Protein-like Fluorescent Components Research Articles

Terrigenous humic substances regulate the concentrations of dissolved Fe and Cu (but not Al, Mn, Ni or Zn) in the Gaoping River plume

The small mountainous rivers of Oceania discharge a large fraction of their dissolved and particulate load of materials within a very small percentage of the time. As a result, the yearly inputs and physicochemical forms of dissolved metals exported to the ocean by these rivers are poorly quantified. We investigated the wet-season distribution patterns of metals and fluorescent organic substances in the surface waters of the Gaoping River plume, SW Taiwan, under both moderate (Sep 2020) and strong flow conditions (Aug 2021). The mixing behaviour of both soluble (<5 kDa) and colloidal (>5 kDa) metals and fluorescent components was examined over the salinity range 3.0–32.2 in 2020 and 5.8–31.1 in 2021. We detected two humic-like and one protein-like fluorescent components, the same on both surveys. The humic-like components, C1 and C3, originated from the Gaoping River and correlated strongly with Cu and Fe, respectively. Component C3 showed a greater enrichment relative to C1 in the colloidal (C3/C1 > 0.8) than in the soluble phase (C3/C1 = 0.4). The protein-like component, C2, came from both terrestrial and marine sources and displayed a more complex mixing behaviour than the other two. One striking result was that the effective zero-salinity concentrations of Fe (∼300 nM) and Cu (∼23 nM) did not change significantly in response to a 10-fold increase in river discharge between Sep 2020 and Aug 2021. Similarly to Fe and Cu, the distribution patterns of Components C1 and C3 did not change significantly between the moderate and the strong plume, and C3 and C1 correlated strongly with Fe and Cu, respectively. We conclude that subtropical mountainous rivers can provide soil-derived humic substances which facilitate and regulate the delivery of Fe and Cu to the ocean, provided mountain forests are preserved.

Investigating the molecular weight distribution of atmospheric water-soluble brown carbon using high-performance size exclusion chromatography coupled with diode array and fluorescence detectors

Atmospheric brown carbon (BrC) contain amounts of organic species, but their molecular weight (MW) distributions is still poorly understood. This study applied high-performance size exclusion chromatography (HPSEC) coupled with a diode array detector (DAD) and fluorescence detector (FLD) to characterize the MW distributions of typical chromophores and fluorophores within water-soluble BrC. The investigation focused on the spring season, encompassing both typical urban and rural aerosols. Our results showed that chromophores (at 254 and 365 nm), and humic-like and protein-like fluorophores identified by excitation-emission matrix parallel factor analysis (EEM-PARAFAC) within BrC were broadly distributed along the MW continuum (∼50–20,000 Da). This suggests that BrC mainly comprises complex chromophores and fluorophores with heterogeneous molecular sizes. High-MW (HMW, >1 kDa) species (66%–74%) dominated the chromophores at 254 and 365 nm. However, the latter chromophores were enriched with more HMW species. This result suggested that the HMW chromophores might contribute more to BrC absorption at longer wavelengths. The PARAFAC-derived fluorescent components also exhibited different MW distributions. Three humic-like substances (HULIS) were all dominated by HMW fractions (51%–74%), but protein-like fluorescent component (PLOM) enriched low-MW (LMW, <1 kDa) species (60%–66%). Furthermore, the molecular size (i.e., weight-averaged and number-averaged MW) and the ratios between HMW and LMW species decreased in the order highly-oxygenated HULIS > less-oxygenated HULIS > PLOM, indicating that the fluorophores with longer Em were generally related to larger MW. To our knowledge, this is the first report on the molecular size of individual fluorescent components within aerosol BrC. The results obtained here enhanced our knowledge of heterogeneous composition, complex physicochemical properties, and potential atmospheric fates of aerosol BrC.

