Influence of dissolved organic matter origin on hydrogen peroxide concentration in aquatic environments of southern Florida
Patricia E. Garcia
A * , Haruka E. Urakawa B , Taylor L. Hancock C and Hidetoshi Urakawa D
A
B
C
D
Abstract
Characterizing dissolved organic matter (DOM) is important for understanding its quality, which is highly linked to its reactivity. The DOM acts as a substrate for the abiotic production of hydrogen peroxide (H2O2). In southern Florida aquatic environments, we found that the origin of DOM has a profound effect on the H2O2 concentrations.
Dissolved organic matter (DOM) is a complex mixture of compounds that is ubiquitous in aquatic ecosystems and is involved in multiple biogeochemical processes. The degradation of DOM due to exposure to solar radiation can produce reactive photoproducts. Among these, reactive oxygen species (ROS), particularly hydrogen peroxide (H2O2), are strong oxidizing agents. We aim to expand our understanding of the complex relationship between DOM and H2O2 in tropical and subtropical aquatic systems in Florida.
Using absorbance and fluorescence-based methods, we characterized the DOM quality. Additionally, we measured H2O2 concentrations in 42 aquatic systems.
Freshwater aquatic ecosystems showed a broad variation in DOM quantity and quality. Based on their origin, the water samples can be grouped int three categories: autochthonous, recently produced allochthonous and allochthonous DOM. Using parallel factor analysis modeling (PARAFAC), we validated five fluorescent components: three humic-like components, one fulvic-component and one protein-like component. Notably, the humic-like component C4 (A), autochthonous and fresh allochthonous DOM, showed a significant direct relationship with H2O2 concentrations. Conversely, in water bodies primarily characterized by allochthonous DOM origin, a significant direct linear relationship was observed between chlorophyll-a and H2O2 concentrations.
Overall, our results support the idea that reactive humic compounds serve as a primary substrate for H2O2 production. However, in the absence of reactive compounds, the biological processes also play a crucial role in the H2O2 production.
Keywords: allochthonous, Aqualog, autochthonous, chlorophyll, lentic, PARAFAC, photosynthesis, reactive compounds, reactive oxygen species, water quality.
References
Aiken GR, Hsu-Kim H, Ryan JN (2011) Influence of dissolved organic matter on the environmental fate of metals, nanoparticles, and colloids. Environmental Science and Technology 45, 3196-3201.
| Crossref | Google Scholar | PubMed |
Amaral JHF, Gaddy JR, Bianchi TS, Osborne TZ, Newman S, Dombrowski J, Morrison ES (2023) Controls on the composition of dissolved organic matter in treatment wetland source waters of south Florida, USA. Ecological Engineering 194, 107047.
| Crossref | Google Scholar |
Battin TJ, Luyssaert S, Kaplan LA, Aufdenkampe AK, Richter A, Tranvik LJ (2009) The boundless carbon cycle. Nature Geoscience 2, 598-600.
| Crossref | Google Scholar |
Clark CD, De Bruyn WJ, Jones JG (2009) Photochemical production of hydrogen peroxide in size-fractionated southern California coastal waters. Chemosphere 76, 141-146.
| Crossref | Google Scholar | PubMed |
Clark CD, de Bruyn W, Jones JG (2014) Photoproduction of hydrogen peroxide in aqueous solution from model compounds for chromophoric dissolved organic matter (CDOM). Marine Pollution Bulletin 79, 54-60.
| Crossref | Google Scholar | PubMed |
Coble PG (1996) Characterization of marine and terrestrial DOM in seawater using excitation–emission matrix spectroscopy. Marine Chemistry 51, 325-346.
| Crossref | Google Scholar |
Constantino IC, Tadini AM, Lima MF, Plicas LM, de A, Moreira AB, Bisinoti MC (2018) Lability of natural organic matter in freshwater: a simple method for detection using hydrogen peroxide as an indicator. Biogeosciences Discussions 2018, 1-16.
| Crossref | Google Scholar |
Cooper WJ, Zika RG (1983) Photochemical formation of hydrogen peroxide in surface and ground waters exposed to sunlight. Science 220, 711-712.
| Crossref | Google Scholar | PubMed |
Cooper WJ, Zika RG, Petasne RG, Plane JMC (1988) Photochemical formation of hydrogen peroxide in natural waters exposed to sunlight. Environmental Science and Technology 22, 1156-1160.
| Crossref | Google Scholar | PubMed |
Cooper WJ, Lean DRS, Carey IH (1989) Spatial and temporal patterns of Hydrogen peroxide in lake water. Canadian Journal of Fisheries and Aquatic Sciences 46, 1227-1231.
| Crossref | Google Scholar |
Cory RM, Harrold KH, Neilson BT, Kling GW (2015) Controls on dissolved organic matter (DOM) degradation in a headwater stream: the influence of photochemical and hydrological conditions in determining light-limitation or substrate-limitation of photo-degradation. Biogeosciences 12, 9793-9838.
