Skip to main content
Log in

New trends in the analytical determination of emerging contaminants and their transformation products in environmental waters

  • Wastewater Reuse Applications and Contaminants of Emerging Concern (WRA & CEC 2012)
  • Published:
Environmental Science and Pollution Research Aims and scope Submit manuscript

Abstract

Since the so-called emerging contaminants were established as a new group of pollutants of environmental concern, a great effort has been devoted to the knowledge of their distribution, fate and effects in the environment. After more than 20 years of work, a significant improvement in knowledge about these contaminants has been achieved, but there is still a large gap of information on the growing number of new potential contaminants that are appearing and especially of their unpredictable transformation products. Although the environmental problem arising from emerging contaminants must be addressed from an interdisciplinary point of view, it is obvious that analytical chemistry plays an important role as the first step of the study, as it allows establishing the presence of chemicals in the environment, estimate their concentration levels, identify sources and determine their degradation pathways. These tasks involve serious difficulties requiring different analytical solutions adjusted to purpose. Thus, the complexity of the matrices requires highly selective analytical methods; the large number and variety of compounds potentially present in the samples demands the application of wide scope methods; the low concentrations at which these contaminants are present in the samples require a high detection sensitivity, and high demands on the confirmation and high structural information are needed for the characterisation of unknowns. New developments on analytical instrumentation have been applied to solve these difficulties. Furthermore and not less important has been the development of new specific software packages intended for data acquisition and, in particular, for post-run analysis. Thus, the use of sophisticated software tools has allowed successful screening analysis, determining several hundreds of analytes, and assisted in the structural elucidation of unknown compounds in a timely manner.

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
Fig. 4
Fig. 5

Similar content being viewed by others

References

  • Agüera A, Gómez-Ramos MM, Fernandez-Alba AR (2012) Chemical evaluation of water treatment processes by LC–(Q)TOF-MS: identification of transformation products. In: Fernandez-Alba AR (ed) TOF-MS within food and environmental analysis. Comprehensive analytical chemistry 58. Elsevier, Amsterdam, pp 217–272

    Google Scholar 

  • Berset JD, Brenneisen R, Mathieu C (2010) Analysis of llicit and illicit drugs in waste, surface and lake water samples using large volume direct injection high performance liquid chromatography - Electrospray tandem mass spectrometry (HPLC-MS/MS). Chemosphere 81:859–866

    Article  CAS  Google Scholar 

  • Bijlsma L, Sancho JV, Pitarch E, Ibáñez M, Hernández F (2009) Simultaneous ultra-high-pressure liquid chromatography–tandem mass spectrometry determination of amphetamine and amphetamine-like stimulants, cocaine and its metabolites, and a cannabis metabolite in surface water and urban wastewater. J Chromatogr A 1216:3078–3089

    Article  CAS  Google Scholar 

  • Boleda MR, Huerta-Fontela M, Ventura F, Galceran MT (2011) Evaluation of the presence of drugs of abuse in tap waters. Chemosphere 84:1601–1607

    Article  CAS  Google Scholar 

  • Cahill MG, Dineen BA, Stack MA, James KJ (2012) A critical evaluation of liquid chromatography with hybrid linear ion trap-Orbitrap mass spectrometry for the determination of acidic contaminants in wastewater effluents. J Chromatogr A 1270:88-95

    Google Scholar 

  • Candela L, Fabregat S, Josa A, Suriol J, Vigués N, Mas J (2007) Assessment of soil and groundwater impacts by treated urban wastewater reuse. A case study: application in a golf course (Girona, Spain). Sci Total Environ 374:26–35

    Article  CAS  Google Scholar 

  • De Jongh CM, Kooij PJF, De Voogt P, Ter Laak TL (2012) Screening and human health risk assessment of pharmaceuticals and their transformation products in Dutch surface waters and drinking water. Sci Total Environ 427–428:70–77

