Chromophoric Dissolved Organic Matter Absorption Research Articles

Parameterization of the light absorption properties of chromophoric dissolved organic matter in the Baltic Sea and Pomeranian lakes

Abstract. This study presents three alternative models for estimating the absorption properties of chromophoric dissolved organic matter aCDOM(λ). For this analysis we used a database containing 556 absorption spectra measured in 2006–2009 in different regions of the Baltic Sea (open and coastal waters, the Gulf of Gdańsk and the Pomeranian Bay), at river mouths, in the Szczecin Lagoon and also in three lakes in Pomerania (Poland) – Obłęskie, Łebsko and Chotkowskie. The variability range of the chromophoric dissolved organic matter (CDOM) absorption coefficient at 400 nm, aCDOM(400), lay within 0.15–8.85 m−1. The variability in aCDOM(λ) was parameterized with respect to the variability over 3 orders of magnitude in the chlorophyll a concentration Chl a (0.7–119 mg m−3). The chlorophyll a concentration and aCDOM(400) were correlated, and a statistically significant, nonlinear empirical relationship between these parameters was derived (R2 = 0.83). On the basis of the covariance between these parameters, we derived two empirical mathematical models that enabled us to design the CDOM absorption coefficient dynamics in natural waters and reconstruct the complete CDOM absorption spectrum in the UV and visible spectral domains. The input variable in the first model was the chlorophyll a concentration, and in the second one it was aCDOM(400). Both models were fitted to a power function, and a second-order polynomial function was used as the exponent. Regression coefficients for these formulas were determined for wavelengths from 240 to 700 nm at 5 nm intervals. Both approximations reflected the real shape of the absorption spectra with a low level of uncertainty. Comparison of these approximations with other models of light absorption by CDOM demonstrated that our parameterizations were superior (bias from −1.45 to 62 %, RSME from 22 to 220 %) for estimating CDOM absorption in the optically complex waters of the Baltic Sea and Pomeranian lakes.

Surfactant control of gas transfer velocity along an offshore coastal transect: results from a laboratory gas exchange tank

Abstract. Understanding the physical and biogeochemical controls of air–sea gas exchange is necessary for establishing biogeochemical models for predicting regional- and global-scale trace gas fluxes and feedbacks. To this end we report the results of experiments designed to constrain the effect of surfactants in the sea surface microlayer (SML) on the gas transfer velocity (kw; cm h−1), seasonally (2012–2013) along a 20 km coastal transect (North East UK). We measured total surfactant activity (SA), chromophoric dissolved organic matter (CDOM) and chlorophyll a (Chl a) in the SML and in sub-surface water (SSW) and we evaluated corresponding kw values using a custom-designed air–sea gas exchange tank. Temporal SA variability exceeded its spatial variability. Overall, SA varied 5-fold between all samples (0.08 to 0.38 mg L−1 T-X-100), being highest in the SML during summer. SML SA enrichment factors (EFs) relative to SSW were ∼ 1.0 to 1.9, except for two values (0.75; 0.89: February 2013). The range in corresponding k660 (kw for CO2 in seawater at 20 °C) was 6.8 to 22.0 cm h−1. The film factor R660 (the ratio of k660 for seawater to k660 for “clean”, i.e. surfactant-free, laboratory water) was strongly correlated with SML SA (r ≥ 0.70, p ≤ 0.002, each n = 16). High SML SA typically corresponded to k660 suppressions ∼ 14 to 51 % relative to clean laboratory water, highlighting strong spatiotemporal gradients in gas exchange due to varying surfactant in these coastal waters. Such variability should be taken account of when evaluating marine trace gas sources and sinks. Total CDOM absorbance (250 to 450 nm), the CDOM spectral slope ratio (SR = S275 − 295∕S350 − 400), the 250 : 365 nm CDOM absorption ratio (E2 : E3), and Chl a all indicated spatial and temporal signals in the quantity and composition of organic matter in the SML and SSW. This prompts us to hypothesise that spatiotemporal variation in R660 and its relationship with SA is a consequence of compositional differences in the surfactant fraction of the SML DOM pool that warrants further investigation.

