Marine Chromophoric Dissolved Organic Matter Research Articles

Composition, variation and contribution of chromophoric dissolved organic matter in Laizhou Bay estuaries, North China

To address the complex biogeochemical processes and potential function of dissolved organic matter (DOM) in estuaries before it enters the sea, water samples were collected seasonally in a dozen Laizhou Bay estuaries and in the Yellow River estuary, North China. The results showed that chromophoric dissolved organic matter (CDOM) varied in abundance but had consistent spectral slopes at the same sampling time. Gradually, CDOM decreased while spectral slopes increased from freshwater to seawater. The spectral slope of CDOM varied temporally (higher in October and lower in August) more than it varied spatially. The fluorescent components and biological indices of CDOM indicated that in situ biological activities were the dominant sources in the waters examined in this study. The CDOM was generally more variable than the dissolved organic carbon (DOC) in most of the estuaries. However, marine CDOM may obviously increase in estuaries when indirectly stimulated by rapidly decomposing terrestrial DOM.

Application of machine learning algorithms for prediction of ultraviolet absorption spectra of chromophoric dissolved organic matter (CDOM) in seawater

The ultraviolet absorption spectra of chromophoric dissolved organic matter (CDOM) can be used to trace its sources and to explore the dynamic of the CDOM pool. In previous studies, only the spectra above 240 nm can be used directly to characterize the CDOM in seawater, due to the overlapping of CDOM absorption spectra below 240 nm with inorganic chemicals such as NO3−, NO2−, Cl- and Br-. In this study, three different machine learning models, back propagation neural network (BPNN), random forest (RF) and extreme gradient boosting (XGBoost), were built to predict the CDOM ultraviolet absorption spectra between 215 and 350 nm after being trained with the raw absorption spectra of seawater. The optimal input wavelength range of the raw seawater spectra is 250-350 nm, and the optimal model parameters of machine learning algorithms were determined by using five-fold cross validation. The results show that the three models can well predict the CDOM absorption spectra. Comparatively, the XGBoost model gave the best prediction results. The reasons might be related to the fact that the XGBoost algorithm focuses on the residuals generated by the last iteration, which can reduce both variance and bias, especially for datasets with small sample sizes. Based on the predicted spectra by XGBoost algorithm, we calculated the spectra slopes of short wavelengths between 215 and 240 nm (S215-240) and between 215 and 275 nm (S215-275). The results show that the S215-240 and S215-275 are ~2 times the widely used spectra slopes between 275 and 295 nm (S275-295) obtained by traditional method based on the raw spectra. Moreover, the S215-240 and S215-275 are more relavant with salinity for marine CDOM than S275-295, suggesting spectra slopes of shorter wavelengths might be the better proxies for marine CDOM than that of longer wavelengths.

Optical Properties and Photochemical Transformation of the Dissolved Organic Matter Released by Sargassum

Chromophoric dissolved organic matter (CDOM) is the dominant absorber of ultraviolet radiation in the ocean, but its sources within the ocean, as well as its chemical composition, remain uncertain. One source of marine CDOM is Sargassum, an epipelagic marine macro brown alga common to the Gulf of Mexico, Caribbean, and Western North Atlantic. Furthermore, Sargassum contains phlorotannins, a class of polyphenols that may have similar optical properties to terrestrial polyphenols. Here, we analyze Sargassum CDOM optical properties, acquired from absorption and fluorescence spectra of filtered samples collected during Sargassum exudation experiments in seawater tanks. To further evaluate the structural basis of Sargassum CDOM optical properties, Sargassum CDOM was collected by solid phase extraction (SPE) and its chemical composition was tested by pH titration and sodium borohydride reduction. These chemical tests revealed that Sargassum CDOM absorption spectra respond similarly to pH titration and borohydride reduction when compared to terrestrially-derived materials, but Sargassum CDOM has unique absorbance peaks in difference spectra that have not been observed in terrestrially-derived CDOM. These absorbance features are consistent with the deprotonation of modified Sargassum phlorotannins, which are likely highly related phenolic acids and polyphenols. Sargassum CDOM was also more rapidly photodegraded when compared to terrestrial CDOM such as Suwannee River Natural Organic Matter. Similar to terrestrial DOM, ultrahigh resolution mass spectrometry revealed that sunlight decreases relative abundances of m/z ions and molecular formulas with an average O/C ratio of 0.6 and an average H/C ratio of 0.9, suggesting preferential photodegradation and/or phototransformation of hydrogen-deficient and oxygenated compounds, such as Sargassum phlorotannins. Assuming a large fraction of Sargassum CDOM is quickly mineralized to CO2 during its rapid photodegradation, Sargassum could play a major role in marine photochemical carbon mineralization during its annual growth cycle.

