Analysis of industrial contaminants in indoor air. Part 2. Emergent contaminants and pesticides

Accepted Manuscript Title: Analysis of industrial contaminants in indoor air. Part 2. Emergent contaminants, pesticides Authors: Carmen Garcia-Jares, Jorge Regueiro, Ruth Barro, Thierry Dagnac, Maria Llompart PII: S0021-9673(08)01776-7 DOI: doi:10.1016/j.chroma.2008.10.020 Reference: CHROMA 349350 To appear in: Journal of Chromatography A Received date: 8-4-2008 Revised date: 11-9-2008 Accepted date: 8-10-2008 Please cite this article as: C. Garcia-Jares, J. Regueiro, R. Barro, T. Dagnac, M. Llompart, Analysis of industrial contaminants in indoor air. Part 2. Emergent contaminants, pesticides, Journal of Chromatography A (2008), doi:10.1016/j.chroma.2008.10.020 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. Page 1 of 69 Accepted Manuscript 1 Analysis of industrial contaminants in indoor air. Part 2. Emergent 1 contaminants and pesticides 2 3 Carmen Garcia-Jares a* , Jorge Regueiro a , Ruth Barro b , Thierry Dagnac c , Maria 4 Llompart a 5 6 a Departamento de Quimica Analitica, Nutricion y Bromatologia, Instituto de 7 Investigacion y Analisis Alimentarios, Universidad de Santiago de Compostela, 8 Santiago de Compostela 15782, Spain 9 b CIEMAT (Centro de Investigaciones Energeticas, Medioambientales y Tecnologicas), 10 Ministerio de Educacion y Ciencia, CEDER-CIEMAT, Carretera Nacional 111 Madrid-11 Soria, km 206, 42290 Lubia, Soria, Spain 12 c INGACAL, Centro de Investigacions Agrarias de Mabegondo (CIAM), Laboratory of 13 Mass Spectromerty, Consellería do Medio Rural, Xunta de Galicia, Apartado 10, E-14 15080 A Coruña, Spain 15 16 17 *Corresponding author. Phone: +34-981563100, ext. 14394, fax: +34-981595012 18 E-mail address: [email protected] 19 20 21 Abstract 22 This article reviews recent literature on the analysis of several contaminants related to 23 the industrial development in indoor air in the framework of the REACH project. In this 24 second part, the attention is focused on emergent contaminants and biocides. Among 25 these chemicals, phthalates, polybrominated and phosphate flame retardants, fragrances, 26 pesticides, as well as other emerging pollutants, are increasing their environmental and 27 health concern and are extensively found in indoor air. Some of them are suspected to 28 behave as priority organic pollutants (POPs) and/or endocrine disrupting compounds 29 (EDC), and can be found both in air and associated to the suspended particulate matter 30 (PM) and settled dust. Main literature considered for this review is from the last ten 31 years, reporting analytical developments and applications regarding the considered 32 contaminants in the indoor environment. Sample collection and pretreatment, analyte 33 extraction or desorption, clean-up procedures, determination techniques, and 34 performance results are summarized and discussed. 35 Page 2 of 69 Accepted Manuscript 2 1 Keywords 2 Indoor air; dust; emergent contaminants; phthalates; flame retardants; synthetic musks; 3 pesticides; review 4 5 Contents 6 1. Introduction 7 2. Phthalate esters 8 2.1. Sampling 9 2.2. Sample treatment 10 2.3. Determination 11 2.4. Concentration in indoor air 12 3. Brominated flame retardants 13 3.1. Sampling 14 3.2. Sample treatment 15 3.3. Determination 16 3.4. Concentration in indoor air 17 4. Organophosphate esters 18 4.1. Sampling 19 4.2. Sample treatment 20 4.3. Determination 21 4.4. Concentration in indoor air 22 5. Synthetic musk fragrances 23 5.1. Sampling 24 5.2. Sample treatment 25 5.3. Determination 26 5.4. Concentration in indoor air 27 6. Pesticides 28 6.1. Sampling 29 6.2. Sample treatment 30 6.3. Determination 31 6.4. Concentration in indoor air 32 7. Other organic contaminants 33 7.1. Sampling, sample treatment and determination 34 7.2. Concentration in indoor air 35 8. Analysis of contaminants in indoor dust and suspended particulate matter (PM) 36 Page 3 of 69 Accepted Manuscript 3 8.1. Phthalates 1 8.2. Brominated flame retardants 2 8.3. Organophosphate esters 3 8.4. Synthetic musk fragrances 4 8.5. Pesticides 5 8.6. Organotin and perfluoroalkyl compounds 6 9. References 7 8 Page 4 of 69 Accepted Manuscript 4 1. Introduction 1 People in developed countries spend up to 90% of their time indoors [1, 2]. Many 2 indoor environments can act as concentrators of emissions from plastics, paints, and 3 other building materials. Inadequate ventilation coupled with the slow indoor 4 degradation processes may increase indoor pollution levels. High temperature and 5 humidity levels can also increase concentrations of some pollutants. Besides, the high 6 comfort achieved in developed countries, increased the demand and the widespread 7 consumption of biocides and fragranced household products. Hence, inhalation of 8 indoor air is potentially the most important exposure pathway to many pollutants [2]. 9 The Registration, Evaluation and Authorisation of CHemicals (REACH) system was 10 created in the European Union (EU) in response to the ever-increasing concern about 11 the production and use of many chemical substances lacking information on their 12 environmental and health effects. REACH applies to all chemicals, not only those used 13 in industrial processes but also those used in the day-to-day life, for example in cleaning 14 products, paints, as well as in articles such as furnitures, clothes or electrical appliances 15 [3]. The chemicals that are extensively found in indoor environments include 16 compounds that are suspected to behave as POPs and endocrine disrupting compounds 17 (EDC) such as phthalate esters, polybrominated and phosphate flame retardants, 18 fragrances, pesticides, biocides, and other compounds (organotin and perfluorinated 19 alkyl compounds) that are of increasing concern as indoor pollutants. An overview of 20 the relative importance of all these compounds as environmental pollutants is presented 21 in the corresponding sections of this review as well as the recent developments and 22 applications of methodology for their analysis in indoor air including the concentration 23 levels found indoors. Sample collection and pretreatment, analyte extraction or 24 desorption, clean-up, determination techniques, and performance results are 25 summarized and discussed. 26 Research literature from the latest ten years has generally been considered. The review 27 focuses on indoor air analysis and hence, methodology developed or applied to 28 atmospheric or ambient air analysis has been excluded. At this point, a recent and useful 29 review by Xie and Ebinghaus [4] considers the determination of emergent pollutants 30 focused on the atmosphere. However, in the present review only procedures that have 31 been developed for indoor analysis, or those that can indistinctly be applied for both 32 indoor and outdoor analysis, have been taken into consideration. Main attention has 33 been paid to the analysis of the gas phase indoors. In addition, the importance of 34 domestic dust and suspended PM as vehicles of these indoor pollutants is highlighted 35 and thus, their occurrence and analysis in these solid matrices has been considered. 36 Page 5 of 69 Accepted Manuscript 5 1 2. Phthalate esters 2 Phthalate esters are extensively used as softeners in the production of polymeric 3 materials such as polyvynylchloride (PVC). Since phthalate esters are not chemically 4 bound to the polymer, they can be easily released into the environment. PVC and other 5 polymers are widely produced for building materials and thus, the surrounding 6 environment can be polluted by phthalates. Due to their high volume production and 7 their widespread use, phthalates, as well as some other chemicals present in the 8 domestic environment, are potentially important indoor contaminants. In addition, 9 people working in industrial plants producing plasticizers or living near such plants may 10 be exposed, via indoor air inhalation, to levels of these pollutants that could constitute a 11 significant contribution to the total daily intake [5]. 12 Due to their ubiquity, phthalates can be found everywhere, including common 13 laboratory equipment and reagents. In consequence, the main problem in phthalate 14 analysis is external contamination coming from the sampling and sample preparation 15 procedure and even the chromatographic analysis. This problem has been extensively 16 studied by Frankhauser and Grob [6]. The analysis of blanks is of great importance, as 17 are all the precautions in the treatment of the material and reagents used in any step of 18 the analytical process. To minimize contamination [7,8], the use of plastic materials 19 should be avoided, the sample preparation procedure should be as simple as possible 20 with minimal extraction steps, and minimal glassware used. Glassware should be 21 properly cleaned by solvent rinsing and thermal treatment at 400ºC. Prior to use, the it 22 should be rinsed with blank tested organic solvent (cyclohexane or isooctane) to 23 deactivate the surface. Organic solvents and laboratory grade water usually contain 24 traces of phthalates, even the ones commonly available for trace analysis, and these 25 must be checked to establish background levels. Also, reagents need to be checked. 26 Additional contamination of material, water solvents, and reagents can occur due to the 27 laboratory air. The material should be stored in a closed container or wrapped in 28 aluminium foil to avoid adsorption of phthalates from the air. As previously commented, 29 phthalates can be present in the chromatographic system and the most important 30 contamination source is located in the inlet and gas supply system, inlet septa, liners and 31 o-rings. Since the caps for autosampler vials also contain phthalates, as general 32 precaution, only one injection should be made from each vial [9]. 33 34 Page 6 of 69 Accepted Manuscript 6 2.1. Sampling 1 In Table 1, details on the analysis of phthalate esters in indoor air samples are illustrated 2 [5,10,11,17]. Sample volumes of 1 to 10 m 3 of air are usually enough [5,10], although 3 procedures working with only 15 L of indoor air samples have also been reported 4 achieving detection limits in the low ng m -3 [15]. The analysis of atmospheric levels of 5 phthalates would however require higher sample volumes of up to 1000 m 3 [18]. The 6 devices currently employed to retain the target compounds are cartridges filled with the 7 sorbent material retained by glass wool. Such material can be polyurethane foam (PUF), 8 Tenax GR, polydimethylsiloxane (PDMS) on Chromosorb, octadecylsilica, charcoal, or 9 combinations of various sorbents like PUF and XAD resin. To prevent possible 10 contamination, sorbent materials are usually preextracted by Soxhlet using different 11 solvents or solvent mixtures [10] Breakthrough air volumes for each analyte need to be 12 previously determined to select the maximum sample volume that can be concentrated 13 [6]. In some studies, phthalates in PM are also the object of analysis. Collection of 14 suspended solid particles can be accomplished by placing a particle quartz fiber filter 15 (QFF) in front of the sorbent [10,11, 14]. 16 17 2.2. Sample treatment 18 Desorption of phthalate esters from cartridges can be performed by extraction with 19 organic solvents or by thermal desorption (TD). Solvent extraction (SE) methods using 20 direct elution [16], Soxhlet extraction [10,11,18,19], pressurized solvent extraction 21 (PSE) [12] or extraction assisted by ultrasounds (US) [5,20] have been reported. 22 In their pioneer study on the presence of phthalate esters in the Swedish atmosphere, 23 Thuren and Larsson used polyurethane filters connected in series [20]. Compounds 24 adsorbed to the PUF filters were extracted with acetone-hexane in an ultrasonic bath. 25 More recently, Otake et al [5] extracted the charcoal tubes with the adsorbed phthalates 26 by sonication with 1 ml of toluene for 10 min. These authors proved that longer 27 sonication times did not improve the efficiency of the extraction (97.5 to 115%). 