Dissolved Organic Matter Molecular Size Research Articles

Dissolved organic matter composition and fluorescence characteristics of the river affected by coal mine drainage

Coal mine drainage (CMD) discharged into surface waters results in serious environmental pollution risk to rivers, lakes, and reservoirs. Coal mine drainage generally contains a variety of organic matter and heavy metals due to coal mining activities. Dissolved organic matter (DOM) plays an important role in the physicochemical and biological processes of many aquatic ecosystems. In this study, the investigations were carried out in the dry and wet seasons in 2021 to assess the characteristics of DOM compounds in coal mine drainage and the CMD-affected river. The results indicated that the pH of CMD-affected river pressed close to coal mine drainage. Besides, coal mine drainage lowered DO by 36% and increased total dissolved solids by 19% in the CMD-affected river. Coal mine drainage decreased absorption coefficient a(350) and absorption spectral slope S275-295 of DOM in the CMD-affected river; hence, DOM molecular size increased with decreasing S275-295. Three-dimensional fluorescence excitation-emission matrix spectroscopy and parallel factor analysis identified humic-like C1, tryptophan-like C2, and tyrosine-like C3 in the CMD-affected river and coal mine drainage. DOM in the CMD-affected river mainly originated from microbial and terrestrial sources, with strong endogenous characteristics. The ultra-high-resolution Fourier transform ion cyclotron resonance mass spectrometry analysis revealed that coal mine drainage had a higher relative abundance of CHO (44.79%), with a higher unsaturation degree of DOM. Coal mine drainage decreased the AImod,wa, DBEwa (double bond equivalents), Owa, Nwa, and Swa values and increased the relative abundance of the O3S1 species with DBE of 3 and carbons number range of 15-17 at the CMD inlet to the river channel. Moreover, coal mine drainage with the higher protein content increased the protein content of water at the CMD inlet to the river channel and the downstream river. DOM compositions and proprieties in coal mine drainage were investigated to further understand the influence of organic matter on heavy metals in future study.

Impact of environmental factors and tributary contributions on tidal dissolved organic matter dynamics

Riverine dissolved organic matter (DOM) transport was a key step in the carbon biogeochemical cycle while we had limited understanding of its contribution to the estuary DOM dynamics. This study focused on the river downstream-to-tidal estuary DOM variation and the control of environmental factors on it. The contributions of three tributaries with varing urbanization degrees to the tidal DOM dynamics were evaluated. Though more aromatics were introduced to the urban tributary, the A250/A365 values and fluorescent index values indicated the DOM molecular size was uniformly reduced due to the enhanced microbial degradation during transport. The tidal DOM showed less varied spectroscopic indexes than the tributary DOM, but tidal cycles strongly impacted the fluorescent DOM quantified by the fluorescence regional integration (FRI). Salinity range can differentiate the fluorescent DOM variation patterns in river tributaries (e.g., <2.5, positive correlations; >2.5, negative correlations) and tidal cycles (>10, negative correlations). For tidal DOM, the high salinity decreased more humic-related components, resulting in increased proportions of protein-related components in high tides. The dissolved oxygen and nitrogen contents were negatively correlated with salinity, suggesting the microbial contributions and anthropogenic inputs in tributaries increased the tidal DOM quantity. The less urbanized tributaries contributed more to the low-tide DOM compositions/properties while the dynamic contribution of the urban tributary impacted more the tidal DOM dynamics. Our results highlighted the uneven declines of FRI values of different components by freshwater-saltwater mixing in estuaries and suggested the different functioning of urban, agro-urban, and suburban tributaries contributed to tidal DOM dynamics.

Does quinone or phenol enrichment of humic substances alter the primary compound from a non-algicidal to an algicidal preparation?

Dissolved organic matter (DOM) has been shown to affect phytoplankton species directly. These interactions largely depend on the origin and molecular size of DOM and are different in prokaryotes and eukaryotes. In a preceding study, however, two humic substance preparations did not adversely affect coccal green algae or cyanobacterial growth even at high concentrations of dissolved organic carbon (DOC). These results contradicted previous findings, showing a clear, negative response of different phototrophs to much lower DOC concentrations. To test whether or not at least defined building blocks of humic substances (HSs) are effective algicidal structures, we enriched two humic preparations with hydroquinone and p-benzoquinone, respectively, and exposed two different green algae, Pseudokirchneriella subcapitata and Monoraphidium braunii, and two cyanobacterial species, Synechocystis sp. and Microcystis aeruginosa, to the unmodified and enriched HSs. As response variables, growth rates in terms of biomass increase, chlorophyll-a content, and photosynthetic yield were measured. The highest concentration (4.17mM DOC) of the modified HSs clearly inhibited growth; the cyanobacterial species were much more sensitive than the green algal species. However, realistic ecological concentrations did not adversely affect growth. Aerating the exposure solution for 24h strongly reduced the inhibitory effect of the modified HSs. The algicidal effect was obviously caused by monomers and not by polymerised high molecular weight HSs themselves. Furthermore, the maximum quantum yield (Φ PSII max) was stimulated in the green algal species by low and medium DOC concentrations, but reduced in the cyanobacterial species upon exposure to higher HS concentrations. The quinone- and phenol-enriched HSs only showed algicidal activity at high concentrations of 4.17mM DOC and lost their effects over time, presumably by oxidation and subsequent polymerisation. This study confirms that the applied humic substances themselves are not effective algicides even if enriched in effective structures.

