Environmental Science and Pollution Research

, Volume 22, Issue 9, pp 6500–6510 | Cite as

Occurrence and behaviors of fluorescence EEM-PARAFAC components in drinking water and wastewater treatment systems and their applications: a review

  • Liyang Yang
  • Jin HurEmail author
  • Wane Zhuang
Review Article


Fluorescence excitation emission matrices-parallel factor analysis (EEM-PARAFAC) is a powerful tool for characterizing dissolved organic matter (DOM), and it is applied in a rapidly growing number of studies on drinking water and wastewater treatments. This paper presents an overview of recent findings about the occurrence and behavior of PARAFAC components in drinking water and wastewater treatments, as well as their feasibility for assessing the treatment performance and water quality including disinfection by-product formation potentials (DBPs FPs). A variety of humic-like, protein-like, and unique (e.g., pyrene-like) fluorescent components have been identified, providing valuable insights into the chemical composition of DOM and the effects of various treatment processes in engineered systems. Coagulation/flocculation-clarification preferentially removes humic-like components, and additional treatments such as biological activated carbon filtration, anion exchange, and UV irradiation can further remove DOM from drinking water. In contrast, biological treatments are more effective for protein-like components in wastewater treatments. PARAFAC components have been proven to be valuable as surrogates for conventional water quality parameter, to track the changes of organic matter quantity and quality in drinking water and wastewater treatments. They are also feasible for assessing formations of trihalomethanes and other DBPs and evaluating treatment system performance. Further studies of EEM-PARAFAC for assessing the effects of the raw water quality and variable treatment conditions on the removal of DOM, and the formation potentials of various emerging DBPs, are essential for optimizing the treatment processes to ensure treated water quality.


Dissolved organic matter Fluorescence excitation emission matrices Parallel factor analysis Drinking water treatment Wastewater treatment Online monitoring 



This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIP) (No.2014R1A2A2A09049496).

Supplementary material

11356_2015_4214_MOESM1_ESM.doc (244 kb)
ESM 1 (DOC 244 kb)


  1. Anderson CA, Bro R (2000) The n-way toolbox for MATLAB. Chemom Intell Lab 52:1–4CrossRefGoogle Scholar
  2. Andrade-Eiroa Á, Canle M, Cerdá V (2013) Environmental applications of excitation-emission spectrofluorimetry: an in-depth review II. Appl Spectrosc Rev 48:77–141CrossRefGoogle Scholar
  3. Baghoth SA, Sharma SK, Guitard M, Heim V, Croue JP, Amy GL (2011a) Removal of NOM-constituents as characterized by LC-OCD and F-EEM during drinking water treatment. J Water Suppl Res T 60:412–424CrossRefGoogle Scholar
  4. Baghoth SA, Sharma SK, Amy GL (2011b) Tracking natural organic matter (NOM) in a drinking water treatment plant using fluorescence excitation-emission matrices and PARAFAC. Water Res 45:797–809CrossRefGoogle Scholar
  5. Baker A (2001) Fluorescence excitation-emission matrix characterization of some sewage-impacted rivers. Environ Sci Technol 35:948–953CrossRefGoogle Scholar
  6. Baker A, Elliott S, Lead JR (2007) Effects of filtration and pH perturbation on freshwater organic matter fluorescence. Chemosphere 67:2035–2043CrossRefGoogle Scholar