    Article  Google Scholar 

  • Durand S, Sancelme M, Besse-Hoggan P, Combourieu B (2010) Biodegradation pathway of mesotrione: complementarities of NMR, LC-NMR and LC-MS for qualitative and quantitative metabolic profiling. Chemosphere 81:372–380

    Article  CAS  Google Scholar 

  • Eichhorn P, Pérez S, Barceló D et al (2012) Time-of-flight mass spectrometry versus Orbitrap-based mass spectrometry for the screening and identification of drugs and metabolites: is there a winner? In: Fernandez-Alba AR (ed) TOF-MS within food and environmental analysis. Comprehensive analytical chemistry 58. Elsevier, Amsterdam, pp 217–272

    Google Scholar 

  • Escher BI, Fenner K (2011) Recent advances in environmental risk assessment of transformation products. Environ Sci Technol 45:3835–3847

    Article  CAS  Google Scholar 

  • Fatta-Kassinos D, Vasquez MI, Kümmerer K (2011a) Transformation products of pharmaceuticals in surface waters and wastewater formed during photolysis and advanced oxidation processes—Degradation, elucidation of byproducts and assessment of their biological potency. Chemosphere 85:693–709

    Article  CAS  Google Scholar 

  • Fatta-Kassinos D, Kalavrouziotis IK, Koukoulakis PH, Vasquez MI (2011b) The risks associated with wastewater reuse and xenobiotics in the agroecological environment. Sci Total Environ 409:3555–3563

    Article  CAS  Google Scholar 

  • Fischer K, Fries E, Körner W, Schmalz C, Zwiener C (2012) New developments in the trace analysis of organic water pollutants. Appl Microbiol Biotechnol 94:11–28

    Article  CAS  Google Scholar 

  • Godejohann M, Heintz L, Daolio C, Berset J-D, Muff D (2009) Comprehensive non-targeted analysis of contaminated groundwater of a former ammunition destruction site using 1H-NMR and HPLC-SPE-NMR/TOF-MS. Environ Sci Technol 43:7055–7061

    Article  CAS  Google Scholar 

  • Godejohann M, Berset J, Muff D (2011) Non-targeted analysis of wastewater treatment plant effluents by high performance liquid chromatography-time slice-solid phase extraction-nuclear magnetic resonance/time-of-flight-mass spectrometry. J Chromatogr A 1218:9202–9209

    Article  CAS  Google Scholar 

  • Gómez MJ, Sirtori C, Mezcua M, Fernández-Alba AR, Agüera A (2008) Photodegradation study of three dipyrone metabolites in various water systems: identification and toxicity of their photodegradation products. Water Res 42:2698–2706

    Article  Google Scholar 

  • Gómez MJ, Gómez-Ramos MM, Malato O, Mezcua M, Férnandez-Alba AR (2010) Rapid automated screening, identification and quantification of organic micro-contaminants and their main transformation products in wastewater and river waters using liquid chromatography-quadrupole-time-of-flight mass spectrometry with an accurate-mass database. J Chromatogr A 1217:7038–7054

    Article  Google Scholar 

  • Gómez MJ, Herrera S, Solé D, García-Calvo E, Fernández-Alba AR (2011) Automatic searching and evaluation of priority and emerging contaminants in wastewater and river water by stir bar sorptive extraction followed by comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry. Anal Chem 83:2638–2647

    Article  Google Scholar 

  • Gómez MJ, Herrera S, Solé D, García-Calvo E, Fernández-Alba AR (2012) Spatio-temporal evaluation of organic contaminants and their transformation products along a river basin affected by urban, agricultural and industrial pollution. Sci Total Environ 420:134–145

    Google Scholar 

  • Gómez-Ramos MM, Pérez-Parada A, García-Reyes JF, Fernández-Alba AR, Agüera A (2011) Use of an accurate-mass database for the systematic identification of transformation products of organic contaminants in wastewater effluents. J Chromatogr A 1218:8002–8012

