Quality Of Chromophoric Dissolved Organic Matter Research Articles

Seasonal dynamics of chromophoric dissolved organic matter in Poyang Lake, the largest freshwater lake in China

Chromophoric dissolved organic matter (CDOM) plays a vital role in the biogeochemical cycles of elements in aquatic ecosystems. Seasonal dynamics of CDOM of the lake are sensitive indicators of the biogeochemical processes and water quality, which are critical to the water security of the lake. Thus, a field investigation of the CDOM and dissolved organic carbon (DOC) properties was conducted during four hydrological seasons in 2016 to track the temporal variability of CDOM and DOC properties and to explore the influence of rivers and wetlands on the quantity and quality of CDOM in Poyang Lake. The results showed that the alternations of flood and dry periods have a different influence on the quantity and quality of CDOM and DOC in the main lake and the river mouths districts. DOC and aromaticity in the main lake district were more influenced by seasonal variations, while CDOM concentrations and molecular weight in the river mouths were more affected. CDOM fluorescent components in both these districts varied obviously across the hydrological seasons. More terrestrial humic-like substances with higher aromaticity and lower DOC in the rising and flood season than in the dry and retreating season. The contributing rate of CDOM and its terrestrial humic-like substances from input rivers to the lake in the rising season can account for more than 50%, which was more than that in the flood season. Flooding causes wetlands to contribute a higher abundance of CDOM and DOC with lower aromaticity to the lake, contrary to the CDOM features in the flood season, highlighting the important role of wetlands in the organic carbon pool. The DOC can be modeled using CDOM fluorescent and optical parameters by the Support Vector Regression (SVR) method, which provides a tool for DOC dynamic monitoring and water quality management.

Photochemical and Microbial Degradation of Chromophoric Dissolved Organic Matter Exported From Tidal Marshes

AbstractWetlands export chromophoric dissolved organic matter (CDOM) to estuaries, where CDOM is removed and transformed through biotic and abiotic process, subsequently impacting nutrient cycling, light availability, ecosystem metabolism, and phytoplankton activity. We examined the bioavailability and photoreactivity of CDOM exported from four Chesapeake Bay tidal marshes across three seasons and along an estuarine salinity gradient using three incubation treatments: 14‐day microbial (MD), 7‐day combined photochemical/microbial (PB + MD), and 7‐day microbial incubation after photobleaching (MD after PB). CDOM absorption at 300 nm (aCDOM300) and dissolved organic carbon (DOC) concentrations showed strong seasonality, with minima in winter, but CDOM quality (absorption spectral slopes, fluorescence component ratios) was less variable seasonally. PB + MD over 7 days decreased aCDOM300 (−56.0%), humic‐like fluorescence (−67.6%), and DOC (−17.8%), but increased the spectral slope ratio SR (=S275–295/S300–350) (+94.8%), suggesting a decrease in CDOM molecular weight. Photochemistry dominated the PB + MD treatment. Photoreactivity was greater during the winter and in marsh/watershed versus down‐estuary sites, likely due to less previous light exposure. Prior photobleaching increased the bioavailability of marsh‐exported CDOM, resulting in a greater loss of aCDOM300 and DOC, and a greater increase in humic‐like fluorescence (−6.0%, −5.9%, and +18.4% change, respectively, over 7‐day MD after PB incubations, vs. −2.8%, −5.5%, and +2.6% change, respectively, over 14‐day MD incubations). CDOM exported from a marsh downstream of a major wastewater treatment plant showed the greatest photoreactivity and bioavailability. This highlights the significance of human activity on estuarine CDOM quality and biogeochemical cycles.

Singlet Oxygen Photogeneration in Coastal Seawater: Prospect of Large-Scale Modeling in Seawater Surface and Its Environmental Significance.