Characteristics of Absorption Spectra of Chromophoric Dissolved Organic Matter in the Pearl River Estuary in Spring

In this study, absorption variation of chromophoric dissolved organic matter (CDOM) was investigated based on spectroscopic measurements of the water surface and bottom during a cruise survey on 2–12 May 2014 in the Pearl River Estuary (PRE). Multiple spectral signatures were utilized, including the absorption ratios E2/E3 (a(250)/a(365)) and E2/E4 (a(254)/a(436))) as well as the spectral slopes over multiple wavelength ranges. The horizontal variations of a(300), E2/E3, spectral slope (S) of Ultraviolet C (SUVC, 250–280 nm), Ultraviolet B (SUVB, 280–315 nm), and S275–295 (275–295 nm) were highly correlated, revealing that CDOM of terrigenous origin in the upper estuary contained chromophores of larger molecular size and weight, while the marine CDOM in the lower estuary comprised organic compounds of smaller molecular size and weight; the molecular size of surface CDOM was generally larger than that at the bottom. Results of Gaussian decomposition methods showed that CDOM in the middle estuary of terrigenous origin produced more Gaussian components per spectrum than those of marine origin in the lower estuary and the adjacent Hong Kong waters. The surface CDOM composition was more diverse than at the bottom, inferred by the finding that the average number of Gaussian components yielded per surface sample (5.44) was more than that of the bottom sample (4.8). A majority of components was centered below 350 nm, indicating that organic compounds with relatively simple structures are ubiquitous in the estuary. Components centered above 350 nm only showed high peaks at the head of the estuary, suggesting that terrigenous CDOM with chromophores in complex structures rapidly lose visible light absorptivity during its transport in the PRE. The relatively low and homogenous peak heights of the components in Hong Kong waters imply higher light stability and composition consistency of the marine CDOM compared with the terrigenous CDOM.

Linking chromophoric organic matter transformation with biomarker indices in a marine phytoplankton growth and degradation experiment

The production and transformation of marine chromophoric dissolved organic matter (CDOM) provides a window into the marine biological pump as it is present at all depths and can be measured both in the field and via satellite. However, outside of lignin for terrestrial DOM, few studies have linked marine CDOM characteristics with biomarker indices. In this study, we quantified five fluorescent components of marine CDOM and base-extractable particulate organic matter (BEPOM) in a growth and degradation experiment using a natural plankton assemblage, and compared those results to bacterial abundances, hydrolytic enzyme activities, and amino acid concentrations and associated diagenetic indices. Rotating glass bottles containing plankton were sampled initially (day 0), during the mid-exponential (day 13) and stationary (day 20) growth phases, and again following a dark degradation period that lasted 42 days. Protein-like fluorescence (tryptophan-like and tyrosine-like) was correlated with the total amino acid concentrations for both the DOM and BEPOM through all phases of the incubation. However, tryptophan-like fluorescence showed a stronger correlation for aromatic amino acids. The concentration of particulate organic carbon changed significantly during each phase of the experiment and this substrate correlated with hydrolytic enzyme activities and bacterial abundance. This heterotrophy diagenetically altered the POM during the stationary phase and ultimately resulted in the increased production of more humic-like CDOM after degradation in the dark. Results from this study indicate that CDOM formation and cycling may play a prominent role in the ocean's nitrogen cycle.