The Variability of CDOM Along the Salinity Gradients of the Seomjin River Estuary During Dry and Wet Seasons

The distribution patterns of Chromophoric Dissolved Organic Matter (CDOM) and the chemical characteristics of CDOM in the Seomjin river estuary were investigated in March, June and July 2012 in order to determine the spatial and temporal variability of CDOM along the salinity gradient considering the effects of mixing, nutrients and Chl a. The average CDOM values were 1.0 ± 0.3 m -1 , 1.3 ± 0.4 m -1 , and 1.4 ± 0.3 m -1 in March, June and July, respectively. A high concentration of CDOM (greater than 1.5 m -1 ) was found at the head of the river which decreased towards the river mouth to as low as less than 0.5 m -1 . The average concentrations of CDOM increased from the dry season (March and June) to the wet season (July), and the average slope values (S 300-500 ), which were used as indicators of CDOM characteristics and sources, were in the range of 0.013 - 0.018 ㎚ -1 . The CDOM and S 300-50 values showed that not only the concentration of CDOM but also the chemical properties of DOM clearly changed between upstream and downstream in the Seomjin river. CDOM and FDOM showed a negative correlation with salinity (R² ＞ 0.8), and CDOM was positively correlated with FDOM. Furthermore, the mixing pattern of CDOM was confirmed as conservative for all seasons. The main environmental factors influencing the concentration of CDOM was confirmed as conservative for all seasons. The main environmental factors influencing the concentration of CDOM were salinity (mixing) and water temperature, which meant the dilution of low CDOM seawater, was the controlling factor for the spatial distribution of CDOM. Increases in water temperature seemed to induce the production of CDOM during summer (June and July) through the biological degradation of DOM either by microbial activity or photo-degradation.

Sources and Transformations of Dissolved Lignin Phenols and Chromophoric Dissolved Organic Matter in Otsuchi Bay, Japan

Dissolved lignin phenols and optical properties of dissolved organic matter (DOM) were measured to investigate the sources and transformations of terrigenous DOM (tDOM) in Otsuchi Bay, Japan. Three rivers discharge into the bay, and relatively high values of syringyl:vanillyl phenols (0.73 ± 0.07) and cinnamyl:vanillyl phenols (0.33 ± 0.10) indicated large contributions of non-woody angiosperm tissues to lignin and tDOM. The physical mixing of river and seawater played an important role in controlling the concentrations and distributions of lignin phenols and chromophoric DOM (CDOM) optical properties in the bay. Lignin phenol concentrations and the CDOM absorption coefficient at 350 nm, a(350), were strongly correlated in river and bay waters. Measurements of lignin phenols and CDOM in bay waters indicated a variety of photochemical and biological transformations of tDOM, including oxidation reactions, photobleaching and a decrease in molecular weight. Photodegradation and biodegradation of lignin and CDOM were investigated in decomposition experiments with river water and native microbial assemblages exposed to natural sunlight or kept in the dark. There was a rapid and substantial removal of lignin phenols and CDOM during the first few days in the light treatment, indicating transformations of tDOM and CDOM can occur soon after discharge of buoyant river water into the bay. The removal of lignin phenols was slightly greater in the dark (34%) than in the light (30%) during the remaining 59 days of the incubation. Comparison of the light and dark treatments indicated biodegradation was responsible for 67% of total lignin phenol removal during the 62-day incubation exposed to natural sunlight, indicating biodegradation is a dominant removal process in Otsuchi Bay.

Inflow rate-driven changes in the composition and dynamics of chromophoric dissolved organic matter in a large drinking water lake

Drinking water lakes are threatened globally and therefore in need of protection. To date, few studies have been carried out to investigate how the composition and dynamics of chromophoric dissolved organic matter (CDOM) in drinking water lakes are influenced by inflow rate. Such CDOM can lead to unpleasant taste and odor of the water and produce undesirable disinfection byproducts during drinking water treatment. We studied the drinking water Lake Qiandao, China, and found that the concentrations of suspended particulate matter (SPM) in the lake increased significantly with inflow rate (p < 0.001). Similarly, close relationships between inflow rate and the CDOM absorption coefficient at 350 nm a(350) and with terrestrial humic-like fluorescence C3 and a negative relationship between inflow rate and the first principal component (PC1) scores, which, in turn, were negatively related to the concentrations and relative molecular size of CDOM (p < 0.001), i.e. the concentration and molecular size of CDOM entering the lake increased proportionately with inflow rate. Furthermore, stable isotopes (δD and δ18O) were depleted in the upstream river mouth relative to downstream remaining lake regions, substantiating that riverine CDOM entering the lake was probably driven by inflow rate. This was further underpinned by remarkably higher mean chlorophyll-a and in situ measured terrestrial CDOM fluorescence (365/480 nm) and apparent oxygen utilization (AOU), and notably lower mean PC1 and CDOM spectral slope (S275–295) recorded in the upstream river mouth than in the downstream main lake area. Strong negative correlations between inflow rate and a(250):a(365), S275–295, and the spectral slope ratio (SR) implied that CDOM input to the lake in rainy period was dominated by larger organic molecules with a more humic-like character. Rainy period, especially rainstorm events, therefore poses a risk to drinking water safety and requires higher removal efficiency of CDOM during drinking water treatment processes.

