Surface Chromophoric Dissolved Organic Matter Research Articles

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.

Variability of chromophoric dissolved organic matter in three freshwater-influenced systems along central-southern Chile

Chromophoric dissolved organic matter (CDOM) is a biologically active component of dissolved organic matter that influences the optical properties of aquatic environments, thereby playing an important role in the photochemical and photobiology processes occurring in the euphotic layer. Three cruises were carried out at three contrasting oceanographic areas off central and southern Chile (36.8°S, 44.6°S, 54.9°S) between November 2013 and July 2017 in order to assess the variability of the CDOM pool's optical properties (a325, SCDOM, SR). Marked differences, including vertical variability, were found for a325, SCDOM, and SR within and among each of the three zones, although surface DOC concentrations remained constant at all sites (87.59 ± 26.04 µmol L−1). At the coastal area close to the Biobio River (36.8°S), a325 values varied between 0.26–1.93 m−1 with maximum measured in surface waters. For the Puyuhuapi fjord in northern Patagonia (44.6°S), a325 ranged between 0.69 and 3.86 m−1, while in the Beagle Channel (54.9°S) it oscillated between 0.59 and 1.73 m−1. We identified the terrestrial organic matter input to surface waters as the main factor influencing surface CDOM concentrations in central Chile. In the Puyuhuapi fjord, terrestrial influence was heterogeneous because of its seasonal variability of the Channel but it was overall less significant than in situ produced CDOM. We also observed the lowest contribution of terrestrial CDOM inputs compared to the in situ production in southern Patagonia (Beagle Channel). We observed that the distribution of CDOM is potentially dominated by biological in situ production below the surface freshwater-influenced layer in the southern area while highly influenced by terrestrial input in the coastal upwelling area at 36°S.Overall, this study shows that the optical properties of dissolved organic matter (mainly SR) can be suitable for identifying different CDOM pools in coastal areas of contrasting oceanographic conditions. In stratified systems, freshwater inputs determine the distribution of surface CDOM while in well-mixed conditions, the in situ production determine the general CDOM concentration.

Dissolved organic matter dynamics in Mediterranean lagoons: The relationship between DOC and CDOM

Coastal lagoons are highly vulnerable to climate change-related pressures, such as floods and increasing temperatures, which lead to higher oxygen consumption, anaerobic metabolism and dystrophic events. Although these factors have a significant impact on the carbon cycle, the dynamics of dissolved organic matter (DOM) in these systems have not been extensively investigated. DOM can be analytically determined from the concentration of dissolved organic carbon (DOC) and/or from the spectral properties of chromophoric dissolved organic matter (CDOM), which is the light-absorbing fraction of DOM. In the present study, we investigated the spatio-temporal distribution of surface water trophic variables (Chl a and DOC) and CDOM in two Mediterranean lagoon systems, the Oristano Lagoon-Gulf system (OLG) and the Varano Lagoon (VL), in order to provide quantitative information on the dynamics of DOM in these systems. Furthermore, we assessed the value of CDOM-related indices (i.e. absorption coefficients, spectral slopes and Specific UV Absorbance at 254 nm [SUVA254]) as tools for describing the dynamics of DOM in coastal lagoons, irrespective of geographical settings, environmental conditions and anthropogenic pressures. In OLG, spatial heterogeneity and compartmentalization, with salinity varying from <1 (riverine sites) to >50 (Mistras Lagoon), affected the distribution of DOC and CDOM, with the lowest values on the south side and at sites far from riverine input. In OLG, the highest DOC and CDOM values were found in the sediment pore-water of the organic-rich Cabras Lagoon, where they were nearly double those of the water column. In VL, salinity was homogeneously distributed throughout the lagoon, which indicated a mixing of freshwater with marine waters. DOC and CDOM values were on average lower in VL than in OLG. However, in VL, DOC and CDOM showed strong peaks following a flood (September 2014) and a dystrophic event (July 2015), demonstrating the quick response of the system to environmental perturbation. In OLG, absorption coefficients at 280 nm and 350 nm were slightly negatively correlated with salinity, which indicated the influence of terrigenous inputs at riverine sites. In contrast, in VL, CDOM varied linearly and positively with salinity as a result of the in situ input of organic matter from phytoplankton during the dry season. Segment analysis showed that besides the differences between the two investigated systems, the trophic variables and optical parameters analyzed in the present study shared a common relationship. These results suggest that CDOM indices can be good predictors for the estimation of DOM. Overall, the present study provides insight into the dynamics of DOC and CDOM in little-studied Mediterranean lagoons and demonstrates that the CDOM indices can be a valuable, cost-effective and simple tool for describing the trophic conditions of these systems.