Selective associations of organic matter components with ferrihydrite: Implications for Fe-organic matter preservation in tidal flat wetlands

The association of organic matter (OM) with iron (Fe) is a critical mechanism to preserve OM in intertidal coastal ecosystems such as salt marshes and mangroves. The present study aimed to investigate the influence of the organic carbon to Fe molar ratio (OC/Fe), ionic strength, and OM composition on Fe-OM association. Fe-OM was prepared using humic acids extracted from salt marsh and mangrove sediments by the adsorption process in the OC/Fe molar ratios of 0.01–1.0 and by the coprecipitation process in the OC/Fe molar ratios of 0.1–9.9. Sample properties were studied by X-ray diffraction, scanning electron microscopy, ultraviolet–visible spectroscopy, attenuated total reflection Fourier transform infrared spectroscopy, three-dimensional fluorescence excitation emission matrix spectroscopy, and pyrolysis–gas chromatography/mass spectrometry. The results showed that selective associations of OM components with ferrihydrite were affected by the association mode (e.g., adsorption and coprecipitation), OC/Fe molar ratio, OM composition and ionic strength. Abundant aliphatic compounds could be adsorbed on ferrihydrite. Moreover, ferrihydrite was prone to preserve humic-like fluorescent components through the adsorption process. The protein-like fluorescent components and aliphatic compounds had high affinity for ferrihydrite during coprecipitation with low OC/Fe molar ratios. An increase in the OC/Fe molar ratio resulted in coprecipitation of aromatic compounds with ferrihydrite. Salinity-induced flocculation caused more amount of aromatic and polycyclic aromatic compounds to associate with ferrihydrite during the coprecipitation process. Compared to the salt marsh OM, more N-compounds and less aliphatic compounds in the mangrove OM were coprecipitated with ferrihydrite. This study provided important insights into the mechanisms of OM preservation with ferrihydrite in tidal wetland ecosystems.

Lake reclamation alters molecular-level characteristics of lacustrine dissolved organic matter – A study of nine lakes in the Yangtze Plain, China

In recent decades, the reclamation of lakes has captured 42% of the total lake area of the Yangtze Plain in China and introduced additional pressure on lacustrine water quality. While lacustrine dissolved organic matter (DOM) is critical in regulating biogeochemical processing and aquatic biodiversity, the impact of reclamation on the molecular-level characteristics of lacustrine DOM remains unexplored. Here, the DOM characteristics altered by reclamation practices in the Yangtze Plain lakes were investigated using fluorescence spectroscopy, nuclear magnetic resonance spectroscopy, and Fourier transform ion cyclotron resonance mass spectrometry. Results demonstrated that reclamation not only elevated the quantity (on average +32%) but also altered the characteristics and composition of lacustrine DOM. Compared to the natural water sites close by, reclamation sites did not significantly alter the DOM aromaticity but significantly lowered the average molecular weight and increased the biolability of DOM. The chromophoric DOM and humic-like fluorescent components were remarkably elevated, but not the protein-like fluorescent components. More lipid-like and condensed aromatic-like components were detected in the lacustrine DOM as compared to the lignin-like, carbohydrate-like, and protein-like components, which may be driven by the increased microbial processing. Overall, the significant alteration in characteristics and composition of lacustrine DOM highlights the potential impact of reclamation on the DOM biogeochemical cycle and the environmental quality in aquatic ecosystems.

Comparing the Pb(II) binding with different fluorescent components of dissolved organic matter from typical sources.

Dissolved organic matter (DOM) is important for determining the speciation, environmental behavior, and effects of metal pollutants in aquatic environments. However, little is known about the difference between DOM from natural and anthropogenic sources for binding Pb(II). This study examined the Pb(II) binding with DOM from four typical sources including river, leaf litter leachate, and the influent and effluent of a wastewater treatment plant, using fluorescence quenching titration and excitation-emission matrices-parallel factor analysis (EEMs-PARAFAC). Four humic-like and one protein-like fluorescent components were identified, with much higher protein-like fraction and lower humification degree for the influent than for other sources. In the river water and leaf litter leachate, the abundant humic-like components were quenched by 6-17% while the protein-like component kept stable (2-4%) by the addition of Pb(II). In contrast, the influent DOM showed stronger fluorescence quenching of the protein-like component (46%) with higher conditional stability constant and binding fraction of fluorophore than the humic-like components (15-21%). The effluent DOM displayed weak quenching for all fluorescent components (4-6%) and thus weak complexation with Pb(II), indicating notable changes in the chemical composition and metal-binding affinity of DOM by wastewater treatments. These results demonstrated significant impacts of DOM source and chemical composition on its Pb(II) complexation properties, which have implications for understanding the interactions between DOM and heavy metals.