  7. Barker DJ, Stuckey DC (1999) A review of soluble microbial products (SMP) in wastewater treatment systems. Water Res 33:3063–3082CrossRefGoogle Scholar
  8. Beggs KMH, Summers RS (2011) Character and chlorine reactivity of dissolved organic matter from a mountain pine beetle impacted watershed. Environ Sci Technol 45:5717–5724CrossRefGoogle Scholar
  9. Bond T, Templeton MR, Graham N (2012) Precursors of nitrogenous disinfection by-products in drinking water—a critical review and analysis. J Hazard Mater 235–236:1–16CrossRefGoogle Scholar
  10. Bro R, Kiers HAL (2003) A new efficient method for determining the number of components in PARAFAC models. J Chemometr 17:274–286CrossRefGoogle Scholar
  11. Bro R, Vidal M (2011) EEMizer: automated modeling of fluorescence EEM data. Chemom Intell Lab 106:86–92CrossRefGoogle Scholar
  12. Carstea EM, Baker A, Bieroza M, Reynolds D (2010) Continuous fluorescence excitation-emission matrix monitoring of river organic matter. Water Res 44:5356–5366CrossRefGoogle Scholar
  13. Carstea EM, Baker A, Bieroza M, Reynolds DM, Bridgeman J (2014) Characterisation of dissolved organic matter fluorescence properties by PARAFAC analysis and thermal quenching. Water Res 61:152–161CrossRefGoogle Scholar
  14. Cawley KM, Butler KD, Aiken GR, Larsen LG, Huntington TG, McKnight DM (2012) Identifying fluorescent pulp mill effluent in the Gulf of Maine and its watershed. Mar Pollut Bull 64:1678–1687CrossRefGoogle Scholar
  15. Chen W, Westerhoff P, Leenheer JA, Booksh K (2003) Fluorescence excitation–emission matrix regional integration to quantify spectra for dissolved organic matter. Environ Sci Technol 37:5701–5710CrossRefGoogle Scholar
  16. Chen B, Nam S-N, Westerhoff PK, Krasner SW, Amy G (2009) Fate of effluent organic matter and DBP precursors in an effluent-dominated river: a case study of wastewater impact on downstream water quality. Water Res 43:1755–1765CrossRefGoogle Scholar
  17. Coble PG (1996) Characterization of marine and terrestrial DOM in seawater using excitation emission matrix spectroscopy. Mar Chem 51:325–346CrossRefGoogle Scholar
  18. Coble PG (2007) Marine optical biogeochemistry: the chemistry of ocean color. Chem Rev 107:402–418CrossRefGoogle Scholar
  19. Cohen E, Levy GJ, Borisover M (2014) Fluorescent components of organic matter in wastewater: efficacy and selectivity of the water treatment. Water Res 55:323–334CrossRefGoogle Scholar
  20. Du ED, Cao PR, Sun Y, Gao NY, Wang LP (2012) Application of fluorescence excitation-emission matrices and parafac analysis for indicating the organic matter removal from micro-polluted raw water in water treatment plant. Fresen Environ Bull 21:4030–4039Google Scholar
  21. Esparza-Soto M, Núñez-Hernández S, Fall C (2011) Spectrometric characterization of effluent organic matter of a sequencing batch reactor operated at three sludge retention times. Water Res 45:6555–6563CrossRefGoogle Scholar
  22. Fellman JB, Miller MP, Cory RM, D’Amore DV, White D (2009) Characterizing dissolved organic matter using PARAFAC modeling of fluorescence spectroscopy: a comparison of two models. Environ Sci Technol 43:6228–6234CrossRefGoogle Scholar
  23. Fellman JB, Hood E, Spencer RGM (2010) Fluorescence spectroscopy opens new windows into dissolved organic matter dynamics in freshwater ecosystems: a review. Limnol Oceanogr 55:2452–2462CrossRefGoogle Scholar
  24. Galinha CF, Carvalho G, Portugal CAM, Guglielmi G, Reis MAM, Crespo JG (2012) Multivariate statistically-based modelling of a membrane bioreactor for wastewater treatment using 2D fluorescence monitoring data. Water Res 46:3623–3636CrossRefGoogle Scholar
