Skip to main content
Log in

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

  • Review Article
  • Published:
Environmental Science and Pollution Research Aims and scope Submit manuscript

Abstract

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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3

Similar content being viewed by others

References

  • Anderson CA, Bro R (2000) The n-way toolbox for MATLAB. Chemom Intell Lab 52:1–4

    Article  Google Scholar 

  • Andrade-Eiroa Á, Canle M, Cerdá V (2013) Environmental applications of excitation-emission spectrofluorimetry: an in-depth review II. Appl Spectrosc Rev 48:77–141

    Article  CAS  Google Scholar 

  • 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 60:412–424

    Article  CAS  Google Scholar 

  • 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 45:797–809

    Article  CAS  Google Scholar 

  • Baker A (2001) Fluorescence excitation-emission matrix characterization of some sewage-impacted rivers. Environ Sci Technol 35:948–953

    Article  CAS  Google Scholar 

  • Baker A, Elliott S, Lead JR (2007) Effects of filtration and pH perturbation on freshwater organic matter fluorescence. Chemosphere 67:2035–2043

    Article  CAS  Google Scholar 

  • Barker DJ, Stuckey DC (1999) A review of soluble microbial products (SMP) in wastewater treatment systems. Water Res 33:3063–3082

    Article  CAS  Google Scholar 

  • Beggs KMH, Summers RS (2011) Character and chlorine reactivity of dissolved organic matter from a mountain pine beetle impacted watershed. Environ Sci Technol 45:5717–5724

    Article  CAS  Google Scholar 

  • Bond T, Templeton MR, Graham N (2012) Precursors of nitrogenous disinfection by-products in drinking water—a critical review and analysis. J Hazard Mater 235–236:1–16

    Article  Google Scholar 

  • Bro R, Kiers HAL (2003) A new efficient method for determining the number of components in PARAFAC models. J Chemometr 17:274–286

    Article  CAS  Google Scholar 

  • Bro R, Vidal M (2011) EEMizer: automated modeling of fluorescence EEM data. Chemom Intell Lab 106:86–92

    Article  CAS  Google Scholar 

  • Carstea EM, Baker A, Bieroza M, Reynolds D (2010) Continuous fluorescence excitation-emission matrix monitoring of river organic matter. Water Res 44:5356–5366

    Article  CAS  Google Scholar 

  • 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 61:152–161

    Article  CAS  Google Scholar 

  • 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 64:1678–1687

    Article  CAS  Google Scholar 

  • 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 37:5701–5710

    Article  CAS  Google Scholar 

  • 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 43:1755–1765

    Article  CAS  Google Scholar 

  • Coble PG (1996) Characterization of marine and terrestrial DOM in seawater using excitation emission matrix spectroscopy. Mar Chem 51:325–346

    Article  CAS  Google Scholar 

  • Coble PG (2007) Marine optical biogeochemistry: the chemistry of ocean color. Chem Rev 107:402–418

    Article  CAS  Google Scholar 

  • Cohen E, Levy GJ, Borisover M (2014) Fluorescent components of organic matter in wastewater: efficacy and selectivity of the water treatment. Water Res 55:323–334

    Article  CAS  Google Scholar 

  • 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 21:4030–4039

    CAS  Google Scholar 

  • 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 45:6555–6563

    Article  CAS  Google Scholar 

  • 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 43:6228–6234

    Article  CAS  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  CAS  Google Scholar 

  • 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 46:3623–3636

    Article  CAS  Google Scholar 

  • Granderson CW, Pifer AD, Fairey JL (2013) An improved chloroform surrogate for chlorine dioxide- and alum-treated waters. J Am Water Works Ass 105:45–46

    CAS  Google Scholar 

  • 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 43:863–881

    Article  CAS  Google Scholar 

  • 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 46:5511–5518

    Article  CAS  Google Scholar 

  • Hudson N, Baker A, Reynolds D (2007) Fluorescence analysis of dissolved organic matter in natural, waste and polluted waters—a review. River Res Appl 23:631–649

    Article  Google Scholar 

  • 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 37:1487–1496

    Article  CAS  Google Scholar 

  • 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 21:7489–7500

    Article  CAS  Google Scholar 

  • 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 46:2006–2017

    Article  CAS  Google Scholar 

  • 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 26:1551–1559

    Article  CAS  Google Scholar 

  • 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 47:4433–4450

    Article  CAS  Google Scholar 

  • Lee W, Westerhoff P, Croue JP (2007) Dissolved organic nitrogen as a precursor for chloroform, dichloroacetonitrile, N-Nitrosodimethylamine, and trichloronitromethane. Environ Sci Technol 41:5485–5490

    Article  CAS  Google Scholar 

  • 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 90:237–244

    Article  CAS  Google Scholar 

  • Leenheer JA, Croue JP (2003) Characterizing aquatic dissolved organic matter. Environ Sci Technol 37:18A–26A