Characterization of dissolved organic matter processing between surface sediment porewater and overlying bottom water in the Yangtze River Estuary

Dissolved organic matter (DOM) exchange in the sediment-water interface of estuaries is essential for the global elemental cycle. To clarify the interface DOM processing, this study applies optical techniques and ultrahigh-resolution mass spectrometry to assess DOM composition of surface sediment porewater and bottom (overlying) water across the Yangtze River Estuary (YRE). Results suggested that DOM exchange in the sediment-water interface mainly followed from sediment porewater to bottom water driven by a significant dissolved organic carbon concentration gradient and hydrodynamic force. We also characterized two porewater DOM sources, including microbial production and byproducts of processed sediments. High microbial activities resulted in the enrichment of protein-like fluorescent components and N-bearing compounds in porewater, potentially decreasing the oxygen concentration of bottom water due to the high lability. And the deamination of N-bearing compounds in the sediment-water interface could likely serve as a N-bearing nutrient source to bottom water. Moreover, due to sediment-specific features in different areas driven by hydrologic sorting and local phytoplankton supply, porewater DOM of muddy areas accumulated more aromatic substances from the degradation of terrestrial organic matter. The release and oxic transformation of oxygen-deficient aromatic compounds could contribute to the refractory carbon pool of estuarine water (carboxyl-rich alicyclic molecules, CRAM), modulating the quality of organic carbon mobilized from the land to the coastal ocean. Considering strong hydrodynamic force in numerous estuaries worldwide, DOM exchange and processing at the sediment-water interface has a meaningful influence on the biogeochemistry of estuarine water columns, which warrants further studies.

Eutrophication and watershed characteristics shape changes in dissolved organic matter chemistry along two river-estuarine transects

Dissolved organic matter (DOM) plays a crucial role in the coastal carbon cycle. However, eutrophication-induced algal blooms and lateral transport from connected tidal marshes may significantly affect DOM cycling, which remains poorly understood. By combining a suite of bulk and optical techniques, and the Fourier transform ion cyclotron resonance mass spectrometry and ion mobility quadrupole time-of-flight mass spectrometry, we determined DOM concentration and composition along two typical river-estuary transects (namely Liao and Daliao rivers), Northeast China, with contrasting eutrophic state and distribution of tidal marshes. The Daliao River is characterized by a higher eutrophication degree and is surrounded with lower reed coverage than the Liao River. Compared to the Liao River, significantly higher dissolved organic carbon concentrations were observed in the Daliao River, where higher stable carbon isotope (δ13C) values and protein-like fluorescent components, characterized relatively higher autochthonous DOM. Further molecular analysis revealed higher peptide and sugar-like compounds but lower isomeric percentages of several molecular formulas in the Daliao River, suggesting higher molecular lability but lower isomeric complexity than the Liao River. Associations between optical and molecular signatures among all DOM samples revealed that a red-shifted humic-like C3 component was significantly correlated with molecular formulas with lower molecular weight and aromaticity, and higher H/C, indicating that C3 was likely a result of phytoplankton production coupled with further heterotrophic processing. Moreover, we found that reed marshes could introduce to both rivers a series of carboxylic-rich alicyclic compounds, highly unsaturated compounds, and polyphenols with high molecular weight and low H/C. This study suggests that eutrophication and reed marsh affect the DOM quality and can be a potential source of recalcitrant DOM compounds to coastal rivers and estuaries, which warrants further investigations considering the increasing worldwide eutrophication and sea-level rise in coastal delta environments.

Groundwater-surface water interactions and flux of organic matter and nutrients in an urban, Mediterranean stream

The chemical quality of dissolved organic matter (DOM) and the speciation of nitrogen exported from urban catchments is of great importance to biogeochemical cycling in riverine and coastal receiving waters. Many urban streams in Mediterranean climates have a flashy hydrologic regime, which would suggest a rapid pulsing and shunting of solutes downstream. However, the role of these systems both as passive pipes for solute transport or as reactors for DOM and nutrient transformation is still an open question for urban, Mediterranean streams. To address this question, we evaluated changes in concentrations of inorganic and organic solutes and DOM optical properties in Alvarado Creek, a perennially-flowing, urban, first-order tributary of the San Diego River in San Diego, CA, USA, during dry weather (baseflow) conditions and during four storm events in 2016–2018. Chloride and sulfate concentrations corroborate the supposed saline groundwater supply that maintains perennial flow and brackish nature in this urban stream. During dry weather, high proportions of protein-like fluorescent component (AC4) and downstream decreases in total dissolved nitrogen (TDN) and nitrate imply in-stream processing (nitrification and denitrification). By contrast, storm hysteresis curves indicate that the supply of DOM and TDN was not exhausted over the duration of a storm event, whereas nitrate was eventually depleted, presumably because nitrification could not keep up with the export of nitrate from source areas. Rapid decreases in chloride during the storm hydrograph coincided with a shift in specific ultraviolet absorbance (SUVA) and fluorescence index (FI) to more terrestrially-derived and aromatic carbon sources, most likely from interflow of stormwater through vadose zone soils. On an annual basis, the export of microbially-derived DOM during dry weather was higher than the export of terrestrially-derived DOM during storm events; both represent important carbon inputs to coastal waters.

