on the parameters (e.g. atmospheric composition, concentration of UV‐absorbing water constituents) that affect the spectral characteristics of the light to which CDOM is exposed. We derived a simple spectral model for describing the effects of solar exposure on CDOM optical quality. The model accurately, and consistently, predicted the observed dependence of CDOM photobleaching on the spectral quality of solar exposure.

Physiological and biogeochemical traits of bleaching and recovery in the mounding species of coral Porites lobata: implications for resilience in mounding corals

Mounding corals survive bleaching events in greater numbers than branching corals. However, no study to date has determined the underlying physiological and biogeochemical trait(s) that are responsible for mounding coral holobiont resilience to bleaching. Furthermore, the potential of dissolved organic carbon (DOC) as a source of fixed carbon to bleached corals has never been determined. Here, Porites lobata corals were experimentally bleached for 23 days and then allowed to recover for 0, 1, 5, and 11 months. At each recovery interval a suite of analyses were performed to assess their recovery (photosynthesis, respiration, chlorophyll a, energy reserves, tissue biomass, calcification, δ13C of the skeletal, δ13C, and δ15N of the animal host and endosymbiont fractions). Furthermore, at 0 months of recovery, the assimilation of photosynthetically acquired and zooplankton-feeding acquired carbon into the animal host, endosymbiont, skeleton, and coral-mediated DOC were measured via 13C-pulse-chase labeling. During the first month of recovery, energy reserves and tissue biomass in bleached corals were maintained despite reductions in chlorophyll a, photosynthesis, and the assimilation of photosynthetically fixed carbon. At the same time, P. lobata corals catabolized carbon acquired from zooplankton and seemed to take up DOC as a source of fixed carbon. All variables that were negatively affected by bleaching recovered within 5 to 11 months. Thus, bleaching resilience in the mounding coral P. lobata is driven by its ability to actively catabolize zooplankton-acquired carbon and seemingly utilize DOC as a significant fixed carbon source, facilitating the maintenance of energy reserves and tissue biomass. With the frequency and intensity of bleaching events expected to increase over the next century, coral diversity on future reefs may favor not only mounding morphologies but species like P. lobata, which have the ability to utilize heterotrophic sources of fixed carbon that minimize the impact of bleaching and promote fast recovery.

Runoff‐mediated seasonal oscillation in the dynamics of dissolved organic matter in different branches of a large bifurcated estuary—The Changjiang Estuary

National Natural Science Foundation of China [41276064, 41076044, 40776041]; Chinese Scholarship Council [2012-3022]

Photobleaching Response of Different Sources of Chromophoric Dissolved Organic Matter Exposed to Natural Solar Radiation Using Absorption and Excitation–Emission Matrix Spectra

CDOM biogeochemical cycle is driven by several physical and biological processes such as river input, biogeneration and photobleaching that act as primary sinks and sources of CDOM. Watershed-derived allochthonous (WDA) and phytoplankton-derived autochthonous (PDA) CDOM were exposed to 9 days of natural solar radiation to assess the photobleaching response of different CDOM sources, using absorption and fluorescence (excitation-emission matrix) spectroscopy. Our results showed a marked decrease in total dissolved nitrogen (TDN) concentration under natural sunlight exposure for both WDA and PDA CDOM, indicating photoproduction of ammonium from TDN. In contrast, photobleaching caused a marked increase in total dissolved phosphorus (TDP) concentration for both WDA and PDA CDOM. Thus TDN∶TDP ratios decreased significantly both for WDA and PDA CDOM, which partially explained the seasonal dynamic of TDN∶TDP ratio in Lake Taihu. Photobleaching rate of CDOM absorption a(254), was 0.032 m/MJ for WDA CDOM and 0.051 m/MJ for PDA CDOM from days 0–9, indicating that phototransformations were initially more rapid for the newly produced CDOM from phytoplankton than for the river CDOM. Extrapolation of these values to the field indicated that 3.9%–5.1% CDOM at the water surface was photobleached and mineralized every day in summer in Lake Taihu. Photobleaching caused the increase of spectral slope, spectral slope ratio and molecular size, indicating the CDOM mean molecular weight decrease which was favorable to further microbial degradation of mineralization. Three fluorescent components were validated in parallel factor analysis models calculated separately for WDA and PDA CDOM. Our study suggests that the humic-like fluorescence materials could be rapidly and easily photobleached for WDA and PDA CDOM, but the protein-like fluorescence materials was not photobleached and even increased from the transformation of the humic-like fluorescence substance to the protein-like fluorescence substance. Photobleaching was an important driver of CDOM and nutrients biogeochemistry in lake water.

