Photobleaching of Dissolved Organic Material from a Tidal Marsh-Estuarine System of the Chesapeake Bay† (original) (raw)
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Limnology and Oceanography, 2008
A new approach for parameterizing dissolved organic matter (DOM) ultraviolet-visible absorption spectra is presented. Two distinct spectral slope regions (275–295 nm and 350–400 nm) within log-transformed absorption spectra were used to compare DOM from contrasting water types, ranging from wetlands (Great Dismal Swamp and Suwannee River) to photobleached oceanic water (Atlantic Ocean). On the basis of DOM size-fractionation studies (ultrafiltration and gel filtration chromatography), the slope of the 275–295-nm region and the ratio of these slopes (SR; 275–295-nm slope : 350–400-nm slope) were related to DOM molecular weight (MW) and to photochemically induced shifts in MW. Dark aerobic microbial alteration of chromophoric DOM (CDOM) resulted in spectral slope changes opposite of those caused by photochemistry. Along an axial transect in the Delaware Estuary, large variations in SR were measured, probably due to mixing, photodegradation, and microbial alteration of CDOM as terrestrially derived DOM transited through the estuary. Further, SR varied by over a factor of 13 between DOM-rich wetland waters and Sargasso Sea surface waters. Currently, there is no consensus on a wavelength range for log-transformed absorption spectra. We propose that the 275–295-nm slope be routinely reported in future DOM studies, as it can be measured with high precision, it facilitates comparison among dissimilar water types including CDOM-rich wetland and CDOM-poor marine waters, and it appears to be a good proxy for DOM MW.
Limnology and Oceanography, 2001
The effect of solar radiation on the dissolved absorption coefficient (a CDOM []), which reflects the concentration of chromophoric dissolved organic matter (CDOM), was investigated in several lakes near Bariloche, Argentina and in northeastern Pennsylvania, USA. Samples of 0.2 m filtered lake water were exposed in quartz tubes to different portions of the solar spectrum using optical cutoff filters to remove parts of the ultraviolet (UV) region of the solar spectrum. Changes in the spectral absorption in these samples and the absorbed incident energy were used to calculate spectral weighting functions (SWFs) for the photobleaching (PB) of CDOM. PB was measured as the loss of a CDOM () (the a CDOM [] was averaged from 280 to 500 nm) per unit absorbed energy. CDOM from humic and clear lakes, as well as from a Sphagnum bog and an algal culture, was used in the experiments covering a wide range of carbon sources. We used an iterative, nonlinear optimization method to fit the measured results to a simple exponential function in order to generate each SWF. Comparing individual SWFs calculated for various CDOM sources, we computed a summary SWF from the experiments using epilimnial CDOM from our study lakes. Our summary SWF was able to explain 80-90% of the observed variance in our exposure experiments, and we were able to predict PB results obtained for other Argentine lakes (mean error 14.5%). Finally, we calculated that the effect of UV-B radiation on PB was small (Ͻ20% of total decrease in the absorption coefficient) compared to UV-A and blue light radiation. This suggested that increased UV-B radiation due to stratospheric ozone depletion would not greatly increase the photobleaching of whole water column CDOM in Patagonian lakes (Ͻ10%).
Increases in the longwave photobleaching of chromophoric dissolved organic matter in coastal waters
Limnology and Oceanography, 2009
Salinity effects on the photobleaching of chromophoric dissolved organic matter (CDOM) due to coastal mixing were investigated through a comparative study of surrogate and surface-water CDOM. Suwannee River humic acid (SRHA) and ultrafiltered river dissolved organic matter (UDOM) added to mixtures of river and seawater permeates (,1 kDa) that varied in salinity from 0 to 33 to mimic coastal mixing. Surface-water CDOM was collected from the Chesapeake Bay in January, June, and September 2002. Shortwave CDOM absorption loss (e.g., 280 nm) did not change with salinity; however, longwave CDOM absorption loss (e.g., 440 nm) often decreased by 10% to 40% with salinity. Apparent quantum yields for average absorption loss from 280 to 550 nm (Q avg ) increased with salinity for both surrogate and surface-water CDOM, providing evidence for an effect of salinity independent of light absorption among different samples. Further, hydrogen peroxide photoproduction from UDOM increased from 15 to 368 nmol L 21 h 21 with salinity, even though pH values were circumneutral. A kinetic model demonstrated that, at circumneutral pH and iron concentrations expected for the Chesapeake Bay, photo-Fenton chemistry could not explain the increase in hydrogen peroxide production quantum yields (Q hp ) with salinity. Using Q avg for the SRHA and UDOM surrogates, a model of the change in surface-water CDOM photoreactivity in the Chesapeake Bay as a function of salinity suggested additional CDOM inputs for the lower Chesapeake Bay. Because estuarine mixing increases photobleaching of longwave CDOM absorption, the modeling of absorption coefficients above 400 nm may underestimate dissolved organic matter in coastal waters. 1 Corresponding author (chris_osburn@ncsu.edu).