Characterization of dissolved organic matter in urban sewage using excitation emission matrix fluorescence spectroscopy and parallel factor analysis

Wastewater dissolved organic matter (DOM) from different processing stages of a sewage treatment plant in Xiamen was characterized using fluorescence and absorption spectroscopy. Parallel factor analysis modeling of excitation-emission matrix spectra revealed five fluorescent components occurring in sewage DOM: one protein-like (C1), three humic-like (C2, C4 and C5) and one xenobiotic-like (C3) components. During the aerated grit chamber and primary sedimentation tank stage, there was only a slight decrease in fluorescence intensity and the absorption coefficient at 350 nm ( a 350). During the second aeration stage, high concentration of protein-like and short-wavelength-excited humic-like components were significantly degraded accompanied by significant loss of DOC (80%) and a 350 (30%), indicating that C1 and C2 were the dominant constituents of sewage DOM. As a result, long-wavelength-excited C4 and C5 became the dominant humic-like components and the DOM molecular size inferred from the variation of spectral slope S (300-650 nm) and specific absorption ( a 280/DOC) increased. Combination use of F max of C1 and the ratio of C1/C5, or a 350 may provide a quantitative indication for the relative amount of raw or treated sewage in aquatic environment.

Molecular size of riverine dissolved organic matter influences coastal phytoplankton communities

MEPS Marine Ecology Progress Series Contact the journal Facebook Twitter RSS Mailing List Subscribe to our mailing list via Mailchimp HomeLatest VolumeAbout the JournalEditorsTheme Sections MEPS 409:17-25 (2010) - DOI: https://doi.org/10.3354/meps08616 Molecular size of riverine dissolved organic matter influences coastal phytoplankton communities Tony Fagerberg*, Therese Jephson, Per Carlsson Department of Limnology and Marine ecology, Lund University/Campus Helsingborg, PO Box 882 25108 Helsingborg, Sweden *Email: tony.fagerberg@limnol.lu.se ABSTRACT: Dissolved organic matter (DOM) concentrations in many northern European freshwater systems have been increasing during the past decades. DOM affects the marine plankton community where rivers discharge into the sea. Large DOM molecules have been suggested to be more available to aquatic plankton than smaller ones due to their more recent origin in the degradation process. In this study, we investigated the effect of riverine DOM molecular size on coastal plankton with the hypothesis that nitrogen associated with large molecules stimulates the plankton more than nitrogen in smaller molecules. Three size fractions of riverine DOM were isolated with tangential ultrafiltration and introduced at similar nitrogen concentrations to mesocosms with a natural coastal marine plankton community under nitrogen limiting conditions. The results show that growth of bacteria and dinoflagellates, but not diatoms, was stimulated by addition of large DOM molecules. Even though organic nitrogen concentrations tended to decrease more in large DOM treatments compared to smaller DOM treatments, no significant differences were detected. However, proteolytic enzyme activities were elevated in treatments with the largest DOM molecules, suggesting that more organic nitrogen was utilized in this treatment. We suggest that input of larger river DOM molecules to nitrogen limited coastal systems may influence the composition of the coastal phytoplankton community in favour of dinoflagellates. KEY WORDS: Dissolved organic matter · DOM · River · DON · Molecular size · Marine phytoplankton Full text in pdf format PreviousNextCite this article as: Fagerberg T, Jephson T, Carlsson P (2010) Molecular size of riverine dissolved organic matter influences coastal phytoplankton communities. Mar Ecol Prog Ser 409:17-25. https://doi.org/10.3354/meps08616 Export citation RSS - Facebook - Tweet - linkedIn Cited by Published in MEPS Vol. 409. Online publication date: June 23, 2010 Print ISSN: 0171-8630; Online ISSN: 1616-1599 Copyright © 2010 Inter-Research.

Advanced characterization of marine dissolved organic matter by combining reversed-phase liquid chromatography and FT-ICR-MS

Marine dissolved organic matter (DOM) was separated by reversed-phase (RP) liquid chromatography method and analyzed with fluorescence/absorption detection and Fourier transform ion cyclotron mass spectrometry (FT-ICR-MS). The three key characteristics of the RP method are: (a) The C18-RP column chosen provides enhanced separation when the aqueous phase is 100% buffer-free water, and it does not degrade over time; (b) the water eluent adjusted to pH 7 significantly improves the resolution of water soluble compounds; (c) the initial flow maintained at low levels improves the separation of polar compounds. In samples, containing “fresh” DOM, specific peaks were detected, which were absent in “old” DOM samples. The combination with size exclusion chromatography (SEC) also demonstrated the relation between polarity and molecular size of DOM. FT-ICR-MS was applied to evaluate the quality of separation on a molecular scale demonstrating that physico-chemical characteristics of DOM can be related to molecular formulas. Sample extracts were separated into 4 preparative fractions, and a large suite of the identified molecular formulas only occurred in specific fractions. This is an important basis for the application of further analytical techniques in order to perform a more target-oriented analysis aiming at the determination of source and process biomarkers for DOM.