Chromophoric-dissolved organic matter (CDOM) acts as the precursor to singlet oxygen (1O2) in natural waters, while water acts as the main scavenger. In this study, we showed that 1O2 in coastal seawater can be successfully predicted from CDOM parameters. The 1O2 steady-state concentration [1O2]ss and photoformation rate (R1O2) varied by a factor of 6 across 13 sampling stations in the Seto Inland Sea, Japan, ranging from 1.2 to 8.2 × 10-14 M and 3.32 to 22.7 × 10-9 M s-1, respectively. Investigation of CDOM optical properties revealed that CDOM abundance measured as the absorption coefficient at 300 nm (a300) had the strongest correlation (r = 0.96, p < 0.001) with [1O2]ss, while parameters indicative of CDOM quality (e.g., spectral slope) did not influence [1O2]ss. A linear relationship between [1O2]ss and a300, normalized to a sunlight intensity of 0.91 kW/m2, was derived as [1O2]ss (10-14 M) = 2.12(a300) + 0.48. This was then used to predict [1O2]ss using a300 values from a subsequent, independent sampling exercise conducted 2 years after the first sampling. There was a good agreement (r = 0.93, p < 0.001) between the predicted values and the experimentally determined values based on a 95% prediction interval plot. Kinetic estimations using [1O2]ss suggest that 1O2 mediates the degradation of tetrabromobisphenol A in surface seawater (t1/2 = 0.63 days) while also contributing to the indirect photolysis of methyl mercury. The findings from this study suggest that large-scale modeling of 1O2 generation in surface seawater from CDOM parameters is possible with useful environmental significance for determining the fate of pollutants.

Polystyrene microplastics increase microbial release of marine Chromophoric Dissolved Organic Matter in microcosm experiments

About 5 trillion plastic particles are present in our oceans, from the macro to the micro size. Like any other aquatic particulate, plastics and microplastics can create a micro-environment, within which microbial and chemical conditions differ significantly from the surrounding water. Despite the high and increasing abundance of microplastics in the ocean, their influence on the transformation and composition of marine organic matter is largely unknown. Chromophoric dissolved organic matter (CDOM) is the photo-reactive fraction of the marine dissolved organic matter (DOM) pool. Changes in CDOM quality and quantity have impacts on marine microbial dynamics and the underwater light environment. One major source of CDOM is produced by marine bacteria through their alteration of pre-existing DOM substrates. In a series of microcosm experiments in controlled marine conditions, we explored the impact of microplastics on the quality and quantity of microbial CDOM. In the presence of microplastics we observed an increased production of CDOM with changes in its molecular weight, which resulted from either an increased microbial CDOM production or an enhanced transformation of DOM from lower to higher molecular weight CDOM. Our results point to the possibility that marine microplastics act as localized hot spots for microbial activity, with the potential to influence marine carbon dynamics.

Distinctive effects of allochthonous and autochthonous organic matter on CDOM spectra in a tropical lake

Abstract. Despite the increasing understanding about differences in carbon cycling between temperate and tropical freshwater systems, our knowledge on the importance of organic matter (OM) pools on light absorption properties in tropical lakes is very scarce. We performed a factorial mesocosm experiment in a tropical lake (Minas Gerais, Brazil) to evaluate the effects of increased concentrations of allochthonous and autochthonous OM, and differences in light availability on the light absorption characteristics of chromophoric dissolved organic matter (CDOM). Autochthonous OM deriving from phytoplankton ( ∼ Chl a) was stimulated by addition of nutrients, while OM from degradation of terrestrial leaves increased allochthonous OM, and neutral shading was used to manipulate light availability. Effects of the additions and shading on DOC, Chl a, nutrients, total suspended solid concentrations (TSM) and spectral CDOM absorption were monitored every 3 days. CDOM quality was characterized by spectral indices (S250–450, S275–295, S350–450, SR and SUVA254). Effects of carbon sources and shading on the spectral CDOM absorption was investigated through principal component (PCA) and redundancy (RDA) analyses. The two different OM sources affected CDOM quality very differently and shading had minor effects on OM levels, but significant effects on OM quality, especially in combination with nutrient additions. Spectral indices (S250–450 and SR) were mostly affected by allochthonous OM addition. The PCA showed that enrichment by allochthonous carbon had a strong effect on the CDOM spectra in the range between 300 and 400 nm, while the increase in autochthonous carbon increased absorption at wavelengths below 350 nm. Our study shows that small inputs of allochthonous OM can have large effects on the spectral light absorption compared to large production of autochthonous OM, with important implications for carbon cycling in tropical lakes.