Optical Characteristics and Distribution of Chromophoric Dissolved Organic Matter in Onega Bay (White Sea) during the Summer Season (Findings from an Expedition from June 22 to 26, 2015)

Onega Bay waters are characterized by a high content of chromophoric dissolved organic matter (CDOM). The absorbance spectra and fluorescence intensity (excitation wavelength 455 nm, emission wavelength >680 nm) were used to assess the distribution of CDOM content in water filtered through a GF/F filter. The CDOM content at different points in Onega Bay showed more than a fourfold difference, as inferred from the measured values. The CDOM content in surface waters was, as a rule, higher than in the deeper horizons. A higher CDOM content was measured near the Onega River, near the middle part of the Onega shore, and near the Pomor shore opposite the town of Belomorsk. River runoff is the major source of CDOM in Onega Bay water. The CDOM chemical composition in Onega Bay waters was heterogeneous. The ratio of the fluorescence intensity to the absorbance value was higher near the mouths of rivers and in intensive mixing zones than in water characterized by high salinity. A highly significant linear correlation (R2 = 0.7825) between water salinity and CDOM fluorescence intensity was demonstrated. The contribution of fluorescent compounds to river runoff CDOM is substantially higher than the contribution to the composition marine CDOM.

Mixing behavior of chromophoric dissolved organic matter in the Pearl River Estuary in spring

Mixing behavior of chromophoric dissolved organic matter (CDOM) in the Pearl River Estuary (PRE) and relevant hydrodynamic parameters such as horizontal transport and vertical mixing are identified and discussed based on a set of sampling data obtained during a cruise in May 2014. Using a theoretical conservative mixing model, the surface CDOM in the PRE in spring is classified into two groups by the CDOM absorption-spectral slope relationship (a(300) vs S(275−295)): First, terrigenous CDOM under a non-conservative mixing condition, and removal processes such as photobleaching are suggested to happen; second, marine CDOM behaves conservatively during mixing. The mixing of CDOM at the bottom is shown to be conservative. Controlled by the two-layer gravitational circulation in the PRE, the northern and western estuary shows higher CDOM absorption and lower spectral slope than the southern and eastern estuary, and the surface CDOM presents higher absorption and lower spectral slope than the bottom. Horizontal transport is hypothesized to be the dominant hydrodynamic mechanism affecting CDOM variation and mixing behavior in the PRE, while the vertical mixing has less influence.

Marine CDOM accumulation during a coastal Arctic mesocosm experiment: No response to elevated pCO2 levels

AbstractA large‐scale multidisciplinary mesocosm experiment in an Arctic fjord (Kongsfjorden, Svalbard; 78°56.2′N) was used to study Arctic marine food webs and biogeochemical elements cycling at natural and elevated future carbon dioxide (CO2) levels. At the start of the experiment, marine‐derived chromophoric dissolved organic matter (CDOM) dominated the CDOM pool. Thus, this experiment constituted a convenient case to study production of autochthonous CDOM, which is typically masked by high levels of CDOM of terrestrial origin in the Arctic Ocean proper. CDOM accumulated during the experiment in line with an increase in bacterial abundance; however, no response was observed to increased pCO2 levels. Changes in CDOM absorption spectral slopes indicate that bacteria were most likely responsible for the observed CDOM dynamics. Distinct absorption peaks (at ~ 330 and ~ 360 nm) were likely associated with mycosporine‐like amino acids (MAAs). Due to the experimental setup, MAAs were produced in absence of ultraviolet exposure providing evidence for MAAs to be considered as multipurpose metabolites rather than simple photoprotective compounds. We showed that a small increase in CDOM during the experiment made it a major contributor to total absorption in a range of photosynthetically active radiation (PAR, 400–700 nm) and, therefore, is important for spectral light availability and may be important for photosynthesis and phytoplankton groups composition in a rapidly changing Arctic marine ecosystem.