Relationships between DOC concentration, molecular size and fluorescence properties of DOM in a stream

The patterns of dissolved organic matter (DOM) fluorescence properties were examined in a Precambrian shield stream over a seven-month field study. Unique spatial and temporal patterns of simultaneous changes were observed in dissolved organic carbon concentration (DOC), humic-like fluorescence intensity, maximum excitation and emission wavelengths and fluorescence index (the ratio of the emission intensity at a wavelength of 450 nm to that at 500 nm at an excitation wavelength of 370 nm). The spatial change indicates the alteration of DOM along the length of the stream, and temporal change corresponded to a drought event in August. In contrast to humic-like fluorescence, the protein-like fluorescence shows considerable variability, suggesting its ephemeral nature. There were strong relationships between humic-like fluorescence intensity, fluorescence index, maximum Ex/Em wavelengths, DOC concentration and molecular size of DOM. This study has significant implications to the understanding of the nature and biogeochemical cycling of DOM.

Modeling Trichloroethylene Adsorption by Activated Carbon Preloaded with Natural Dissolved Organic Matter Using a Modified IAST Approach

A model was developed, using an approach based on the Ideal Adsorbed Solution Theory (IAST), to predict trichloroethylene (TCE) adsorption by granular activated carbon (GAC) preloaded with natural dissolved organic matter (DOM) isolated from three surface water sources. The IAST model was formulated for a bi-solute system in which TCE and DOM single-solute uptakes were described by the Langmuir-Freundlich and Freundlich isotherms, respectively. The effect of DOM molecular size and polarity (as measured by XAD 8 resin fractionation) on TCE uptake by preloaded GAC was assessed to identify a reactive fraction of natural water DOM for the purpose of modeling competitive adsorption. Consistent with previous work that identified low molecular weight species as the most reactive with regard to preloading effects (i.e., reducing target compound uptake), the low molecular weight components of the polar (hydrophilic) and nonpolar (hydrophobic) DOM fractions, isolated using ultrafiltration (1 kDa molecular weight cutoff membrane), exhibited significant competitive effects. Furthermore, the effects of these fractions on TCE uptake were similar; therefore, theywere considered together to represent a single "reactive fraction" of DOM. On the basis of this finding, isotherms for the <1 kDa low molecular weight DOM fraction of the whole water were measured, and molar concentrations were computed based on an average molecular weight determined using size-exclusion chromatography. The IAST model was modified to incorporate surface area reduction due to pore blockage by DOM and to reflectthe hypothesis thatTCE molecules can access adsorption sites which humic molecules cannot, thus preventing competition on these sites. The model was calibrated with data for TCE uptake by carbon preloaded with the <1 kDa low molecular weight DOM fraction and was verified by predicting TCE uptake by carbon preloaded with whole natural waters for both constant GAC dose (hence constant DOM loading) and variable GAC dose (hence variable DOM loading) TCE isotherms. Preloading by DOM reduced volume in GAC pores having widths smaller than 1.25 nm (likely accessible only to TCE) to a greater extent than total pore volume, suggesting preferential blockage of micropores. Such preferential pore blockage may explain, in part, why increased DOM loading decreases the fraction of the total surface area on which no competition between TCE and DOM occurs.

Water solubility enhancement of some organic pollutants and pesticides by dissolved humic and fulvic acids

Water solubility enhancements by dissolved humic and fulvic acids from soil and aquatic origins and by synthetic organic polymers have been determined for selected organic pollutants and pesticides (p,p'-DDT,2,4,5,2',5'-PCB, 2,4,4'-PCB, 1,2,3,-trichlorobenzene, and lindane). Significant solubility enhancements of relatively water-insoluble solutes by dissolved organic matter (DOM) of soil and aquatic origins may be described in terms of a partition-like interaction of the solutes with the microscopic organic environment of the high-molecular-weight DOM species; the apparent solute solubilities increase linearly with DOM concentration and show no competitive effect between solutes. The K/sub dom/ values of solutes with soil-derived humic acid are approximately 4 times greater than with soil fulvic acid and 5-7 times greater than with aquatic humic and fulvic acids. The effectiveness of DOM in enhancing solute solubility appears to be largely controlled by the DOM molecular size and polarity. The relative inability of high-molecular-weight poly(acrylic acids) to enhance solute solubility is attributed to their high polarities and extended chain structures that do not permit the formation of a sizable intramolecular nonpolar environment. 41 references, 6 figures, 3 tables.