  25. Granderson CW, Pifer AD, Fairey JL (2013) An improved chloroform surrogate for chlorine dioxide- and alum-treated waters. J Am Water Works Ass 105:45–46Google Scholar
  26. Henderson RK, Baker A, Murphy KR, Hambly A, Stuetz RM, Khan SJ (2009) Fluorescence as a potential monitoring tool for recycled water systems: a review. Water Res 43:863–881CrossRefGoogle Scholar
  27. Herzsprung P et al (2012) Variations of DOM quality in inflows of a drinking water reservoir: linking of van Krevelen diagrams with EEMF spectra by rank correlation. Environ Sci Technol 46:5511–5518CrossRefGoogle Scholar
  28. Hudson N, Baker A, Reynolds D (2007) Fluorescence analysis of dissolved organic matter in natural, waste and polluted waters—a review. River Res Appl 23:631–649CrossRefGoogle Scholar
  29. Hur J, Shin J, Kang M, Cho J (2014a) Tracking variations in fluorescent-dissolved organic matter in an aerobic submerged membrane bioreactor using excitation–emission matrix spectra combined with parallel factor analysis. Bioprocess Biosyst Eng 37:1487–1496CrossRefGoogle Scholar
  30. Hur J, Nguyen H-M, Lee B-M (2014b) Influence of upstream land use on dissolved organic matter and trihalomethane formation potential in watersheds for two different seasons. Environ Sci Pollut R 21:7489–7500CrossRefGoogle Scholar
  31. Ishii SKL, Boyer TH (2012) Behavior of reoccurring PARAFAC components in fluorescent dissolved organic matter in natural and engineered systems: a critical review. Environ Sci Technol 46:2006–2017CrossRefGoogle Scholar
  32. Johnstone DW, Sanchez NP, Miller CM (2009) Parallel factor analysis of excitation-emission matrices to assess drinking water disinfection byproduct formation during a peak formation period. Environ Eng Sci 26:1551–1559CrossRefGoogle Scholar
  33. Krasner SW, Mitch WA, McCurry DL, Hanigan D, Westerhoff P (2013) Formation, precursors, control, and occurrence of nitrosamines in drinking water: a review. Water Res 47:4433–4450CrossRefGoogle Scholar
  34. Lee W, Westerhoff P, Croue JP (2007) Dissolved organic nitrogen as a precursor for chloroform, dichloroacetonitrile, N-Nitrosodimethylamine, and trichloronitromethane. Environ Sci Technol 41:5485–5490CrossRefGoogle Scholar
  35. Lee BM, Shin HS, Hur J (2013) Comparison of the characteristics of extracellular polymeric substances for two different extraction methods and sludge formation conditions. Chemosphere 90:237–244CrossRefGoogle Scholar
  36. Leenheer JA, Croue JP (2003) Characterizing aquatic dissolved organic matter. Environ Sci Technol 37:18A–26ACrossRefGoogle Scholar
  37. Li WH, Sheng GP, Liu XW, Yu HQ (2008) Characterizing the extracellular and intracellular fluorescent products of activated sludge in a sequencing batch reactor. Water Res 42:3173–3181CrossRefGoogle Scholar
  38. Li Y, Li AM, Xu J, Li WW, Yu HQ (2013) Formation of soluble microbial products (SMP) by activated sludge at various salinities. Biodegradation 24:69–78CrossRefGoogle Scholar
  39. Li W-T, Chen S-Y, Xu Z-X, Li Y, Shuang C-D, Li A-M (2014a) Characterization of dissolved organic matter in municipal wastewater using fluorescence PARAFAC analysis and chromatography multi-excitation/emission scan: a comparative study. Environ Sci Technol 48:2603–2609CrossRefGoogle Scholar
  40. Li X, Dai X, Takahashi J, Li N, Jin J, Dai L, Dong B (2014b) New insight into chemical changes of dissolved organic matter during anaerobic digestion of dewatered sewage sludge using EEM-PARAFAC and two-dimensional FTIR correlation spectroscopy. Bioresour Technol 159:412–420CrossRefGoogle Scholar