| Crossref | Google Scholar |
Cory RM, Davis TW, Dick GJ, Johengen T, Denef VJ, Berry MA, Page SE, Watson SB, Yuhas K, Kling GW (2016) Seasonal dynamics in dissolved organic matter, Hydrogen peroxide and cyanobacterial blooms in Lake Erie. Frontiers in Marine Science 3, 54.
| Crossref | Google Scholar |
Dalrymple RM, Carfagno AK, Sharpless CM (2010) Correlations between dissolved organic matter optical properties and quantum yields of singlet oxygen and hydrogen peroxide. Environmental Science and Technology 44, 5824-5829.
| Crossref | Google Scholar | PubMed |
Del Vecchio R, Blough NV (2002) Photobleaching of chromophoric dissolved organic matter in natural waters: kinetics and modeling. Marine Chemistry 78, 231-253.
| Crossref | Google Scholar |
Diaz JM, Plummer S (2018) Production of extracellular reactive oxygen species by phytoplankton: past and future directions. Journal of Plankton Research 40, 655-666.
| Crossref | Google Scholar | PubMed |
Dixon TC, Vermilyea AW, Scott DT, Voelker BM (2013) Hydrogen peroxide dynamics in an agricultural headwater stream: evidence for significant nonphotochemical production. Limnology and Oceanography 58, 2133-2144.
| Crossref | Google Scholar |
Du Y, Chen F, Zhang Y, He H, Wen S, Huang X, Song C, Li K, Wang J, Keellings D, Lu Y (2023) Human activity coupled with climate change strengthens the role of lakes as an active pipe of dissolved organic matter. Earths Future 11, e2022EF003412.
| Crossref | Google Scholar |
Fellman JB, Hood E, D’Amore DV, Edwards RT, White D (2009) Seasonal changes in the chemical quality and biodegradability of dissolved organic matter exported from soils to streams in coastal temperate rainforest watersheds. Biogeochemistry 95, 277-293.
| Crossref | Google Scholar |
Fichot CG, Benner R (2012) The spectral slope coefficient of chromophoric dissolved organic matter (S275–295) as a tracer of terrigenous dissolved organic carbon in river-influenced ocean margins. Limnology and Oceanography 57, 1453-1466.
| Crossref | Google Scholar |
Garcia RD, Reissig M, Queimaliños CP, Garcia PE, Dieguez MC (2015) Climate-driven terrestrial inputs in ultraoligotrophic mountain streams of Andean Patagonia revealed through chromophoric and fluorescent dissolved organic matter. Science of The Total Environment 521–522, 280-292.
| Crossref | Google Scholar | PubMed |
García PE, Queimaliños CP, Diéguez MC (2019) Natural levels and photo-production rates of hydrogen peroxide (H2O2) in Andean Patagonian aquatic systems: influence of the dissolved organic matter pool. Chemosphere 217, 550-557.
| Crossref | Google Scholar | PubMed |
Garcia PE, Gerea M, Diéguez MC (2020) Natural levels of hydrogen peroxide (H2O2) in deep clear south temperate lakes: field and laboratory evidence of photo- and biotic production. Science of The Total Environment 727, 138641.
| Crossref | Google Scholar | PubMed |
Garg S, Rose AL, Waite TD (2011) Photochemical production of superoxide and hydrogen peroxide from natural organic matter. Geochimica et Cosmochimica Acta 75, 4310-4320.
| Crossref | Google Scholar |
Häder D-P, Williamson CE, Wängberg SÅ, Rautio M, Rose KC, Gao K, Helbling EW, Sinha RP, Worrest R (2015) Effects of UV radiation on aquatic ecosystems and interactions with other environmental factors. Photochemical & Photobiological Sciences 14, 108-126.
| Crossref | Google Scholar | PubMed |
Häkkinen PJ, Anesio AM, Granéli W (2004) Hydrogen peroxide distribution, production, and decay in boreal lakes. Canadian Journal of Fisheries and Aquatic Sciences 61, 1520-1527.
| Crossref | Google Scholar |
Hancock TL, Dahedl EK, Kratz MA, Urakawa H (2024a) Synechococcus dominance induced after hydrogen peroxide treatment of Microcystis bloom in the Caloosahatchee River, Florida. Environmental Pollution 345, 123508.
| Crossref | Google Scholar |
Hancock TL, Dahedl EK, Kratz MA, Urakawa H (2024b) The synchronicity of bloom-forming cyanobacteria transcription patterns and hydrogen peroxide dynamics. Environmental Pollution 348, 123812.
| Crossref | Google Scholar |
Hansel CM, Ferdelman TG, Tebo BM (2015) Cryptic cross-linkages among biogeochemical cycles: novel insights from reactive intermediates. Elements 11, 409-414.