Fingerprinting the sources of suspended sediment delivery to a large municipal drinking water reservoir: Falls Lake, Neuse River, North Carolina, USA

PurposeWe employ a geochemical-fingerprinting approach to estimate the source of suspended sediments collected from tributaries entering Falls Lake, a 50-km2 drinking water reservoir on the Neuse River, North Carolina, USA. Many of the major tributaries to the lake are on North Carolina’s 303(d) list for impaired streams, and in 2008, the lake was added to that list because of high values of turbidity, likely sourced from tributary streams.Materials and methodsSuspended sediments were collected from four streams with a time-integrated sampler during high-flow events. In addition, composite sediment samples representing potential sources were collected from stream banks, forests, pastures, construction sites, dirt and paved roads, and road cuts within tributary basins. Radiocarbon dating and magnetic susceptibility measurements were used to determine the origin of stream bank alluvial deposits. Sediment samples were analyzed for the concentrations of 55 elements and two radionuclides in order to identify tracers capable of distinguishing between potential sediment sources. The relative sediment source contributions were determined by applying a Monte Carlo simulation that parameterized the geochemical tracer data in a mixing model.Results and discussionRadiocarbon and magnetic susceptibility measurements confirmed the presence of “legacy” sediment in the Ellerbe and New Light Creek valley bottoms. Mixing model results demonstrate that stream bank erosion is the largest contributor to the suspended sediment load in New Light Creek (62%), Ellerbe Creek (58%), and Little Lick Creek (33%), and is the second largest contributor in Lick Creek (27%) behind construction sites (43%).ConclusionsWe find that stream bank erosion is the largest nonpoint source contributor to the suspended sediment load in three of the four catchments and is therefore a significant source of turbidity in Falls Lake. The presence of legacy sediment appears to coincide with increased contributions from stream bank erosion in Ellerbe and New Light creeks. Active construction sites and timber harvesting were also significant sources of suspended sediment. Water quality mitigation efforts need to consider nonpoint-source contributions from stream bank erosion of valley bottom sediments aggraded after European settlement.

Deepwater Horizon oil in Gulf of Mexico waters after 2 years: transformation into the dissolved organic matter pool.

Recent work has shown the presence of anomalous dissolved organic matter (DOM), with high optical yields, in deep waters 15 months after the Deepwater Horizon (DWH) oil spill in the Gulf of Mexico (GOM). Here, we continue to use the fluorescence excitation-emission matrix (EEM) technique coupled with parallel factor analysis (PARAFAC) modeling, measurements of bulk organic carbon, dissolved inorganic carbon (DIC), oil indices, and other optical properties to examine the chemical evolution and transformation of oil components derived from the DWH in the water column of the GOM. Seawater samples were collected from the GOM during July 2012, 2 years after the oil spill. This study shows that, while dissolved organic carbon (DOC) values have decreased since just after the DWH spill, they remain higher at some stations than typical deep-water values for the GOM. Moreover, we continue to observe fluorescent DOM components in deep waters, similar to those of degraded oil observed in lab and field experiments, which suggest that oil-related fluorescence signatures, as part of the DOM pool, have persisted for 2 years in the deep waters. This supports the notion that some oil-derived chromophoric dissolved organic matter (CDOM) components could still be identified in deep waters after 2 years of degradation, which is further supported by the lower DIC and partial pressure of carbon dioxide (pCO2) associated with greater amounts of these oil-derived components in deep waters, assuming microbial activity on DOM in the current water masses is only the controlling factor of DIC and pCO2 concentrations.

Optical Proxies for Terrestrial Dissolved Organic Matter in Estuaries and Coastal Waters

Optical proxies, especially DOM fluorescence, were used to track terrestrial DOM fluxes through estuaries and coastal waters by comparing models developed for several coastal ecosystems. Key to using optical properties is validating and calibrating them with chemical measurements, such as lignin-derived phenols - a proxy to quantify terrestrial DOM. Utilizing parallel factor analysis (PARAFAC), and comparing models statistically using the OpenFluor database (http://www.openfluor.org) we have found common, ubiquitous fluorescing components which correlate most strongly with lignin phenol concentrations in several estuarine and coastal environments. Optical proxies for lignin were computed for the following regions: Mackenzie River Estuary, Atchafalaya River Estuary, Charleston Harbor, Chesapeake Bay, and Neuse River Estuary. The slope of linear regression models relating CDOM absorption at 350 nm (a350) to DOC and to lignin, varied 5 to 10 fold among systems. Where seasonal observations were available from a region, there were distinct seasonal differences in equation parameters for these optical proxies. Despite variability, overall models using single linear regression were developed that related dissolved organic carbon (DOC) concentration to CDOM (DOC = 40×a350+138; R2 = 0.77; N = 130) and lignin (Σ8) to CDOM (Σ8 = 2.03×a350-0.5; R2 = 0.87; N = 130). This wide variability suggested that local or regional optical models should be developed for predicting terrestrial DOM flux into coastal oceans and taken into account when upscaling to remote sensing observations and calibrations.

2,4,6-Trinitrotoluene mineralization and bacterial production rates of natural microbial assemblages from coastal sediments.

The nitrogenous energetic constituent, 2,4,6-Trinitrotoluene (TNT), is widely reported to be resistant to bacterial mineralization (conversion to CO(2)); however, these studies primarily involve bacterial isolates from freshwater where bacterial production is typically limited by phosphorus. This study involved six surveys of coastal waters adjacent to three biome types: temperate broadleaf, northern coniferous, and tropical. Capacity to catabolize and mineralize TNT ring carbon to CO(2) was a common feature of natural sediment assemblages from these coastal environments (ranging to 270+/-38 μg C kg(-1) d(-1)). More importantly, these mineralization rates comprised a significant proportion of total heterotrophic production. The finding that most natural assemblages surveyed from these ecosystems can mineralize TNT ring carbon to CO(2) is consistent with recent reports that assemblage components can incorporate TNT ring carbon into bacterial biomass. These data counter the widely held contention that TNT is recalcitrant to bacterial catabolism of the ring carbon in natural environments.