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Fractionation of Dissolved Organic Matter by Co-Precipitation with Iron: Effects of Composition

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Abstract

Interactions between dissolved organic matter (DOM) and different physical-chemical forms of iron (Fe) represent important biogeochemical processes in the organic carbon cycle. Due to the effect of climate change and anthropogenic activities such as land-use change, the loading of terrestrial DOM into aquatic systems is increasing, and thus, enhancing the organic matter-based acidity in aquatic ecosystems. While complexation of Fe with DOM and the sorption of DOM on iron oxides and (oxy)hydroxides have been reported, less is known about how co-precipitation processes might affect by DOM composition. Here the co-precipitation of two DOM standards, namely the Suwannee River Standard Humic Acid Standard II (SRHA) and Nordic Aquatic Fulvic Acid Reference (NAFA), with Fe was investigated in a pH range of 4.0–8.0. The DOM remaining after co-precipitating with Fe was systematically characterized by various analytical methods to reveal the molecular fractionation of DOM. The co-precipitation of SRHA or NAFA with Fe was enhanced by decreasing the pH, where at pH 4.0, about 70~80% DOC of SRHA or NAFA was removed at Fe(III)/C ratios higher than 0.12. The decrease in SUVA254 and the humification index (HIX) during the co-precipitation process suggests that DOM with high aromatic character was preferentially co-precipitated with Fe. DOM molecular weight influenced the selectivity to co-precipitation, with high molecular weight (HMW) DOM showing a stronger affinity. DOM co-precipitation with Fe was clearly dependent on DOM composition, showing an affinity order of terrestrial humic-like> ubiquitous humic-like> microbial humic-like components. The difference in the reactivity and the relative abundances of excitation emission matrix fluorescence combined with parallel factor analysis (EEM-PARAFAC) components explained the difference in DOC removal efficiency between SRHA and NAFA. This study provides direct insights into the effects of DOM composition on its fractionation specifically through co-precipitation with Fe, and suggests that for aquatic systems rich in iron-based (oxy)hydroxides, and for environmental redox interfaces, co-precipitation of DOM with iron might affect optical properties of the aqueous phase, and represent an important sink for terrestrially-derived organic matter.

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References

  • Buffam I, Laudon H, Seibert J, Mörth C-M, Bishop K (2008) Spatial heterogeneity of the spring flood acid pulse in a boreal stream network. Sci Total Environ 407:708–722

    Article  Google Scholar 

  • Chen M, Price RM, Yamashita Y, Jaffé R (2010) Comparative study of dissolved organic matter from groundwater and surface water in the Florida coastal Everglades using multi-dimensional spectrofluorometry combined with multivariate statistics. Appl Geochem 25:872–880

    Article  Google Scholar 

  • Chen WB, Smith DS, Guéguen C (2013) Influence of water chemistry and dissolved organic matter (DOM) molecular size on copper and mercury binding determined by multiresponse fluorescence quenching. Chemosphere 92:351–359

    Article  Google Scholar 

  • Chen C, Dynes JJ, Wang J, Sparks DL (2014) Properties of Fe-organic matter associations via coprecipitation versus adsorption. Environ Sci Technol 48:13751–13759

    Article  Google Scholar 

  • Chen ML, He W, Choi I, Hur J (2016) Tracking the monthly changes of dissolved organic matter composition in a newly constructed reservoir and its tributaries during the initial impounding period. Environ Sci Pollut Res 23:1274–1283

    Article  Google Scholar 

  • Cole JJ, Prairie YT, Caraco NF, McDowell WH, Tranvic LJ, Striegl RG, Duarte CM, Kortelainen P, Downing JA, Middelburg JJ, Melack J (2007) Plumbing the global carbon cycle: integrating inland waters into the terrestrial carbon budget. Ecosystems 10:172–185

    Article  Google Scholar 

  • Cory RM, McKnight DM (2005) Fluorescence spectroscopy reveals ubiquitous presence of oxidized and reduced quinones in dissolved organic matter. Environ Sci Technol 39:8142–8149