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.

Surface Gradients in Dissolved Organic Matter Absorption and Fluorescence Properties along the New Zealand Sector of the Southern Ocean

The Southern Ocean plays a critical role in global carbon cycling; dissolved organic matter (DOM), a component in the carbon cycle, can be characterized optically. Sea surface chromophoric dissolved organic matter (CDOM) absorption and fluorescence properties were examined in the New Zealand sector of the Southern Ocean (NZSSO) along a transect encompassing various hydrographic fronts associated with the Antarctic Circumpolar Current (ACC) during summer. Phytoplankton chlorophyll, dissolved organic carbon (DOC) and CDOM absorption were observed to be most elevated off the New Zealand shore and then decreased to low values (chlorophyll: 0.21 ± 0.06 mg m-3; DOC: 54.19 ± 4.02 μM; and CDOM absorption coefficient at 325 nm (ag325): 0.097 ± 0.061 m-1) between the Subtropical (STF) and Antarctic Polar (APF) Fronts. Increases in phytoplankton biomass and DOC concentrations between the fronts were associated with meanders or eddies observed in satellite sea surface salinity and chlorophyll imagery. Overall, CDOM absorption was the dominant contributor to total absorption at 443 nm with implications for ocean color. Beyond the APF in the Antarctic Zone, an elevated chlorophyll band likely associated with upwelled waters transitioned to low chlorophyll in the summer ice edge zone that influenced DOM optical properties. A latitudinal increase in ag325 and corresponding decrease in spectral slope S (µm-1) poleward from the STF could be due to the a number of factors including, decreasing CDOM photooxidation, upwelling of high-CDOM waters or bacterial CDOM production in the Antarctic Zone. Parallel factor (PARAFAC) analysis of fluorescence spectra identified two protein-like (C1 and C2) and two humic-like (C3 and C4) components common in the global ocean. ag325 and the humic-like C4 fluorescent component, were positively correlated to chlorophyll indicating biological control. Surface distribution of the protein-like C1 and C2 and the marine humic-like C3 components showed patterns that appeared to be influenced by both physical and biological processes. This study provides insights into surface CDOM optical properties and its transformation along a complex topographically influenced sector of the Southern Ocean that could be used to trace changes linked to the meridional overturning circulation. I

Fluorescence and absorption properties of chromophoric dissolved organic matter (CDOM) in coastal surface waters of the northwestern Mediterranean Sea, influence of the Rhône River

Abstract. Seawater samples were collected monthly in surface waters (2 and 5 m depths) of the Bay of Marseilles (northwestern Mediterranean Sea; 5°17'30" E, 43°14'30" N) during one year from November 2007 to December 2008 and studied for total organic carbon (TOC) as well as chromophoric dissolved organic matter (CDOM) optical properties (absorbance and fluorescence). The annual mean value of surface CDOM absorption coefficient at 350 nm [aCDOM(350)] was very low (0.10 ± 0.02 m−1) in comparison to values usually found in coastal waters, and no significant seasonal trend in aCDOM(350) could be determined. By contrast, the spectral slope of CDOM absorption (SCDOM) was significantly higher (0.023 ± 0.003 nm−1) in summer than in fall and winter periods (0.017 ± 0.002 nm−1), reflecting either CDOM photobleaching or production in surface waters during stratified sunny periods. The CDOM fluorescence, assessed through excitation emission matrices (EEMs), was dominated by protein-like component (peak T; 1.30–21.94 QSU) and marine humic-like component (peak M; 0.55–5.82 QSU), while terrestrial humic-like fluorescence (peak C; 0.34–2.99 QSU) remained very low. This reflected a dominance of relatively fresh material from biological origin within the CDOM fluorescent pool. At the end of summer, surface CDOM fluorescence was very low and strongly blue shifted, reinforcing the hypothesis of CDOM photobleaching. Our results suggested that unusual Rhône River plume eastward intrusion events might reach Marseilles Bay within 2–3 days and induce local phytoplankton blooms and subsequent fluorescent CDOM production (peaks M and T) without adding terrestrial fluorescence signatures (peaks C and A). Besides Rhône River plumes, mixing events of the entire water column injected relative aged (peaks C and M) CDOM from the bottom into the surface and thus appeared also as an important source of CDOM in surface waters of the Marseilles Bay. Therefore, the assessment of CDOM optical properties, within the hydrological context, pointed out several biotic (in situ biological production, biological production within Rhône River plumes) and abiotic (photobleaching, mixing) factors controlling CDOM transport, production and removal in this highly urbanized coastal area.