  41. Lyon BA, Cory RM, Weinberg HS (2014) Changes in dissolved organic matter fluorescence and disinfection byproduct formation from UV and subsequent chlorination/chloramination. J Hazard Mater 264:411–419CrossRefGoogle Scholar
  42. Markechová D, Tomková M, Sádecká J (2013) Fluorescence excitation-emission matrix spectroscopy and parallel factor analysis in drinking water treatment: a review. Pol J Environ Stud 22:1289–1295Google Scholar
  43. Mash CA, Winston BA, II DAM, Pifer AD, Scott JT, Zhang W, Fairey JL (2014) Assessing trichloromethane formation and control in algal-stimulated waters amended with nitrogen and phosphorus. Environ Sci: Processes Impacts 16:1290-1299Google Scholar
  44. Matilainen A, Vepsäläinen M, Sillanpää M (2010) Natural organic matter removal by coagulation during drinking water treatment: a review. Adv Colloid Interface 159:189–197CrossRefGoogle Scholar
  45. Matthews BJH, Jones AC, Theodorou NK, Tudhope AW (1996) Excitation-emission-matrix fluorescence spectroscopy applied to humic acid bands in coral reefs. Mar Chem 55:317–332CrossRefGoogle Scholar
  46. Mobed JJ, Hemmingsen SL, Autry JL, McGown LB (1996) Fluorescence characterization of IHSS humic substances: total luminescence spectra with absorbance correction. Environ Sci Technol 30:3061–3065CrossRefGoogle Scholar
  47. Murphy KR, Stedmon CA, Waite TD, Ruiz GM (2008) Distinguishing between terrestrial and autochthonous organic matter sources in marine environments using fluorescence spectroscopy. Mar Chem 108:40–58CrossRefGoogle Scholar
  48. Murphy KR, Hambly A, Singh S, Henderson RK, Baker A, Stuetz R, Khan SJ (2011) Organic matter fluorescence in municipal water recycling schemes: toward a unified PARAFAC model. Environ Sci Technol 45:2909–2916CrossRefGoogle Scholar
  49. Murphy KR, Stedmon CA, Wenig P, Bro R (2014) OpenFluor—an online spectral library of auto-fluorescence by organic compounds in the environment. Anal Methods 6:658–661CrossRefGoogle Scholar
  50. Ni B-J, Fang F, Xie W-M, Sun M, Sheng G-P, Li W-H, Yu H-Q (2009) Characterization of extracellular polymeric substances produced by mixed microorganisms in activated sludge with gel-permeating chromatography, excitation–emission matrix fluorescence spectroscopy measurement and kinetic modeling. Water Res 43:1350–1358CrossRefGoogle Scholar
  51. Ou H-S, Wei C-H, Mo C-H, Wu H-Z, Ren Y, Feng C-H (2014a) Novel insights into anoxic/aerobic1/aerobic2 biological fluidized-bed system for coke wastewater treatment by fluorescence excitation–emission matrix spectra coupled with parallel factor analysis. Chemosphere 113:158–164CrossRefGoogle Scholar
  52. Ou H-S, Wei C-H, Deng Y, Gao N-Y, Ren Y, Hu Y (2014b) Principal component analysis to assess the efficiency and mechanism for enhanced coagulation of natural algae-laden water using a novel dual coagulant system. Environ Sci Pollut R 21:2122–2131CrossRefGoogle Scholar
  53. Ou H-S, Wei C-H, Deng Y, Gao N-Y (2014c) Integrated principal component analysis of Microcystis aeruginosa dissolved organic matter and assessment of UV-C pre-treatment on Cyanobacteria-containing water. CLEAN – Soil Air Water 42:442–448CrossRefGoogle Scholar
  54. Parlanti E, Wörz K, Geoffroy L, Lamotte M (2000) Dissolved organic matter fluorescence spectroscopy as a tool to estimate biological activity in a coastal zone submitted to anthropogenic inputs. Org Geochem 31:1765–1781CrossRefGoogle Scholar
  55. Parr TB, Ohno T, Cronan CS, Simon KS (2014) comPARAFAC: a library and tools for rapid and quantitative comparison of dissolved organic matter components resolved by parallel factor analysis. Limnol Oceanogr-Meth 12:114–125CrossRefGoogle Scholar