28 Fromme et al [12] determined phthalate esters and musk compounds in indoor air using 29 a procedure implying PSE (5% DCM in hexane) of PUF sampling cartridges (2 m 3 air 30 collected) and gas chromatography-mass spectrometry (GC/MS) of the concentrated 31 extracts with determination limits of 10 ng m -3 . Rudel et al [10,11] performed an 32 extraction of QFF-PUF-XAD sampling cartridges in a Soxhlet apparatus using 200 mL 33 of 6% ether in hexane for 16 h. Prior to the extraction, p-terpenyl-d 14 was added as a 34 surrogate standard. With this procedure recovery of the target phthalates ranged from 40 35 Page 7 of 69 Accepted Manuscript 7 to 220% (%RSD= 15-25) and detection limits (LODs) of 2-75 ng m -3 have been 1 achieved [11]. 2 Extracts are usually concentrated to achieve sufficient overall method sensitivity or for 3 solvent exchanging for further analysis. Before concentration, the addition of anhydrous 4 sodium sulphate avoids the presence of residual water traces in the organic extracts. 5 Either a gentle stream of nitrogen or Kuderna–Danish (K-D) can be used for the 6 concentration of the extracts [17]. Cleanup procedures including the use of fuming 7 concentrated sulphuric acid [20] or silica gel columns [17,18] have been reported. 8 Thermal desorption of the sampling cartridges presents some advantages over the 9 solvent-based extraction methods, much of them derived of the absence of solvent 10 manipulation. In addition, since all the retained compounds are thermally desorbed into 11 the GC, high sensitivity can be achieved. Nevertheless, some limitations deal with the 12 high temperatures needed for quantitative desorption of the less volatile phthalates from 13 typical sorbents, such as Tenax or carbon materials. An alternative to these sorbents 14 could be the use of silicones as sorptive material. A procedure based on the use of this 15 adsorbent for enrichment, thermal desorption-GC-MS was described by David et al [8]. 16 An estimation of the LODs achieved sampling 15 L air ranged between 1 and 10 ng m -3 . 17 18 2.3. Determination 19 Phthalate diesters are sufficiently volatile and thermally stable to be analyzed by GC 20 [21]. Although several detector types have been applied to phthalate GC analysis in 21 environmental samples, most of the recently proposed methods involve the use of MSD 22 working in the electron ionization (EI) mode [9]. Most phthalates fragmentize with 23 characteristic ions, such as m/z 149. This is the case of diethyl phthalate (DEP), dibutyl 24 phthalate (DBP), butylbenzyl phthalate (BBP), bis-(2-ethylhexyl) phthalate (DEHP), 25 and diisobutyl phthalate DIBP). Dimethyl phthalate (DMP) fragmetinze with m/z 163, 26 and diisononyl and diisodecyl phthalates (DINP, DIDP) with m/z 307. These 27 fragmentation patterns allow a very sensitive and selective detection, particularly when 28 operating in the selected ion monitoring (SIM) mode [5,10,11,12,16]. Separation 29 columns are usually 25 to 30 m x 0.25 to 0.32 mm I.D. coated with phenyl 30 methylpolysiloxane or dimethylpolysiloxane stationary phases, which allow 31 programming separations in a wide range of temperatures (typically, from about 50 to 32 300ºC at 10 ºC min -1 ) with low bleeding. As commented above, the ubiquity of 33 phthalate esters constitutes a very real problem through the analysis process, requiring a 34 Page 8 of 69 Accepted Manuscript 8 careful check for blank concentrations for which values of >100 ng m -3 have been 1 reported [5,16]. 2 3 2.4.Concentration in indoor air 4 Phthalate indoors concentrations highly depend on the building materials and the type 5 of furniture at each sampling emplacement. Hence, a broad range of values have been 6 reported for the analyzed compounds (see Table 2). Sheldon et al [22], reported the 7 results on 24 h phthalate monitorization in 125 homes in California (USA) showing a 8 clear predominance of DBP and DEP in indoor air, with mean values of 410 and 350 ng 9 m -3 , respectively. They also found DEHP (110 ng m -3 ) and BBP (35 ng m -3 ). Higher 10 concentrations of total phthalates (>1000 ng m -3 ) have been quantified in apartments 11 and homes, as reported in other studies [5,12,16], which demonstrate that DBP 12 predominates in the gas phase of domestic indoor environments. Fromme et al [12] 13 extended the study of indoor occurrence of phthalates and musk compounds to 14 kindergartens, finding mainly DMP and DBP at similar mean concentrations (1100-15 1200 ng m -3 ). DBP and DEHP have also been quantified in office rooms by Toda et al 16 [16], at concentrations in the broad range found in homes. In a very interesting study on 17 the indoor exposure to EDCs, Rudel et al [11] found that phthalates were the most 18 abundant among 89 organic chemicals considered in the 120 homes surveyed. Total 19 concentrations of DEP, DBP; DEHP and BBP ranged from <90 to 7000 ng m -3 , 20 indicating that the sources of these chemicals must be located indoors and highlighting 21 the importance of indoor environments in the total exposure to chemicals. 22 23 3. Brominated flame retardants 24 Polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), 25 tetrabromobisphenol-A (TBBPA) and polybrominated biphenyls (PBBs), are among the 26 most used brominated flame retardants (BFRs) and have attracted enormous attention 27 over the past decade [23]. Other less known BFRs like bis(2,4,6-28 tribromophenoxy)ethane (BTBPE) and decabromodiphenyl ethane (DeBDethane) have 29 an increasing interest due to their emerging use as substitutes of octaBDE and decaBDE 30 commercial mixtures, respectively [24]. Similarly to other persistent organic pollutants 31 (POPs), all these BFRs, with the exception of TBBPA, appear to be lipophilic and 32 bioaccumulate in biota and humans [25]. Their widespread production and use, together 33 with the increasing contamination of the environment, wildlife and people, highlights 34 Page 15 of 69 Accepted Manuscript 15 employed at flow rates ranging from 1 to 10 L min -1 . Most of sampling devices consist 1 on a GFF or QFF for collecting the PM and one or several PUF plugs for the gas phase 2 [35, 57,61]. Saito et al. [42] and Yoshida et al [68] described active sampling methods 3 for organophosphate compounds in air using a QFF disk followed by a C18 SPE disk. 4 The main advantage of this disk-type configuration is the lower restriction of the flow 5 rate. The use of aminopropyl silica SPE cartridges has also been proposed as a simple 6 alternative for collecting both the gas phase and the PM [65,69]. 7 Air sampling using solid-phase microextraction (SPME) has mostly been applied to 8 more volatile compounds than organophosphate flame retardants. As known, semi-9 volatile compounds diffuse more slowly than VOCs, and thus require longer sampling 10 periods to reach their air/fibre partition equilibrium. However, a dynamic air sampling 11 method based on SPME was developed by Isetun et al [63,64,66], in which a controlled 12 linear air flow is generated over the fibre in order to increase agitation and thus 13 minimize the static layer surrounding the fibre. As a result, an increase in the extraction 14 rate is produced and consequently the equilibration time is shortened. Extracted 15 compounds are almost entirely from the gaseous phase, so no information about 16 contribution of airborne PM is obtained. 17 The organophosphates are present primarily in the particle-associated phase rather than 18 in the gaseous phase. Carlsson et al [61] observed that OP esters were mainly recovered 19 from the GFF while the part passing into the PUF plugs was less than 1%. 20 21 4.2. Sample treatment 22 Ultrasound-assisted extraction (USAE) is the most widely used technique for recovering 23 OP compounds from filters and sorbents. Sjodin et al. [35] carried out the extraction 24 with 5 mL DCM for 20 min in an ultrasonic bath (power 50 W, frequency 48 KHz). The 25 extraction procedure was repeated once using fresh solvent and recoveries higher than 26 95 % were obtained after concentration to 0.1 mL. Soxhlet extraction has also been 27 applied by Ingerowski et al [62] with n-hexane/Acetone (4:1) for 8 h. In the case of 28 sampling with SPE cartridges [65,69], extraction can be performed by elution or 29 fractionation with a suitable solvent. Staaf et al [69] extracted organophosphate triesters 30 from aminopropyl silica cartridges by using 5 mL methyl tert-buthyl ether (MTBE) 31 reaching quantitative recoveries. 32 The use of very selective and sensitive detectors such as nitrogen phosphorus detector 33 (NPD), allows a simple extract preparation, which usually consists on a filtration step 34 followed by concentration to a small extract volume prior to the analysis by GC 35 Page 16 of 69 Accepted Manuscript 16 [57,61,65]. In spite of it, LODs in the level of low ng m -3 are achieved for most of 1 reported methods. 2 3 4.3. Determination 4 Organophosphate flame retardants in indoor air and PM have been mainly determined 5 by GC. In most of cases, NPD is the selected technique for their quantification due to its 6 high selectivity and sensitivity for this kind of compounds. Carlsson et al [57,61] 7 achieved LODs lower than 0.1 ng m -3 with no further extract preparation than filtration 8 through glass wool followed by volume concentration. However, NPD does not offer 9 the possibility for positive identification, so MS is sometimes required for confirmation 10 [35,57,61,65]. Furthermore, MS in the EI mode with SIM has also been employed 11 [58,62,68] for quantification. Hartmann et al [58] determined OP flame retardants and 12 plasticizers in indoor air obtaining LODs from 0.073 to 0.41 ng m -3 . 13 Positive chemical ionization (PCI)-tandem mass spectrometry (MS/MS) in the selected-14 reaction monitoring (SRM) mode has been applied by Bjorklund et al [67] in indoor air 15 samples. A comparative study was performed between EI-MS and PCI-MS/MS under 16 identical sampling and extraction conditions. LODs utilizing GC/PCI-MS/MS were 17 found to be in the range 0.1-1.4 ng m -3 , which is about 50-fold lower than those 18 obtained with GC/EI-SIM. 19 Recently, Saito et al [42] have used a flame photometric detector (FPD) for 20 determination of organophosphate flame retardants indoors. This detector presents some 21 of the advantages of the NPD such as high selectivity for phosphorous compounds. 22 LODs between 0.24 and 3.5 ng m -3 were achieved with this detection technique. 23 The selection of suitable surrogate and internal standards (ISs) is conditioned by the 24 extensive use of NPD and the impossibility of using isotopically labeled compounds 25 with this detector. Several compounds such as tripropyl phosphate (TPP) and tripentyl 26 phosphate (TPeP) are among the most frequently used ISs. 27 28 4.4. Concentration in indoor air 29 Organophosphate flame retardants have been found in indoor air in a number of homes 30 [42,64,65,67] with concentrations ranging from less than 1 ng m -3 up to several µg m -3 31 (see Table 2). Marklund et al [65] reported the presence of these compounds in 32 different indoor environments such as homes, offices, public buildings and domestic 33 establishments. The chlorinated OPs, TCEP and TCPP, were the most abundant and 34 Page 17 of 69 Accepted Manuscript 17 were present in all the sampled environments at concentrations up to 730 ng m -3 and 1 570 ng m -3 , respectively. 2 Levels of OPs were measured in schools and an office building by Carlsson et al [61]. 3 TCEP was detected in the range 11-250 ng m -3 , whereas TBP was present at 4 concentrations from 17 ng m -3 to 35 ng m -3 . Concentrations of triphenyl phosphate 5 (TPhP) were lower with values up to 0.7 ng m -3 , which may be attributed to a lower 6 migration rate because of its lower volatility. 7 Hartman et al [58] determined OPs in several workplaces, e.g. public buildings and cars 8 at concentrations and up to 56 ng m -3 (for TCEP) and 29 ng m -3 (for TBP), TPhP levels 9 were generally lower than 1 ng m -3 , which was consistent with the results reported by 10 Carlsson et al [61]. 11 12 5. Synthetic musk fragrances 13 Synthetic musk fragrances are added in large amounts to toiletries, cosmetics, 14 household products, and a wide variety of other consumer products. In addition, 15 synthetic fragrances such as air fresheners are used in products to scent the environment. 