Regional chlorophyll a algorithms in the Arctic Ocean and their effect on satellite-derived primary production estimates

The Arctic is warming at approximately twice the global rate in response to anthropogenic climate change, resulting in disappearing sea ice, increased open water area, and a longer growing season (IPCC, 2013). This loss of sea ice has resulted in a 30% increase in annual net primary production (NPP) by Arctic Ocean phytoplankton between 1998 and 2012 (Arrigo and van Dijken, 2015). To quantify NPP, many algorithms require input of chlorophyll a (Chl a) concentration, which serves as a biomass proxy for phytoplankton. While satellites provide temporally and spatially extensive data, including Chl a, the standard global ocean color algorithms are prone to errors in Arctic Ocean waters due to higher than average phytoplankton pigment-packaging and chromophoric dissolved organic matter (CDOM) concentrations. Here, we evaluate retrievals of Chl a using existing ocean color algorithms, test and develop a new empirical ocean color algorithm for use in the Chukchi Sea, and evaluate the effect of using different satellite Chl a products as input to an NPP algorithm. Our results show that in the Chukchi Sea, Chl a was overestimated by the global algorithm (MODIS OC3Mv6) at concentrations lower than 0.9mgm−3 because of contamination by CDOM absorption, but underestimated at higher concentrations because of pigment packaging. Only within the in situ Chl a range of 0.6–2mgam−3 was the satellite retrieval error by the OC3Mv6 algorithm below the ocean color community goal of <35%. Using coincident in situ Chl a concentrations and optical data, a new linear empirical algorithm is developed (OC3L) that yields the lowest statistical error when estimating Chl a in the Chukchi Sea, compared to existing ocean color algorithms (OC3Mv6, OC4L, OC4P). When we estimated regional NPP using different Chl a satellite products as input, three distinct bio-optical provinces within the Arctic Ocean emerged. These provinces correspond to the inflow shelves, interior shelves, and outflow shelves+deep basin as defined by Carmack et al. (2006). Eleven sub-regions within the Arctic Ocean were grouped into each of these three provinces based on their mean value for R, the ratio of blue to green remote sensing reflectance (RRS). Our results suggest that three algorithms tuned to each of the three bio-optical provinces may be sufficient to capture the bio-optical heterogeneity within the Arctic Ocean. Currently, only within the inflow shelf province do we feel confident that Chl a and NPP can be accurately estimated by satellite using the OC3L algorithm. The interior and outflow shelf+basin provinces require development of ocean color algorithms specific to their respective bio-optical conditions.

The potential role of sea ice melt in the distribution of chromophoric dissolved organic matter in the Chukchi and Beaufort Seas

We investigated chromophoric dissolved organic matter (CDOM) in sea ice and the underlying water column in the Chukchi and Beaufort seas of the Pacific Arctic region and its relationship with both physical and biogeochemical parameters. Sea ice, water and melt pond samples were collected as sea ice melted in June–July 2010 and 2011. CDOM absorption was found to be significantly lower in sea ice compared to under-ice waters. In particular, the average CDOM absorption coefficient at 254nm was approximately four times greater in the underlying water column than in the overlying ice. This indicates that melting sea ice did not contribute to net CDOM at this point in the melt season, but rather diluted CDOM in the under-ice water column. In the 2011 under-ice water column samples, the average CDOM absorption coefficients at 440nm were twice as high along a transect associated with high phytoplankton biomass, which may have been contributed through subsequent microbial generation of CDOM. Less extensive sea ice cover with melt ponds may also have increased the presence of CDOM owing to increases in light transmission, leading to under-ice phytoplankton blooms and associated microbial production. However, oxygen isotope analysis of these waters with high under-ice phytoplankton biomass also indicates the presence of prior sea ice melt, including potentially sea ice algae and microbes, which could have also contributed to this anomalously high CDOM. These observations suggest that while melting sea ice may not necessarily contribute to increased CDOM concentrations, there are circumstances where CDOM in underlying waters may be higher than expected, either due to enhanced light transmission and higher under-ice production, and/or prior ice melt that provided significant contributions to under-ice CDOM.