Molecules
Chromophoric dissolved organic matter (CDOM) is the main sunlight absorber in surface waters and a very important photosensitiser towards the generation of photochemically produced reactive intermediates (PPRIs), which take part in pollutant degradation. The absorption spectrum of CDOM (ACDOM(λ), unitless) can be described by an exponential function that decays with increasing wavelength: ACDOM(λ) = 100 d DOC Ao e− Sλ, where d [m] is water depth, DOC [mgC L−1] is dissolved organic carbon, Ao [L mgC−1 cm−1] is a pre-exponential factor, and S [nm−1] is the spectral slope. Sunlight absorption by CDOM is higher when Ao and DOC are higher and S is lower, and vice versa. By the use of models, here we investigate the impact of changes in CDOM spectral parameters (Ao and S) on the steady-state concentrations of three PPRIs: the hydroxyl radical (•OH), the carbonate radical (CO3•−), and CDOM excited triplet states (3CDOM*). A first finding is that variations in both Ao and S have impacts com...
Limnology and Oceanography, 2006
We performed laboratory studies to determine the effects of salinity on the photodegradation of dissolved organic matter (DOM) from the Great Dismal Swamp, Virginia, an important source of terrestrial DOM to the lower Chesapeake Bay. Samples were created by mixing Great Dismal Swamp water (ionic strength < 0 mol L 21 ) with modified artificial seawater solutions of differing salinities while keeping the final dissolved organic carbon (DOC) concentration constant. These samples were then irradiated for 24 h in a light box providing ultraviolet (UV) light similar to that of natural sunlight. Light absorbance and DOC concentrations decreased after photoexposure, whereas dissolved inorganic carbon (DIC) concentrations increased. Variations in salinity affected both DIC production and UV absorption, with the higher salinity samples showing lower DIC production and less photobleaching. Addition of an iron chelator eliminated the relationship between photochemistry and salinity by reducing both photobleaching and DIC production at low salinities. As terrigenous DOM transits through an estuary, its photochemical reactivity and optical properties may change significantly as a function of salinity, probably as a result of changes in DOM conformation or changes in iron-DOM photochemistry, or both.
Limnology and Oceanography, 2008
The role of tidal marshes as a source of dissolved organic carbon (DOC) and colored dissolved organic matter (CDOM) for adjacent estuarine waters was studied in the Rhode River subestuary of the Chesapeake Bay. Water in a tidal creek draining brackish, high-elevation marshes was sampled every hour during several semidiurnal tidal cycles in order to examine the tidal exchange of dissolved organic matter (DOM). Water leaving the marsh during ebbing tide was consistently enriched in DOC compared to water entering the marsh during flooding tide. There was a net DOC export from the marsh to the estuary during seasons of both low and high marsh plant biomass. Optical analysis demonstrated that, in addition to contributing to the carbon budgets, the marsh had a strong influence on the estuary's CDOM dynamics. Marsh-exported CDOM had optical properties that were consistently and markedly different from those of CDOM in the adjacent estuary. Specifically, marsh CDOM had: (1) considerably stronger absorption, (2) larger DOC-specific absorption, (3) lower exponential spectral slope, (4) larger fluorescence signal, (5) lower fluorescence per unit absorbance, and (6) higher fluorescence at wavelengths .400 nm. These optical characteristics are indicative of relatively complex, high-molecular-weight, aromatic-rich DOM, and this was confirmed by results of molecular-weight-distribution analysis. Our findings illustrate the importance of tidal marshes as sources of optically and chemically distinctive dissolved organic compounds, and their influence on CDOM dynamics, DOC budgets, and, thus, photochemical and biogeochemical processes, in adjacent estuarine ecosystems.