16 They have been measured in workplaces and other crowded indoor environments, 17 although there is an important lack of information about their concentration levels in 18 domestic indoor air (Table 2). Owing to their chemical structures, synthetic musks can 19 roughly be classified in two main categories: nitromusks and polycyclic musks. Among 20 them, the polycyclic musks Galaxolide (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8- 21 hexamethylcyclopenta-(g) 2- benzopyrane, HHCB) and Tonalide (7-acetyl-1,1,3,4,4,6-22 hexamethyl-tetraline, AHTN) are used in the highest quantities, being the latter included 23 in the United States Environmental Protection Agency (US EPA) high production 24 volume (HPV) chemical list [73]. In 1997, the nitromusks musk xylene (1-tert-butyl-25 3,5-dimethyl-2,4,6-trinitrobenzene, MX) and musk ketone (4-tert-butyl-3,5-dinitro-2,6-26 dimethylacetophenone, MK) were added to the list of chemicals for priority action of 27 the EU and in 1998 MX was added to the corresponding list of the Oslo and Paris 28 Commission (OSPARCOM) [74]. 29 Although created to replace the more expensive and rare natural musks, polycyclic and 30 nitromusks are not structurally or chemically similar to their natural counterparts. Their 31 physical-chemical properties have more in common with hydrophobic and semivolatile 32 organic pollutants that are known to biomagnify through the food chain [75]. 33 Considering the tremendous use and exposure, there is limited information available 34 related to health effects of synthetic musks. Nevertheless, fragrances can impact indoor 35 Page 18 of 69 Accepted Manuscript 18 air quality and there is suggestive evidence that may play an important role in 1 respiratory diseases and long-term impact [77]. In addition, there are environmental 2 concerns, as synthetic musks contribute to both air and water pollution [74]. Hence, 3 synthetic musks present enough properties which make them worth considering as a 4 group of indoor air pollutants. 5 6 5.1. Sampling 7 Few studies have reported the analysis of musk compounds in indoor air and PM, as can 8 be seen in Table 5. In all of them, synthetic musk have been collected by active 9 sampling, using sample volumes ranging from 2 to 100 m 3 and, in general, reduced flow 10 rates [12,70,71]. In a similar way to phthalates, special care should be taken to reduce 11 the risk of contamination during the analysis due to the extensive presence of musk 12 fragrances in soaps, perfumes and cosmetics [71]. Polyurethane foam is the most typical 13 sorbent for sampling this kind of compounds in the gas phase, whereas a glass fibre 14 filter is usually used to collect the airborne PM [70-72]. Chen et al [72] studied the 15 distribution of musk fragrances between gas phase and PM for an indoor air sample 16 from a cosmetic plant. Since the percentage of musks in the gas phase to the total was 17 higher than 97 %, the authors point out the low affinity of these compounds towards the 18 PM. 19 20 5.2. Sample treatment 21 Extraction of musk compounds from sorbents is typically carried out by Soxhlet using 22 different solvent mixtures. Kallenborn et al [70,71] used this extraction technique with 23 300 mL n-hexane/diethyl ether (9:1) for 8 h followed by volume concentration under a 24 gentle stream of nitrogen. Chen et al [72] extracted musks from PUF plugs with DCM 25 for 72 h, showing recoveries ranging from 57 to 107 %. PSE has also been used for 26 extraction of musk fragrances from sorbents with satisfactory yields. In this way, 27 Fromme et al [12] extracted PUF with n-hexane/diethyl ether (19:1), which gave 28 recovery rates between 91 and 100 %. Very recently, Regueiro et al. [76] have applied 29 for the first time the SPME as an alternative to solvent extraction in the analysis of 30 synthetic musks in air including polycyclic and nitro musks. By active sampling, musk 31 compounds are adsorbed onto an amount of only 25 mg Tenax located in a glass SPE 32 device. After addition of 100 µL acetone to the sorbent to favour the desorption, 33 analytes are transferred to a DVB/CAR/PDMS fiber in the headspace (HS) mode. 34 Page 19 of 69 Accepted Manuscript 19 Detection limits in the pg m -3 level were achieved for a sample volume of 5 m 3 using a 1 GC/MS system operated in the full scan mode. 2 Regarding the clean-up procedure, most of authors have employed column 3 chromatography on silica gel [70,71] or a combination of silica gel and alumina [72]. 4 Kallenborn et al. [70,71] developed an extract fractionation on a silica column for 5 selective elution of musk fragrances with 50 mL n-hexane/ethyl acetate (9:1) and further 6 concentration under a stream of nitrogen. On the other side, no purification steps of the 7 PSE extracts were performed by Fromme et al [12], but higher LODs, in the level of ng 8 m -3 , were obtained. 9 10 5.3. Determination 11 Determination of synthetic musk fragrances is usually performed by GC using 12 conventional capillary columns (30 m x 0.25 mm I.D., 0.25 µm film thickness) with 13 common stationary phases, including 5 % phenyl substituted methylpolysiloxane and 14 dimethylpolysiloxane. MS is the most extended detection technique for musk 15 compounds and it is commonly operated in the EI mode with SIM [12,70,71], which 16 leads to LODs in the pg m -3 level. However, nitromusk compounds have also been 17 analyzed in the NCI mode [70,71] achieving LODs between 100-fold and 60-fold lower 18 with regards to EI mode. 19 Deuterated musk xylene and AHTN standards are commercially available for use as 20 surrogate and ISs. Nevertheless, deuterated AHTN has been reported to undergo partial 21 deuterium to hydrogen exchange during analysis which may result in a inaccurate 22 surrogate recovery [78]. A variety of other surrogate and ISs have also been used in 23 different environmental matrices such as deuterated polycyclic aromatic hydrocarbons, 24 pentachloronitrobenzene, hexamethylbenzene and various labeled and unlabeled 25 polychlorinated byphenyls (PCBs). LODs, repeatabilities and recoveries reported in the 26 analysis of musk compounds in air and PM are summarized in Table 5. 27 28 5.4. Concentration in indoor air 29 Kallenborn et al. [71] reported atmospheric concentrations of nitromusk and polycyclic 30 musk in Norwegian air samples, not only in urban areas but also in remote areas. In one 31 indoor laboratory air sample analyzed during the same sampling campaign, 32 concentrations up to 2.5 ng m -3 of HHCB were measured, i.e. 10-fold higher than 33 detected in outdoor air, which raise the suspicion that air as a transport and transfer 34 medium for synthetic musk is still underestimated. 35 Page 20 of 69 Accepted Manuscript 20 Musk compounds were further studied in several indoor workplace environments [70]. 1 Highest values were found in a hairdresser facility with 44 ng m -3 HHCB, although a 2 coffee bar contained also high synthetic musk burden with 35 ng m -3 HHCB and 12 ng 3 m -3 AHTN, respectively. The presence of synthetic musk fragrances was also evaluated 4 in indoor air samples from kindergartens in Berlin [12]. HHCB gave the highest levels 5 ranging from 15 to 299 ng m -3 , whereas AHTN and Phantolide (6-acetyl-1,1,2,3,3,5-6 hexamethyl-indane, AHMI) where found at average concentrations of 47 and 22 ng m -3 , 7 respectively. Chen et al. [72] measured polycyclic musk fragrances in a typical cosmetic 8 plant and surroundings. Concentrations in the gaseous phase of the workshop were 9 found to range from 32 to 4505 ng m -3 . Synthethic musks have been recently 10 determined by Regueiro et al [76] in indoor air samples from homes of North-western 11 Spain. Measured concentrations of HHCB and AHTN were in the range from 143 to 12 1129 ng m -3 and from 21 to 77 ng m -3 , respectively. Celestolide (4-acetyl-1,1-dimethyl-13 6-tert. –butylindane, ADBI) and AHMI were also found in one sample at concentrations 14 of 2.6 and 8.5 ng m -3 , respectively, while Cashmeran (6,7-dihydro-1,1,2,3,3-15 pentamethyl-4(5H)indanone, DPMI), Traseolide (5-acetyl-1,1,2,6-tetramethyl-3-iso- 16 propyldihydroindane, ATII), and musk moskene (4,6-dinitro-1,1,3,3,5-17 pentamethylindane, MM), were not found in any of the samples. These concentrations 18 were higher than those measured by Kallenborn et al [71], but in the order of those 19 reported by Fromme et al [12] in air of German kindergartens. 20 21 6. Pesticides 22 The extensive use of pesticides to improve agricultural productivity played an important 23 role during the last century [79]. Although some of them have been banned and clasified 24 by the United Nations (UN) as POPs, they or their metabolites are still present in the 25 environment because of their persistence and lipophilic properties. Inhalation is an 26 important route of exposure for humans, especially just after spraying application in 27 domestic indoors or agricultural close areas. Table 6 summarizes recent publications 28 where pesticides have been determined in indoor or workplace air. 29 30 6.1. Sampling 31 US EPA Methods TO-4A and TO-10A determined pesticides in air [104]. These 32 methodologies have already been commented within the chapter dedicated to PCBs. 33 Pesticide sampling usually consists of collecting known volumes of contaminated air 34 using sampling cartridges filled with one or more adsorbents where the compounds are 35 Page 21 of 69 Accepted Manuscript 21 retained. PUF [87, 89-92,95, 98,105], XAD-2 resin [80,82, 90,106], mixtures of both 1 adsorbents [11,90,107], Tenax [85, 96, 99-101,108], Florisil [86,109-111], Supelpak 2 [84], Empore disks [68], octadecyl silica bonded (C 18 ) [84], or silica gel [102] are 3 adsorbents used to retain certain pesticides in indoor or workplace air. NIOSH methods 4 5600 and 5601 collect organophosphorus and organotitrogen pesticides, respectively in 5 OVS-2 tubes [112]. These tubes contain a QFF and XAD-2 resin (270 mg /140 mg). 6 Dobson et al. compared the efficiencies of PUF, XAD-2, XAD-4, and two different 7 sandwich combinations; PUF/XAD-2/PUF and PUF/XAD-4/PUF at trapping currently 8 used pesticides in the gaseous phase using high volume (hi-vol) samplers [113]. The 9 sandwiches were only slightly more efficient than XAD-2 and XAD-4 resins, followed 10 by PUFs. Therefore, and taking into account that losses of pumping efficiency were 11 found using the sandwich designs, XAD-2 is the adsorbent recommended. Tsiropoulos 12 et al. investigated the trapping efficiency of XAD-2, XAD-4, Supelpak-2, Florisil and 13 C 18 for five pesticides [84]. No breakthrough was observed at least when 480 L air was 14 pumped. Supelpak-2 or C 18 were selected as the best adsorbents, based on their 15 performance characteristics, such as sufficient trapping efficiency, no dependence on 16 the relative humidity, extended range of concentration levels, good recoveries and 17 storage stability. Yoshida et al. tried to determine 92 SVOCs, including insecticides, 18 synergists and fungicides, using QFFs and Empore disks [68]. Nevertheless, 20 19 pesticides, i.g. fenthion, piperonyl butoxide, allethrin or tetramethrin, could not be 20 sufficiently collected by the disks, obtaining low retention efficiencies. A possible 21 explanation is that some compounds may be decomposed by daylight during air 22 sampling. Therefore, other adsorbents may be necessary for their collection. Other 13 23 pesticides, such as fenitrothion, pentachlorophenol or deltamethrin could not be 24 quantified accurately as their calibration curves were not linear. Elflein et al. also 25 underlined recovery problems when sampling 17 household insecticides by means of a 26 GFFs and two PUFs [91]. They assumed a decomposition mechanism for four 27 pyrethroids on the filter during the spiking experiment. In addition, they sentenced that 28 PUF contributes to the “matrix-induced chromatographic response enhancement”. 29 When adsorbents are used, calibration is usually performed by direct spiking of 30 adsorbents with solutions of target analytes at known concentrations. Nevertheless, 31 Cessna and Kerr introduced another procedure to calibrate trifluralin and triallate [114]. 32 A polytetrafluoroethylene (PTFE) U-tube was fortified with a solution of pesticides in 33 hexane and immersed in a water bath at 50 ºC. Then, air was continuously drawn 34 through a U-tube (0.1 L min -1 ) and subsequently through two mini-tubes packed with 35 Page 22 of 69 Accepted Manuscript 22 Tenax TA arranged in series. In this way, an easy and realistic calibration was feasible, 1 simulating different concentrations of air samples. 