Integrated Role of SST, PAR and CDOM in Summer Reef Bleaching during 2010 and 2011 along the Lakshadweep Islands

The role of sea-surface temperature (SST), photosynthetically active radiation (PAR) and chromophoric dissolved organic matter (CDOM) on bleaching events along the Lakshadweep archipelago was studied for the summer of 2010 and 2011. The present study revealed similar SST pattern (30.8-31.9°C) and high PAR availability (48-50 E m -2 day -1 ) during the summer weeks of 2010 and 2011. However, the CDOM content varied significantly between 0.5 and 7 during 2010 and 2011. Stress from the elevated SST and PAR levels coinciding with low CDOM content (ultra violet radiation (UVR) transparent water column) might have resulted in large-scale bleaching during 2010. Low PAR and high CDOM (UVR opaque water column) might have prevented Lakshadweep corals from large-scale bleaching during 2011. Statistical analysis also confirmed that the high bleaching event of 2010 was due to coupled stress imparted by SST, PAR, CDOM and the unusually calm state of the sea.

Changes in optical characteristics of surface microlayers hint to photochemically and microbially mediated DOM turnover in the upwelling region off the coast of Peru

Abstract. The coastal upwelling system off the coast of Peru is characterized by high biological activity and a pronounced subsurface oxygen minimum zone, as well as associated emissions of atmospheric trace gases such as N2O, CH4 and CO2. From 3 to 23 December 2012, R/V Meteor (M91) cruise took place in the Peruvian upwelling system between 4.59 and 15.4° S, and 82.0 to 77.5° W. During M91 we investigated the composition of the sea-surface microlayer (SML), the oceanic uppermost boundary directly subject to high solar radiation, often enriched in specific organic compounds of biological origin like chromophoric dissolved organic matter (CDOM) and marine gels. In the SML, the continuous photochemical and microbial recycling of organic matter may strongly influence gas exchange between marine systems and the atmosphere. We analyzed SML and underlying water (ULW) samples at 38 stations focusing on CDOM spectral characteristics as indicator of photochemical and microbial alteration processes. CDOM composition was characterized by spectral slope (S) values and excitation–emission matrix fluorescence (EEMs), which allow us to track changes in molecular weight (MW) of DOM, and to determine potential DOM sources and sinks. Spectral slope S varied between 0.012 to 0.043 nm−1 and was quite similar between SML and ULW, with no significant differences between the two compartments. Higher S values were observed in the ULW of the southern stations below 15° S. By EEMs, we identified five fluorescent components (F1–5) of the CDOM pool, of which two had excitation/emission characteristics of amino-acid-like fluorophores (F1, F4) and were highly enriched in the SML, with a median ratio SML : ULW of 1.5 for both fluorophores. In the study region, values for CDOM absorption ranged from 0.07 to 1.47 m−1. CDOM was generally highly concentrated in the SML, with a median enrichment with respect to the ULW of 1.2. CDOM composition and changes in spectral slope properties suggested a local microbial release of DOM directly in the SML as a response to light exposure in this extreme environment. In a conceptual model of the sources and modifications of optically active DOM in the SML and underlying seawater (ULW), we describe processes we think may take place (Fig. 1); the production of CDOM of higher MW by microbial release through growth, exudation and lysis in the euphotic zone, includes the identified fluorophores (F1, F2, F3, F4, F5). Specific amino-acid-like fluorophores (F1, F4) accumulate in the SML with respect to the ULW, as photochemistry may enhance microbial CDOM release by (a) photoprotection mechanisms and (b) cell-lysis processes. Microbial and photochemical degradation are potential sinks of the amino-acid-like fluorophores (F1, F4), and potential sources of reworked and more refractory humic-like components (F2, F3, F5). In the highly productive upwelling region along the Peruvian coast, the interplay of microbial and photochemical processes controls the enrichment of amino-acid-like CDOM in the SML. We discuss potential implications for air–sea gas exchange in this area.

Characterization of CDOM from urban waters in Northern-Northeastern China using excitation-emission matrix fluorescence and parallel factor analysis.