    Article  Google Scholar 

  • González-Mariño I, Benito Quintana J, Rodríguez I, Rodil R, González-Peñas J, Cela R (2009) Comparison of molecularly imprinted, mixed-mode and hydrophilic balance sorbents performance in the solid-phase extraction of amphetamine drugs from wastewater samples for liquid chromatography–tandem mass spectrometry determination. J Chromatogr A 1216:8435–8441

    Article  Google Scholar 

  • Grabic R, Fick J, Lindberg RH, Fedorova G, Tysklind M (2012) Multi-residue method for trace level determination of pharmaceuticals in environmental samples using liquid chromatography coupled to triple quadrupole mass spectrometry. Talanta 100:183–195

    Article  CAS  Google Scholar 

  • Gros M, Rodríguez-Mozaz S, Barcelo D (2012) Fast and comprehensive multi-residue analysis of a broad range of human and veterinary pharmaceuticals and some of their metabolites in surface and treated waters by ultra-high-performance liquid chromatography coupled to quadrupole-linear ion trap tandem mass spectrometry. J Chromatogr A 1248:104–121

    Article  CAS  Google Scholar 

  • Hernández F, Ibáñez M, Pozo OJ, Sancho JV (2008) Investigating the presence of pesticide transformation products in water by using liquid chromatography-mass spectrometry with different mass analyzers. J Mass Spectrom 43:173–184

    Article  Google Scholar 

  • Hill DW, Kertesz TM, Fontaine D, Friedman R, Grant DF (2008) Mass spectral metabonomics beyond elemental formula: chemical database querying by matching experimental with computational fragmentation spectra. Anal Chem 80:5574–5582

    Article  CAS  Google Scholar 

  • Hogenboom AC, Van Leerdam JA, De Voogt P (2009) Accurate mass screening and identification of emerging contaminants in environmental samples by liquid chromatography-hybrid linear ion trap Orbitrap mass spectrometry. J Chromatogr A 1216:510–519

    Article  CAS  Google Scholar 

  • Huntscha S, Singer HP, McArdell CS, Frank CE, Hollender J (2012) Multiresidue analysis of 88 polar organic micropollutants in ground, surface and wastewater using online mixed-bed multilayer solid-phase extraction coupled to high performance liquid chromatography-tandem mass spectrometry. J Chromatogr A 1268:74–83

    Article  CAS  Google Scholar 

  • Ibáñez M, Sancho JV, Pozo OJ, Hernández F (2011) Use of quadrupole time-of-flight mass spectrometry to determine proposed structures of transformation products of the herbicide bromacil after water chlorination. Rapid Commun Mass Spectrom 25:3103–3113

    Article  Google Scholar 

  • Kasprzyk-Horderna B, Dinsdale RM, Guwy AJ (2009) The removal of pharmaceuticals, personal care products, endocrine disruptors and illicit drugs during wastewater treatment and its impact on the quality of receiving waters. Water Res 43:363–380

    Article  Google Scholar 

  • Kaufmann A, Butcher P, Maden K, Walker S, Widmer M (2010) Comprehensive comparison of liquid chromatography selectivity as provided by two types of liquid chromatography detectors (high resolution mass spectrometry and tandem mass spectrometry): “where is the crossover point?”. Anal Chim Acta 673:60–72

    Article  CAS  Google Scholar 

  • Kind T, Fiehn O (2010) Advances in structure elucidation of small molecules using mass spectrometry. Bioanal Rev 2:23–60

    Article  Google Scholar 

  • Krauss M, Hollender J (2008) Analysis of nitrosamines in wastewater: exploring the trace level quantification capabilities of a hybrid linear ion trap/Orbitrap mass spectrometer. Anal Chem 80:834–842

