Achievements and future trends in the analysis of emerging organic contaminants in environmental samples by mass spectrometry and bioanalytical techniques

doi:10.1016/j.chroma.2012.07.024

Journal of Chromatography A

Volume 1259, 12 October 2012, Pages 86-99

https://doi.org/10.1016/j.chroma.2012.07.024 Get rights and content

Abstract

Several groups of organic compounds have emerged as particularly relevant as environmental pollutants. These compounds, including new brominated flame retardants, disinfection by-products, drugs of abuse and their metabolites, hormones and other endocrine disrupting compounds, nanomaterials, perfluoroalkyl substances, pharmaceuticals and siloxanes among others, constitute new risks for environmental and human health. In order to face up to these new risk challenges there is an increasing need to assess their occurrence and behaviour in the environment, as well as, that of their degradation products. Therefore, during recent years an important part of research has been focused on to the improvement of analytical schemes for complex matrices, in which the new tendencies in sample preparation (e.g. online clean up systems), the development of new materials and new mass spectrometry analysers have played an important role. This paper presents a general overview of new analytical trends and potentials in trace analysis of emerging pollutants in the environment, including chromatographic techniques coupled to mass spectrometry, and bio analytical approaches (biosensors).

Highlights

► Overview of new trends for the analysis of emerging pollutants in the environment. ► Online sample pre-treatments are presented and discussed. ► New clean up tendencies are discussed. ► Advanced LC separation and tandem mass spectrometric detection are revised. ► Biosensing technologies are also presented as complementary tools.

Introduction

At present one of the great challenges in environmental analysis is the control of the risks associated to mixtures of emerging contaminants, which are continuously changing. Therefore, one of the major trends in analytical chemistry is to develop fast and efficient procedures for the trace analysis of target and non-target organic compounds in complex matrices. The improvements achieved during the last years in terms of sensitivity are mostly due to the development of hyphenated chromatography-mass spectrometry techniques, which are today's methods of choice for the determination of trace organic analytes in environmental and biological samples. However, multi-residue methods, shortening of the analytical run times, increasing the automation of analytical processes and reducing the volumes of solvent involved in the whole analytical process continue being a challenge.

In order to face up to such needs and to improve the analytical schemes for complex matrices, the new tendencies in sample preparation, online clean up systems, the development of new materials and new mass spectrometry analysers have played an important role.

Today, there are several groups of organic compounds that emerge as particularly relevant, including:

•
Brominated flame retardants – new groups in addition to PBDEs.
•
Disinfection by-products.
•
Drugs of abuse and their metabolites.
•
Hormones and other endocrine disrupting compounds.
•
Nanomaterials.
•
Organophosphate flame-retardants and plasticizers.
•
Perfluorinated compounds.
•
Pharmaceuticals and personal care products.
•
Polar pesticides and their degradation/transformation products.
•
Siloxanes

During recent years different review articles [1], [2], [3], [4], [5], [6], [7], [8] have presented and discussed the main analytical techniques used for the determination of the above mentioned groups of analytes, therefore, in this review we will focus on new trends in analysis of these emerging pollutants, including new bio analytical approaches.

Section snippets

Sample preparation

Trace analysis of organic contaminants in environmental samples is always challenging due to the complexity and diversity of sample matrices. Matrix-dependent signal suppression or enhancement represents a major drawback in quantitative analysis of complex samples with LC coupled to atmospheric pressure ionization (API)-MS. Because matrix effects might exert a detrimental impact on important method parameters (limit of detection (LOD), limit of quantification (LOQ), linearity, accuracy, and

Recent trends and advances in LC separation

Nowadays, main objective of analytical laboratories analysing emerging contaminants in environmental samples is to develop reliable, fast and efficient procedures for performing quantitative target analysis and less frequently qualitative non-target analysis. Impressive improvements in detection limits for organic contaminants have pushed the target concentrations from the microgram to the nanograms, or picograms per litre range. Detection at sub-ppt concentrations is becoming routine for many

Multidimensional gas chromatography approaches

During recent years the most significant advances related to gas chromatography approaches for environmental analysis have been achieved through multidimensional gas chromatography, and different reviews have summarized recent publications [61], [62]. In general, these techniques offer increased peak capacity, improved resolution and enhanced mass sensitivity.