Water mass age and aging driving chromophoric dissolved organic matter in the dark global ocean

AbstractThe omnipresence of chromophoric dissolved organic matter (CDOM) in the open ocean enables its use as a tracer for biochemical processes throughout the global overturning circulation. We made an inventory of CDOM optical properties, ideal water age (τ), and apparent oxygen utilization (AOU) along the Atlantic, Indian, and Pacific Ocean waters sampled during the Malaspina 2010 expedition. A water mass analysis was applied to obtain intrinsic, hereinafter archetypal, values of τ, AOU, oxygen utilization rate (OUR), and CDOM absorption coefficients, spectral slopes and quantum yield for each one of the 22 water types intercepted during this circumnavigation. Archetypal values of AOU and OUR have been used to trace the differential influence of water mass aging and aging rates, respectively, on CDOM variables. Whereas the absorption coefficient at 325 nm (a325) and the fluorescence quantum yield at 340 nm (Φ340) increased, the spectral slope over the wavelength range 275–295 nm (S275–295) and the ratio of spectral slopes over the ranges 275–295 nm and 350–400 nm (SR) decreased significantly with water mass aging (AOU). Combination of the slope of the linear regression between archetypal AOU and a325 with the estimated global OUR allowed us to obtain a CDOM turnover time of 634 ± 120 years, which exceeds the flushing time of the dark ocean (&gt;200 m) by 46%. This positive relationship supports the assumption of in situ production and accumulation of CDOM as a by‐product of microbial metabolism as water masses turn older. Furthermore, our data evidence that global‐scale CDOM quantity (a325) is more dependent on aging (AOU), whereas CDOM quality (S275–295, SR, Φ340) is more dependent on aging rate (OUR).

Seasonal changes in estuarine dissolved organic matter due to variable flushing time and wind-driven mixing events

This study examined the seasonality of dissolved organic matter (DOM) sources and transformations within the Neuse River estuary (NRE) in eastern North Carolina between March 2010 and February 2011. During this time, monthly surface and bottom water samples were collected along the longitudinal axis of the NRE, ranging from freshwater to mesohaline segments. The monthly mean of all surface and bottom measurements made on collected samples was used to clarify larger physical mixing controls in the estuary as a whole. By comparing monthly mean trends in DOM and chromophoric dissolved organic matter (CDOM) properties in surface and bottom waters during varying hydrological conditions, we found that DOM and CDOM quality in the NRE is controlled by a combination of discharge, wind speed, and wind direction. The quality of DOM was assessed using C:N ratios, specific ultraviolet absorption at 254 nm (SUVA254), the absorption spectral slope ratio (SR), and the humification (HIX) and biological (BIX) indices from fluorescence. The NRE reflects allochthonous sources when discharge and flushing time are elevated at which times SUVA254 and HIX increased relative to base flow. During periods of reduced discharge and long flushing times in the estuary, extensive autochthonous production modifies the quality of the DOM pool in the NRE. This was evidenced by falling C:N values, and higher BIX and SR values. Lastly, a combination of increased wind speed and shifts in wind direction resulted in benthic resuspension events of degraded, planktonic OM. Thus, the mean DOM characteristics in this shallow micro-tidal estuary can be rapidly altered during episodic mixing events on timescales of a few weeks.