2 Regarding outdoor air, some papers should be emphasized due to their possible 3 workplace implications. Cartridges with Florisil were used to estimate the leaf-air 4 transfer of pesticides in vegetables [109,110] or to measure atrazine and alachlor 5 concentrations in agricultural areas [111]. Egea Gonzalez and co-workers developed a 6 screening method to analyze more than 70 pesticides in air of urban locations 7 surrounded by greenhouses [115]. Three different adsorbents (Tenax TA, Chromosorb 8 106 and Supelpak) were tested obtaining the poorest recoveries with Supelpak. 9 Several authors have reviewed the ambient air passive sampling of pesticides, among 10 other organic pollutants [116-118]. Nevertheless, passive sampling studies for collecting 11 pesticides in indoor air are scarce. Esteve-Turrillas and co-workers sampled pyrethroid 12 insecticides with SPMDs [83]. The membranes were suspended about 2 m height for a 13 total time of 48 h in a dark and closed room treated with different insecticide sprays. 14 Dai et al. sampled chlorpyrifos (a termiticide) for one month in indoor air in houses 15 using a passive sampler consisting of a porous PTFE tube filled with 0.75 g of Supelpak 16 adsorbent resins [93]. Ramesh and Vijayalakshmi collected three pyrethroids in air of 17 rooms treated with insecticides using an airtight syringe and then dissolved them in 18 acetone [94]. 19 An alternative for sampling pesticides in indoor air is by exposing a SPME fiber to the 20 contaminated atmosphere. Ferrari et al. published a multiresidue method using SPME 21 for the determination of 11 pesticides selected from different chemical families with a 22 large range of saturated vapour pressures in confined atmospheres [88]. A PDMS fiber 23 was immersed for 40 min in a 250-mL flask through which air samples were 24 dynamically pumped from the analysed atmosphere. As a field application, the proposed 25 method was applied for the determination of procymidone concentrations as a function 26 of time in a greenhouse. This method completely avoids the use of solvents and can be 27 applied to determine pesticide concentrations in workplace environments, like in the 28 breathing zone of workers in greenhouses. Besides, Paschke et al. compared the 29 applicability of SPME and SPMDs for semi-volatile chlorinated organic compounds in 30 a landfill, where large amounts of lindane by-products were deposited in the past, 31 together with other hazardous chemical residues [119]. Both samplers yielded 32 comparable time-weighted average (TWA) air concentrations of lindane and its isomers 33 and of dichloro-diphenyl-trichloroethane (DDT) with its metabolites. Cisper and 34 Hemberger developed another method for the on-line detection of SVOCs, including 35 pesticides, using membrane introduction mass spectrometry (MIMS) [120], clearly 36 Page 23 of 69 Accepted Manuscript 23 expanding the practical limits of MIMS analysis. The method used a composite 1 membrane made by plasma deposition of a thin PDMS layer on a microporous 2 polypropylene support fiber. Sample air flowed over the outside of the fibres 3 countercurrent to the helium flow. Concentrations were found in the pptv range. 4 5 6.2. Sample treatment 6 Once the analytes are retained on the adsorbent, an appropriate solvent is required, 7 usually at high volumes, to quantitatively elute them. This, in turns, leads to time-8 consuming steps for concentration and clean up of the organic extracts, with the risk of 9 analyte losses. An additional problem could arise from the possible photodecomposition 10 of some of the pesticides, which has been reported in some multi-pesticide studies 11 [68,91,102], showing that determination of some pesticides in air might require 12 performing a rapid and careful trapping-extraction process. Classical extraction 13 processes include Soxhlet with large volumes of solvents [11,80,81,90,92,95,98,107] or 14 solvent extraction with acetone [84,99,100], methanol [111,121], acetonitrile [106], 15 ethyl acetate [84,103], hexane and dichloromethane (DCM) [87], toluene [93], or 16 mixtures of solvents [89], normally accompanied by shaking for several minutes. 17 Deriving of the large volumes of solvents used for the extraction, a further concentration 18 step is required. In addition, long and tedious drying with anhydrous sodium sulphate 19 [109], filtration through silanized glass wool [97,100], HPLC fractionation [103], or 20 cleaning procedures are generally needed, such as liquid-liquid extraction, SPE with 21 Florisil [80,107], silica gel [87,98,109], alumina [83] , or C 18 [83]. 22 Besides the conventional solvent extraction procedures, other techniques have been 23 proposed for the extraction of pesticides from the trapping sorbents. In a large number 24 of papers, extraction of analytes is helped by sonication over a period of 2-15 minutes 25 [68,82,85,91,97,105,110,115]. Using only 25 mg Tenax as trapping sorbent allowed 26 Barro et al developing a method to determine several pesticides in indoor air based on 27 US-assisted solvent extraction with a volume of ethyl acetate as low as 1 mL [85]. 28 Detection limits for this simple and fast method ranged from 0.03 to 4.1 ng m -3 (1 m 3 ), 29 with no need of concentration or further treatment of the extracts. Esteve-Turrillas et al. 30 extracted insecticides from SPMDs by solvent re-extractions with 30 mL of a mixture of 31 hexane-acetone and microwave extraction for 20 min [83]. Concentration, reconstitution 32 of the extracts, as well as different clean up stages derived from the matrix effect of 33 SPMDs were required to achieve good recoveries. A great reduction of solvent 34 consumption (from 400 to 60 mL) and analysis time (from 48 to 1 h) was achieved 35 Page 24 of 69 Accepted Manuscript 24 using the proposed method compared to the dialysis reference method. Detection limits 1 ranged from 0.3 to 0.9 ng per membrane. 2 When a thermally desorbable adsorbent such as Tenax is used, thermal desorption is 3 another alternative. Some authors extracted chlordanes [101], two herbicides (trifluralin 4 and triallate) [114], or 10 pesticides including triazines, carbamates and organochlorides 5 from Tenax by thermal desorption [122]. Baroja et al. determined fenothrion and its 6 main metabolites in forestry air by sampling on Tenax and extracting using a thermal 7 desorption cold trap (TCT) [123]. The use of HS-SPME has been proposed as an 8 alternative to solvent and thermal desorption, enhancing the selectivity and the 9 sensitivity of the analysis. In this way, Barro et al. collected 10 pesticides in indoor air 10 using 25 mg of Florisil [86], and after addition of 100 µL acetone to the adsorbent, the 11 SPME was carried out by exposing a polyacrilate fiber to the HS of the vial. Thus, the 12 fiber was thermally desorbed in the injection port of a gas chromatograph. Method 13 detection limits as low as 0.001 ng m -3 (1 m 3 air) were achieved for several insecticides 14 when µECD detection was utilised. 15 16 6.3. Determination 17 GC/ECD [81,85,86,90,94,97,99,103,107,109,110,114] and GC/MS [80,89-92, 18 98,100,101,105,107,111,123] are the techniques of choice for the determination of 19 pesticides in air. Although less common, other detectors such as thermoionic specific 20 detector (TSD) [81], or NPD [84,99] may be used with GC. When higher sensitivity is 21 required, GC/MS/MS [95] can also be used. Egea Gonzalez et al. determined 70 22 pesticides in a multiresidue method by GC/MS/MS using a large volume injection 23 technique [115]. Injecting a higher volume of sample extract (10 µL) increases the 24 sensitivity, achieving limits of quantification ranging from 0.2 for chlorothalonil to 27 25 ng m -3 for cypermethrin, based on a 1.44 m 3 air sampled. 26 However, the use of HPLC-UV [81,84,97,106] has also been reported. Vincent et al. 27 determined quaternary ammonium compounds by cationic preconcentration column by 28 ion chromatography (IC) or LC/MS/MS [82]. In this particular case, IC appears to be a 29 good alternative because it is not expensive and its use is very simple compared to 30 LC/MS/MS. Moreover, the limit of detection could be reduced by a factor of 100 with 31 an injection volume of 50 µL. 32 6.4. Concentration in indoor air 33 Pesticide control indoors is getting increasing attention. Concentrations found in several 34 indoor environments are summarized in Table 2. Concentrations of common household 35 Page 31 of 69 Accepted Manuscript 31 dispersed with 0.5 g Florisil in a glass mortar. After loading the blend in a cartridge 1 containing alumina on the bottom, compounds were eluted with acetone and finally 2 volume reduced. Recoveries higher than 80 % and RSD lower than 13 % were achieved. 3 Separation and quantification is typically performed by GC with NPD [149-151], 4 although GC coupled to MS in the EI mode with SIM has also been used [62]. 5 6 8.4. Synthetic musk fragrances 7 Synthetic musk fragrances have been mainly extracted from house dust by PSE [11,145]. 8 Fromme et al. [12] carried out the PSE extraction of both polycyclic and nitromusk in 9 indoor dust with n-hexane/DE (19:1) and further determination by GC/MS operating in 10 the EI mode with SIM. Recently, Peck et al [153] reported the extraction of musk 11 compounds from the indoor dust standard reference material SRM 2585 with DCM at 12 100 ºC and 2000 psi. After clean-up on an alumina SPE cartridge, a GPC column and 13 volume concentration, recoveries in the range 73-90 % were obtained. 14 MAE has also been applied for the extraction of nitromusk compounds from house dust 15 samples [152]. Dust (0.8 g) was extracted at 80 ºC for 10 min using a mixture of 8 mL 16 n-hexane and 4 mL H 2 SO 4 (aq) 1M containing ascorbic acid 0.10 %. Clean-up was 17 performed by addition and shaking of partially deactivated Florisil. Extracts were 18 further analyzed by GC/µECD. Under these conditions, recoveries between 88 and 97 % 19 and LODs from 1.03 to 3.26 ng g -1 were reported. 20 21 8.5 . Pesticides 22 Common household pesticide levels are generally higher indoors, and are also present in 23 dust and PM. Analytical procedures for the determination of pesticides in dust and PM 24 are reported in Tables 8 and 10 Mukerjee et al [124] measured 24 pesticide, including 25 18 insecticides, two herbicides, and a fungicide concentrations and their overall 26 occurrence in house dust by season. Rudel et al identified EDC, including phthalates, 27 alkylphenols, pesticides, PBDEs, among other compounds, in dust from 120 homes [11]. 28 In this study, 27 pesticides were detected in dust, the most abundant being permethrins 29 and the synergist piperonyl butoxide. The 90th percentile concentrations for these 30 pesticides ranged from 1.7 to 17 µg g -1 in dust. The prevalence indoors of pesticides that 31 have been banned or restricted for many years, such as DDT, chlordane, heptachlor, 32 methoxychlor, dieldrin and pentachlorophenol, suggests that degradation is negligible 33 indoors. This observation is further supported by the abundance of DDT in dust relative 34 to its degradation product 1,1-dichloro-2,2-bis(p-dichlorodiphenyl)ethylene (DDE). 