    Article  CAS  Google Scholar 

  • Krauss M, Singer H, Hollender J (2010) LC-high resolution MS in environmental analysis: from target screening to the identification of unknowns. Anal Biochem Chem 397:943–951

    CAS  Google Scholar 

  • Lajeunesse A, Gagnon C, Sauvé S (2008) Determination of basic antidepressants and their N-desmethyl metabolites in raw sewage and wastewater using solid-phase extraction and liquid chromatography-tandem mass spectrometry. Anal Chem 80:5325–5333

    Article  CAS  Google Scholar 

  • Langford K, Thomas KV (2011) Input of selected human pharmaceutical metabolites into the Norwegian aquatic environment. J Environ Monit 13:416–421

    Article  CAS  Google Scholar 

  • Leclercq M, Mathieu O, Gomez E, Casellas C, Fenet H, Hillaire-Buys D (2009) Presence and fate of carbamazepine, oxcarbazepine, and seven of their metabolites at wastewater treatment plants. Arch Environ Contam Toxicol 56:408–415

    Article  CAS  Google Scholar 

  • Li D, Yang M, Hu J, Zhang Y, Chang H, Jin F (2008) Determination of penicillin G and its degradation products in a penicillin production wastewater treatment plant and the receiving river. Water Res 42:307–317

    Article  CAS  Google Scholar 

  • Loos R, Locoro G, Contini S (2010) Occurrence of polar organic contaminants in the dissolved water phase of the Danube River and its major tributaries using SPE-LC-MS2 analysis. Water Res 44:2325–2335

    Article  CAS  Google Scholar 

  • López-Serna R, Petrovic M, Barceló D (2012) Direct analysis of pharmaceuticals, their metabolites and transformation products in environmental waters using on-line TurboFlowTM chromatography–liquid chromatography–tandem mass spectrometry. J Chromatogr A 1252:115–129

    Article  Google Scholar 

  • Malato O, Lozano A, Mezcua M, Agüera A, Fernandez-Alba AR (2011) Benefits and pitfalls of the application of screening methods for the analysis of pesticide residues in fruits and vegetables. J Chromatogr A 1218:7615–7626

    Article  CAS  Google Scholar 

  • Martínez Bueno MJ, Agüera A, Gómez MJ, Hernando MD, García-Reyes JF, Fernández-Alba AR (2007) Application of liquid chromatography/quadrupole-linear ion trap mass spectrometry and time-of-flight mass spectrometry to the determination of pharmaceuticals and related contaminants in wastewater. Anal Chem 79:9372–9384

    Article  Google Scholar 

  • Martínez Bueno MJ, Agüera A, Hernando MD, Gómez MJ, Fernández-Alba AR (2009) Evaluation of various liquid chromatography–quadrupole-linear ion trap–mass spectrometry operation modes applied to the analysis of organic pollutants in wastewaters. J Chromatogr A 1216:5995–6002

    Article  Google Scholar 

  • Martínez Bueno MJ, Hernando MD, Herrera S, Gómez MJ, Fernández-Alba AR, Bustamante I, García-Calvo E (2010) Pilot survey of chemical contaminants from industrial and human activities in river waters of Spain. Int J Environ Anal Chem 90:321–343

    Article  Google Scholar 

  • Martínez Bueno MJ, Uclés S, Hernando MD, Fernández-Alba AR (2011a) Development of a solvent-free method for the simultaneous identification/quantification of drugs of abuse and their metabolites in environmental water by LC-MS/MS. Talanta 85:157–166

    Article  Google Scholar 

  • Martínez Bueno MJ, Uclés S, Hernando MD, Dàvoli E, Fernández-Alba AR (2011b) Evaluation of selected ubiquitous contaminants in the aquatic environment and their transformation products. A pilot study of their removal from a sewage treatment plant. Water Res 45:2331–2341