Photooxidation of dimethylsulfide (DMS) in the Canadian Arctic

Abstract. Photolysis of dimethylsulfide (DMS), a secondary photochemical process mediated by chromophoric dissolved organic matter (CDOM), has previously been demonstrated to be an important loss term of DMS in the surface layer of warm seas and the Southern Ocean. The role of photolysis in regulating the DMS dynamics in northern polar seas remains, however, less clear. This study for the first time determined the apparent quantum yield (AQY) spectra of DMS photooxidation in Canadian Arctic seas covering Baffin Bay, the Mackenzie estuary and shelf, and the Canada Basin. The DMS AQY was fairly invariant at salinities < 25 but rose rapidly with further increasing salinity in an exponential manner. Salinity can therefore be used as a quantitative indicator of the DMS AQY. The DMS AQY in the ultraviolet (UV) wavelengths was linearly and positively correlated with the spectral slope coefficient (275–295 nm) of the CDOM absorption spectrum, suggesting that marine CDOM photosensitizes the degradation of DMS more efficiently than does terrestrial CDOM or that coastal waters contain higher concentrations of substrates (most likely dissolved organic matter and redox metals) that compete for DMS-oxidizing radical intermediates. High concentrations of nitrate (~ 12 μmol L−1) in deep water samples boosted DMS photooxidation by 70–80%, due likely to radical chemistry of nitrate photolysis. Coupled optical-photochemical modeling, based on the obtained DMS AQY spectra, shows that UV-A (320–400 nm) accounted for 60–75% of the DMS photolysis in the sunlit surface layer and that photochemistry degraded DMS on an e-folding time from 9 to 100 d (mean: 29 d). The photooxidation term on average accounted for 21% of the DMS gross loss rate and was comparable to the atmospheric DMS ventilation rate estimated for the same geographic regions. The methodology adopted here to study the relationship between CDOM quality/origin and DMS AQYs, if applicable to other ocean areas, may bring results of global significance for DMS cycling and might have implications for probing other CDOM-driven photochemical processes.

Spectrally resolved efficiencies of carbon monoxide (CO) photoproduction in the western Canadian Arctic: particles versus solutes

Abstract. Spectrally resolved efficiency (i.e. apparent quantum yield, AQY) of carbon monoxide (CO) photoproduction is a useful indicator of substrate photoreactivity and a crucial parameter for modeling CO photoproduction rates in the water column. Recent evidence has suggested that CO photoproduction from particles in marine waters is significant compared to the well-known CO production from chromophoric dissolved organic matter (CDOM) photodegradation. Although CDOM-based CO AQY spectra have been extensively determined, little is known of this information on the particulate phase. Using water samples collected from the Mackenzie estuary, shelf, and Canada Basin in the southeastern Beaufort Sea, the present study for the first time quantified the AQY spectra of particle-based CO photoproduction and compared them with the concomitantly determined CDOM-based CO AQY spectra. CO AQYs of both particles and CDOM decreased with wavelength but the spectral shape of the particulate AQY was flatter in the visible regime. This feature resulted in a disproportionally higher visible light-driven CO production by particles, thereby increasing the ratio of particle- to CDOM-based CO photoproduction with depth in the euphotic zone. In terms of depth-integrated production in the euphotic zone, CO formation from CDOM was dominated by the ultraviolet (UV, 290–400 nm) radiation whereas UV and visible light played roughly equal roles in CO production from particles. Spatially, CO AQY of bulk particulate matter (i.e. the sum of organics and inorganics) augmented from the estuary and shelf to the basin while CO AQY of CDOM trended inversely. Water from the deep chlorophyll maximum layer revealed higher CO AQYs than did surface water for both particles and CDOM. CO AQY of bulk particulate matter exceeded that of CDOM on the shelf and in the basin, but the sequence reversed in the estuary. Without consideration of the potential role of metal oxides (e.g. iron oxides) in particle photochemistry, mineral absorption-corrected CO AQY of particulate organic matter (POM) could, however, surpass its CDOM counterpart in all three sub-regions and displayed magnitudes in the estuary that overtook those in shelf and offshore waters. In terms of CO photoproduction, POM was thus more photoreactive than CDOM, irrespective of the organic matter's origins (i.e. terrigenous or marine). Riverine CDOM exhibited higher photoreactivity than marine CDOM and land-derived POM appeared more photoreactive than marine POM. AQY-based modeling indicates that CO photoproduction in the study area is underestimated by 12–32% if the particulate term is ignored.