Estuarine, Coastal and Shelf Science, 2020
Dissolved organic matter (DOM) is an important source of carbon in aquatic ecosystems, and colored DOM (CDOM), which is smaller than 0.2 μm and interacts with ultraviolet (UV) and visible light, affects the spectral quality and quantity of light in water. In this study, the spatial and temporal variations of CDOM with changes in environmental conditions were investigated from March 2014 to May 2017 in the coastal waters and two estuaries (Zuari and Mandovi) of Goa, western India, and the major sources and sinks controlling the optical properties of these waters were identified. The CDOM absorption in the estuaries was two times higher than that of the coastal waters. It was also determined that the CDOM absorption at 412 nm (a g 412) in the coastal and estuarine waters significantly varied between seasons. The a g 412 was found to be higher in the coastal waters during the spring inter-monsoon (SIM) and fall inter-monsoon (FIM) than during the northeast monsoon (NEM). The high absorption during the SIM was of autochthonous origin, while terrigenous DOM was the primary contributor mainly during the FIM. The photobleaching of CDOM was highest during the SIM, resulting in the predominance of low-molecular-weight DOM in the coastal waters. This photobleaching of DOM also resulted in deeper UV light penetration, as indicated by the diffuse attenuation coefficient K d at 350 nm. In the Mandovi and Zuari estuaries, higher levels of CDOM were observed during the southwest monsoon (SWM) and SIM than the FIM and NEM. The terrigenous DOM contribution was higher in the estuaries during the SWM, while phytoplankton contributed to a higher level of CDOM during the SIM. CDOM exhibited non-conservative mixing behavior in the study region, as it decreased in estuaries with lower salinities and increased at salinities between 20 and 31. Considering the importance of CDOM in the carbon cycle, this study highlights the various sources and sinks of CDOM controlling the optical properties and biogeochemical processes of coastal and estuarine waters.
Freshwater Biology, 2005
1. We examined the absorption of solar radiation by phytoplankton and chromophoric dissolved organic matter (CDOM) taking into account riparian shading in the rivers, reservoirs, swamps of the Neuse River Estuary and its drainage basin. 2. In the streams, CDOM typically absorbed 55 and 64% of photons in the spectral range of 400-700 nm (photosynthetically active radiation, PAR) and 500-600 nm, respectively. The large proportion of photons absorbed by CDOM indicates high potential for abiotic photochemial reactions in the 500-600 nm region. 3. Despite the high concentration of nutrients, phytoplankton contributed little (2%) to the total absorption of PAR in the streams. Small (<30 m wide) streams typically received only 7% of incident PAR that impinged onto the more exposed reservoirs and estuary. Riparian shading and the low contribution of phytoplankton to the total absorption resulted in conditions where phytoplankton absorbed nearly two orders of magnitude less PAR in the streams than in the estuary and reservoirs. 4. The results indicated that riparian shading and non-algal absorbing components can significantly restrict phytoplankton production in nutrient-rich streams with a high concentration of CDOM flowing throughout forested catchments.
Marine Chemistry, 2011
The optical properties of coloured dissolved organic matter (CDOM)absorption coefficient, induced fluorescence, and fluorescence quantum yieldwere determined in the coastal eutrophic system of the Ría de Vigo (NW Spain) under two contrasting situations: a downwelling event in September 2006 and an upwelling event in June 2007. Significantly different optical properties were recorded in the shelf surface (higher absorption coefficient and lower quantum yield) and bottom (lower absorption coefficient and higher quantum yield) waters that entered the embayment during downwelling and upwelling conditions, respectively. Continental waters presented distinctly high CDOM levels. The spatial and temporal variability of the induced fluorescence to absorption coefficient ratio during the mixing of shelf and continental waters was used to quantify the relative importance of photochemical and microbial processes under these contrasting hydrographic conditions. Photochemical processes were dominant during the downwelling episode: 86% of the variability of CDOM can be explained by photochemical degradation. On the contrary, microbial processes prevailed during the upwelling event: 77% of the total variability of CDOM was explained by microbial respiration.
Chemosphere, 2006
Chromophoric Dissolved Organic Matter (CDOM) is an important component in freshwater and marine ecosystems and plays direct and indirect role in biogeochemical cycles. CDOM originates from the degradation process of organic materials, usually macrophytes and planktons. The present work examines the importance of wetland derived CDOM on the optical and bio-optical properties of two bays of Lake Victoria (Uganda, Africa). This was achieved by determining the attenuation and extinction coefficients of filtered and unfiltered water samples from two equatorial bays on the Ugandan coastline of Lake Victoria. Katonga Bay is a wetland lined bay that receives water from the Katonga river, while Bunjako Bay is an outer bay between Katonga Bay and Lake Victoria. The results showed that attenuation was highest in Katonga Bay and the role of CDOM is most dominant near the river inlet. The quantity and quality of CDOM is extremely different in the two bays: in Katonga Bay it is possible to hypothesize a terrestrial origin of CDOM (transported by the wetland river). On the contrary, in Bunjako Bay, spectral measurements of absorption indicate a modified CDOM and/ or alternative CDOM source. The terrestrial CDOM in Katonga Bay is more capable of absorbing harmful UV radiation than the CDOM present in the Bunjako Bay. The resulting optical environment in the former bay presented a water column with a very limited penetration of harmful UV radiation, while a higher penetration was observed in the Bunjako Bay.