  56. Pifer AD, Fairey JL (2012) Improving on SUVA254 using fluorescence-PARAFAC analysis and asymmetric flow-field flow fractionation for assessing disinfection byproduct formation and control. Water Res 46:2927–2936CrossRefGoogle Scholar
  57. Pifer AD, Fairey JL (2014) Suitability of organic matter surrogates to predict trihalomethane formation in drinking water sources. Environ Eng Sci 31:117–126CrossRefGoogle Scholar
  58. Pifer AD, Cousins SL, Fairey JL (2014) Assessing UV- and fluorescence-based metrics as disinfection byproduct precursor surrogate parameters in a water body influenced by a heavy rainfall event. J Water Suppl Res T 63:200–211CrossRefGoogle Scholar
  59. Richardson SD, Plewa MJ, Wagner ED, Schoeny R, DeMarini DM (2007) Occurrence, genotoxicity, and carcinogenicity of regulated and emerging disinfection by-products in drinking water: a review and roadmap for research. Mutat Res 636:178–242CrossRefGoogle Scholar
  60. Sanchez NP, Skeriotis AT, Miller CM (2013) Assessment of dissolved organic matter fluorescence PARAFAC components before and after coagulation–filtration in a full scale water treatment plant. Water Res 47:1679–1690CrossRefGoogle Scholar
  61. Sanchez NP, Skeriotis AT, Miller CM (2014) A PARAFAC-based long-term assessment of DOM in a multi-coagulant drinking water treatment scheme. Environ Sci Technol 48:1582–1591CrossRefGoogle Scholar
  62. Saraceno JF, Pellerin BA, Downing BD, Boss E, Bachand PAM, Bergamaschi BA (2009) High-frequency in situ optical measurements during a storm event: assessing relationships between dissolved organic matter, sediment concentrations, and hydrologic processes. J Geophys Res-Biogeosci 114:G00F09. doi: 10.1029/2009JG000989 CrossRefGoogle Scholar
  63. Shao S, Liang H, Qu F, Yu H, Li K, Li G (2014) Fluorescent natural organic matter fractions responsible for ultrafiltration membrane fouling: identification by adsorption pretreatment coupled with parallel factor analysis of excitation–emission matrices. J Membr Sci 464:33–42CrossRefGoogle Scholar
  64. Sharma VK, Zboril R, McDonald TJ (2014) Formation and toxicity of brominated disinfection byproducts during chlorination and chloramination of water: a review. J Environ Sci Heal B 49:212–228CrossRefGoogle Scholar
  65. Shen Y-x, Xiao K, Liang P, Sun J-y, Sai S-j, Huang X (2012) Characterization of soluble microbial products in 10 large-scale membrane bioreactors for municipal wastewater treatment in China. J Membr Sci 415–416:336–345CrossRefGoogle Scholar
  66. Sheng G-P, Yu H-Q (2006) Characterization of extracellular polymeric substances of aerobic and anaerobic sludge using three-dimensional excitation and emission matrix fluorescence spectroscopy. Water Res 40:1233–1239CrossRefGoogle Scholar
  67. Sheng G-P, Yu H-Q, Li X-Y (2010) Extracellular polymeric substances (EPS) of microbial aggregates in biological wastewater treatment systems: a review. Biotechnol Adv 28:882–894CrossRefGoogle Scholar
  68. Shon HK, Vigneswaran S, Snyder SA (2006) Effluent organic matter (EfOM) in wastewater: constituents, effects, and treatment. Crit Rev Env Sci Tec 36:327–374CrossRefGoogle Scholar
  69. Shutova Y, Baker A, Bridgeman J, Henderson RK (2014) Spectroscopic characterisation of dissolved organic matter changes in drinking water treatment: from PARAFAC analysis to online monitoring wavelengths. Water Res 54:159–169CrossRefGoogle Scholar