Chromophoric dissolved organic matter (CDOM) plays an important role in aquatic systems, but high concentrations of organic materials are considered pollutants. The fluorescent component characteristics of CDOM in urban waters sampled from Northern and Northeastern China were examined by excitation-emission matrix fluorescence and parallel factor analysis (EEM-PARAFAC) to investigate the source and compositional changes of CDOM on both space and pollution levels. One humic-like (C1), one tryptophan-like component (C2), and one tyrosine-like component (C3) were identified by PARAFAC. Mean fluorescence intensities of the three CDOM components varied spatially and by pollution level in cities of Northern and Northeastern China during July-August, 2013 and 2014. Principal components analysis (PCA) was conducted to identify the relative distribution of all water samples. Cluster analysis (CA) was also used to categorize the samples into groups of similar pollution levels within a study area. Strong positive linear relationships were revealed between the CDOM absorption coefficients a(254) (R (2) = 0.89, p < 0.01); a(355) (R (2) = 0.94, p < 0.01); and the fluorescence intensity (F max) for the humic-like C1 component. A positive linear relationship (R (2) = 0.77) was also exhibited between dissolved organic carbon (DOC) and the F max for the humic-like C1 component, but a relatively weak correlation (R (2) = 0.56) was detected between DOC and the F max for the tryptophan-like component (C2). A strong positive correlation was observed between the F max for the tryptophan-like component (C2) and total nitrogen (TN) (R (2) = 0.78), but moderate correlations were observed with ammonium-N (NH4-N) (R (2) = 0.68), and chemical oxygen demand (CODMn) (R (2) = 0.52). Therefore, the fluorescence intensities of CDOM components can be applied to monitor water quality in real time compared to that of traditional approaches. These results demonstrate that EEM-PARAFAC is useful to evaluate the dynamics of CDOM fluorescent components in urban waters from Northern and Northeastern China and this method has potential applications for monitoring urban water quality in different regions with various hydrological conditions and pollution levels.

Seasonal Dynamics in Dissolved Organic Matter, Hydrogen Peroxide, and Cyanobacterial Blooms in Lake Erie

Hydrogen peroxide (H2O2) has been suggested to influence cyanobacterial community structure and toxicity. However, no study has investigated H2O2 concentrations in freshwaters relative to cyanobacterial blooms when sources and sinks of H2O2 may be highly variable. For example, photochemical production of H2O2 from chromophoric dissolved organic matter (CDOM) may vary over the course of the bloom with changing CDOM and UV light in the water column, while microbial sources and sinks of H2O2 may change with community biomass and composition. To assess relationships between H2O2 and harmful algal blooms dominated by toxic cyanobacteria in the western basin of Lake Erie, we measured H2O2 weekly at six stations from June – November, 2014 and 2015, with supporting physical, chemical, and biological water quality data. Nine additional stations across the western, eastern, and central basins of Lake Erie were sampled during August and October, 2015. CDOM sources were quantified from the fluorescence fraction of CDOM using parallel factor analysis (PARAFAC). CDOM concentration and source were significantly correlated with specific conductivity, demonstrating that discharge of terrestrially-derived CDOM from rivers can be tracked in the lake. Autochthonous sources of CDOM in the lake increased over the course of the blooms. Concentrations of H2O2 in Lake Erie ranged from 47 ± 16 nM to 1570 ± 16 nM (average of 371 ± 17 nM; n = 225), and were not correlated to CDOM concentration or source, UV light, or estimates of photochemical production of H2O2 by CDOM. Temporal patterns in H2O2 were more closely aligned with bloom dynamics in the lake. In 2014 and 2015, maximum concentrations of H2O2 were observed prior to peak water column respiration and chlorophyll a, coinciding with the onset of the widespread Microcystis blooms in late July. The spatial and temporal patterns in H2O2 concentrations suggested that production and decay of H2O2 from aquatic microorganisms can be greater than photochemical production of H2O2 from CDOM and abiotic decay pathways. Our study measured H2O2 concentrations in the range where physiological impacts on cyanobacteria have been reported, suggesting that H2O2 could influence the structure and function of cyanobacterial communities in Lake Erie.

Optical properties and bioavailability of dissolved organic matter along a flow-path continuum from soil pore waters to the Kolyma River mainstem, East Siberia