Chromophoric dissolved organic matter (CDOM) in the Equatorial Atlantic Ocean: Optical properties and their relation to CDOM structure and source

Extensive data exist on the optical properties of CDOM from terrestrial and coastal environments, yet the open oceans have been historically under-sampled. Consequently, the source and structural basis of marine CDOM optical properties are still debated. To address this issue, detailed optical measurements were acquired for both untreated and sodium borohydride (NaBH4) reduced natural waters and C18 extracts (C18-OM) across the Equatorial Atlantic Ocean. Except in regions of upwelling or in the vicinity of the Congo River outflow, CDOM absorption coefficients and visible emission intensity were far smaller for surface waters (aCDOM(355): 0.057–0.162m−1; λex/λem=350/450nm: 0.396–1.431 qse) than for waters below the mixed layer (aCDOM(355) 0.084–0.344m−1; λex/λem=350/450nm: 0.903–3.226 qse), while spectral slopes were higher (surface: 0.019 to 0.025nm−1; deep: 0.013 to 0.019nm−1), consistent with photobleaching of CDOM in surface waters. Distinct emission bands were observed in the ultraviolet, primarily at excitation/emission wavelengths (λex/λem)=280/320nm, but also at λex/λem=300/340, 300/405 and 320/380nm for some stations and depths. In contrast, visible emission exhibited maxima that continuously redshifted with increasing λex (>330nm), a property characteristic of CDOM from estuarine and coastal environments. Further evidence that CDOM in the offshore waters of this region is composed of a major terrestrial component includes: 1) similar spectral dependencies of the emission maxima and fluorescence quantum yields; 2) a large Stokes shift in the emission maxima with short-wavelength excitation (λex=280nm); 3) correlation of visible emission intensities with absorption at λex=280, 320 and 450nm, with absorption to fluorescence ratios comparable to those found in estuarine and coastal environments; 4) affinity of C18 cartridges for the long wavelength (visible) absorbing and emitting material, but not the UV emitting material; 5) preferential loss of visible absorption and substantially enhanced blue-shifted emission in the visible following borohydride reduction of both the Equatorial Atlantic waters and the C18-OM of these waters. These results support the occurrence in offshore waters of a major terrestrial CDOM component that absorbs in the UV and visible and emits in the visible, as well as marine CDOM components that absorb and emit in the UV. The results further demonstrate that the simultaneous acquisition of complete spectral absorption and emission properties, combined with chemical tests (C-18 extractions, borohydride reduction) can provide a far clearer picture of the sources and cycling of CDOM within the oceans.

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.

Analytical intercomparison between type I and type II long‐pathlength liquid core waveguides for the measurement of chromophoric dissolved organic matter

In the past decade, technological advances in optical sensors have facilitated an increased understanding of the relationship between optical characteristics and biogeochemistry of our oceans. In particular, long‐pathlength liquid core waveguide cells (LCWs) are being used to “map” chromophoric dissolved organic matter (CDOM), as a biogeochemical tracer, in various coastal and open ocean regions. At present, two LCW cell types are used in the study of marine CDOM, and concerns about discrepancies in data collected with the different cell types and problems with baseline offsets have arisen. We conducted a direct comparison of absorption coefficient spectra of a dissolved spectrophotometric standard, molecular weight standard (MWS), and dilution series of natural seawater obtained in type I and type II LCWs to assess data agreement and potential colloid‐mediated biases. Although no statistical difference was observed for the dissolved standard, we found the type I to have a slight bias toward higher absorption coefficient values for MWS 14–150 kDa (within 95% confidence interval) and natural seawater. Seawater CDOM spectral slopes differed significantly between type I and type II LCWs, with a maximum difference in slope of 0.0006 nm−1. Fastidious elimination of microbubbles from the capillary cells greatly reduced baseline offsets and markedly improved CDOM spectral slope precision.