Seasonal variability and controls on chromophoric dissolved organic matter in a large river‐dominated coastal margin

The spring‐to‐summer seasonal transition in the spatial and vertical distribution of chromophoric dissolved organic matter (CDOM) optical properties was examined during surveys conducted in March, May, July, and August of 2005 in the waters influenced by the Mississippi‐Atchafalaya River system of the northwestern Gulf of Mexico. Strong seasonal river influences and a well‐correlated inverse relationship between CDOM absorption at 412 nm and salinity during spring of 2005 suggests conservative mixing in the water column between the riverine freshwater sources and the oceanic end members. Trends in the CDOM absorption and the spectral absorption slope (S) and deviations from the end‐member conservative mixing line in surface and bottom waters during the summer suggest apparent sources and sinks of CDOM. Elevated CDOM in lower‐salinity surface waters at many stations appears to be linked to high concentrations of dissolved oxygen (DO; &gt;10 mg L−1) and elevated chlorophyll concentrations. Effects of photo‐oxidation in surface waters were observed as increasing S and enhanced CDOM loss in the ~27‐32 salinity range and were attributed to seasonal stratification and the increased solar radiation during the summer. In the bottom waters, elevated CDOM levels in the ~32‐36 salinity range were associated with low DO and relatively higher bacterial abundance; this suggests a potential CDOM source due to microbial remineralization of organic matter in the hypoxic zone in bottom waters. Seasonal dynamics associated with CDOM loss in surface waters and CDOM gains in bottom waters may be another pathway influencing hypoxia in coastal waters.

Spectral characterization of chromophoric dissolved organic matter (CDOM) in a fjord (Doubtful Sound, New Zealand)

Doubtful Sound, Fiordland National Park, New Zealand has a stable low salinity layer (LSL) at the surface due to the high annual rainfall and an additional freshwater input from the discharge of a hydroelectric power plant. Chromophoric dissolved organic matter (CDOM) distribution dynamics in this LSL were analyzed using Excitation Emission Matrix (EEM) fluorescence and UV/Vis absorption measurements. The levels of CDOM in surface water in Doubtful Sound were much higher than previously reported for coastal zones. CDOM analyzed by UV/Vis absorbance and EEM fluorescence decreased by about 90% within the first 5 m depth. In the first 5 m, the salinity gradient was extreme (5 – 34 salinity), creating a vertical mixing gradient, which appeared to be stable over time. The spectral slope S and the fluorescence index increased during vertical mixing within the first 5 m depth indicating changes in the CDOM chromophores. Observations during a strong rain event revealed that CDOM in a freshwater stream initially increased, but decreased with additional rain (same flow rate), which is an indication that most CDOM was quickly exported within these catchments. Furthermore, the lower CDOM input after substantial rain diluted the surface CDOM level and created a subsurface CDOM maximum. However, shortly after the rain event (<24 h) the surface CDOM maximum with a steady decrease with depth was restored. The combination of extreme rainfall, pristine temperate rain forest and steep mountains with distinct watersheds creates a highly dynamic environment with very high terrestrial CDOM input. These CDOM dynamics and the high degree of scatter in the linear correlations between CDOM levels and salinity cannot be explained solely in terms of conservative mixing, but suggest that biophysical controls in the catchments and mixing with marine derived CDOM are involved in the dynamics of CDOM in this system.

Spatial and temporal distribution of chromophoric dissolved organic matter (CDOM) fluorescence and its contribution to light attenuation in UK waterbodies