Abstract. The Kolyma River in northeast Siberia is among the six largest Arctic rivers and drains a region underlain by vast deposits of Holocene-aged peat and Pleistocene-aged loess known as yedoma, most of which is currently stored in ice-rich permafrost throughout the region. These peat and yedoma deposits are important sources of dissolved organic matter (DOM) to inland waters that in turn play a significant role in the transport and ultimate remineralization of organic carbon to CO2 and CH4 along the terrestrial flow-path continuum. The turnover and fate of terrigenous DOM during offshore transport largely depends upon the composition and amount of carbon released to inland and coastal waters. Here, we measured the ultraviolet-visible optical properties of chromophoric DOM (CDOM) from a geographically extensive collection of waters spanning soil pore waters, streams, rivers, and the Kolyma River mainstem throughout a ∼ 250 km transect of the northern Kolyma River basin. During the period of study, CDOM absorption coefficients were found to be robust proxies for the concentration of DOM, whereas additional CDOM parameters such as spectral slopes (S) were found to be useful indicators of DOM quality along the flow path. In particular, the spectral slope ratio (SR) of CDOM demonstrated statistically significant differences between all four water types and tracked changes in the concentration of bioavailable DOC, suggesting that this parameter may be suitable for clearly discriminating shifts in organic matter characteristics among water types along the full flow-path continuum across this landscape. However, despite our observations of downstream shifts in DOM composition, we found a relatively constant proportion of DOC that was bioavailable ( ∼ 3–6 % of total DOC) regardless of relative water residence time along the flow path. This may be a consequence of two potential scenarios allowing for continual processing of organic material within the system, namely (a) aquatic microorganisms are acclimating to a downstream shift in DOM composition and/or (b) photodegradation is continually generating labile DOM for continued microbial processing of DOM along the flow-path continuum. Without such processes, we would otherwise expect to see a declining fraction of bioavailable DOC downstream with increasing residence time of water in the system. With ongoing and future permafrost degradation, peat and yedoma deposits throughout the northeast Siberian region will become more hydrologically active, providing greater amounts of DOM to fluvial networks and ultimately to the Arctic Ocean. The ability to rapidly and comprehensively monitor shifts in the quantity and quality of DOM across the landscape is therefore critical for understanding potential future feedbacks within the Arctic carbon cycle.

A new insight into black blooms: Synergies between optical and chemical factors

Black blooms have been associated with fish-kills and the loss of benthic fauna as well as closure of potable water supplies. Their frequency and duration has increased in recent decades in rivers, inland lakes and reservoirs, and has often been associated with the decay and release of organic matter (planktonic algae, aquatic macrophytes, sediment release, etc.). However, the interactions between microbial, chemical, hydrodynamic and optical conditions necessary for black blooms are poorly understood. The present study combines field investigations and laboratory mesocosm studies to show that black blooms are caused by a combination of high CDOM (chromophoric dissolved organic matter) absorption, the formation of CDOM-Fe complexes and low backscattering. Mesocosm experiments showed that black bloom conditions occur after 4 days, with a significant increase in the concentrations of Fe2+ and ∑S2−. Total absorption (excluding absorption due to water) at 440 nm increased by 30% over this time to 7.3 m−1. In addition, the relative contribution of CDOM absorption to the non-water total absorption increased from 18% to 50%. Regression analyses between chemical and bio-optical data in both field and mesocosm experiments indicated that the concentrations of Fe2+ co-varied positively with CDOM absorption ag(440) (R2 > 0.70), and the specific CDOM absorption (ag(440)/DOC). Conditions that favored the development of black blooms were elevated algal or macrophyte biomass and limited water column mixing.

Seasonal characterization of CDOM for lakes in semiarid regions of Northeast China using excitation–emission matrix fluorescence and parallel factor analysis (EEM–PARAFAC)

Abstract. The seasonal characteristics of fluorescent components in chromophoric dissolved organic matter (CDOM) for lakes in the semiarid region of Northeast China were examined by excitation–emission matrix (EEM) spectra and parallel factor analysis (PARAFAC). Two humic-like (C1 and C2) and protein-like (C3 and C4) components were identified using PARAFAC. The average fluorescence intensity of the four components differed under seasonal variation from June and August 2013 to February and April 2014. Components 1 and 2 exhibited a strong linear correlation (R2 = 0.628). Significantly positive linear relationships between CDOM absorption coefficients a(254) (R2 = 0.72, 0.46, p &lt; 0.01), a(280) (R2 = 0.77, 0.47, p &lt; 0.01), a(350) (R2 = 0.76, 0.78, p &lt; 0.01) and Fmax for two humic-like components (C1 and C2) were exhibited, respectively. A significant relationship (R2 = 0.930) was found between salinity and dissolved organic carbon (DOC). However, almost no obvious correlation was found between salinity and EEM–PARAFAC-extracted components except for C3 (R2 = 0.469). Results from this investigation demonstrate that the EEM–PARAFAC technique can be used to evaluate the seasonal dynamics of CDOM fluorescent components for inland waters in the semiarid regions of Northeast China, and to quantify CDOM components for other waters with similar environmental conditions.