35 Page 32 of 69 Accepted Manuscript 32 Schieweck et al [108] analyzed biocides in dust samples in different rooms of a 1 museum. A distinction between old and fresh dust was made. While the age of old dust 2 is unknown, fresh dust was defined as dust whose age is determined by the 3 measurement planning and is known exactly, usually 1-2 weeks. The concentrations of 4 pentachlorophenol and lindane in a sample of old dust taken directly from a sculpture 5 were exceptionally high with 117 and 14 µg g -1 , respectively. In the fresh dust samples 6 taken from the floor, considerably increased concentration up to 30 (for 7 pentachlorophenol, PCP) and 5 µg g -1 (for lindane) were also found, which probably 8 resulted from the intensive treatment of the wooden sculpture for purposes of 9 conservation. This result gave evidence for a possible exposure of museum staff and 10 visitors. Berger-Preiss et al measured indoor pyrethroid exposure in 80 homes with 11 woollen textile floor coverings [160]. While permethrin concentrations in house dust 12 were high (mean: 53.7 µg g -1 ), the permethrin concentrations in suspended particles 13 were very low (mean: 2.8 ng m -3 ). Leng et al. found positive correlations between 14 pyrethroids in house dust and in airborne particles, especially one day after pest control 15 operation [158]. Concentrations of pyrethroids in indoor suspended PM and household 16 dust were also measured over a period of 25 months in an experiment simulating indoor 17 pest control [97]. House dust was collected using a modified vacuum cleaner, where the 18 usual dust bag was replaced by Soxhlet filter tubes, which were preferred as they 19 allowed a quantitative transfer of the particles into de Soxhlet extractor. Moreover, it 20 was found that the Soxhlet filter tubes retained (90%) smaller particles better than the 21 usual dust bags (30%). Initial concentrations of deltamethrin and permethrin were 150-22 800 and 50 µg g -1 , depending on the commercial formulation applied. The concentration 23 levels of both compounds decreased by a factor of about 10 within the first 12 months, 24 but remained practically constant the following year. Roinestad et al identified 30 25 pesticides in household dust ranging from 80 (diazinon) to 15000 (chlorpyrifos) ng g -1 26 [100]. Permethrin levels decreased from 2550-3850 (just after application) to 550-675 27 ng g -1 8 weeks after pesticide application. However, dichlorvos and o-phenylphenol 28 levels remained relatively constant suggesting that dust sampling may be a more 29 appropriate method for determining chronic risk assessment of indoor pesticides than air. 30 Children of agricultural families are likely to be exposed to agricultural chemicals, even 31 it they are not involved in farm activities. Household dust samples were collected in 59 32 residences [161]. Household dust concentrations for all four organophosphorous 33 pesticides were significantly lower in reference homes (up to 820 ng g -1 ) when 34 compared to farmer homes (up to 17100 ng g -1 ). A statistical comparison indicated that 35 agricultural families had significantly higher concentrations of azinphosmethyl, 36 Page 33 of 69 Accepted Manuscript 33 chlorpyrifos, and parathion. These results demonstrate that children of agricultural 1 families have higher potential for exposure to these chemicals than children of non-farm 2 families. In this way, Lu et al [89] estimated organophosphorus exposures of preschool 3 children in agricultural and non-agricultural areas. Detectable levels of diazinon and 4 azinphosmethyl in house dust were found in most of the agricultural homes, whereas 5 only diazinon was found in the metropolitan homes in the summer. 6 7 8.6 . Organotin and perfluoroalkyl compounds 8 Extraction of perfluoroalkyl compounds has been carried out by both Soxhlet [129] and 9 USAE [154,155]. Moriwaki et al [154] developed a US-based method for the 10 determination of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) 11 in indoor dust. Compounds were US extracted with methanol for 60 min and 12 determined using LC coupled to ESI MS/MS. Recoveries higher than 73 % and LODs 13 in the range 10-50 ng g -1 were reached. Soxhlet extraction with DCM during 24 h was 14 applied by Shoeib et al [129] for the extraction of perfluoralkyl sulfonamides (PFASs) 15 in indoor dust. No further extract preparation than volume concentration was performed 16 before analysis by GC/EI-MS in the SIM mode. 17 Organotin compounds have also been determined in house dust [156]. USAE was 18 conducted with ethanol, followed by derivatization with sodium tetraethylborate 19 (STEB) and liquid-liquid extraction with n-hexane. Recoveries higher than 70 % and 20 average LODs of 10 ng g -1 were reported. 21 22 23 Page 34 of 69 Accepted Manuscript 34 9. References 1 [1] L. Molhave, G. Clausen, B. Berglund, J. De Ceaurriz, A. Kettrup, T. Lindvall, M. 2 Maroni, A.C. Pickering , U. Risse, H. Rothweiler, B. Seifert, M. Younes, Indoor Air 7 3 (1997) 225. 4 [2] S.K. Brown, M.R. Sim, M.J. Abramson, C.N. Gray, Indoor Air 4 (1994) 123. 5 [3] European Chemical Agency (ECHA), http://echa.europa.eu. 6 [4] Z. Xie, R. Ebinghaus, Anal. Chim. Acta 610 (2008) 156. 7 [5] T. Otake, J. Yoshinaga, Y. Yanigisawa, Environ. Sci. Technol. 35 (2001) 3099. 8 [6] A. Frankhauser, K. Grob, Anal. Chim. Acta 582 (2007) 353. 9 [7] M. Gomez-Hens, M.P. Aguilar-Caballos, Trends Anal. Chem. 22 (2003) 847. 10 [8] F. David, P. Sandra, B. Tienpont, F. Vanwalleghen, Analytical methods review, The 11 Handbook of Environmental Chemistry, Part Q, Phthalate Esters, Vol. 3, Staples, C.A., 12 Ed., Springer-Verlag, Berlin, 2003. 13 [9] M. Llompart, C. García-Jares, P. Landín, Phthalates in Chromatographic Analysis of 14 the Environment, L.M.L. Nollet ed. (2007), 3rd Ed, CRC Press, Boca Raton, FL, p. 15 1103. 16 [10] R.A. Rudel, J.G. Brody, J.D. Spengler, J. Vallarino, P.W. Geno, A. Yau, J. 17 Air&Waste Manage Assoc. 51 (2001) 499. 18 [11] R.A. Rudel, D.E. Camann, J.D. Spengler, L.R. Korn, J.G. Brody, Environ. Sci. 19 Technol. 37 (2003) 4543. 20 [12] H. Fromme, T. Lahrz, M. Piloty, H. Gebhart, A. Oddoy, H. Rüden, Indoor Air 14 21 (2004) 188. 22 [13] Y. Kang, W. Den, H. Bai, F.H. Ko, J. Chromatogr. A 1070 (2005) 137. 23 [14] H. Fromme, M. Albrecht, H. Drexler, L. Gruber, M. Schlummer, H. Parlar, W. 24 Körner, A. Wanner, D. Heitmann, E. Roscher, G. Bolte, Int. J. Hyg. Environ. Health 25 210 (2007) 345. 26 [15] W.J.G.M. Peijnenburg, J. Struijs, Ecotoxicol. Environ. Safety 63 (2006) 204. 27 [16] H. Toda, K. Sako, Y. Yagome, T. Nakamura, Anal. Chim. Acta 519 (2004) 213. 28 [17] X.K. Wang, Chin. Chem. Lett. 13 (2002) 557. 29 [18] Z. Xie, J. Selzer, R. Ebinghaus, A. Caba, W. Ruck, Anal. Chim. Acta 546 (2006) 30 198. 31 [19] B. Tomiyasu, T. Hoshi, M. Owari, Y. Nihei, Appl. Surf. Sci. 203 (2003) 775. 32 [20] A. Thuren, P. Larsson, Environ. Sci. Technol. 24 (1990) 554. 33 [21] D. Helmig, J. Chromatogr. A 843 (1999) 129. 34 [22] L. Sheldon, A. Clayton, J. Keever, R. Perritt, D. Whitaker, PTEAM: Monitoring of 35 Phthalates and PAHs in Indoor and Outdoor Air Samples in Riverside, California: Final 36 Page 35 of 69 Accepted Manuscript 35 Report, Volume II, California Air Resources Board, Research Division, Contract No. 1 A933-144, Sacramento, CA, December 1992. 2 [23] A. Covaci, S. Voorspoels, J. de Boer, Environ. Inter. 29 (2003) 735. 3 [24] M. Karlsson, A. Julander, B. van Bavel, L. Hardell, Environ. Int. 33 (2007) 62. 4 [25] C. de Wit, Chemosphere 46 (2002) 583. 5 [26] A. Sjödin, O. Päpke, E. McGahee, R. Jones, J.F. Focant, T. Pless-Mulloli, L.M. 6 Toms, R. Wang, Y. Zhang, L. Needham, T. Herrmann, D. Patterson, Organohal. Comp. 7 66 (2004) 3817. 8 [27] S. Harrad, M. Diamond, Atmos. Environ. 40 (2006) 1187. 9 [28] H.A. Jones-Otazo, J.P. Clarke, M.L. Diamond, J.A. Archbold, G. Ferguson, T. 10 Harner, G.M. Richardson, J.J. Ryan, B. Wilford, Environ. Sci. Technol. 39 (2005) 5121. 11 [29] G.M. Currado, S. Harrad, Environ. Sci. Technol. 34 (2000) 78. 12 [30] O. Päpke, P. Fürst, T. Herrmann, Talanta 63 (2004) 1203. 13 [31] A. Covaci, S. Voorspoels, L. Ramos, H. Neels, R. Blust, J. Chromatogr. A 1153 14 (2007) 145. 15 [32] C. Thomsen, H. Leknes, E. Lundanes, G. Becher, J. Chromatogr. A 923 (2001) 299. 16 [33] T. Herrmann, B. Schilling, O. Päpke, Organohalogen Compd. 63 (2003) 361. 17 [34] J. de Boer, D.E. Wells, Trends Anal. Chem. 25 (2006) 364. 18 [35] A. Sjödin, H. Carlsson, K. Thuresson, S. Sjölin, A. Bergman, C. Östman, Environ. 19 Sci. Technol. 35 (2001) 448. 20 [36] A. Pettersson-Julander, B. van Bavel, M. Engwall, H. Westberg, J. Environ. Monit. 21 6 (2004) 874. 22 [37] C.M. Butt, M.L. Diamond, J. Truong, M.G. Ikonomou, A.F.H. ter Schure, Environ. 23 Sci. Technol. 38 (2004) 724. 24 [38] S. Harrad, R. Wijesekera, S. Hunter, C. Halliwell, R. Baker, Environ. Sci. Technol. 25 38 (2004) 2345. 26 [39] B.H. Wilford, T. Harner, J. Zhu, M. Shoeib, K.C. Jones, Environ. Sci. Technol. 38 27 (2004) 5312. 28 [40] S. Harrad, S. Hazrati, C. Ibarra, Environ. Sci. Technol. 40 (2006) 4633. 29 [41] B. Gevao, M. Al-Bahloul, A.N. Al-Ghadban, L. Ali, A. Al-Omair, M. Helaleh, K. 30 Al-Matrouk, J. Zafar, Atmos. Environ. 40 (2006) 1419. 31 [42] I. Saito, A. Onuki, H. Seto, Indoor Air 17 (2007) 28. 32 [43] J.G. Allen, M.D. McClean, H.M. Stapleton, J.W. Nelson, T.F. Webster, Environ. 33 Sci. Technol. 41 (2007) 4574. 34 [44] T.M. Cahill, D. Groskova, M.J. Charles, J.R. Sanborn, M.S. Denison, L. Baker, 35 Environ. Sci. Technol. 41 (2007) 6370. 36 Page 36 of 69 Accepted Manuscript 36 [45] M. Shoeib, T. Harner, M. Ikonomou, K. Kannan, Environ. Sci. Technol. 38 (2004) 1 1313. 2 [46] J. Bjorklund, P. Tollback, C. Ostman, J. Sep. Sci. 26 (2003) 1104. 3 [47] S. Hazrati, S. Harrad, Chemosphere 67 (2007) 448. 4 [48] L. Chen, B. Mai, Z. Xu, X. Peng, J. Han,Y. Ran, G. Sheng, J. Fu, Atmos. Environ. 5 42 (2008) 78. 6 [49] J. Tollbäck, C. Creszenci, E. Dyremark, J. Chromatogr. A 1104 (2006) 106. 7 [50] J. Zhu, Y. Hou, Y. Feng, M. Shoeib, T. Harner, Environ. Sci. Technol. 42 (2008) 8 386. 9 [51] A. Kierkegaard, J. Bjorklund, U. Friden, Environ. Sci. Technol. 38 (2004) 3247. 10 [52] J. de Boer, W.P. Cofino, Chemosphere 46 (2002) 625. 11 [53] J. Björklund (2003) Gas chromatography and mass spectrometry of 12 polybrominated diphenyl ethers. Ph. D. Thesis, Department of Analytical Chemistry, 13 Stockholm University, Stockholm, Sweden. 14 [54] A. Covaci, J. de Boer, J.J. Ryan, S. Voorspoels, P. Schepens, Anal. Chem. 74 15 (2002) 790. 16 [55] J. Björklund, P. Tollbäck, C. Hiärne, E. Dyremark, C. Östman J. Chromatogr. A 17 1041 (2004) 201. 18 [56] J. Regueiro, M. Llompart, C. Garcia-Jares, R. Cela, Anal. Bioanal. Chem. 388 19 (2007) 1095. 20 [57] H. Carlsson, U. Nilsson, C. Östman, Environ. Sci. Technol. 34 (2000) 3885. 21 [58] P.C. Hartmann, D. Burgi, W. Giger, Chemosphere 57 (2004) 781. 22 [59] WHO (1991) Environmental Health Criteria 112 (Tri-n-butyl phosphate) 23 International Programme on Chemical Safety, WHO, Geneva. 24 [60] WHO (1998) Environmental Health Criteria 209 (Flame retardants: 25 tris(chloropropyl) phosphate and tris(2-chloroethyl) phosphate). International 26 Programme on Chemical Safety, WHO, Geneva. 27 [61] H. Carlsson, U. Nilsson, G. Becker, C. Östman, Environ. Sci. Technol. 31 (1997) 28 2931. 29 [62] G. Ingerowski, A. Friedle, J. Thumulla, Indoor Air 11 (2001) 145. 30 [63] S. Isentun, U. Nilsson, A. Colmsjö, R. Johansson, Anal. Bioanal. Chem. 378 31 (2004) 1847. 32 [64] S. Isetun, U. Nilsson, A. Colmsjö, Anal. Bioanal. Chem. 380 (2004) 319. 33 [65] A. Marklund, B. Andersson, P. Haglund, J. Environ. Monit. 7 (2005) 814. 34 [66] S. Isetun, U. Nilsson, Analyst 130 (2005) 94. 35 Page 37 of 69 Accepted Manuscript 37 [67] J. Bjorklund, S. Isetun, U. Nilsson, Rapid Commun. Mass Spectrom. 18 (2004) 1 3079. 2 [68] T. Yoshida, I. Matsunaga, H. Oda, J. Chromatogr. A 1023 (2004) 255. 3 [69] T. Staaf, C. Östman, J. Environ. Monit. 7 (2005) 344. 4 [70] R. Kallenborn, R. Gatermann, Synthetic Musks in Ambient and Indoor Air, in The 5 Handbook of Environmental Chemistry Vol. 3, Part X (2004) p. 85. 6 [71] R. Kallenborn, R. Gatermann, S. Planting, G.G. Rimkus, M. Lund, M. Schlabach, 7 I.C. Burkow, J. Chromatogr. A 846 (1999) 295. 8 [72] D. Chen, X. Zeng, Y. Sheng, X. Bi, H. Gui, G. Sheng, J. Fu, Chemosphere 66 9 (2007) 252. 10 [73] US EPA, High production volume (HPV) Chemical List database June 8, 2003 11 (http:/www.epa.gov/chemrtk/opptsrch.htm). 12 [74] R. Kallenborn, R. Gatermann, G.G. Rimkus, J. Environ. Monit. 1 (1999) 70N. 13 [75] A.M. Peck, K.C. Hornbuckle, Environ. Sci. Technol. 38 (2004) 367. 14 [76] J. Regueiro, J.P.Lamas, M. Llompart, C. Garcia-Jares, R. Cela, J. Chromatogr. A 15 (in press). 16 [77] B. Bridges, Flavour Fragr. J. 17 (2002) 361. 17 [78] I.J. Buerge, H.R. Buser, M.D. Muller, T. Poiger, Environ. Sci. Technol. 37 (2003) 18 5636. 19 [79] F.J. Santos, M.T. Galceran, Trends Anal. Chem. 21 (2002) 672. 20 [80] N.K. Wilson, J.C. Chuang, M.K. Morgan, R.A. Lordo, L.S. Sheldon, Environ. Res. 21 103 (2007) 9. 22 [81] G. Bouvier, O. Blanchard, I. Momas, N. Seta, Sci. Total Environ. 366 (2006) 74. 23 [82] G. Vincent, M.C. Kopferschmitt-Kubler, P. Mirabel, G. Pauli, M. Millet, Environ. 24 Monit. Assess. 133 (2007) 25. 25 [83] F.A. Esteve-Turrillas, A. Pastor, M. de la Guardia, Anal. Chim. Acta 560 (2006) 26 118. 27 [84] N.G. Tsiropoulos, E.B. Bakeas, V. Raptis, S.S. Batistatou, Anal. Chim. Acta 573 28 (2006) 209. 29 [85] R. Barro, C. Garcia-Jares, M. Llompart, M.H. Bollain, R. Cela, J. Chromatogr. A 30 1111 (2006) 1. 31 [86] R. Barro, C. Garcia-Jares, M. Llompart, R. Cela, J. Chromatogr. Sci. 44 (2006) 430. 32 [87] J.H. Offenberg, Y.Y. Naumova, B.J. Turpin, S.J. Eisenreich, M.T. Morandi, T. 33 Stock, S.D. Colome, A.M. Winer, D.M. Spektor, J. Zhang, C.P. Weisel, Environ. Sci. 34 Technol. 