Dissolved organic carbon and chromophoric dissolved organic matter properties of rivers in the USA

Dissolved organic carbon (DOC) concentration and chromophoric dissolved organic matter (CDOM) parameters were measured over a range of discharge in 30 U.S. rivers, covering a diverse assortment of fluvial ecosystems in terms of watershed size and landscape drained. Relationships between CDOM absorption at a range of wavelengths (a254, a350, a440) and DOC in the 30 watersheds were found to correlate strongly and positively for the majority of U.S. rivers. However, four rivers (Colorado, Colombia, Rio Grande and St. Lawrence) exhibited statistically weak relationships between CDOM absorption and DOC. These four rivers are atypical, as they either drain from the Great Lakes or experience significant impoundment of water within their watersheds, and they exhibited values for dissolved organic matter (DOM) parameters indicative of autochthonous or anthropogenic sources or photochemically degraded allochthonous DOM and thus a decoupling between CDOM and DOC. CDOM quality parameters in the 30 rivers were found to be strongly correlated to DOM compositional metrics derived via XAD fractionation, highlighting the potential for examining DOM biochemical quality from CDOM measurements. This study establishes the ability to derive DOC concentration from CDOM absorption for the majority of U.S. rivers, describes characteristics of riverine systems where such an approach is not valid, and emphasizes the possibility of examining DOM composition and thus biogeochemical function via CDOM parameters. Therefore, the usefulness of CDOM measurements, both laboratory‐based analyses and in situ instrumentation, for improving spatial and temporal resolution of DOC fluxes and DOM dynamics in future studies is considerable in a range of biogeochemical studies.

Changes in the Quality of Chromophoric Dissolved Organic Matter Leached from Senescent Leaf Litter during the Early Decomposition

Chromophoric dissolved organic matter (CDOM) leached from leaf litter is a major source of humus in mineral soil of forest ecosystems. While their functions and refractoriness depend on the physicochemical structure, there is little information on the quality of CDOM, especially for that leached in the very early stages of litter decomposition when a large amount of dissolved organic matter (DOM) is leached. This study aimed to better understand the variations/changes in the composition of CDOM leached from senescent leaf litter from two tree species during the early stage of decomposition. Leaf litter from a conifer tree (Japanese cedar, D. Don) and a deciduous broad-leaved tree (Konara oak, Thunb.) were incubated in columns using simulated rainfall events periodically for a total of 300 d at 20°C. The quality of CDOM was investigated based on the fluorescence properties by using a combination of excitation-emission matrix fluorescence (EEM) and parallel factor analysis (PARAFAC). In addition, the phenolic composition of DOM was investigated at a molecular level by thermally assisted hydrolysis and methylation-gas chromatography-mass spectrometry (THM-GC-MS) in the presence of tetramethylammonium hydroxide (TMAH). The EEM was statistically decomposed into eight fluorescence components (two tannin/peptide-like peaks, one protein-like peak, and five humic-like peaks). A significant contribution of tannin/peptide-like peaks was observed at the beginning of incubation, but these peaks decreased quickly and humic-like peaks increased within 1 mo of incubation. The composition of humic-like peaks was different between tree species and changed over the incubation period. Since tannin-derived phenolic compounds were detected in the DOM collected after 254 d of incubation on THM-GC-MS, it was suggested that tannins partially changed its structure, forming various humic-like peaks during the early decomposition.

The effect of surface irradiance on the absorption spectrum of chromophoric dissolved organic matter in the global ocean