Pan-Arctic Trends in Terrestrial Dissolved Organic Matter from Optical Measurements

Climate change is causing extensive warming across arctic regions resulting in permafrost degradation, alterations to regional hydrology, and shifting amounts and composition of dissolved organic matter (DOM) transported by streams and rivers. Here, we characterize the DOM composition and optical properties of the six largest arctic rivers draining into the Arctic Ocean to examine the ability of optical measurements to provide meaningful insights into terrigenous carbon export patterns and biogeochemical cycling. The chemical composition of aquatic DOM varied with season, spring months were typified by highest lignin phenol and dissolved organic carbon (DOC) concentrations with greater hydrophobic acid content, and lower proportions of hydrophilic compounds, relative to summer and winter months. Chromophoric DOM (CDOM) spectral slope (S275-295) tracked seasonal shifts in DOM composition across river basins. Fluorescence and parallel factor analysis identified seven components across the six Arctic rivers. The ratios of ‘terrestrial humic-like’ versus ‘marine humic-like’ fluorescent components co-varied with lignin monomer ratios over summer and winter months, suggesting fluorescence may provide information on the age and degradation state of riverine DOM. CDOM absorbance (a350) proved a sensitive proxy for lignin phenol concentrations across all six river basins and over the hydrograph, enabling for the first time the development of a single pan-arctic relationship between a350 and terrigenous DOC (R2 = 0.93). Combining this lignin proxy with high-resolution monitoring of a350, pan-arctic estimates of annual lignin flux were calculated to range from 156 to 185 Gg, resulting in shorter and more constrained estimates of terrigenous DOM residence times in the Arctic Ocean (spanning 7 months to 2½ years). Furthermore, multiple linear regression models incorporating both absorbance and fluorescence variables proved capable of explaining much of the variability in lignin composition across rivers and seasons. Our findings suggest that synoptic, high-resolution optical measurements can provide improved understanding of northern high-latitude organic matter cycling and flux, and prove an important technique for capturing future climate-driven changes.

Spatiotemporal patterns in the export of dissolved organic carbon and chromophoric dissolved organic matter from a coastal, blackwater river

We examined seasonal and spatial patterns in dissolved organic carbon (DOC) and chromophoric dissolved organic matter (CDOM) in the Chowan River watershed, North Carolina, a blackwater river which discharges into the second largest estuary in the United States, the Albemarle–Pamlico Estuarine System. From April 2008 to May 2010, DOC concentration did not significantly vary across seasons (range 7.69–30.39 mg L−1); however, CDOM molecular size and aromaticity increased throughout the spring, decreased during the summer and fall, and remained relatively low in the winter. Spectral slope ratios suggested microbial processing of CDOM in the spring and photodegradation of CDOM in the summer and fall. Spatially, DOC and CDOM concentrations were similar in the mainstem and at the mouths of two tributaries, Bennetts Creek and Wiccacon River, but were significantly higher upstream on the tributaries. DOC concentration was positively correlated with CDOM absorbance coefficients at 254 and 350 nm; however, these optical proxies explained only ~60 % of the variance. DOC and CDOM absorption loads to the Albemarle Sound ranged from 2.63 × 1010 g year−1 and 9.84 × 1010 m2 year−1, respectively, in a dry year and 7.9 × 1010 g year−1 and 2.2 × 1011 m2 year−1, respectively, in a wet year, which are comparable to non-blackwater rivers with larger watersheds. Blackwater rivers may therefore represent “hotspots” in coastal carbon chemistry, with seasonal variations in the quality and quantity of DOC and CDOM influencing estuarine food web dynamics and net ecosystem metabolism.

Influence of environmental factors on spectral characteristics of chromophoric dissolved organic matter (CDOM) in Inner Mongolia Plateau, China

Abstract. Spectral characteristics of chromophoric dissolved organic matter (CDOM) were examined in conjunction with environmental factors in the waters of rivers and terminal lakes within the Hulun Buir plateau, northeast China. Dissolved organic carbon (DOC), total nitrogen (TN), and total phosphorous (TP) were significantly higher in terminal lakes than rivers waters (p &lt; 0.01). Principal component analysis (PCA) indicated that non-water light absorption and anthropogenic nutrient disturbances were the likely causes of the diversity of water quality parameters. CDOM absorption in river waters was significantly lower than terminal lakes. Analysis of the ratio of absorption at 250 to 365 nm (E250 : 365), specific ultraviolet (UV) absorbance (SUVA254), and the spectral slope ratio (Sr) indicated that CDOM in river waters had higher aromaticity, molecular weight, and vascular plant contribution than in terminal lakes. Furthermore, results showed that DOC concentration, CDOM light absorption, and the proportion of autochthonous sources of CDOM in plateau waters were all higher than in other freshwater rivers reported in the literature. The strong evapoconcentration, intense ultraviolet irradiance, and landscape features of the Hulun Buir plateau may be responsible for the above phenomenon. Redundancy analysis (RDA) indicated that the environmental variables total suspended matter (TSM), TN, and electrical conductivity (EC) had a strong correlation with light absorption characteristics, followed by total dissolved solid (TDS) and chlorophyll a. In most sampling locations, CDOM was the dominant non-water light-absorbing substance. Light absorption by non-algal particles often exceeded that by phytoplankton in the plateau waters. Study of these optical–physicochemical correlations is helpful in the evaluation of the potential influence of water quality factors on non-water light absorption in cold plateau water environments. The construction of a correlation between DOC concentration and water quality factors may help contribute to regional estimates of carbon sources and fate for catchment carbon budget assessments.