    Article  Google Scholar 

  • Eusterhues K, Rennert T, Knicker H, Kögel-Knabner I, Totsche KU, Schwertmann U (2011) Fractionation of organic matter due to reaction with ferrihydrite: coprecipitation versus adsorption. Environ Sci Technol 45:527–533

    Article  Google Scholar 

  • Evans CD, Chapman PJ, Clark JM, Monteith DT, Cresser MS (2006) Alternative explanations for rising dissolved organic carbon export from organic soils. Glob Chang Biol 12:2044–2053

    Article  Google Scholar 

  • Fellman JB, Hood E, Spencer RGM (2010) Fluorescence spectroscopy opens new windows into dissolved organic matter dynamics in freshwater ecosystems: a review. Limnol Oceanogr 55:2452–2462

    Article  Google Scholar 

  • Freeman C, Evans CD, Monteith DT, Reynolds B, Fenner N (2001) Export of organic carbon from peat soils. Nature 412:785–785

    Article  Google Scholar 

  • Gontijo ESJ, Watanabe CH, Monteiro ASC, da Silva GA, Roeser HMP, Rosa AH, Friese K (2017) Effects of Fe(III) and quality of humic substances on as(V) distribution in freshwater: use of ultrafiltration and Kahonen neutral network. Chemosphere 188:208–217

    Article  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. Limnol Oceanogr 53:955–969

    Article  Google Scholar 

  • Henneberry YK, Kraus TEC, Nico PS, Horwath WR (2012) Structural stability of co-precipitated natural organic matter and ferric iron under reducing conditions. Org Geochem 48:81–89

    Article  Google Scholar 

  • Huguet A, Vacher L, Relexans S, Saubusse S, Froidefond JM, Parlanti E (2009) Properties of fluorescent dissolved organic matter in the Gironde estuary. Org Geochem 40:706–719

    Article  Google Scholar 

  • Jaffé R, Cawley KM, Yamashita Y (2014) Applications of excitation emission matrix fluorescence with parallel factor analysis (EEM-PARAFAC) in assessing environmental dynamics of natural dissolved organic matter (DOM) in aquatic environments: a review. In: Rosario F (ed) Advances in the Physicochemical Characterization of Dissolved Organic Matter: Impact on Natural and Engineered Systems, ACS Book series, vol 1160. American Chemical Society, Washington DC, pp 27–73

  • Jickells TD et al (2005) Global iron connections between desert dust, ocean biogeochemistry, and climate. Science 308:67–71

    Article  Google Scholar 

  • Kaiser K, Guggenberger G (2000) The role of DOM sorption to mineral surfaces in the preservation of organic matter in soils. Org Geochem 31:711–725

    Article  Google Scholar 

  • Khadka B, Munir TM, Strack M (2015) Effect of environmental factors on production and bioavailability of dissolved organic carbon from substrates available in a constructed and reference fens in the Athabasca oil sands development region. Ecol Eng 84:596–606

    Article  Google Scholar 

  • Lakowicz JR (2006) Principles of fluorescence spectroscopy, 3rd edn. Springer Science+Business Media, LLC, New York

    Book  Google Scholar 

  • Lalonde K, Mucci A, Ouellet A, Gelinas Y (2012) Preservation of organic matter in sediments promoted by iron. Nature 483:198–200

    Article  Google Scholar 

  • Liu Y, Yang C, Cheng P, He X, Zhu Y, Zhang Y (2016) Influences of humic acid on the bioavailability of phenanthrene and alkyl phenanthrenes to early life stages of marine medaka (Oryzias melastigma). Environ Pollut 210:211–216

    Article  Google Scholar 

  • Lu Y, Allen HE (2002) Characterization of copper complexation with natural dissolved organic matter (DOM)—link to acidic moieties of DOM and competition by ca and mg. Water Res 36:5083–5101

    Article  Google Scholar 

  • Lu YH, Bauer JE, Canuel EA, Yamashita Y, Chambers RM, Jaffé R (2013) Photochemical and microbial alteration of dissolved organic matter in temperate headwater streams associated with different land use. J. Geophys Res Biogeosci 118:566–580