Photobleaching of chromophoric dissolved organic matter (CDOM) in rainwater

Significant photodegradation of chromophoric dissolved organic matter (CDOM) in rainwater was observed after exposure to simulated sunlight. Fluorescence excitation emission spectra (EEMS) of precipitation revealed the presence of four major peaks all of which degraded upon photolysis with the greatest loss in the region characteristic of marine CDOM. Photobleaching of absorbance also occurred in the wavelength region between 250 and 375 nm with the greatest loss of absorbance in the upper end of the UV-A region near 275 nm. There was a strong positive correlation between absorbance loss and total integrated fluorescence loss suggesting these optical properties and the degree to which they are photobleached in rainwater are directly related. The quantum yield of CDOM photodegradation in rainwater decreased dramatically with increasing wavelength and decreasing energy of incoming radiation with the average quantum yield at 325 nm approximately an order of magnitude greater than at 460 nm. The similarity of photolytic response between rainwater and Cape Fear estuarine CDOM indicates that some fraction of the compounds that make up rainwater CDOM may be derived from surface sources and/or that the processes that produce or modify humic-like substances in the atmosphere result in similar types of compounds as non-atmospheric processes.

Factors Affecting the Efficiency of Carbon Monoxide Photoproduction in the St. Lawrence Estuarine System (Canada)

This study examined the effects of water temperature and the origin (terrestrial vs marine) and light history of chromophoric dissolved organic matter (CDOM) on the apparent quantum yields of carbon monoxide (CO) photoproduction for water samples collected along a salinity gradient (salinity range: 0-33) in the St. Lawrence estuarine system (Canada). The solar insolation-weighted mean apparent quantum yield of CO (phico) decreased as much as fourfold with increasing salinity and showed a strong positive correlation with the dissolved organic carbon-specific absorption coefficient at 254 nm. This suggests that terrestrial CDOM is more efficient at photochemically producing CO than is marine algae-derived CDOM and that aromatic moieties are likely involved in this photoprocess. CDOM photobleaching, mainly at the very early stage, dramatically decreased phico (by up to 6.4 times) for low-salinity samples, but photobleaching had little effect on the most marine sample. For a 20 degree C increase in temperature, phico increased by approximately 70% for low-salinity samples and 30-40% for saline samples. This study demonstrates that water temperature, as well as the CDOM's origin and light history, strongly affect the efficiency of CO photoproduction. These factors should be taken into account in modeling the photochemical fluxes of CO and other related CDOM photoproducts on varying spatiotemporal scales.

Fluorescence variability of marine and terrestrial colloids: Examining size fractions of chromophoric dissolved organic matter in the Damariscotta River estuary

Marine chromophoric dissolved organic matter (CDOM) imparts highly variable optical signatures in surface waters over short spatial and temporal scales, but the cause of that variability is poorly understood. A major fraction of dissolved organic matter in seawater is colloidal in size and can cycle quite rapidly, potentially contributing to the observed variability in CDOM. The relationship between marine colloids and CDOM optical variability was examined using flow field-flow fractionation (FlFFF) to partition the colloidal organic phase into a continuum of molecular sizes for optical characterization by excitation emission matrix spectroscopy (EEMS). Colloidal organic matter in surface seawater of the Damariscotta River estuary showed 2 major peaks in apparent abundance, spanning at ∼ 1–5 kDa and ∼ 15–150 kDa in size, respectively. The relative magnitude of these peaks changed systematically with the phase of phytoplankton blooms during 2003 and 2004, implying a relationship between colloid size distribution and bloom dynamics. Of the two colloidal sizes, the 1–5 kDa fraction was far more variable in apparent abundance than the larger colloidal matter. EEMS results reveal a compositional partitioning of protein-like and humic-like fluorescence between size fractions. Protein-like materials occurred primarily in the smallest colloid size fraction while humic-type materials resided mainly in the larger colloidal phase. These findings suggest that the fluorescence signature of bulk dissolved organic matter results from a collage of chromophores having optical characteristics that differ according to size of the molecular constituents. The colloidal-sized fluorescence characteristics of marine derived CDOM were contrasted with bulk CDOM to provide fundamental information on the distribution and forms of CDOM in Maine coastal waters. The findings here indicate that colloidal processes will have significant effects on the character and variability in the optical signature of surface seawaters.