  70. Spencer RGM, Bolton L, Baker A (2007a) Freeze/thaw and pH effects on freshwater dissolved organic matter fluorescence and absorbance properties from a number of UK locations. Water Res 41:2941–2950CrossRefGoogle Scholar
  71. Spencer RGM et al (2007b) Diurnal variability in riverine dissolved organic matter composition determined by in situ optical measurement in the San Joaquin River (California, USA). Hydrol Process 21:3181–3189CrossRefGoogle Scholar
  72. Stedmon CA, Bro R (2008) Characterizing dissolved organic matter fluorescence with parallel factor analysis: a tutorial. Limnol Oceanogr-Meth 6:572–579CrossRefGoogle Scholar
  73. Stedmon CA, Markager S, Bro R (2003) Tracing dissolved organic matter in aquatic environments using a new approach to fluorescence spectroscopy. Mar Chem 82:239–254CrossRefGoogle Scholar
  74. Stedmon CA, Seredyńska-Sobecka B, Boe-Hansen R, Le Tallec N, Waul CK, Arvin E (2011) A potential approach for monitoring drinking water quality from groundwater systems using organic matter fluorescence as an early warning for contamination events. Water Res 45:6030–6038CrossRefGoogle Scholar
  75. Woods GC, Simpson MJ, Koerner PJ, Napoli A, Simpson AJ (2011) HILIC-NMR: toward the identification of individual molecular components in dissolved organic matter. Environ Sci Technol 45:3880–3886CrossRefGoogle Scholar
  76. Yang L, Choi JH, Hur J (2014a) Benthic flux of dissolved organic matter from lake sediment at different redox conditions and the possible effects of biogeochemical processes. Water Res 61:97–107CrossRefGoogle Scholar
  77. Yang L, Shin H-S, Hur J (2014b) Estimating the concentration and biodegradability of organic matter in 22 wastewater treatment plants using fluorescence excitation emission matrices and parallel factor analysis. Sensors-Basel 14:1771–1786CrossRefGoogle Scholar
  78. Yang L, Kim D, Uzun H, Karanfil T, Hur J (2015) Assessing trihalomethanes (THMs) and N-nitrosodimethylamine (NDMA) formation potentials in drinking water treatment plants using fluorescence spectroscopy and parallel factor analysis. Chemosphere 121:84–91Google Scholar
  79. Yu GH, He PJ, Shao LM (2010) Novel insights into sludge dewaterability by fluorescence excitation-emission matrix combined with parallel factor analysis. Water Res 44:797–806CrossRefGoogle Scholar
  80. Yu HB, Song YH, Tu X, Du ED, Liu RX, Peng JF (2013) Assessing removal efficiency of dissolved organic matter in wastewater treatment using fluorescence excitation emission matrices with parallel factor analysis and second derivative synchronous fluorescence. Bioresour Technol 144:595–601CrossRefGoogle Scholar
  81. Yu H, Qu F, Liang H, Han Z-s, Ma J, Shao S, Chang H, Li G (2014) Understanding ultrafiltration membrane fouling by extracellular organic matter of Microcystis aeruginosa using fluorescence excitation–emission matrix coupled with parallel factor analysis. Desalination 337:67–75CrossRefGoogle Scholar
  82. Zhou Z, Meng F, Chae S-R, Huang G, Fu W, Jia X, Li S, Chen G-H (2012) Microbial transformation of biomacromolecules in a membrane bioreactor: implications for membrane fouling investigation. Plos One 7:e42270CrossRefGoogle Scholar
  83. Zhou A, Du J, Varrone C, Wang Y, Wang A, Liu W (2014) VFAs bioproduction from waste activated sludge by coupling pretreatments with Agaricus bisporus substrates conditioning. Process Biochem 49:283–289CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  1. 1.Department of Environment & EnergySejong UniversitySeoulSouth Korea
  2. 2.College of Life SciencesFujian Agriculture and Forestry UniversityFuzhouChina

Personalised recommendations