Determination of seven pyrethroids biocides and their synergist in indoor air by thermal-desorption gas chromatography/mass spectrometry after sampling on Tenax TA s passive tubes Caroline Raeppel a,b , Brice M. Appenzeller b , Maurice Millet a,n a Institut de Chimie et Procédés pour l'Energie, l'Environnement et la Santé (ICPEES UMR 7515 CNRS – Université de Strasbourg) – 1 rue Blessig – F-67084 Strasbourg Cedex, France b Laboratory of Analytical Human Biomonitoring – CRP-Santé – Université du Luxembourg – 162 A Avenue de la Faïencerie – L-1511 Luxembourg, France article info Article history: Received 17 June 2014 Received in revised form 26 July 2014 Accepted 31 July 2014 Available online 8 August 2014 Keywords: Pyrethroids biocides TD–GC/MS Tenax TA s passive sampling Indoor air abstract A method coupling thermal desorption and gas chromatography/mass spectrometry (GC/MS) was developed for the simultaneous determination of 7 pyrethroids (allethrin, bifenthrin, cyphenothrin, imiprothrin, permethrin, prallethrin and tetramethrin) and piperonyl butoxide adsorbed on Tenax TA s passive samplers after exposure in indoor air. Thermal desorption was selected as it permits efficient and rapid extraction without solvent used together with a good sensitivity. Detection (S/N 43) and quantification (S/N410) limits varied between 0.001 ng and 2.5 ng and between 0.005 and 10 ng respectively with a reproducibility varied between 14% (bifenthrin) and 39% (permethrin). The method was used for the comparison indoor air contamination after low-pressure spraying and fumigation application in a rubbish chute situated in the basement of a building. & 2014 Elsevier B.V. All rights reserved. 1. Introduction Biocidal products are defined in the European directive 98/8/CE from 16 February 1998 as “Active substances and preparations containing one or more active substances, put up in the form in which they are supplied to the user, intended to destroy, deter, render harmless, prevent the action of, or otherwise exert a controlling effect on any harmful organism by chemical or biolo- gical means”. They are classified in four main categories “Disin- fectants and general biocidal products (i.e. human hygiene biocidal products, private area and public health area disinfectants and other biocidal products, etc.)”, “Preservatives (i.e. wood preserva- tives, in-can preservatives, etc.)”, “Pest control (i.e. rodenticides, acaricides, etc.)” and “Other biocidal products (i.e. preservatives for food or feedstocks, antifouling products, etc.)”. Biocides are used by professional and non professional users in diverse activities like the textile and leather industry where biocides are used during manufacturing and storage to protect against moths, bacteria or algae development, or the wood industry against insects or fungus contamination. Among biocides molecules, synthetic pyrethroids are widely used indoors to control households insects like mosquitoes, termites, etc. in place of more toxic insecticides such as organophosphorous and organochlorine molecules. Indeed, they are much more effective against a wide spectrum of pests than the organochlorine, organo- phosphate, and carbamate insecticides. Consequently, they are used in many applications like surface sprays in common houses, air- planes, in active or passive evaporators, in incense products, or to make textiles insect resistant [1]. Among pyrethroids available, allethrin, phenothrin, tetrame- thrin and cyphenothrin are mainly used for household insects commercially combined with synergist compounds like piperonyl butoxide [2]. When applied in confined atmosphere, their release in air is the most important route of human exposure through inhalation. Their quantification in indoor atmosphere remains consequently important for exposure assessment. Due to relatively low expected concentrations in air, sampling of airborne pyrethroids are made by pumping a large amount of air through filters and one of a combination of different adsorbents like Porapak C 18 , Chromosorb 102, Tenax GC, Carbowax 20M or polyurethane foam [4]. Analytes adsorbed on traps were solvent extracted, cleaned and analysed by gas chromatography coupled to electron capture or mass spectrometer detectors [2–4]. These sampling systems are well efficient but are requiring excessive time and are expensive especially due to the many steps involved which, in addition, could enhance the risk of analytes losses. For the particular case of pyrethroids, a risk of photode- composition has been reported [3] and a rapid and careful trapping-extraction process is recommended [2]. In addition, Contents lists available at ScienceDirect journal homepage: www.elsevier.com/locate/talanta Talanta http://dx.doi.org/10.1016/j.talanta.2014.07.098 0039-9140/& 2014 Elsevier B.V. All rights reserved. n Corresponding author. E-mail address: mmillet@unistra.fr (M. Millet). Talanta 131 (2015) 309–314