Tandem mass spectrometric detection

LC coupled to single quadrupole gained popularity and became one of the preferred techniques for analysing polar compounds in biological, environmental and food samples [36], [85]. The combination of atmospheric pressure ionization (API)-MS with separation techniques, such as LC or ultra performance LC (UPLC), became the method of choice in the analysis of small polar organic molecules. Single quadrupole offered good sensitivity, but when very complex matrices were investigated, insufficient

Bioanalytical techniques

The use of bioanalytical results as complementary information to chemical analysis on micro contaminants in mixtures, as well as the development of biosensors and other biological approaches, has grown steadily for environmental analysis in recent years. Biomonitoring is an essential tool for rapid and cost effective environmental monitoring and during the last fifteen years relevant support has been provided by public institutions for biosensor research in the USA, Japan and, especially, in

Perspectives

In the analysis of emerging polar organic compounds in environmental samples, LC–MS techniques are the best established ones. Sample preparation, extraction and clean up steps have also presented a high improved during recent years, specially in terms of automation and the development on online SPE technologies, reducing the sample manipulation, the time of analysis and minimising the quantities of sample required for the analysis. In addition, in these first steps of the analysis (sample

Acknowledgements

This material is based upon work supported by the Spanish Ministry of Economy and Competitiveness through the projects SCARCE (Consolider-Ingenio 2010 CSD2009-00065), CEMAGUA (CGL2007-64551/HID), and Nano-Trojan (CTM-2011-24051).

References (173)

L. Kantiani et al.
Trend Anal. Chem.
(2009)
S.D. Richardson
Encyclopedia Environ. Health
(2011)
M.S. Díaz-Cruz et al.
Trend Anal. Chem.
(2009)
T.H. Boles et al.
J. Chromatogr. A
(2010)
E. Björklund et al.
Trend Anal. Chem.
(2006)
R. Carabias-Martínez et al.
J. Chromatogr. A
(2005)
D.L. Deng et al.
J. Chromatogr. A
(2012)
Y. Li et al.
J. Chromatogr. A
(2011)
Y. Qiao et al.
Talanta
(2009)
J. Ding et al.
Anal. Chim. Acta
(2009)

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ReviewAchievements and future trends in the analysis of emerging organic contaminants in environmental samples by mass spectrometry and bioanalytical techniques

Abstract

Highlights

Introduction

Section snippets

Sample preparation

Recent trends and advances in LC separation

Multidimensional gas chromatography approaches

Tandem mass spectrometric detection

Bioanalytical techniques

Perspectives

Acknowledgements

Trend Anal. Chem.

Encyclopedia Environ. Health

Trend Anal. Chem.

J. Chromatogr. A

Trend Anal. Chem.

J. Chromatogr. A

J. Chromatogr. A

J. Chromatogr. A

Talanta

Anal. Chim. Acta

Talanta

Anal. Chim. Acta

J. Chromatogr. A

J. Chromatogr. A

Anal. Chim. Acta

Biosens. Bioelectron.

J. Chromatogr. A

J. Chromatogr. A

Anal. Chim. Acta

J. Chromatogr. A

TRAC–Trend Anal. Chem.

J. Chromatogr. A

J. Chromatogr. A

J. Chromatogr. A

J. Chromatogr. A

Talanta

J. Chromatogr. A

J. Chromatogr. A

J. Chromatogr. A

Trend Anal. Chem.

J. Chromatogr. A

J. Chromatogr. A

Anal. Chim. Acta

J. Chromatogr. A

J. Chromatogr. A

J. Chromatogr. A

Anal. Chim. Acta

J. Chromatogr. A

Trend Anal. Chem.

Trend Anal. Chem.

J. Chromatogr. A

J. Chromatogr. A

J. Chromatogr. A

J. Chromatogr. A

Anal. Chim. Acta

J. Chromatogr. A

J. Chromatogr. A

J. Chromatogr. A

J. Chromatogr. A

J. Chromatogr. A

Review
Achievements and future trends in the analysis of emerging organic contaminants in environmental samples by mass spectrometry and bioanalytical techniques