    Article  Google Scholar 

  • Maie N, Yamashita Y, Cory RM, Boyer JN, Jaffé R (2012) Application of excitation emission matrix fluorescence monitoring in the assessment of spatial and seasonal drivers of dissolved organic matter composition: sources and physical disturbance controls. Appl Geochem 27:917–929

    Article  Google Scholar 

  • Mattsson T, Kortelainen P, Lepistö A, Räike A (2007) Organic and minerogenic acidity in Finnish rivers in relation to land use and deposition. Sci Total Environ 383:183–192

    Article  Google Scholar 

  • McKnight DM, Boyer EW, Westerhoff PK, Doran PT, Kulbe T, Andersen DT (2001) Spectrofluorometric characterization of dissolved organic matter for indication of precursor organic material and aromaticity. Limnol Oceanogr 46:38–48

    Article  Google Scholar 

  • Mikutta C, Mikutta R, Bonneville S, Wagner F, Voegelin A, Christl I, Kretzschmar R (2008) Synthetic coprecipitates of exopolysaccharides and ferrihydrite. Part I: characterization. Geochim Cosmochim Acta 72:1111–1127

    Article  Google Scholar 

  • Mladenov N, Zheng Y, Miller MP, Nemergut DR, Legg T, Simone B, Hageman C, Rahman MM, Ahmed K, McKnight DM (2010) Dissolved organic matter sources and consequences for iron and arsenic mobilization in Bangladesh aquifers. Environ Sci Technol 44:123–128

    Article  Google Scholar 

  • Mladenov N, Zheng Y, Simone B, Bilinski TM, McKnight DM, Nemergut D, Radloff KA, Rahman MM, Ahmed KM (2015) Dissolved organic matter quality in a shallow aquifer of Bangladesh: implications for arsenic mobility. Environ Sci Technol 49:10815–10824

    Article  Google Scholar 

  • Moran MA, Zepp RG (1997) Role of photoreactions in the formation of biologically labile compounds from dissolved organic matter. Limnol Oceanogr 42:1307–1316

    Article  Google Scholar 

  • Murphy KR, Stedmon CA, Graeber D, Bro R (2013) Fluorescence spectroscopy and multi-way techniques. PARAFAC. Anal Methods 5:6557–6566

    Article  Google Scholar 

  • Nierop KGJJ, Jansen B, Verstraten JM (2002) Dissolved organic matter, aluminium and iron interactions: precipitation induced by metal/carbon ratio, pH and competition. Sci Total Environ 300:201–211

    Article  Google Scholar 

  • O’Day PA, Vlassopoulos D, Root R, Rivera N (2004) The influence of sulfur and iron on dissolved arsenic concentrations in the shallow subsurface under changing redox conditions. Proc Natl Acad Sci 101:13707–13708

    Google Scholar 

  • Ohno T, Amirbahman A, Bro R (2008) Parallel factor analysis of excitation-emission matrix fluorescence spectra of water soluble soil organic matter as basis for the determination of conditional metal binding parameters. Environ Sci Technol 42:186–192

    Article  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. Limnol Oceanogr 56:2371–2390

    Article  Google Scholar 

  • Peuravuori J, Pihlaja K (1997) Molecular size distribution and spectroscopic properties of aquatic humic substances. Anal Chim Acta 337:133–149

    Article  Google Scholar 

  • Poulin BA, Ryan JN, Aiken GR (2014) Effects of iron on optical properties of dissolved organic matter. Environ Sci Technol 48:10098–10106

    Article  Google Scholar 

  • Poulton SW, Raiswell R (2002) The low-temperature geochemical cycle of iron: from continental fluxes to marine sediment deposition. Am J Sci 302:774–805

    Article  Google Scholar 

  • Riedel T, Zak D, Biester H, Dittmar T (2013) Iron traps terrestrially derived dissolved organic matter at redox interfaces. Proc Natl Acad Sci 110:10101–10105

    Article  Google Scholar 

  • Romera-Castillo C, Chen M, Yamashita Y, Jaffé R (2014) Fluorescence characteristics of size-fractionated dissolved organic matter: implications for a molecular assembly based structure? Water Res 55:40–51