Restriction of dissolved organic matter on the stabilization of Cu(II) by phosphate.

The precipitation of Cu(II) by phosphate and the influence of dissolved organic matter (DOM) on the precipitation are essential for the fate of Cu(II) in aquatic environments. In this study, the influence of DOM on the reaction of phosphate with Cu(II) was investigated. Here, 51.61%, 29.75%, and 24.32% of the added Cu(II) (50 μM) precipitated without DOM and with the addition of fulvic acid (FA) and humic acid (HA), respectively, owing to the reaction with phosphate (50 μM). Excitation-emission matrix spectroscopy-parallel factor (PARAFAC) and two-dimensional ultraviolet-visible correlation spectroscopy analyses were conducted to characterize the influence of DOM on the precipitation of Cu(II) with phosphate. One humic-like and two protein-like fluorescent components were identified by the PARAFAC model for FA, whereas two humic-like fluorescent components and one protein-like fluorescent component were validated for HA. The humic-like components had primary roles, whereas the protein-like components had secondary roles in limiting the precipitation of Cu(II) with phosphate. Cu(II) binding to DOM chromophores initially occurred at shorter wavelengths, and then at longer wavelengths. Phenolic and carboxylic constituents had important roles, and HA exhibited more binding sites than FA. Therefore, humic-like fluorescent components and chromophores containing phenolic and carboxylic groups and functional groups with peaks at short wavelengths (200-220 nm) were primarily responsible for restricting the precipitation of Cu(II) with phosphate.

Distribution and photo-reactivity of chromophoric and fluorescent dissolved organic matter in the Northeastern North Pacific Ocean

Deep waters in the Northeastern North Pacific Ocean store the most aged, largely biologically refractory dissolved organic matter (DOM) in the global ocean. We conducted high resolution vertical profiles to survey the optical properties of this DOM in the Gulf of Alaska (GoA) onboard the R/V Melville using ultraviolet/visible (UV/Vis) absorbance spectra and excitation-emission matrix spectra (EEMs) along with parallel factor analysis (PARAFAC). Chromophoric DOM (CDOM) absorption coefficients in the GoA were similar to the global open ocean waters reported elsewhere outside the Northeastern North Pacific. Three humic-like and two protein-like fluorescent components were identified. Profiles of fluorescent DOM (FDOM) showed a low signal for the humic-like organic matter in the surface that increased in the subsurface and remained fairly constant at depth. In contrast, the protein-like components had elevated levels in surface samples that decreased with depth. Both CDOM and FDOM optical proxies remained spatially uniform within the deep ocean water masses. Photochemical irradiations performed onboard showed that photochemistry of the FDOM from deep seawater transformed the deep ocean fluorescent organic matter signals into a fluorescent component distribution that resembled surface water with a dominance of protein-like fluorescent material. This work contributes to the global ocean survey database of chromophoric and fluorescent DOM and provides evidence of a role for the photochemical alteration of deep, biologically refractory DOM once it is mixed back into the sunlit surface ocean.

Spectral and isotopic characteristics of particulate organic matter in a subtropical estuary under the influences of human disturbance

Abstract Particulate organic matter (POM) in the coastal zone plays an important role in global carbon cycle, yet its spectral properties under human disturbance are not well understood. This study investigated the source and dynamics of POM in a typical coastal area (Minjiang Estuary, China) under the influences of estuarine mixing, urbanization and dam construction, based on spectral and isotopic analysis. The yield of particulate organic carbon from the watershed (0.38 g m−2 yr−1) was in part limited by the historical decrease in sediment discharge downstream hydropower station. The absorption and fluorescence indices of POM suggested an important contribution from biological production with a low humic content. The importance of river and estuarine production was supported by elemental and isotopic analysis, in particular for N-bound constituents of POM. Three humic-like and two protein-like fluorescent components were identified from POM using fluorescence excitation-emission matrices-parallel factor analysis (EEMs-PARAFAC). They showed weak correlations with salinity, suggesting non-conservative behaviors of fluorescent POM during the estuarine mixing. Principal component analysis (PCA) identified two principal factors, which were related to the level of chromophoric POM (PC1) and biological production (PC2), respectively. The PCA results indicated stronger influence of biological production in the estuarine zone and potential effect of sediment re-suspension and/or wastewater discharge in the urban zone. Overall, our results demonstrated significant influences of human disturbance on the flux, source and dynamics of POM in the coastal zone, which could be assessed by spectral and stable isotopic analysis.