    Article  Google Scholar 

  • Martínez Bueno MJ, Gomez MJ, Herrera S, Hernando MD, Agüera A, Fernández-Alba AR (2012a) Occurrence and persistence of organic emerging contaminants and priority pollutants in five sewage treatment plants of Spain: two years pilot survey monitoring. Environ Pollut 164:267–273

    Article  Google Scholar 

  • Martínez Bueno MJ, Ulaszewska MM, Gomez MJ, Hernando MD, Fernández-Alba AR (2012b) Simultaneous measurement in mass and mass/mass mode for accurate qualitative and quantitative screening analysis of pharmaceuticals in river water. J Chromatogr A 1256:80–88

    Article  Google Scholar 

  • Mueller CA, Weinmann W, Dresen S, Schreiber A, Gergov M (2005) Development of a multi-target screening analysis for 301 drugs using a QTrap liquid chromatography/tandem mass spectrometry system and automated library searching. Rapid Commun Mass Spectrom 19:1332–1338

    Article  CAS  Google Scholar 

  • Muñoz I, Gómez-Ramos MJ, Agüera A, Fernández-Alba AR, García-Reyes JF, Molina-Díaz A (2009) Chemical evaluation of contaminants in wastewater effluents and the environmental risk of reusing effluents in agriculture. Trends Anal Chem 28:676–694

    Article  Google Scholar 

  • Regulation (EC) N◦ 1907/2006 of the Parliament and of the Council of 18 December 2006), concerning the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) establishing a European Chemicals Agency, amending Directive 1999/45/EC and repealing Council Regulation (EEC) N◦ 793/93 and Commission Regulation (EC) N◦ 1488/94 as well as Council Directive 76/769/EEC

  • Neumann S, Böcker S (2010) Computational mass spectrometry for metabolomics: identification of metabolites and small molecules. Anal Bioanal Chem 398:2779–2788

    Article  CAS  Google Scholar 

  • Pérez S, Eichhorn P, Barceló D (2007) Structural characterization of photodegradation products of enalapril and its metabolite enalaprilat obtained under simulated environmental conditions by hybrid quadrupole-linear ion trap-MS and quadrupole-time-of-flight-MS. Anal Chem 79:8293–8300

    Article  Google Scholar 

  • Pérez-Parada A, Gómez-Ramos MM, Martínez Bueno MJ, Uclés S, Uclés A, Fernández-Alba AR (2012) Analytical improvements of hybrid LC-MS/MS techniques for the efficient evaluation of emerging contaminants in river waters: a case study of the Henares River (Madrid, Spain). Environ Sci Pollut Res 19:467–481

    Article  Google Scholar 

  • Petrovic M, Farré M, Lopez de Alda M, Perez S, Postigo C, Köck M, Radjenovic J, Gros M, Barcelo D (2010) Recent trends in the liquid chromatography–mass spectrometry analysis of organic contaminants in environmental samples. J Chromatogr A 1217:4004–4017

    Article  CAS  Google Scholar 

  • Postigo C, Lopez de Alda MJ, Barcelo D (2008) Fully automated determination in the low nanogram per liter level of different classes of drugs of abuse in Sewage water by on-line solid-phase extraction-liquid chromatography-electrospray-tandem mass spectrometry. Anal Chem 80:3123–3134

    Article  CAS  Google Scholar 

  • Prakash C, Shaffer CL, Nedderman A (2007) Analytical strategies for identifying drug metabolites. Mass Spectrom Rev 26:340

    Article  CAS  Google Scholar 

  • Prasse C, Wagner M, Schulz R, Ternes TA (2011) Biotransformation of the antiviral drugs acyclovir and penciclovir in activated sludge treatment. Environ Sci Technol 45:2761–2769

    Article  CAS  Google Scholar 

  • Richardson SD (2011) Environmental mass spectrometry: emerging contaminants and current issues. Anal Chem 84:747–778