Larvaceans and copepods excrete fluorescent dissolved organic matter (FDOM)

Chromophoric dissolved organic matter (CDOM) can play an important role in regulating biological production in coastal environments. Fluorescent dissolved organic matter (FDOM) is a subset of the larger CDOM pool that can be used to look at sources of CDOM. Experiments were conducted with copepods and the pelagic larvacean, Oikopleura dioica to determine if these two types of zooplankton excrete FDOM. Shipboard bottle experiments were conducted with copepods in the Gulf of Mexico, in the Mississippi River Plume in April 2001 and laboratory experiments with the pelagic larvacean, O. dioica were conducted in Oviedo, Spain in June 2001. Both copepods and O. dioica were found to excrete FDOM. Excitation/emission matrices revealed that both animals contributed to fluorescent protein pools (ex/em 275/315–350 nm) and to humic-like material (maximum ex/em 300/420 nm). The humic-like material excreted by the copepods and larvaceans was shifted toward shorter wavelengths, providing a possible unique fluorescent signature for zooplankton. Using a ratio of the humic-like fluorescence excreted by the animals (ex/em 300/420) to the humic-like fluorescence maximum in controls (ex/em 320/420 nm) showed the zooplankton could contribute nearly 50% of the Peak M fluorescence. Molecular weight analysis of the CDOM in an O. dioica excretion study showed that O. dioica excreted CDOM was primarily < 30 kDa. Both copepods and larvaceans are sources of marine FDOM and CDOM and can potentially influence the amount and type of CDOM present in coastal waters.

The colloidal size spectrum of CDOM in the coastal region of the Mississippi Plume using flow field-flow fractionation

Chromophoric dissolved organic matter (CDOM) is a major component of the total dissolved organic matter in seawater, and it can interfere significantly with oceanographic remote sensing in nearshore waters. Coastal marine CDOM comprises an undefined, likely rapidly changing mixture of terrestrially and marine-derived substances. Flow Field-Flow Fractionation (FlFFF) offers a novel approach for separating the colloidal (high molecular weight) fraction of CDOM into broad size continuums that can offer insights to the characteristics and reactivity of CDOM constituents. FlFFF analyses of seawaters in and around the Mississippi Plume were performed during high and low flow conditions and the results compared to analyses of phytoplankton cultures and waters from a coastal estuary having low freshwater inputs. FlFFF fractograms displayed major differences in the size distribution of CDOM between offshore in the Gulf of Mexico (GOMex) and the Mississippi River plume. Colloidal size distributions in nearshore surface waters out of the immediate influence of the Mississippi Plume contained a mixture of features seen in offshore waters, plume waters, and in phytoplankton cultures. Plume waters had a high abundance of larger colloidal phases but continued dilution with coastal waters led to preferential losses of mid-sized colloidal matter. Colloidal size spectra in offshore waters of the GOMex during spring were similar to that observed in estuarine waters after the spring bloom. These preliminary findings suggest that the colloidal size spectrum of CDOM may provide information on its provenance and the relative mixtures of terrestrial and marine components.

The optics of chromophoric dissolved organic matter (CDOM) in the Greenland Sea: An algorithm for differentiation between marine and terrestrially derived organic matter

The optics of chromophoric dissolved organic matter (CDOM) in the Greenland Sea were investigated and compared to results from earlier studies in the Southeastern North Sea. Absorption at 375 nm (a375) in the Greenland Sea varied from 0.77 m−1 to the detection limit of our instrument (0.05 m−1), with the highest values found during summer. The spectral slope coefficient (S) ranged from 8.2 to 26.4 µm−1 with the highest values occurring during winter. Seasonal variations in the in situ production and degradation of CDOM where shown to be responsible for the trends seen. A negative correlation between S and a375 was evident in the Greenland Sea and differed noticeably from that found in coastal waters. The differing S‐a375 behavior of CDOM known to be of terrestrial origin allowed the development of an algorithm for the differentiation between marine and terrestrial organic matter. The behavior of marine CDOM was modeled by S = 7.4 + 1.1/a375.