Organic carbon source-dependent properties of soluble microbial products in sequencing batch reactors and its effects on membrane fouling

This study investigated the influence of three different organic carbon sources including sodium acetate (SOD), glucose (GLU), and starch (STAR), on soluble microbial products (SMP), which presumably have dissimilar uptake rates and metabolic pathways, in sequencing batch reactors (SBR) and their subsequent effects on membrane fouling of ultrafiltration (UF). SMP were mainly characterized by fluorescence excitation emission matrix coupled with parallel factor analysis (EEM-PARAFAC) and size exclusion chromatography (SEC). SMP produced in SOD-fed SBR showed higher abundances of protein-like fluorescent component and large sized aliphatic biopolymer (BP) than GLU- or STAR-fed counterpart did, while the STAR-based operation resulted in more SMP enriched with humic-like fluorescence. The differences in SMP exerted marked effects on UF membrane fouling as indicated by the highest fouling potential with reversibility shown for the SMP from the SOD-fed reactor. Regardless of the carbon source, BP fraction and protein-like component exhibited the greatest extent of reversible fouling, suggesting that size exclusion plays a critical role. However, notable differences in the reversible fouling propensity of relatively smaller size fractions among the three SBRs signified the possible involvement of chemical interactions as a secondary fouling mechanism and its dependency on different carbon sources. Our results provide a new insight into the roles of carbon sources in the characteristics of SMP in biological treatment systems and their effects on the post-treatment using membrane filtration, which is ultimately beneficial to the optimization of biological treatment design and membrane filtration operation.

Molecular weight-dependent spectral and metal binding properties of sediment dissolved organic matter from different origins

The metal binding potential of dissolved organic matter (DOM) is highly related with its inherent properties such as molecular weight (MW). Here sediment DOMs with different origins, i.e., algae- and macrophyte-dominated sediment DOM (named as ASDOM and MSDOM, respectively), were size-fractionated into low MW (LMW-, <1 kDa) and high MW (HMW-, 1 kDa~0.45 μm) fractions, with the spectral and metal binding properties in different MW fractions exploring via total organic carbon, absorption spectroscopy, fluorescence parallel factor (PARAFAC) analysis, and Cu(II) titration techniques. The MSDOM contained more organic carbon, lower specific UV absorbance, lower fluorescence index, higher humification index, and lower biological index compared to the ASDOM. As for the MW-fractionated samples, the humic- and fulvic-like fluorophores were mainly distributed in the LMW-DOM, while the protein-like ones were located richly in the HMW-DOM. Thus, obvious MW- and origin-dependent heterogeneities in abundance and spectral properties were observed for sediment DOMs. One humic-like, one fulvic-like, and two protein-like fluorescent components were identified by PARAFAC analysis, with different components exhibiting different variable patterns in response to Cu(II) addition. Irrespective of sample sources, humic- and fulvic-like components had higher condition stability constants (logKM > 4.96) than protein-like components (logKM < 4.86). As for the MW-fractionated samples, the HMW-DOM, especially the HMW humic-/fulvic-like components, exhibited higher metal binding potential than the bulk and LMW counterparts. This study highlighted the importance of HMW-DOM in manipulating the behavior, fate, and bioavailability of heavy metals in lake sediments.

Differences in fluorescence characteristics and bioavailability of water-soluble organic matter (WSOM) in sediments and suspended solids in Lihu Lake, China.