    Article  Google Scholar 

  • Rúa-Gómez PC, Püttmann W (2012) Occurrence and removal of lidocaine, tramadol, venlafaxine, and their metabolites in German wastewater treatment plants. Environ Sci Pollut Res 19:689–699

    Article  Google Scholar 

  • Santiago-Morales J, Agüera A, Gómez MDM, Fernández-Alba AR, Giménez J, Esplugas S, Rosal R (2013) Transformation products and reaction kinetics in simulated solar light photocatalytic degradation of propranolol using Ce-doped TiO2. Appl Catal B Environ 129:13-29

    Google Scholar 

  • Schriks M, Van Leerdam JA, Van Der Linden SC, Van Der Burg B, Van Wezel AP, De Voogt P (2010) High-resolution mass spectrometric identification and quantification of glucocorticoid compounds in various wastewaters in The Netherlands. Environ Sci Technol 44:4766–4774

    Article  CAS  Google Scholar 

  • Sirtori C, Zapata A, Oller I, Gernjak W, Agüera A, Malato S (2009) Solar photo-fenton as finishing step for biological treatment of a pharmaceutical wastewater. Environ Sci Technol 43:1185–1191

    Article  CAS  Google Scholar 

  • Skotnicka-Pitak J, Khunjar WO, Love NG, Aga DS (2009) Characterization of metabolites formed during the biotransformation of 17α-ethinylestradiol by Nitrosomonas europaea in batch and continuous flow bioreactors. Environ Sci Technol 43:3549–3555

    Article  CAS  Google Scholar 

  • Sturm S, Seger C (2012) Liquid chromatography-nuclear magnetic resonance coupling as alternative to liquid chromatography-mass spectrometry hyphenations: curious option or powerful and complementary routine tool? J Chromatogr A 1259:50–61

    Article  CAS  Google Scholar 

  • Terzic S, Ahel M (2011) Nontarget analysis of polar contaminants in freshwater sediments influenced by pharmaceutical industry using ultra-highpressure liquid chromatography-quadrupole time-of-flight mass spectrometry. Environ Pollut 159:557–566

    Article  CAS  Google Scholar 

  • Trovó AG, Nogueira RFP, Agüera A, Sirtori C, Fernández-Alba AR (2009) Photodegradation of sulfamethoxazole in various aqueous media: persistence, toxicity and photoproducts assessment. Chemosphere 77:1292–1298

    Article  Google Scholar 

  • Van Nuijs ALN, Tarcomnicu I, Bervoets L, Blust R, Jorens PG, Neels H, Covaci A (2009) Analysis of drugs of abuse in wastewater by hydrophilic interaction liquid chromatography–tandem mass spectrometry. Anal Bioanal Chem 395:819–828

    Article  Google Scholar 

  • Vasskog T, Anderssen T, Pedersen-Bjergaard S, Kallenborn R, Jensen E (2008) Occurrence of selective serotonin reuptake inhibitors in sewage and receiving waters at Spitsbergen and in Norway. J Chromatogr A 1185:194–205

    Article  CAS  Google Scholar 

  • Viglino L, Aboulfadl K, Daneshvar Mahvelat A, Prévost M, Sauve S (2008) On-line solid phase extraction and liquid chromatography/tandem mass spectrometry to quantify pharmaceuticals, pesticides and some metabolites in wastewaters, drinking, and surface waters. J Environ Monit 10:482–489

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors acknowledge the Spanish Ministry of Science and Innovation-FEDER (Project CTQ2010-20740-C03-03) for economical support.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Ana Agüera.

Additional information

Responsible editor: Hongwen Sun

Rights and permissions

Reprints and permissions

About this article

Cite this article

Agüera, A., Martínez Bueno, M.J. & Fernández-Alba, A.R. New trends in the analytical determination of emerging contaminants and their transformation products in environmental waters. Environ Sci Pollut Res 20, 3496–3515 (2013). https://doi.org/10.1007/s11356-013-1586-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-013-1586-0

Keywords

Navigation