38 (2004) 2760. 35 [88] F. Ferrari, A. Sanusi, M. Millet, M. Montury, Anal. Bioanal. Chem. 379 (2004) 476. 36 Page 38 of 69 Accepted Manuscript 38 [89] C. Lu, G. Kedan, J. Fisker-Andersen, J.C. Kissel, R.A. Fenske, Environ. Res. 96 1 (2004) 283. 2 [90] D.M. Stout II, M.A. Mason, Atmos. Environ. 37 (2003) 5539. 3 [91] L. Elflein, E. Berger-Preiss, K. Levsen, G. Wünsch, J. Chromatogr. A 985 (2003) 4 147. 5 [92] R.M. Whyatt, D.B. Barr, D.E. Carmann, P.L. Kinney, J.R. Barr, H.F. Andrews, 6 L.A. Hoepner, R. Garfinkel, Y. Hazi, A. Reyes, J. Ramirez, Y. Cosme, P. Perera, 7 Environ. Health. Perspect. 111 (2003) 749. 8 [93] H. Dai, F. Asakawa, S. Suna, T. Hirao, T. Karita, I. Fukunaga, F. Jitsunari, Environ. 9 Health Prev. Med. 8 (2003) 139. 10 [94] A. Ramesh, A. Vijayalakshmi, J. Environ. Monit. 3 (2001) 191. 11 [95] M. Cruz Márquez, F.J. Arrebola, F.J. Egea González, M.L. Castro Cano, J.L. 12 Martínez Vidal, J. Chromatogr. A 939 (2001) 79. 13 [96] J. Demel, W. Buchberger, H. Malissa Jr., J. Chromatogr. A 931 (2001) 107. 14 [97] E. Berger-Preiss, A. Preiss, K. Sielaff, M. Raabe, B. Ilgen, K. Levsen, Indoor Air 7 15 (1997) 248. 16 [98] J.C. Wallace, L.P. Brzuzy, S.L. Simonich, S.M. Visscher, R.A. Hites, Environ. Sci. 17 Technol. 30 (1996) 2715. 18 [99] J. Siebers, P. Mattusch, Chemosphere 33 (1996) 1597. 19 [100] K.S. Roinestad, J.B. Louis, J.D. Rosen, J. AOAC Int. 76 (1993) 1121. 20 [101] K. Haraguchi, E. Kitamura, T. Yamashita, A. Kido, Atmos. Environ. 28 (1994), 21 1319. 22 [102] T.J. Class, J. Kintrup, Fresenius J. Anal. Chem. 340 (1991) 446. 23 [103] J.N. Seiber, D.E. Glotfelty, A.D. Lucas, M.M. McChesney, J.C. Sagebiel, T.A. 24 Wehner, Arch. Environ. Contam. Toxicol. 19 (1990) 583. 25 [104] US EPA, Compendium of Methods for the Determination of Toxic Organic 26 Compounds in Ambient Air, Office of Research and Development, National Risk 27 Management Research Laboratory, Center for Environmental Research Information, 28 Cincinnati, Ohio, 2nd Ed, 1999, http://www.epa.gov/ttn/amtic/airtox.html. 29 [105] E. Berger-Preiss, L. Elflein, Methods Biotechnol. 19 (2006) 179. 30 [106] E.R. Kennedy, J.J. Lin, J.M. Reynolds, J.B. Perkins, Am. Ind. Hyg. Assoc. J. 58 31 (1997) 720. 32 [107] Y. Yao, L. Tuduri, T. Harner, P. Blanchard, D. Waite, L. Poissant, C. Murphy, W. 33 Belzer, F. Aulagnier, Y.F. Li, E. Sverko, Atmos. Environ. 40 (2006) 4339. 34 [108] A. Schieweck, W. Delius, N. Siwinski, W. Vogtenrath, C. Genning, T. 35 Salthammer, Atmos. Environ. 41 (2007) 3266. 36 Page 39 of 69 Accepted Manuscript 39 [109] X. Yang, X. Jiang, G. Yu, F. Yao, Y. Bian, F. Wang, Environ. Pollut. 148 (2007) 1 555. 2 [110] J. Castro, R.A. Pérez, E. Miguel, C. Sánchez-Brunete, J.L. Tadeo, J. Chromatogr. 3 A 947 (2002) 119. 4 [111] C. E. Roach, L. G. Anderson, W. T. Foreman, Determination of Atmospheric 5 Atrazine and Alachlor Concentrations by Reverse Phase Liquid Chromatography and 6 Gas Chromatography Mass Spectrometry, in Proc.AWMA Annual Meeting, 90th, 1997, 7 Paper No. 97-RA122.03. 8 [112] NIOSH, National Institute for Occupational Safety and Health Manual of 9 Analytical Methods (NMAM), http://www.cdc.gov/niosh/nmam/. 10 [113] R. Dobson, A. Scheyer, A.L. Rizet, P. Mirabel, M. Millet, Anal. Bioanal. Chem. 11 386 (2006) 1781. 12 [114] A.J. Cessna, L.A. Kerr, J. Chromatogr. 642 (1993) 417. 13 [115] F.J. Egea Gonzalez, A. Mena Granero, C.R. Glass, A. Garrido Frenich, J.L. 14 Martinez Vidal, Rapid Commun. Mass Spectrom. 18 (2004) 537. 15 [116] P. Bohlin, K.C. Jones, B. Strandberg, J. Environ. Monit. 9 (2007) 501. 16 [117] F.A. Esteve-Turrillas, V. Yusá, A. Pastor, M. de la Guardia, Talanta 74 (2008) 17 443. 18 [118] M. Partyka, B. Zabiegala, J. Namiesnik, Crit. Rev. Anal. Chem. 37 (2007) 51. 19 [119] A. Paschke, B. Vrana, P. Popp, G. Schürmann, Environ. Pollut. 144 (2006) 414. 20 [120] M.E. Cisper, P.H. Hemberger, Rapid Commun. Mass Spectrom. 11 (1997) 1449. 21 [121] S. Oepkemeier, S. Schreiber, D. Breuer, G. Key, W. Kleiböhmer, Anal. Chim. 22 Acta 393 (1999) 103. 23 [122] O. Briand, M. Millet, F. Bertrand, M. Clément, R. Seux, Anal. Bioanal. Chem. 24 374 (2002) 848. 25 [123] O. Baroja, N. Unceta, M.C. Sampedro, M.A. Goicolea, R.J. Barrio, J. Chromatogr. 26 A 1059 (2004) 165. 27 [124] S. Mukerjee, W.D. Ellenson, R.G. Lewis, R.K. Stevens, M.C. Somerville, D.S. 28 Shadwick, R.D. Willis, Environ. Int. 23 (1997) 657. 29 [125] Y. Gil, C. Sinfort, Atmos. Environ. 39 (2005) 5183. 30 [126] L. Baraud, D. Tessier, J.J. Aaron, J.P. Quisefit, J. Pinart, Anal. Bioanal. Chem. 31 377 (2003) 1148. 32 [127] A. Sanusi, M. Millet, P. Mirabel, H. Wortham, Sci. Total Environ. 263 (2000) 263. 33 [128] J.P. Giesy, K. Kannan, Environ. Sci. Technol. 36 (2002) 146A. 34 [129] M. Shoeib T. Harner, B.H. Wilford, K.C. Jones, J. Zhu, Environ. Sci. Technol. 39 35 (2005) 6599. 36 Page 40 of 69 Accepted Manuscript 40 [130] A. Jahnke, S. Huber, C. Temme, H. Kylin, U. Berger, J. Chromatogr. A 1164 1 (2007) 1. 2 [131] K. Kawata, M. Minagawa, Y. Fujieda, J. Chromatogr. 653 (1993) 369. 3 [132] G.M. Cooke, Toxicol. Lett. 126 (2002) 121. 4 [133] M. Shoeib, T. Harner, M. Ikonomou, K. Kannan, Environ. Sci. Technol. 38 5 (2004) 1313. 6 [134] M. Shoeib, T. Harner, S.C. Lee, D. Lane, J. Zhu, Anal. Chem. 80 (2008) 675. 7 [135] US EPA, Exposure Factors Handbook, National Centre for Environmental 8 Assessment, Washington, DC, 1997. 9 [136] R.M. Maertens, J. Bailey, P.A. White, Mutat. Res. 567 (2004) 401. 10 [137] W. Butte, B. Heinzow, Rev. Environ. Contam. Toxicol. 175 (2002) 1. 11 [138] R.G. Lewis, R.C. Fortmann, D. Camann, Arch. Environ. Contam. Toxicol. 26 12 (1994) 37. 13 [139] C.G. Bornehag, B. Lundgren, C.J. Weschler, T. Sisgaard, L. Hagerhed-Engman, J. 14 Sundell, Environ. Health Perspect. 113 (2005) 1399. 15 [140] H.P. Hutter, H. Moshammer, P. Wallner, B. Damberger, P.Tappler, M. Kundi, Int. 16 J. Hyg. Environ. Health 209 (2006) 65. 17 [141] W. Knoth, W. Mann, R. Meyer, J. Nebhuth, Organohal. Comp. 58 (2002) 213. 18 [142] H.M. Stapleton, N.G. Dodder, J.H. Offenberg, M.M. Schantz, S.A. Wise, Environ. 19 Sci. Technol. 39 (2005) 925. 20 [143] H.M. Stapleton, T. Harner, M. Shoeib, J.M. Keller, M.M. Schantz, S.D. Leigh, 21 S.A. Wise, Anal. Bioanal. Chem. 384 (2006) 791. 22 [144] J. Regueiro, M. Llompart, C. Garcia-Jares, R. Cela, J. Chromatogr. A, 1137 23 (2006) 1. 24 [145] B. Gevao, M. Al-Bahloul, A.N. Al-Ghadban, A. Al-Omair, L. Ali, J. Zafar, M. 25 Léale, Chemosphere 64 (2006) 603. 26 [146] J. Tan, S.M. Cheng, A. Loganath, Y.S. Chong, J. P. Obrad, Chemosphere 66 27 (2007) 985. 28 [147] B.H. Wilford, M. Shoeib, T. Harner, J. Zhu, K.C. Jones, Environ. Sci. Technol. 39 29 (2005) 7027. 30 [148] M.A. Abdallah, S. Harrad, C. Ibarra, M. Diamond, L. Melymuk, M. Robson, A. 31 Covaci, Environ. Sci. Technol. 42 (2008) 459. 32 [149] M. Garcia, I. Rodriguez, R. Cela, Anal. Chim. Acta 590 (2007) 17. 33 [150] M. Garcia, I. Rodriguez, R. Cela, J. Chromatogr. A 1152 (2007) 280. 34 [151] A. Marklund, B. Andersson, P. Haglund, Chemosphere 53 (2003) 1137. 35 Page 47 of 69 Accepted Manuscript 6 Table 3. Analytical procedures for the determination of BFR in indoor air Ref. Analytes Sampling Desorption/Extraction Extract preparation Determination Recovery (%) RSD (%) LOD 11 Tetra- PentaBDEs Active (10-14 m 3 , 8-9 L min - 1 ) with 3 URG cartridges in parallel containing a QFF and XAD-2 resin between 2 PUF plugs Soxhlet with 150 mL hexane-DE (6%) containing a deuterated SS (p-terphenyl-d 14 ), 16 h Concentration to 2 mL and addition of deuterated IS (PAHs) GC/EI-MS (SIM) 40-220 NR NR 24 Tri-DecaBDE, BTBPE, DeBDethane Hi-vol sampler (25 m 3 , flow 50 L min -1 ) using n GFF, cellulose pad and XAD-2 Soxhlet with toluene, 16 h, previous addition of 13 C-labeled SS Clean-up on treated (KOH+ H 2 SO 4 ) silica column, elution with hexane, clean-up on a GPC-system, elution with hexane-DCM 1:1, concentration to a small volume and addition of tetradecane and 13 C- labeled IS GC/NCI-MS (SIM) 12-97 NR 2.30-173 pg m -3 36 Tri- HeptaBDEs, TBBPA, 2,4,6-TBPh 1) Passive: adsorption on glass funnel surface. 2) Lovol sampler (0.18 m 3 , flow 4 L min -1 ) collection on SPE cartridge (Isolute ENV+, 200 mg, 6mL) Elution with 6 mL DCM-MeOH 7:3 Concentration to 30 µL, derivatization with 50µL diazomethane and addition of IS (TBB) GC/NCI-MS NR NR NR 39 Tetra- DecaBDE, BTBPE, BB- 209, TBBPA 1) Lo-vol sampler (1.5 m 3 , flow 3 L min -1 ): collection on GFF and 2 PUF plugs in series. 2) Hi-vol sampler (3.6 m 3 , flow 9 L min -1 ): collection on GFF, cellulose pad and 2 PUF plugs in series US (bath 50 W, 48 kHz) extraction with 5 mL DCM 20 min (x2), addition of SS (BDE- 128, TrBCBPA) Solvent exchange to hexane, concentration to 0.1 mL and LLE with 2 mL methanolic KOH (≥ 50 %) twice: 1) Neutral fraction (hexane): clean-up on a silica/ H 2 SO 4 (2:1) column and elution with 8 mL hexane 2) Aqueous fraction: acidification with HCl and LLE with hexane/MTBE 1:1. Separation of organic phase, concentration to 1 mL and derivatization of phenolic compounds with 0.2 mL diazomethane, 1h, in a refrigerator. Clean-up on a silica/ H 2 SO 4 (2:1) column and elution with 8 mL DCM GC/NCI-MS (SIM) ~97 (23- 60 for BTBPE, TBBPA) 3-10 LOQ: 3- 100 pg m -3 40 Tri-DecaBDE, BTBPE, DeBDethane Personal sampler (1 m 3 , flow 2 L min -1 ) with GFF, cellulose pad and XAD-2 Soxhlet with 250 mL toluene, 16 h , previous addition of 13 C-labeled SS Concentration to 0.5 mL, clean-up on treated (KOH+ H 2 SO 4 ) silica column and GPC, solvent exchange to nonane and concentration to 40 µL GC/NCI-MS (SIM) NR 0.3- 9.5 0.01-1.3 ng m -3 Page 48 of 69 Accepted Manuscript 7 41 TriheptaBDEs Passive using organic films from window surfaces (exposition < 4 months) collected using kimwipes wetted with isopropyl alcohol Soxhlet with tolueneacetone (4:1), 18 h, previous addition of 13 C-labeled SS Acid-base washing (H 2 SO 4 and KOH), concentration to dryness, reconstitution in DCM- hexane 1:1. Clean-up on a multilayer acidic/basic silica column, elution with DCM-hexane 1:1 and solvent exchange to hexane. Clean-up on a copper column, elution with hexane, clean-up on an alumina column, elution with DCM-hexane 1:1, concentration to dryness and reconstitution in toluene GC/EI-MS (SIM) 35-119 NR NR 42 Tetra- HexaBDEs Hi-vol sampler (300 m 3 flow 0.6-0.8 m 3 min -1 ) using a GFF and a PUF plug Soxhlet with DCM- hexane 1:1, 16-24 h, previous addition of 13 C-labeled SS Treatment with H 2 SO 4(c) , clean-up on acidic silica, elution with hexane, clean-up on florisil, concentration to a small volume and solvent exchange to nonane GC/EI-MS (SIM) 54-104 4-22 1 pg m -3 43 Tri- HexaBDEs Passive with a PUF disk (21 days, uptake rate 2.5 m 3 day - 1 : 50 m 3 ) previous addition of SS (BDE-3, d6-γ-HCH, PCB-107, PCB-198) Soxhlet with PE, 21 h, previous addition of SS (BDE-2, BDE-35) Concentration to 0.5 mL, solvent exchange to isooctane and addition of IS (Mirex) GC/NCI-MS (SIM) 110-116 16- 25 1.2-18 pg m -3 44 Tri- HexaPBDEs Passive with a PUF disk (28 days, uptake rate 1.1-1.9 m 3 day -1 : 31-53 m 3 ), previous addition of SS (PCB19, PCB147) Soxhlet with hexane, 8 h, previous addition of 13 C-labeled SS Concentration to 2 mL, treatment with 2 mL H 2 SO 4(c) , LLE with DMSO, clean-up on florisil, elution with 20 mL hexane. Concentration to a small volume, solvent exchange to 20 µL nonane and addition of IS (PCB-29, PCB-129) GC/EI-MS (SIM) 45-67 0.9- 6 0.1 pg m -3 45 TriheptaBDEs Passive with a PUF disk (42 days, uptake rate 2.5 m 3 day - 1 : 105 m 3 ) Soxhlet with DCM- hexane 1:1, previous addition of SS (BDE- 35, BDE-181) Concentration to a small volume, solvent exchange to hexane, clean-up on a silica/alumina (2:1) column, elution with 100 mL hexane-DCM 1:1, concentration to a small volume, solvent exchange to dodecane and addition of IS (Mirex) GC/NCI-MS (SIM) 80-90 NR 0.2-0.5 pg m -3 46 Di-decaBDE, 2,4,6-TBPh, PBPh, HBB, HBCD Active (14.4 m 3 , flow 10 L min -1 ) using QFF and SPE disk (Empore C18) US extraction with 10 mL acetone Concentration of 5 mL of extract to 0.5 mL and addition of deuterated IS GC/AED 81 -91 2-9 0.47-9.9 ng m -3 Page 49 of 69 Accepted Manuscript 8 47 Tri-DecaBDE Lo-vol sampler (9 m 3 , 2 L min -1 ) using GFF and a PUF plug PSE extraction (100 ºC, 1500 psi, 5 min, 3 cycles): GFF with DCM and PUF with PE, previous addition of 13 C-labeled SS Concentration to 0.2 mL and filtration through glass wool GC/NCI-MS (SIM) NR ~6 NR 48 Tri-DecaBDE Lo-vol sampler (6-26 m 3 , flow 13-18 L min -1 ) using QFF and XAD-2 Soxhlet with DCM, 24 h Concentration to a small volume, clean-up on silica, elution with 50 mL DCM, concentration to 0.3-0.5 mL, solvent exchange to isooctane and addition of IS GC/NCI-MS (SIM) 64-90 NR NR 49 Tetra- HeptaBDEs Hi-vol sampler (100-200 m 3 , flow 0.4 m 3 min -1 ) using 2 GFF and 2 PUF plugs in series Soxhlet 18-24h: GFF with DCM and PUF with PE-acetone 1:1 Concentration to 1 mL, solvent exchange to isooctane, addition of 13 C-labeled SS, clean-up on a multilayer (basic, neutral, acidic, neutral) silica column and elution with 60 mL DCM-hexane 1:1. Clean-up on alumina, elution with 60 mL DCM- hexane 1:1, concentration to < 10 mL and addition of 13 C-labeled IS GC/EI-MS > 98 NR 0.3-20 pg m -3 50 Mono- DecaBDE Lo-vol sampler (2 m 3 , flow 3 L min -1 ) with a GFF and 2 PUF plugs in series US extraction with 5 mL DCM, 20 min (x2), previous addition of 13 C-labeled SS Concentration to 1 mL, solvent exchange to hexane, concentration to 1 mL, clean-up on a SPE cartridge (Isolute NH 2 ) GC/NICI-MS (SIM) NR NR NR 51 TripentaBDEs Passive with a PUF disk (50 days, uptake rate 1.12-1.95 m 3 day -1 : 56-98 m 3 ), previous addition of SS (PCB-19, PCB-147) Soxhlet with 200 mL hexane, 8 h , previous addition of 13 C-labeled SS Concentration to 2 mL, treatment with 2 mL H 2 SO 4(c) , LLE with DMSO, clean-up on florisil, elution with 20 mL hexane. Concentration to a small volume, solvent exchange to 20 µL nonane and addition of IS (PCB-29, PCB-129) GC/EI-MS (SIM) 42-80 ~18 NR 52 Tri-DecaBDE Hi-vol sampler (0.4-0.7 m 3 min -1 , indoor: 175-385 m 3 ) using a GFF and a PUF plug Soxhlet with acetonehexane 1:1, 72 h, previous addition of 13 C-labeled SS Addition of activated copper, concentration to a small volume and clean-up on an acid/basic multilayer silica column, concentration to 0.2 mL and addition of 13 C-labeled IS GC/NCI-MS (SIM) 74-87 < 15 0.28-28.6 pg m -3 55 TBBPA Lo-vol sampler (3 m 3 , 3 L min -1 ) with a GFF and 2 PUF plugs in series US extraction with 5 mL ACN, 20 min (x2), previous addition of 13 C- labeled SS Concentration to 0.5 mL, filtration through a syringe filter, elution with 5 mL MeOH, concentration to 0.1 mL and addition of 0.075 mL water LC/ESI-MS (SIM) 75-107 4.9- 6.4 NR Page 50 of 69 Accepted Manuscript 9 56 HCDBCO Passive using a PUF disk (21 days, uptake rate 2.5 m 3 day - 1 : 52.5 m 3 ) Soxhlet with PE, 21 h Concentration to 0.5 mL, solvent exchange to isooctane GC/NCI-MS (SIM) NR NR 1.3 pg m -3 57 DeBDethane Lo-vol sampler (1 m 3 , 3 L min -1 ) with a GFF and 2 PUF plugs in series US extraction with 10 mL DCM, 20 min (x2), previous addition of SS (Dechlorane) Solvent exchange to hexane, concentration to 1 mL, clean-up on SPE cartridge (Isolute NH 2 ) and elution with 10 mL hexane GC/NCI-MS NR NR NR Page 51 of 69 Accepted Manuscript 10 Table 4. Analytical procedures for the determination of OP esters in indoor air Ref. Analytes Sampling Desorption/Extraction Extract treatment Determination Recovery (%) RSD (%) LOD 35 TPhP, IPPDPP, PPDPP, TBPDPP, TBP, TCEP, TCPP, TBEP 1) Lo-vol sampler (1.5 m 3 , 3 L min -1 ) with GFF and 2 PUF plugs in series 2) High-vol sampler (3.6 m 3 , 9 L min -1 ) with GFF, cellulose pad and 2 PUF plugs in series US (bath 50 W, 48 kHz) extraction with 5 mL DCM 20 min (x2), previous addition of SS (MDPP) Concentration to 0.1 mL GC/NPD > 95 NR NR 42 TMP, TEP, TPP, TBP, TCPP, TCEP, TEHP, TBEP, TDCPP, TPhP, TCrP Active (14.4 m 3 , flow 10 L min -1 ) Collected on QFF and SPE disk (Empore C18) US extraction with 10 mL acetone Concentration of 5 mL of extract to 0.5 mL and addition of IS (tris(1H,1H,5H- octafluoropentyl)phosphate) GC/FPD 90-100 1.2-7 0.24-3.5 ng m -3 57,61 TiBP, TBP, TCEP, TCPP, TPhP, TBEP, TEHP Personal sampler (2.1 m 3 , flow 3.0 L min -1 ) with a GFF and 2 PUF plugs in series US (bath 50 W, 48 kHz) extraction with 5 mL DCM 20 min (x2), previous addition of SS (TPP) Filtration through glass wool, concentration to a small volume and addition of IS (ABP) GC/NPD >95 8-22 0.1 ng m -3 58 TBP, TCEP, TPhP, TBEP, TEHP, TCrP, TCPP, TDCPP Lo-vol sampler (1.4-3.4 m 3 ,flow 4 L min -1 ) with a PUF plug US (bath 50 W, 48 kHz) extraction with 37 mL DCM, 20 min (x2), previous addition of SS (TPP) Solvent exchange to hexane, concentration to 0.1 mL and addition of IS (Phenanthrene-d 10 ) GC/EI-MS 62-100 NR 0.073-0.41 ng m -3 62 TCEP, TCPP Lo-vol sampler (1 m 3 , 5 L min -1 ) with a PUF cartridge (Orbo 1000, Supelco) Soxhlet with hexane-acetone 4:1, 8 h Concentration to small volume GC/EI-MS (SIM) NR NR 1 ng m -3 (LOQ) 63 TEP, TPP, TiPP, TiBP, TCEP, TCPP Dynamic sampling with controlled linear airflow (7cm s -1 ) using nonequilibrium SPME (100 µm PDMS, 60 min) Thermal desorption (2 min, 250 ºC) - GC/NPD NR 8-10 ~2 ng m -3 64 TEP, TPP, TiBP, TBP, TCEP, TCPP Dynamic sampling with controlled linear airflow (10 cm s -1 )using equilibrium SPME (7 µm PDMS 12 h or 100 µm PDMS 24 h) Thermal desorption (2 min, 250 ºC) - GC/NPD NR 5-17 7 µm PDMS 0.1 ng m -3 100 µm PDMS 0.01 ng m -3 Page 52 of 69 Accepted Manuscript 11 65 TMP, TPP, TBP, TCPP, TCEP, TDCPP,TPhP, TBEP, TEHP, DOPP, TEEdP, CLP1 Lo-vol sampler (1.0-2.7 m 3 , flow 2.5 L min -1 ) with a SPE cartridge (Isolute NH 2 , 25 mg, 1 mL) Elution with 10 mL DCM, previous addition of SS (TPeP) Concentration to dryness, dissolution in DCE and concentration to 0.1 mL GC/NPD 82-110 (34–58 TEEdP, TMP, TPhP) 4-18 0.1-3.9 ng m -3 66 TEP, TPP, TiBP, TCEP, TCPP Dynamic sampling with controlled linear airflow (10-35 cm s -1 : flow 1.1- 3.8 L min -1 ) using non-equilibrium SPME (100 µm PDMS, 40-90 min) or equilibrium SPME (30 µm PDMS, >18 h) TD (2 min, 250 ºC) - GC/NPD NR 13-18 NR 67 TMP, TEP, TPP, TiPP, TiBP, TBP, TCEP, TCPP, TPhP, TTP Lo-vol sampler (1.4 m 3 , flow 3 L min -1 ) with a GFF and a cellulose filter, previous addition of SS (MDPhP) US extraction with DCM, 20 min (x2) Concentration to a small volume GC/PCIMS/MS NR 4-22 0.1-1.4 ng m -3 68 TCrP, TEP, TPhP, TPP, TBEP, TCEP, TDCPP, TEHP Active with a QFF disk and an SPE disk (Empore C18) (7.2 m 3 , flow 5 L min -1 ) US extraction with 8 mL acetone, 15 min, and shaking, 10 min Centrifugation (2000 rpm, 10 min), decantation of 5 mL supernatant, addition of IS (fluoranthene-d 10 ) and concentration to 0.3 mL GC/EI MS (SIM) 94-112 1.3-12 0.1-0.6 ng m -3 69 TEP, TiPP, TPP, TBP, TCEP, TCPP, TDCPP, TBEP, TPhP, DPEHP, TEHP, TTP Active (1.5 m 3 , flow 2.5-3.3 L min -1 ) with SPE cartridge (Isolute NH 2 , 25 mg, 1 mL) Elution with 5 mL MTBE, previous addition of SS (THP) Addition of IS (TPeP) GC/NPD ~ 100 % 1-9 0.1-0.3 ng m -3 Page 53 of 69 Accepted Manuscript 12 Table 5. Analytical procedures for the determination of synthetic musks in indoor air Ref. Analytes Sampling Desorption/Extraction Extract preparation Determination Recovery (%) RSD (%) LOD 12 HHCB, AHTN, ATII, ADBI, AHMI, DPMI, MX, MK Lo-vol sampler (2 m 3 , 5 L min -1 ) using a PUF plug PSE with hexane-DE 19:1, previous addition of deuterated SS Concentration to a small volume GC/EI-MS (SIM) 91-100 NR 10 ng m -3 70,71 HHCB, AHTN, ATII, MX, MK Lo-vol sampler (36-108 m 3 , 25-38 L min -1 ) using GFF and 2 PUF plugs in series Soxhlet with 300 mL hexane-DE 9:1, 8h, previous addition of deuterated SS Concentration to 0.5 mL, cleanup on silica, elution with 50 mL of hexane EtAcO 9:1, concentration to 0.2 mL and addition of IS (TCN) GC/EI-MS (SIM), GC/NCI-MS (SIM) for nitromusks 69-126 1-9 EI: Polycyclic (5-45 pg m -3 ) NCI: Nitromusk (4-12 pg m -3 ) 72 HHCB, AHTN, ATII, ADBI, AHMI,DPMI Hi-vol sampler (72 m 3 , 0.3-0.4 m 3 min -1 ) with a GFF and a PUF plug Soxhlet with DCM, 72 h Concentration, clean-up on a silica-alumina (2:1) column, elution with DCM, solvent exchange to hexane, concentration to 0.2-0.5 mL and addition of IS (HMB) GC/EI-MS 57-107 3-12 60-120 pg m -3 76 HHCB, AHTN, ATII, ADBI, AHMI, DPMI, MX, MK, MM Lo-vol sampler (1-10 m 3 , 100 L min -1 ) using a SPE device filled with 25 mg Tenax Addition of 100 µL acetone followed by HSSPME (DVB/CAR/PDMS fiber, (30 min, 100ºC) None GC/EI-MS (ITD) 85-103 3-15 29-380 pg m -3 Page 54 of 69 Accepted Manuscript 13 Table 6. Analytical procedures for the determination of pesticides in indoor air Ref Analyte Sampling Desorption/Extraction Extract treatment Determination Recovery (%) RSD (%) Limits of detection 11 39 pesticides Active with cartridges containing an impactor, QFFs and XAD-2 resin sandwiched between 2 PUF plugs (4-9 L min -1 , 24 h, 4-14 m 3 ) Soxhlet with 150 mL DE in hexane (6%), 16 h Addition of a deuterated surrogate, drying with sodium sulphate, concentration and adjusting to a final volume of 2 mL using 10% DE in hexane GC/EI-MS (SIM) 60-150 < 20% 1-6 ng m -3 68 19 insecticides, 1 synergist, 1 fungicide Active with a QFF and an Empore disk (5 L min -1 , 24 h, 7.2 m 3 ) US with 8 mL acetone (15 min) followed by shaking (10 min) Centrifugation 2000 rpm (10 min). Addition of IS and concentration (N 2 ) to 0.3 mL GC/EI-MS (SIM) >85 <14 0.1-2.0 ng m -3 (7.2 m 3 ) 80 Pentachlorophenol, bisphenol- A and nonylphenol Active using glass cartridge containing a QFF followed by XAD-2 resin (48 h, 4 L min -1 ) Soxhlet with DCM Concentration (K-D), SPE with florisil and concentration. Addition of SS GC/MS 55-120 NR 0.09 ng m -3 81 38 pesticides: herbicides, pyrethroids, organophosphate and organochlorine insecticides, fungicides Active using a glass cartridge containing PUF and a QFF (24 h, 5 L min -1 , 7.1 m 3 ) Soxhlet with 150 mL DCM, 16 h Concentration in a rotary evaporator to 100 µL followed by dilution in 2 mL acetone GC/ECD, GC/TSD, HPLC/UV (DAD) 73.1- 120.2 <8 LOQs = 0.1- 562 ng m -3 82 Disinfectants: Quaternary Ammonium Compounds (QACs) Active with a tube containing XAD-2 resin (1 Lmin -1 , 100 L) US with 5 mL ACN, 10 min None IC (Cationic preconcentration column), LCMS/MS 99.83- 101.00 NR 28 µg m -3 (100 L, IC), 5 ng m -3 (100 L, LC-MS-MS) 83 Insecticides (pyrethroids) Passive with SPMDs suspended about 2 m height (48 h) MAE (2x20 min) with 30 mL hexane-acetone (1:1). Concentration (rotary evaporator), reconstitution in 5 mL hexane, and extraction with ACN (3x5 mL). Clean-up with alumina-C 18 and elution with 10 mL ACN. Evaporation almost to dryness in a rotary evaporator and finally to dryness with N2. Addition of IS in isooctane GC/EI-MS/MS 61-103 (after 2 nd extraction ) 2.9-9.4 0.3-0.9 ng per SPMD 84 4 fungicides, 1 insecticide and 1 acaricide Active using stainless steel tubes filled with Supelpak or C18 distributed in 2 beds (front one 250 mg and back one 150 mg) SE with acetone or EtOAc by shaking (20 min) Centrifugation at 3500 rpm (10 min) GC/NPD, HPLC/UV 79-102 (Supelpak ), 84-106 (C 18 ) 0.23-6.3 LOQ=0.2-20 µg m -3 (60 L) Page 55 of 69 Accepted Manuscript 14 85 11 pyrethroids, 1 synergist, 1 fungicide, 1 carbamate Active with a glass tube containing 25 mg Tenax (100 L min -1 , 1 m 3 ) US with 1 mL EtOAc, 10 min None GC/MS (ITD), GC/µECD 81-114 <10 0.03-4.1 ng m - 3 (µECD), 1.4- 9.1 ng m -3 (MS) 86 10 pyrethroids, 1 synergist, 1 fungicide, 1 carbamate Active with a glass tube containing 25 mg Florisil (100 L min -1 , 1 m 3 ) Addition of 100 µL acetone followed by HS-SPME (PA fiber, 30 min, 100ºC) None GC/MS (ITD), GC/µECD 76-119 <20 0.001-2.1 ng m -3 (µECD), 0.046-7.1 ng m -3 (MS) 87 3 chlordanes and 2 nonachlors Active with a MSP sampler modified by addition of a stainless steel cylinder with a PUF plug and QFFs (10 L min -1 , 29 m 3 ) SE with 40 mL of hot (50ºC) hexane-DCM 4:1 (1h, for PUF) Rinsed (x2) with 20 mL of hot hexane:DCB (4:1). Concentration by rotary evaporation followed by concentration with N 2 . Clean-up on microcolumns of silicic acid. Elution with 2 mL hexane:DCM 9:1. Reduction (N 2 ) to ~0.1 mL, addition of deuterated PAHs as IS and final reduction to ~0.05 mL GC/EI-MS (SIM) 82-91 ≤17 0.018-0.140 ng (gas phase) 88 11 pesticides: pyrethroids, carbamates, organophosphorous, etc The output knob of a 250-mL glass flask is connected to a pump and the input knob is just open to the air. The SPME fiber (PDMS) is inserted into the sampling flask through a septum and exposed to the air stream (dynamic mode, 40 min) TD - GC/EI-MS (ITD, SIM) NR 1.9-7.6 0.03-76.7 µg m -3 89 8 pesticides : malathion, chlorpyrifos, diazinon, etc Active using PUF cartridges (30-40 L min -1 , 24 h) SE with 2 mL tolueneacetone 9:1 (NIOSH 5600) None GC/MS (SIM) NR NR 0.001-0.002 µg m -3 90 Chlorpyrifos Active using OVS samplers (QFF