    Article  CAS  Google Scholar 

  • 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 42:3173–3181

    Article  CAS  Google Scholar 

  • Li Y, Li AM, Xu J, Li WW, Yu HQ (2013) Formation of soluble microbial products (SMP) by activated sludge at various salinities. Biodegradation 24:69–78

    Article  CAS  Google Scholar 

  • 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 48:2603–2609

    Article  CAS  Google Scholar 

  • 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 159:412–420

    Article  CAS  Google Scholar 

  • 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 264:411–419

    Article  CAS  Google Scholar 

  • 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 22:1289–1295

    Google Scholar 

  • 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 16:1290-1299

  • Matilainen A, Vepsäläinen M, Sillanpää M (2010) Natural organic matter removal by coagulation during drinking water treatment: a review. Adv Colloid Interface 159:189–197

    Article  CAS  Google Scholar 

  • Matthews BJH, Jones AC, Theodorou NK, Tudhope AW (1996) Excitation-emission-matrix fluorescence spectroscopy applied to humic acid bands in coral reefs. Mar Chem 55:317–332

    Article  CAS  Google Scholar 

  • Mobed JJ, Hemmingsen SL, Autry JL, McGown LB (1996) Fluorescence characterization of IHSS humic substances: total luminescence spectra with absorbance correction. Environ Sci Technol 30:3061–3065

    Article  CAS  Google Scholar 

  • 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 108:40–58

    Article  CAS  Google Scholar 

  • 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 45:2909–2916

    Article  CAS  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. Anal Methods 6:658–661

    Article  CAS  Google Scholar 

  • 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 43:1350–1358

    Article  CAS  Google Scholar 

  • 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 113:158–164

    Article  CAS  Google Scholar 

  • 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 21:2122–2131

    Article  CAS  Google Scholar 

  • 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 42:442–448

    Article  CAS  Google Scholar 

  • 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 31:1765–1781

    Article  CAS  Google Scholar 

  • 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 12:114–125

    Article  CAS  Google Scholar 

  • 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 46:2927–2936

    Article  CAS  Google Scholar 

  • Pifer AD, Fairey JL (2014) Suitability of organic matter surrogates to predict trihalomethane formation in drinking water sources. Environ Eng Sci 31:117–126

    Article  CAS  Google Scholar 

  • 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 63:200–211

    Article  CAS  Google Scholar 

  • 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 636:178–242

    Article  CAS  Google Scholar 

  • 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 47:1679–1690

    Article  CAS  Google Scholar 

  • 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 48:1582–1591

    Article  CAS  Google Scholar 

  • 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

    Article  Google Scholar 

  • 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 464:33–42

    Article  CAS  Google Scholar 

  • 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 49:212–228

    Article  CAS  Google Scholar 

  • 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 415–416:336–345

    Article  Google Scholar 

  • 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 40:1233–1239

    Article  CAS  Google Scholar 

  • 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 28:882–894

    Article  CAS  Google Scholar 

  • Shon HK, Vigneswaran S, Snyder SA (2006) Effluent organic matter (EfOM) in wastewater: constituents, effects, and treatment. Crit Rev Env Sci Tec 36:327–374

    Article  CAS  Google Scholar 

  • 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 54:159–169

    Article  CAS  Google Scholar 

  • 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 41:2941–2950

    Article  CAS  Google Scholar 

  • 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 21:3181–3189

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  • Stedmon CA, Markager S, Bro R (2003) Tracing dissolved organic matter in aquatic environments using a new approach to fluorescence spectroscopy. Mar Chem 82:239–254

    Article  CAS  Google Scholar 

  • 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 45:6030–6038

    Article  CAS  Google Scholar 

  • 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 45:3880–3886

    Article  CAS  Google Scholar 

  • 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 61:97–107

    Article  CAS  Google Scholar 

  • 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 14:1771–1786

    Article  CAS  Google Scholar 

  • 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 121:84–91

  • Yu GH, He PJ, Shao LM (2010) Novel insights into sludge dewaterability by fluorescence excitation-emission matrix combined with parallel factor analysis. Water Res 44:797–806

    Article  CAS  Google Scholar 

  • 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 144:595–601

    Article  CAS  Google Scholar 

  • 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 337:67–75

    Article  CAS  Google Scholar 

  • 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:e42270

    Article  CAS  Google Scholar 

  • 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 49:283–289

    Article  CAS  Google Scholar 

Download references

Acknowledgments

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

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Jin Hur.

Additional information

Responsible editor: Philippe Garrigues

Electronic supplementary material

Below is the link to the electronic supplementary material.

ESM 1

(DOC 244 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Yang, L., Hur, J. & Zhuang, W. Occurrence and behaviors of fluorescence EEM-PARAFAC components in drinking water and wastewater treatment systems and their applications: a review. Environ Sci Pollut Res 22, 6500–6510 (2015). https://doi.org/10.1007/s11356-015-4214-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-015-4214-3

Keywords

Navigation