| Crossref | Google Scholar |
Helms JR, Stubbins A, Ritchie JD, Minor EC, Kieber DJ, Mopper K (2008) Absorption spectral slopes and slope ratios as indicators of molecular weight, source, and photobleaching of chromophoric dissolved organic matter. Limnology and Oceanography 53, 955-969.
| Crossref | Google Scholar |
Kothawala DN, Stedmon CA, Müller RA, Weyhenmeyer GA, Köhler SJ, Tranvik LJ (2014) Controls of dissolved organic matter quality: evidence from a large-scale boreal lake survey. Global Change Biology 20, 1101-1114.
| Crossref | Google Scholar | PubMed |
Maie N, Jaffé R, Miyoshi T, Childers DL (2006) Quantitative and qualitative aspects of dissolved organic carbon leached from senescent plants in an oligotrophic wetland. Biogeochemistry 78, 285-314.
| Crossref | Google Scholar |
McKnight DM, Boyer EW, Westerhoff PK, Doran PT, Kulbe TK, Andersen DT (2001) Spectrofluorometric characterization of dissolved organic matter for indication of precursor organic material and aromaticity. Limnology and Oceanography 46, 38-48.
| Crossref | Google Scholar |
Morris DP, Zagarese HE, Williamson CE, Balseiro EG, Hargreaves BR, Modenutti B, Moeller R, Queimaliños CP (1995) The attenuation of solar radiation in lakes and the role of dissolved organic carbon. Limnology and Oceanography 40, 1381-1391.
| Crossref | Google Scholar |
Mostofa KMG, Sakugawa H (2003) Spatial and temporal variation of hydrogen peroxide in stream and river waters: effect of photo-biophysio- chemical processes of aquatic matters. Goldschmidt Conference Abstracts 67, A309.
| Google Scholar |
Mostofa KMG, Liu C-Q, Sakugawa H, Vione D, Minakata D, Wu F (2013) Photoinduced and microbial generation of hydrogen peoxide and organic peroxide in natural water. In ‘Photobiogeochemistry of Organic Matter: Principles and Practices in Water Environments’. (Eds K Mostofa, T Yoshioka, A Mottaleb, D Vione) pp. 139–207. (Springer) doi:10.1007/978-3-642-32223-5_2
Murphy KR, Butler KD, Spencer RGM, Stedmon CA, Boehme JR, Aiken GR (2010) Measurement of dissolved organic matter fluorescence in aquatic environments: an interlaboratory comparison. Environmental Science and Technology 44, 9405-9412.
| Crossref | Google Scholar | PubMed |
Murphy KR, Stedmon CA, Graeber D, Bro R (2013) Fluorescence spectroscopy and multi-way techniques. PARAFAC. Analytical Methods 5, 6557-6566.
| Crossref | Google Scholar |
Murphy KR, Stedmon CA, Wenig P, Bro R (2014) OpenFluor – an online spectral library of auto-fluorescence by organic compounds in the environment. Analytical Methods 6, 658-661.
| Crossref | Google Scholar |
Ndungu LK, Steele JH, Hancock TL, Bartleson RD, Milbrandt EC, Parson ML, Urakawa H (2019) Hydrogen peroxide measurements in subtropical aquatic systems and their implications for cyanobacterial blooms. Ecological Engineering 138, 444-453.
| Crossref | Google Scholar |
Omanović D, Santinelli C, Marcinek S, Gonnelli M (2019) ASFit – an all-inclusive tool for analysis of UV–Vis spectra of colored dissolved organic matter (CDOM). Computers & Geosciences 133, 104334.
| Crossref | Google Scholar |
Omanović D, Marcinek S, Santinelli C (2023) TreatEEM—a software tool for the interpretation of fluorescence excitation–emission matrices (eems) of dissolved organic matter in natural waters. Water 15, 2214.
| Crossref | Google Scholar |
Osburn CL, Wigdahl CR, Fritz SC, Saros JE (2011) Dissolved organic matter composition and photoreactivity in prairie lakes of the U.S. Great Plains. Limnology and Oceanography 56, 2371-2390.
| Crossref | Google Scholar |
Palenik B, Morel FMM (1988) Dark production of H2O2 in the Sargasso Sea. Limnology and Oceanography 33, 1606-1611.
| Crossref | Google Scholar |
Queimaliños C, Reissig M, Pérez GL, Soto Cárdenas C, Gerea M, Garcia PE, García D, Diéguez MC (2019) Linking landscape heterogeneity with lake dissolved organic matter properties assessed through absorbance and fluorescence spectroscopy: spatial and seasonal patterns in temperate lakes of southern Andes (Patagonia, Argentina). Science of the Total Environment 686, 223-235.