The spectral characteristics, spatial distribution, and bioavailability of water-soluble organic matter (WSOM) in suspended solids and surface sediments of Lihu Lake, China, were investigated through excitation-emission matrix spectra and parallel factor analysis. The average content of dissolved organic carbon (DOC) in the sediments reached 643.28 ± 58.34mg C/kg and that in suspended solids was 714.87 ± 69.24mg C/kg. The fluorescence intensity of WSOM totaled 90.87± 5.65 and 115.42 ± 8.02 RU/g for the sediments and suspended solids, respectively. The DOC and fluorescence intensity of the WSOM showed an increasing trend moving from the west to the east of the lake. The WSOM in sediments and suspended solids contained two humic-like (C1 and C2) and one tryptophan-like (C3) components. These components had different fluorescent peaks and relative proportions. In the sediments, the relative proportions of C1, C2, and C3 were 33.71% ± 0.71, 26.83% ± 0.68, and 39.50% ± 0.71%, respectively. Meanwhile, C1 (35.77 ± 0.84%), C2 (34.07 ± 0.61%), and C3 (30.16 ± 0.75%) had similar relative percentages in suspended solids. The sediments had a lower humification index (3.02 ± 0.08) than the suspended solids (4.04 ± 0.15). Exchangeable nitrogen for the sediments and suspended solids was dominated by exchangeable ammonium nitrogen and soluble organic nitrogen, respectively. WSOM plays an important role in migration and transformation of nitrogen in sediments and suspended solids. The sediment-derived WSOM exhibited higher lability and biological activity than did the suspended solid-derived WSOM. The relative ratio of the intensity of protein-like fluorescent component to that of the humic-like one can be used as a reference index to evaluate the lability and biological activity of WSOM in sediments and suspended solids.

Toward Quantitative Understanding of the Bioavailability of Dissolved Organic Matter in Freshwater Lake during Cyanobacteria Blooming

Occurrence of cyanobacterial harmful algal blooms (CyanoHAB) can induce considerable patchiness in the concentration and bioavailability of dissolved organic matter (DOM), which could influence biogeochemical processes and fuel microbial metabolism. In the present study, a laboratory 4-stage plug-flow bioreactor was used to successfully separate the CyanoHAB-derived DOM isolated from the eutrophic Lake Taihu (China) into continuum classes of bioavailable compounds. A combination of new state-of-the-art tools borrowed from analytical chemistry and microbial ecology were used to characterize quantitatively the temporary evolution of DOM and to get deeper insights into its bioavailability. The results showed a total 79% dissolved organic carbon loss over time accompanied by depletion of protein-like fluorescent components, especially the relatively hydrophilic ones. However, hydrophilic humic-like fluorescent components exhibited bioresistant behavior. Consistently, ultrahigh resolution mass spectrometry (FTICR-MS) revealed that smaller, less aromatic, more oxygenated, and nitrogen-rich molecules were preferentially consumed by microorganisms with the production of lipid-like species, whereas recalcitrant molecules were primarily composed of carboxylic-rich alicyclic compounds. Moreover, the bioavailability of DOM was negatively correlated with microbial community diversity in the bioreactor. Results from this study provide deeper insights into the fate of DOM and relevant biogeochemical processes in eutrophic lakes.

Fluorescent components and spatial patterns of chromophoric dissolved organic matters in Lake Taihu, a large shallow eutrophic lake in China.

Water samples at both surface and bottom layers were taken from 102 sites in Lake Taihu to study the fluorescent components and spatial patterns of chromophoric dissolved organic matters (CDOM). Three-dimensional excitation-emission matrix data obtained from the samples were analyzed by parallel factor approach in which four humic-like and two protein-like fluorescent components (named C1-C6) were identified. The results showed that fluorescence intensities were higher in the northern and western lake regions, and notable declines of fluorescence maxima (F max) were observed from the northwest to the center and then to the southeast of the lake. Calculated biological index (BIX) values ranged from 0.88 to 1.44 and humification index (HIX) values from 0.64 to 3.37 for all the samples. The spatial variations of BIX and HIX values suggested stronger allochthonous CDOM characteristics in Zhushan Bay and the western area and autochthonous characteristics in the southern and eastern areas. Vertically, the average F max value of the surface samples was about 6% less than that of the bottom samples, but noticeable variations existed among different sampling sites and components. These distribution characteristics of CDOM were mainly attributed to the spatial heterogeneity of sources and wind-induced transportation process. Interestingly, the C6 component (Exmax/Emmax=250/455nm) seemed to be unique in samples from Zhushan Bay and probably resulted from the discharge of the Taige River. Therefore, it could be used as an indicator of point-source discharge and a tracer to study the fate of CDOM in the lake.