Predicting Dissolved Lignin Phenol Concentrations in the Coastal Ocean from Chromophoric Dissolved Organic Matter (CDOM) Absorption Coefficients

Dissolved lignin is a well-established biomarker of terrigenous dissolved organic matter (DOM) in the ocean, and a chromophoric component of DOM. Although evidence suggests there is a strong linkage between lignin concentrations and chromophoric DOM (CDOM) absorption coefficients in coastal waters, the characteristics of this linkage and the existence of a relationship that is applicable across coastal oceans remain unclear. Here, 421 paired measurements of dissolved lignin concentrations (sum of 9 lignin phenols) and CDOM absorption coefficients (ag(λ)) were used to examine their relationship along the river-ocean continuum (0-37 salinity) and across contrasting coastal oceans (sub-tropical, temperate, high-latitude). Overall, lignin concentrations spanned four orders of magnitude and revealed a strong, non-linear relationship with ag(λ). The characteristics of the relationship (shape, wavelength dependency, lignin-composition dependency) and evidence from degradation indicators were all consistent with lignin being an important driver of CDOM variability in coastal oceans, and suggested physical mixing and long-term photodegradation were important in shaping the relationship. These observations were used to develop two simple empirical models for estimating lignin concentrations from ag(λ) with a +/- 20% error relative to measured values. The models are expected to be applicable in most coastal oceans influenced by terrigenous inputs.

Indirect photochemical transformations of acyclovir and penciclovir in aquatic environments increase ecological risk.

Acyclovir and penciclovir, 2 antiviral drugs, are increasingly detected in aquatic environments. The present study explores the natural photochemical transformation mechanisms and fate of these drugs, examining direct and indirect photochemical transformation under simulated sunlight irradiation. The 2 antiviral drugs are photostable under certain conditions but significantly degrade in the presence of chromophoric dissolved organic matter (DOM). The degradation rate associated with the drugs' indirect photochemical transformation scaled with chromophoric DOM concentration. Quenchers and sensitizers were used to identify indirect photochemical transformation mechanism. Results suggested that both pharmaceuticals could be transformed by reacting with (1)O2, (•)OH, and excited chromophoric DOM. The (1)O2 played an important role in indirect photochemical transformation. Furthermore, the reaction kinetics between their substructural molecules, guanine, isocytosine, and imidazole, with different reactive oxygen species were evaluated to determine which substrate functionalities were most susceptible to singlet oxygenation. Imidazole was identified as the reaction site for (1)O2, and preliminary (1)O2 oxidation mechanisms were further evaluated based on liquid chromatographic-tandem mass spectrometric results. Finally, aquatic ecotoxicity assessment of phototransformed solutions revealed that the degradation of acyclovir and penciclovir may not ultimately diminish environmental risk because of either formation of more toxic intermediates than parent pharmaceuticals or some synergistic effects existing between the intermediates.

Using a Gaussian decomposition approach to model absorption spectra of chromophoric dissolved organic matter

The chromophoric dissolved organic matter (CDOM) is a significant water constituent influencing inherent and apparent optical properties of natural waters and plays a key role in ecosystem functioning. The spectral slope (S) describing the approximate exponential decline in CDOM absorption with increasing wavelength is widely used for tracing changes in the chemical composition of CDOM. The currently accepted method of characterizing CDOM absorption (i.e., fitting a simple exponential model) can lead to loss of information and large errors. We propose a better method for modeling CDOM absorption spectra based on a Gaussian decomposition approach that removes the errors associated with the choice of the spectral range used to estimate S. Using artificially generated spectra with known parameters (n=1000), we show that our method provides robust estimates of S closely resembling the original values. On average, the error on S estimations was 0.16% for the proposed method compared to 27% and 11% for the traditional modeling approaches fitted over 300–700nm and 240–700nm respectively. We further demonstrate the ability of the method to decompose and model chromophores present in complex spectra from oceanic water samples from around the world. The proposed method opens avenues for long-term or cross-site comparison studies of the dynamics of the CDOM pool and constitutes a promising supplement to techniques based on CDOM fluorescence.