| Crossref | Google Scholar | PubMed |
Roe KL, Schneider RJ, Hansel CM, Voelker BM (2016) Measurement of dark, particle-generated superoxide and hydrogen peroxide production and decay in the subtropical and temperate North Pacific Ocean. Deep-Sea Research – I. Oceanographic Research Papers 107, 59-69.
| Crossref | Google Scholar |
Romera-Castillo C, Sarmento H, Álvarez-Salgado XA, Gasol JM, Marrasé C (2010) Production of chromophoric dissolved organic matter by marine phytoplankton. Limnology and Oceanography 55, 446-454.
| Crossref | Google Scholar |
Romera-Castillo C, Alvarez-Salgado XA, Gali M, Gasol JM, Marrase C (2013) Combined effect of light exposure and microbial activity on distinct dissolved organic matter pools. A seasonal field study in an oligotrophic coastal system (Blanes Bay, NW Mediterranean). Marine Chemistry 148, 44-51.
| Crossref | Google Scholar |
Rusak SA, Richard LE, Peake BM, Cooper WJ, Bodeker GE (2010) The influence of solar radiation on hydrogen peroxide concentrations in freshwater. Marine and Freshwater Research 61, 1147-1153.
| Crossref | Google Scholar |
Scully NM, McQueen DJ, Lean DRS (1996) Hydrogen peroxide formation: the interaction of ultraviolet radiation and dissolved organic carbon in lake waters along a 43–75°N gradient. Limnology and Oceanography 41, 550-548.
| Crossref | Google Scholar |
Southworth BA, Voelker BM (2003) Hydroxyl radical production via the photo-Fenton reaction in the presence of fulvic acid. Environmental Science and Technology 37, 1130-1136.
| Crossref | Google Scholar | PubMed |
Stedmon CA, Markager S (2005) Resolving the variability in dissolved organic matter fluorescence in a temperate estuary and its catchment using PARAFAC analysis. Limnology and Oceanography 50, 686-697.
| Crossref | Google Scholar |
Stedmon CA, Bro R (2008) Characterizing dissolved organic matter fluorescence with parallel factor analysis: a tutorial. Limnology and Oceanography: Methods 6(11), 572-579.
| Crossref | Google Scholar |
Urakawa H, Ndungu LK, Hancock TL, Steele JH, Bartleson RD (2021) Subtropical freshwater cyanobacterial blooms as hydrogen peroxide hot spots. Environmental Science & Technology Letters 8, 911-917.
| Crossref | Google Scholar |
Van Gaelen N, Verschoren V, Clymans W, Poesen J, Govers G, Vanderborght J, Diels J (2014) Controls on dissolved organic carbon export through surface runoff from loamy agricultural soils. Geoderma 226–227, 387-396.
| Crossref | Google Scholar |
Vermilyea AW, Hansard SP, Voelker BM (2010) Dark production of hydrogen peroxide in the Gulf of Alaska. Limnology and Oceanography 55, 580-588.
| Crossref | Google Scholar |
Weishaar JL, Aiken GR, Bergamaschi BA, Fram MS, Fujii R, Mopper K (2003) Evaluation of specific ultraviolet absorbance as an indicator of the chemical composition and reactivity of dissolved organic carbon. Environmental Science and Technology 37, 4702-4708.
| Crossref | Google Scholar | PubMed |
Wilson HF, Xenopoulos MA (2008) Ecosystem and seasonal control of stream dissolved organic carbon along a gradient of land use. Ecosystems 11, 555-568.
| Crossref | Google Scholar |
Xenopoulos MA, Barnes RT, Boodoo KS, Butman D, Catalán N, D’Amario SC, Fasching C, Kothawala DN, Pisani O, Solomon CT, Spencer RGM, Williams C-J, Wilson HF (2021) How humans alter dissolved organic matter composition in freshwater: relevance for the Earth’s biogeochemistry. Biogeochemistry 154, 323-348.
| Crossref | Google Scholar |
Yamashita Y, Jaffé R, Maie N, Tanoue E (2008) Assessing the dynamics of dissolved organic matter (DOM) in coastal environments by excitation–emission matrix fluorescence and parallel factor analysis (EEM-PARAFAC). Limnology and Oceanography 53, 1900-1908.
| Crossref | Google Scholar |
Yamashita Y, Scinto LJ, Maie N, Jaffé R (2010) Dissolved organic matter characteristics across a subtropical wetland’s landscape: application of optical properties in the assessment of environmental dynamics. Ecosystems 13, 1006-1019.
| Crossref | Google Scholar |
Zsolnay A, Baigar E, Jimenez M, Steinweg B, Saccomandi F (1999) Differentiating with fluorescence spectroscopy the sources of dissolved organic matter in soils subjected to drying. Chemosphere 38, 45-50.
| Crossref | Google Scholar | PubMed |