The cycling pathways of chromophoric dissolved organic matter (CDOM) within marine systems must be constrained to better assess the impact of CDOM on surface ocean photochemistry and remote sensing of ocean color. Photobleaching, the loss of absorption by CDOM due to light exposure, is the primary sink for marine CDOM. Herein the susceptibility of CDOM to photobleaching by sea surface-level solar radiation was examined in 15 samples collected from wide-ranging open ocean regimes. Samples from the Pacific, Atlantic, Indian and Southern Oceans were irradiated over several days with full-spectrum light under a solar simulator at in situ temperature in order to measure photobleaching rate and derive an empirical matrix, εsurf (m−1μEin−1), which quantifies the effect of surface irradiance on the spectral absorption of CDOM. Irradiation responses among the ocean samples were similar within the ultraviolet (UV) region of the spectrum spanning 300–360nm, generally exhibiting a decrease in the CDOM absorption coefficient (m−1) and concomitant increase in the CDOM spectral slope parameter, S (nm−1). However, an unexpected irradiation-induced increase in CDOM absorption between approximately 360 and 500nm was observed for samples from high-nutrient low-chlorophyll (HNLC) environments. This finding was linked to the presence of dissolved nitrate and may explain discrepancies in action spectra for dimethylsulfide (DMS) photobleaching observed between the Equatorial Pacific and Subtropical North Atlantic Oceans. The nitrate-to-phosphate ratio explained 27–70% of observed variability in εsurf at observation wavelengths of 330–440nm, while the initial spectral slope of the samples explained up to 52% of variability in εsurf at observation wavelengths of 310–330nm. These results suggest that the biogeochemical and solar exposure history of the water column, each of which influence the chemical character and thus the spectral quality of CDOM and its photoreactivity, are the main factors regulating the susceptibility of CDOM to photodegradation in the surface ocean. The εsurf parameter reported herein may be applied to remote sensing retrievals of CDOM to estimate photobleaching at the surface on regional to global scales.

Characterizing chromophoric dissolved organic matter in Lake Tianmuhu and its catchment basin using excitation-emission matrix fluorescence and parallel factor analysis

Chromophoric dissolved organic matter (CDOM) is an important optically active substance that transports nutrients, heavy metals, and other pollutants from terrestrial to aquatic systems and is used as a measure of water quality. To investigate how the source and composition of CDOM changes in both space and time, we used chemical, spectroscopic, and fluorescence analyses to characterize CDOM in Lake Tianmuhu (a drinking water source) and its catchment in China. Parallel factor analysis (PARAFAC) identified three individual fluorophore moieties that were attributed to humic-like and protein-like materials in 224 water samples collected between December 2008 and September 2009. The upstream rivers contained significantly higher concentrations of CDOM than did the lake water ( a(350) of 4.27 ± 2.51 and 2.32 ± 0.59 m −1, respectively), indicating that the rivers carried a substantial load of organic matter to the lake. Of the three main rivers that flow into Lake Tianmuhu, the Pingqiao River brought in the most CDOM from the catchment to the lake. CDOM absorption and the microbial and terrestrial humic-like components, but not the protein-like component, were significantly higher in the wet season than in other seasons, indicating that the frequency of rainfall and runoff could significantly impact the quantity and quality of CDOM collected from the catchment. The different relationships between the maximum fluorescence intensities of the three PARAFAC components, CDOM absorption, and chemical oxygen demand (COD) concentration in riverine and lake water indicated the difference in the composition of CDOM between Lake Tianmuhu and the rivers that feed it. This study demonstrates the utility of combining excitation-emission matrix fluorescence and PARAFAC to study CDOM dynamics in inland waters.

Temporal controls on dissolved organic matter and lignin biogeochemistry in a pristine tropical river, Democratic Republic of Congo