Depth-dependent photodegradation of marine dissolved organic matter

Marine dissolved organic matter (DOM) in surface and deep waters of the eastern Atlantic Ocean and Sargasso Sea was analyzed by excitation emission matrix (EEM) fluorescence spectroscopy and parallel factor analysis (PARAFAC). Photo-degradation with semi-continuous monitoring of EEMs and absorbance spectra was used to measure the photo-degradation kinetics and changes of the PARAFAC components in a depth profile of DOM at the Bermuda Atlantic Time Series (BATS) station in the Sargasso Sea. A five component model was fit to the EEMs, which included traditional terrestrial-like, marine-like, and protein-like components. Terrestrial-like components showed the expected high photo-reactivity, but surprisingly, the traditional marine-like peak showed slight photo-production in surface waters, which may account for its prevalence in marine systems. Surface waters were depleted in photo-labile components while protein-like fluorescent components were enriched, consistent with previous studies. Ultra-high resolution mass spectrometry detected unique aliphatic compounds in the surface waters at the BATS site, which may be photo-produced or photo-stable. Principle component and canonical analysis showed strong correlations between relative contributions of unsaturated/aromatic molecular formulas and depth, with aliphatic compounds more prevalent in surface waters and aromatic compounds in deep waters. Strong correlations were seen between these aromatic compounds and humic-like fluorescent components. The rapid photo-degradation of the deep-sea fluorescent DOM in addition to the surface water relative depletion of aromatic compounds suggests that deep-sea fluorescent DOM is very unlikely to survive overturning circulation.

Characterization of dissolved organic matter under contrasting hydrologic regimes in a subtropical watershed using PARAFAC model

Dissolved organic matter (DOM) was characterized during five basin-scale investigations (either after storms or in droughts) in Jiulong River, China that is affected by the Asian Monsoon, tropical storms and anthropogenic activities. Dissolved organic carbon concentration, DOM absorption and fluorescence (excitation-emission matrix spectra, EEMs) were measured. Parallel factor analysis (PARAFAC) of EEMs identified three humic-like and two protein-like fluorescent components. DOM concentration was highest at two polluted stations in droughts while lowest in pristine headwaters (station N1). DOM concentration increased most evidently after storms in May, 2009, indicating effective flushing of DOM from land to the river close to the onset of flood season. The protein-like fraction in PARAFAC results decreased after storms in May and June, 2009, highlighting changes in DOM composition and thus its environmental role. Dam constructions likely increased the residence time of DOM in river, making the inflow of DOM during storms have more implications for the riverine (in comparison with estuarine) biogeochemical processes. The effect of storm in August, 2008 after intense DOM flushing during several preceding storms, was not evident. A severe dinoflagellate algal bloom occurred during the extreme drought in the lower watershed, which increased DOM concentration and the protein-like fraction at impacted stations. Different DOM compositions during and after algal bloom were discriminated using the two protein-like components. This study demonstrates the importance of hydrologic regimes and anthropogenic activities on freshwater DOM and its environmental role, which has implications for a number of other rivers that share similar characteristics.

Comparison of dissolved organic matter fractions in a secondary effluent and a natural water

This research compared the structural and chemical characteristics among dissolved organic matter (DOM) fractions within the same source and among different origins. Samples taken from the Taiping Wastewater Treatment Plant (TWTP) (Harbin, China) and from the Songhuajing River (SR), Heilongjiang Province, China were chosen to represent waters containing DOM of wastewater origin and of natural-water origin, respectively. DOM was fractionated using XAD resins into five fractions: hydrophobic acid (HPO-A), hydrophobic neutral (HPO-N), transphilic acid (TPI-A), transphilic neutral (TPI-N) and hydrophilic fraction (HPI). The SR fractions were more UV-sensitive and more reactive with chlorine in formation of trihalomethanes (THMs) than the TWTP secondary effluent (TSE) fractions. The aromatic character peaks in the Fourier-transform infrared (FT-IR) spectra of SR fractions were clearer than those of TSE fractions. On the other hand, the peaks of carbohydrates in TSE fractions were more prominent in comparison with SR fractions. In addition, the amide-2 peak was present in the spectra of all the five TSE fractions but not visible in the spectra of SR fractions. The fluorescence results showed that SR DOM fractions contained more fulvic acid-like fluorescent compounds while TSE DOM fractions had higher amounts of protein-like fluorescent components.