    Article  Google Scholar 

  • Saarinen T, Vuori K-M, Alasaarela E, Kløve B (2010) Long-term trends and variation of acidity, CODMn and colour in coastal rivers of western Finland in relation to climate and hydrology. Sci Total Environ 408:5019–5027

    Article  Google Scholar 

  • Satoh Y, Kikuchi K, Kinoshita S, Sasaki H (2006) Potential capacity of coprecipitation of dissolved organic carbon (DOC) with iron(III) precipitates. Limnology 7:231–235

    Article  Google Scholar 

  • Senesi N (1990) Molecular and quantitative aspects of the chemistry of fulvic acid and its interactions with metal ions and organic chemicals : part II. The fluorescence spectroscopy approach. Anal Chim Acta 232:77–106

    Article  Google Scholar 

  • Smith KS, Ranville JF, Lesher EK, Diedrich DJ, McKnight DM, Sofield RM (2014) Fractionation of fulvic acid by iron and aluminum oxides—influence on copper toxicity to Ceriodaphnia dubia. Environ Sci Technol 48:11934–11943

    Article  Google Scholar 

  • Spencer RG, Butler KD, Aiken GR (2012) Dissolved organic carbon and chromophoric dissolved organic matter properties of rivers in the USA. J Geophys Res Biogeosci 117:G3

    Article  Google Scholar 

  • Stedmon CA, Bro R (2008) Characterizing dissolved organic matter fluorescence with parallel factor analysis: a tutorial. Limnol Oceanogr Methods 6:572–579

    Article  Google Scholar 

  • Stedmon CA, Markager S (2005) Tracing the production and degradation of autochthonous fractions of dissolved organic matter by fluorescence analysis. Limnol Oceanogr 50:1415–1426

    Article  Google Scholar 

  • Stedmon CA, Markager S, Tranvik L, Kronberg L, Slätis T, Martinsen W (2007) Photochemical production of ammonium and transformation of dissolved organic matter in the Baltic Sea. Mar Chem 104:227–240

    Article  Google Scholar 

  • Sulzberger B, Durisch-Kaiser E (2009) Chemical characterization of dissolved organic matter (DOM): a prerequisite for understanding UV-induced changes of DOM absorption properties and bioavailability. Aquat Sci 71:104–126

    Article  Google Scholar 

  • Torn MS, Trumbore SE, Chadwick OA, Vitousek PM, Hendricks DM (1997) Mineral control of soil organic carbon storage and turnover. Nature 389:170–173

    Article  Google Scholar 

  • Vuorenmaa J, Forsius M, Mannio J (2006) Increasing trends of total organic carbon concentrations in small forest lakes in Finland from 1987 to 2003. Sci Total Environ 365:47–65

    Article  Google Scholar 

  • Wagai R, Mayer LM (2007) Sorptive stabilization of organic matter in soils by hydrous iron oxides. Geochim Cosmochim Acta 71:25–35

    Article  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. Environ Sci Technol 37:4702–4708

    Article  Google Scholar 

  • Yadav IC, Linthoingambi N, Singh DS (2014) Reductive dissolution of iron-oxyhydroxides directs groundwater arsenic mobilization in the upstream of Ganges River basin, Nepal. J Geochem Explor 148:150–160

    Article  Google Scholar 

  • Yamashita Y, Jaffé R (2008) Characterizing the interactions between trace metals and dissolved organic matter using excitation−emission matrix and parallel factor analysis. Environ Sci Technol 42:7374–7379

    Article  Google Scholar 

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Acknowledgements

Funding for this work was provided by the National Science Foundation through the FCE-LTER program (DEB-1237517) and through the George Barley endowment (to RJ). Additional support through the National Science Foundation of China (No. 41371122, 41671099; to YD) is acknowledged. The authors thank Drs. C. Ya, C. Romera-Castillo and S. Wagner for assistance with DOM measurements and Dr. P. R. Gardinali for access to the ICP/MS system. This is contribution #850 from the Southeast Environmental Research Center.

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Du, Y., Ramirez, C.E. & Jaffé, R. Fractionation of Dissolved Organic Matter by Co-Precipitation with Iron: Effects of Composition. Environ. Process. 5, 5–21 (2018). https://doi.org/10.1007/s40710-017-0281-4

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