Vertical attenuation of light through the water column ( K d) is attributable to the optically active components of phytoplankton, suspended particulate material (SPM) and chromophoric dissolved organic matter (CDOM). Of these, CDOM is not routinely monitored and was the main focus of this study. Concentrations and spatio-temporal patterns of CDOM fluorescence were investigated between August 2004 and March 2006, to quantify the correlation coefficient between CDOM and salinity and to better characterise the contribution of CDOM to K d. Sampling was conducted at a broad range of UK and Republic of Ireland locations; these included more than 15 estuaries, 30 coastal and 70 offshore sites in the southern North Sea, Irish Sea, Liverpool Bay, Western Approaches and the English Channel. An instrument package was used; a logger with multi-sensor array was deployed vertically through the water column and concurrent water samples were taken to determine salinity, CDOM fluorescence and SPM. Surface CDOM fluorescence values ranged between 0.05 and 16.80 S.Fl.U. (standardised fluorescence units). A strong, negative correlation coefficient of CDOM to salinity ( r 2 = 0.81) was found. CDOM absorption ( aCDOM λ) was derived from fluorescence measurements and was in the range 0.02–2.2 m − 1 with mean 0.15 m − 1. These results were comparable with direct measurements of aCDOM λ in the same geographic regions, as published by other workers. Spatial differences in CDOM fluorescence were generally explicable by variation in salinity, in local conditions or catchment areas; e.g. CDOM at the freshwater end was 3.54–11.30 S.Fl.U., reflecting the variety of rivers sampled and their different catchments. Temporal changes in CDOM fluorescence were related to salinity. A significant and positive correlation was found between CDOM and K d, and although CDOM was found to be less influential than SPM on K d, it was still of significance particularly in coastal and offshore waters of lower turbidity.

Hydrography of chromophoric dissolved organic matter in the North Atlantic

The distribution and optical absorption characteristics of chromophoric dissolved organic matter (CDOM) were systematically investigated along three meridional transects in the North Atlantic Ocean and Caribbean Sea conducted as part of the 2003 US CLIVAR/CO 2 Repeat Hydrography survey. Hydrographic transects covered in aggregate a latitudinal range of 5° to 62° north along longitudes 20°W (line A16N, Leg 1), 52°W (A20), and 66°W (A22). Absorption spectra of filtered seawater samples were collected and analyzed for depths ranging from the surface to ∼6000 m, sampling all the ocean water masses in the western basin of the subtropical North Atlantic and several stations on the North and South American continental slopes. The lowest surface abundances of CDOM (< 0.1 m −1 absorption coefficient at 325 nm) were found in the central subtropical gyres while the highest surface abundances (∼0.7 m −1) were found along the continental shelves and within the subpolar gyre, confirming recent satellite-based assessments of surface CDOM distribution. Within the ocean interior, CDOM abundances were relatively high (0.1–0.2 m −1 absorption coefficient at 325 nm) except in the subtropical mode water, where a local minimum exists due to the subduction of low CDOM surface waters during mode water formation. In the subthermocline water masses of the western basin, changes in CDOM abundance are not correlated with increasing ventilation age as assessed using chlorofluorocarbon (CFC) concentrations and the atmospheric CFC history. But dissolved organic carbon (DOC) mass-specific absorption coefficients of CDOM increase with increasing ventilation age in the deep sea, indicating that CDOM is a refractory component of the DOC pool. The overall CDOM distribution in the North Atlantic reflects the rapid advection and mixing processes of the basin and demonstrates that remineralization in the ocean interior is not a significant sink for CDOM. This supports the potential of CDOM as a tracer of ocean circulation processes for subducted water masses.

Chromophoric dissolved organic matter (CDOM) source characterization in the Louisiana Bight

Chromophoric dissolved organic matter (CDOM) in the Mississippi plume region may have several distinct sources: riverine (terrestrial soils), wetland (terrestrial plants), biological production (phytoplankton, zooplankton, microbial), and sediments. Complex mixing, photodegradation, and biological processes make differentiation of the specific sources of CDOM difficult. Using a combination of high resolution in situ observations on an undulating vehicle, the ECOShuttle, a pumping system mounted on the vehicle, and detailed chemical and biological analyses of discrete samples allowed us to characterize two specific sources of CDOM in the Louisiana Bight: the river water constrained in the upper 12 m of the Mississippi River plume and several subsurface layers of CDOM below the plume. The subsurface CDOM maxima were coincident with steep pycnoclines and sometimes with maxima in chlorophyll a fluorescence. Both sources were actively supplying CDOM to the same location by entirely different processes. The subsurface CDOM was more biologically labile and photochemically refractory than the surface CDOM. Optical properties were also different with a relatively higher protein fluorescence and a lower spectral slope coefficient in the subsurface CDOM. The geographical extent of the two sources was determined by three-dimensional mapping of the area, and due to the relatively calm conditions in the summer of 2000, thin layers of CDOM produced in the subsurface were observed throughout the region. While riverine inputs dominated the distribution of CDOM in surface waters <12 m in depth, biological production of CDOM, probably due to the bacterial degradation of phytoplankton produced DOM dominated the subsurface waters.