Dissolved organic carbon (DOC), lignin biomarkers, and the optical properties of dissolved organic matter (DOM) were measured in the Epulu River (northeast Democratic Republic of Congo) with the aim of investigating temporal controls on the quantity and chemical composition of DOM in a tropical rainforest river. Three different periods defined by stages of the hydrologic regime of the region, (1) post dry flushing period, (2) intermediary period, and (3) start of the dry period/post flush, were sampled. Temporal variability in DOM quantity and quality was observed with highest DOC, lignin concentration (Σ8) and carbon‐normalized (Λ8) values during the flushing period attributed to greater surface runoff and leaching of organic‐rich horizons, with lowest values in the dry period/post flush once source materials were well leached. Chromophoric DOM (CDOM) was strongly correlated to DOC and Σ8 (r2 = 0.85 and 0.83, respectively; p &lt; 0.001), and CDOM quality measurements (SUVA254, spectral slope ratio and fluorescence index) were strongly correlated to Λ8 values (r2 = 0.77, 0.69, and 0.75, respectively; p &lt; 0.001), demonstrating the ability to derive DOC and lignin export and to track DOM quality in tropical riverine systems from simple optical measurements. This study demonstrates similar effects in the variability of DOM quantity and quality due to changing hydrologic inputs for a tropical river as has been previously reported for temperate and northern high‐latitude rivers. Therefore, flushing periods in tropical rivers warrant further study, as they are critical toward understanding ecosystem biogeochemistry as maximal export of freshly leached plant material occurs during this time period.

Biogeneration of chromophoric dissolved organic matter by bacteria and krill in the Southern Ocean

Chromophoric dissolved organic matter (CDOM), the optically active fraction of dissolved organic matter, is primarily generated by pelagic organisms in the open ocean. In this study, we experimentally determined the quantity and spectral quality of CDOM generated by bacterioplankton using two different substrates (with and without photoproducts) and by Antarctic krill Euphausia superba and evaluated their potential contributions to CDOM dynamics in the peninsular region of the Southern Ocean. CDOM was generated by bacteria in all experiments, and the presence of photoproducts influenced both the quantity and the spectral quality of the resultant CDOM. We confirmed a direct link between bacterial production and CDOM generation, which yielded in situ CDOM duplication times from 31 to 33 d. Antarctic krill as a direct source of CDOM was also confirmed experimentally. We estimated that CDOM generation by krill would lead to CDOM duplication times from 0.48 to 0.80 d within krill swarms. Our findings highlight the potential significance of bacteria and Antarctic krill swarms in the generation of CDOM and underscore the dynamic nature of CDOM in this area.

Spatial, geomorphological, and seasonal variability of CDOM in estuaries of the Florida Coastal Everglades

This paper demonstrates the usefulness of fluorescence techniques for long-term monitoring and assessment of the dynamics (sources, transport and fate) of chromophoric dissolved organic matter (CDOM) in highly compartmentalized estuarine regions with non-point water sources. Water samples were collected monthly from a total of 73 sampling stations in the Florida Coastal Everglades (FCE) estuaries during 2001 and 2002. Spatial and seasonal variability of CDOM characteristics were investigated for geomorphologically distinct sub-regions within Florida Bay (FB), the Ten Thousand Islands (TTI), and Whitewater Bay (WWB). These variations were observed in both quantity and quality of CDOM. TOC concentrations in the FCE estuaries were generally higher during the wet season (June–October), reflecting high freshwater loadings from the Everglades in TTI, and a high primary productivity of marine biomass in FB. Fluorescence parameters suggested that the CDOM in FB is mainly of marine/microbial origin, while for TTI and WWB a terrestrial origin from Everglades marsh plants and mangroves was evident. Variations in CDOM quality seemed mainly controlled by tidal exchange/mixing of Everglades freshwater with Florida Shelf waters, tidally controlled releases of CDOM from fringe mangroves, primary productivity of marine vegetation in FB and diagenetic processes such as photodegradation (particularly for WWB). The source and dynamics of CDOM in these subtropical estuaries is complex and found to be influenced by many factors including hydrology, geomorphology, vegetation cover, landuse and biogeochemical processes. Simple, easy to measure, high sample throughput fluorescence parameters for surface waters can add valuable information on CDOM dynamics to long-term water quality studies which can not be obtained from quantitative determinations alone.

The role of wetlands in the chromophoric dissolved organic matter release and its relation to aquatic ecosystems optical properties. A case of study: Katonga and Bunjako Bays (Victoria Lake; Uganda)

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.