with two beds of XAD-2 sandwiched between PUF partitions, 1.0 L min -1 , 24 h) and PUF tubes (3.8 L min -1 , 24 h) Soxhlet with 5% DE in hexane (PUF) SE with 5% DE in hexane followed by shaking (2500 rpm, 1 h) Addition of decachlorobiphenyl as surrogate and 2,4,5- tribromobiphenyl as IS GC/ECD, GC/MS (confirmation) 98-120 30 NR 91 17 insecticides and acaricides: pyrethroids, organophosphates, carbamates, etc Active with PUF plugs and GFFs (50 L min -1 ) SE soaking in 50 mL EtOAc, and squeezed periodically in an US bath for 2 min (PUF plugs). US with 10 mL EtOAc for 5 min (x3) (GFFs) Concentration (N 2 ) to 0.5 mL, filtration through a pipette with silanized glass wool, washing with 0.4 mL ethyl acetate and adjusting to 1 mL. GC/EI-MS (SIM) 85-109 (matrixmatched calibratio n) 2.8-11.4 0.1-5 ng m -3 (10 m 3 ) Page 56 of 69 Accepted Manuscript 15 92 29 pesticides: 9 organophosphates, 6 carbamates, 2 pyrethroids, 6 herbicides, 5 fungicides, 1 repellant Active with a filter and a PUF plug (4 L min - 1 , 48 h, 11.5 m 3 ). Spiked with terphenyls-d 14 as a recovery surrogate Soxhlet with 6% DE in hexane, 16 h Concentration to 1 mL GC/MS NR NR 0.2-0.7 ng m -3 (air) 93 Chlorpyrifos Passive with a porous PTFE tube filled with 0.75 g Supelpak SE with 3 mL toluene by shaking (1 h) Concentration to almost dryness (N 2 ) in a K-D evaporator with a cooling pump GC/MS (SIM) NR NR NR 94 5 insecticides pyrethroids 100 mL air dissolved in 25 mL acetone using a syringe The syringe is washed with 10 mL acetone (x4) The washings are combined and concentrated GC/ECD NR 9.6-11.4 NR 95 Insecticide and acaricide (malathion and some of its metabolites) Active with a PUF plug (2 L min -1 ) Soxhlet with 100 mL acetone (8 h) Evaporation until almost dryness. Addition of IS and dilution to 4 mL GC/MS-MS 93.2-94.1 ≤6 0.01-0.07 ng L -1 96 11 pesticides: 2 fungicides, 1 carbamate, 2 pyrethroids, 1 dinitroaniline, etc Active with sampling tubes containing 100 mg (front layer) and 50 mg (backup layer) Tenax and intermediate glass wool plugs (2.1 L min -1 , 8 h) Incubation with 5 mL methanol (5 min) with occasional shaking and US (3 min) After sedimentation, 1 mL of the supernatant is filtered through a 0.45 µm GFF. Addition of IS and adjusting to the final volume with water HPLC/UV (DAD) 70-100 ≤4 1.0-9.1 µg m -3 (1 m 3 ) 97 Insecticides: pyrethrins, pyrethroids and a synergist Active with GFF and 2 PUF plugs (3 m 3 h -1 , 10 m 3 ) US with 10 mL EtOAc (x3) (GFFs) US with 150 mL EtOAc (x3) (PUF) The extracts were combined, filtered through silanized glass wool and reduced (rotary evaporator) to a final volume of 1 mL GC/ECD, GC/FID, HPLC/UV 75.5- 113.9 4.9-13.2 NR 98 aldrin, dieldrin, 4 chlordanes, pentachloroanisole and HCHs Active using 2 hi-vol samplers with PUF plugs (30 m 3 h -1 , 50-100 m 3 ) Spiking with isotopically labelled IS. Soxhlet with hexane in acetone (50%) 24 h Reduction to 0.1 mL, purification using SPE cartridges containing 1 g silica and final elution using 10 mL hexane, 10 mL 50% hexane in DCM and 10 mL DCM GC/MS NR NR NR 99 7 pesticides: 1 carbamate, 3 pyrethroids, 1 phenylsulfamide, etc Active with tubes containing Tenax and glass wool plugs (0.528-1.261 L min -1 , 60 min) SE with 2 mL acetone followed by shaking (5 min) Filtration through a paper filter, rinsing with 2 mL acetone, evaporation (N 2 ) and redissolution with n-hexane or acetone GC/ECD, GC/NPD 75-89 NR LOQs=0.1-0.2 µg m -3 100 23 pesticides Active with tubes packed with 25 mg Tenax and plugged with 2 portions of silanized glass wool (4h, 1m 3 ) SE with 5 mL acetone followed by shaking (30 min) Filtration through glass wool. Addition of filtered acetone, concentration (N 2 ) to 200 µL, addition of IS and final concentration (N 2 ) to 40 µL GC/CI-MS 50.7- 110.9 <15 0.5-30 ng m -3 (1 m 3 air) 101 Insecticides (chlordanes) Active with a glass-lined stainless-steel tube packed with 0.4 g Tenax and sealed with 2 silica-wool plugs (1-2 L min -1 , 50-100 L) TD - GC/EI-MS (SIM) NR 1.1-5.1 0.25 ng m -3 (20 L) Page 63 of 69 Accepted Manuscript 22 10 PAHs, phthalates, PCBs, pesticides Dust (1.4-12.1 g) collected in a cellulose thimble Soxhlet with 200 mL hexane-DE 94:6, 16 h, after addition of a deuterated surrogate Treatment with anhydrous sodium sulphate, concentration to 2.5 mL cleanup with florisil, concentration to 2 mL in 10% DE in hexane and silylation GC/EI-MS (SIM) 110-378 12- 175 NR 141 Tetra- DecaBDE Dust (10 g) from vacuum cleaners Soxhlet with 300 mL toluene, 24 h Addition of 13 C-labelled SS, clean-up on a multilayer (acidic, neutral, basic, neutral) silica column and elution with 150 mL hexane. Clean-up on alumina, elution with 100 mL hexane/DCM 1:1, clean-up on a GPC column, elution with cyclohexane/EtAcO 1:1, clean-up on alumina, elution with 10 mL hexane/DCM 1:1, addition of 13 C-labeled IS and concentration to 0.1mL. GC/EI-MS (SIM) NR NR NR 11 TetrapentaBDEs Dust (0.047-1.6 g) from vacuum cleaners passed through a 150µm mesh sieve Soxhlet with hexane/DE 6%, 16 h, previous addition of deuterated SS Concentration to 10 mL, clean-up on florisil of an 1 mL aliquot, elution with 20 mL acetone/hexane (10 %), solvent exchange to DE/hexane (10 %) and concentration to 2 mL GC/EI-MS (SIM) 40-220 < 20 0.2-0.4 µg g -1 142 Tri-DecaBDE Dust (0.1-0.5 g) from vacuum cleaners passed through a 1mm mesh sieve PSE (100 ºC, 2000 psi, 5 min, 3 cycles) with DCM, previous addition of 13 C- labeled SS Concentration to 0.5 mL, solvent exchange to hexane, clean-up on SPE cartridge (Silica Sep-Pak), elution with 20 mL hexane, and concentration to 0.5 mL GC/NCI-MS (SIM) NR < 25 1-6 ng g -1 40 Tri-HexaBDEs Dust (1 g) from vacuum cleaners passed through a 500 µm mesh sieve PSE (150 ºC, 1500 psi, 5 min, 1 cycle) with hexane and florisil on the bottom of extraction cell, previous addition of 13 C-labeled SS Concentration to 2 mL, treatment with 2 mL H 2 SO 4(c) , LLE with DMSO, clean-up on florisil, elution with 20 mL hexane, concentration to a small volume, solvent exchange to 20 µL nonane, and addition of IS (PCB-29, PCB-129) GC/EI-MS (SIM) 45-67 0.9-6 0.03 ng g -1 Page 64 of 69 Accepted Manuscript 23 143 Tri-DecaBDE Dust (0.5-1 g) from vacuum cleaners (SRM 2585) passed through a 100 µm mesh sieve 1) PSE (100 ºC, 2000 psi, 5 min, 3 cycles) with DCM, previous addition of 13 C- labeled SS. 2) Soxhlet with DCM, previous addition of 13 C-labeled SS 1A) Concentration to a small volume, cleanup on SPE cartridge (Silica Sep Pak), elution with 20 mL hexane, concentration to 0.5 mL. 1B) Concentration to a small volume, cleanup on a SPE cartridge (alumina), elution with 10 mL DCM/hexane (35%), clean-up on a GPC column, concentration and solvent exchange to 0.5 mL isooctane. 2) Concentration to a small volume, clean-up on alumina, elution with 20 mL PE, concentration to a small volume, solvent exchange to isooctane GC/EI-MS (SIM), GC/NCI-MS (SIM) NR NR NR 144 Tetra- HexaBDEs Dust (0.8 g) from vacuum cleaners passed through a 60 µm mesh sieve MAE (80 ºC, 15 min) with a mixture of 8 mL hexane and 4 mL NaOH 10 % (w/w), previous addition of 13 C-labeled SS Centrifugation, separation of organic phase, on-batch clean-up by addition of 100 mg florisil per mL extract, shaking 2 min, and filtration. An aliquot of 2 mL concentrated to 0.2 mL GC/EI-MS (MS/MS) 92-114 11-16 0.29-0.55 ng g - 1 145 Tri-DecaBDE Dust (3.4 g) from vacuum cleaners passed through a 2 mm mesh sieve Soxhlet with DCM/hexane (1:1), previous addition of SS (BDE-35, BDE-181) Concentration to a small volume, solvent exchange, clean-up on a silica-alumina column 2:1, elution with 100 mL hexane/DCM (1:1), addition of 50 µL dodecane, concentration to < 0.1 mL, and addition of IS (Mirex) GC/NCI-MS (SIM) 70-84 5-10 0.032-0.305 ng g -1 56 Tetra- DecaBDE Dust (0.8 g) from vacuum cleaners passed through a 60 µm mesh sieve MAE (80 ºC, 15 min) with a mixture of 8 mL hexane and 4 mL NaOH 10 % (w/w), previous addition of SS (PCB-30) Centrifugation, separation of organic phase, on-batch clean-up by addition of 100 mg florisil per mL extract, shaking 2 min and filtration. GC/µECD 90-108 4-13 0.0439-1.44 ng g -1 146 Tri-DecaBDE Dust (0.2 g) from air conditioning units MAE (115ºC, 15 min) with 25 mL hexane/DCM (1:1) in the presence of Na2SO4, previous addition of 1 3C- labeled SS Clean-up on acidic silica (H 2 SO 4 ) column, elution with 100 mL hexane and 50 mL hexane/DCM 2:3, clean-up on a GPC, elution with 30 mL hexane/DCM 1:1, addition of dodecane, concentration to 25 µL, and addition of 13 C-labeled IS GC/NCI-MS (SIM) 71-130 0.4-32 0.02-40 ng g -1 Page 65 of 69 Accepted Manuscript 24 147 Tri-DecaBDE Dust (0.25 g) from vacuum cleaners passed through a 150 µm mesh sieve Soxhlet with DCM, 15 h, previous addition of SS (BDE-35) Concentration to 4 mL, solvent exchange to PE/isooctane up to 10 mL, a 5 mL aliquot concentrated to 3 mL, and treatment with 1-2 mL H 2 SO 4 (x2). Concentration to 1 mL in isooctane and addition of IS (Mirex) GC/NCI-MS (SIM) ≈ 99 ≈ 19 0.1-14 ng g -1 41 Tri-DecaBDE, BTBPE, DeBDethane Dust from vacuum cleaners Soxhlet with toluene, 16 h , previous addition of 13 C- labeled SS Clean-up on treated (KOH+ H 2 SO 4 ) silica column, elution with hexane, clean-up on GPC, elution with hexane/DCM 65:35, concentration to a small volume, and addition of tetradecane and 13 C-labeled IS GC/NCI-MS (SIM) 45-184 NR 0.169-10.1 ng g -1 148 HBCD (α,β,γ) Dust (1 g) from vacuum cleaners passed through a 500 µm mesh sieve PSE (90 ºC, 1500 psi, 5 min, 3 cycles) with hexane/DCM (1:1) and florisil on the bottom of extraction cell, previous addition of 13 C-labeled SS Concentration to 0.5 mL, treatment with H 2 SO 4 , clean-up on florisil, elution with 30 mL hexane/DCM 1:1, concentration to a small volume, solvent exchange to MeOH and addition of deuterated IS LC/ESNCI-MS (MS/MS) 82-88 5-8 0.1 ng g -1 62 TCEP, TCPP Dust from vacuum cleaners Soxhlet with hexane/acetone (4:1) 8 h, previous addition of SS Concentration to a small volume GC/EI-MS (SIM) NR NR 100 ng g -1 149 TiBP, TBP, TCEP, TCPP, TDCPP, TPhP, TBEP Dust from vacuum cleaners passed through a 60µm mesh sieve MSPD: 0.5 g dust mixed with Na 2 SO 4 (0.5 g) and dispersed with florisil (0.5 g) in a glass mortar Loading the blend in a cartridge containing alumina on the bottom, rinsing with 2 mL hexane, and elution with 3 mL acetone. Addition of 1 mL EtAcO, concentration to 0.5 mL and addition of IS (TPP) GC/NPD 80-116 4-13 LOQ: 40-50 ng g -1 150 TiBP, TBP, TCEP, TCPP, TDCPP, TPhP, TBEP, TEHP, TPPO Dust (0.5 g) from vacuum cleaners passed through a 60µm mesh sieve MAE with 10 mL acetone (130ºC, 30 min) Centrifugation (3000 rpm, 5 min), decantation, addition to 500 mL ultrapure water, SPE (Oasis HLB), elution with 2 mL EtAcO, clean-up on a silica cartridge, elution with 5 mL EtAcO and concentration to 1 mL GC/NPD 85-104 3-13 LOQ: 40-50 ng g -1 151 TBEP, TCEP, TCPP, TDCPP, TPhP, TEEdP, TEHP, TBP, DOPP, CLP1, TPhP, TMP Dust (1-2 g) from vacuum cleaners US with 25 mL DCM 20 min Filtration through paper filters, concentration to a small volume and addition of IS (TEP) GC/NPD 97 6-18 7-60 ng g -1 Page 66 of 69 Accepted Manuscript 25 12 HHCB, AHTN, ATII, ADBI, AHMI, DPMI, MX, MK Fine dust fraction from vacuum cleaners (1 g) PSE with hexane/DE (19:1), previous addition of deuterated SS - GC/EI-MS (SIM) NR NR LOQ: 500 ng g - 1 152 MX, MK, MM Dust (0.8 g) from vacuum cleaners passed through a 60µm mesh sieve MAE with a mixture of 8 mL hexane and 4 mL H 2 SO 4 (aq) 1M containing ascorbic acid 0.10 % (w/w) (80 ºC, 10 min), previous addition of SS (PCB-166, PCB-195) Centrifugation, separation of organic phase, on-batch clean-up by addition of 100 mg florisil per mL extract, shaking 2 min and filtration GC/µECD 88-97 6-8 1.03-3.26 ng g - 1 153 HHCB, AHTN, ATII, ADBI, AHMI, MX, MK SRM 2585 Organics in House Dust PSE: Dust mixed with H 2 SO 4 and extracted (100 ºC, 2000 psi) with DCM, previous addition of deuterated IS (Fluoroanthene-d 10 ) Concentration to a small volume, solvent exchange to 0.5 mL isooctane, clean-up on SPE cartridge (5 % deactivated alumina), elution with 9 mL DCM/hexane (35 %), concentration to a small volume, solvent exchange to 1 mL DCM, clean-up on GPC, elution with 5.5 mL DCM, concentration to 1mL GC/EI-MS (SIM) 73-90 4-13 NR 154 PFOS, PFOA Dust (0.5 g) from vacuum cleaners US with 10 mL MeOH 60 min Centrifugation (1500 rpm) 10 min, filtration, and addition of deuterated IS LC/ESI-MS (MS/MS) 73-89 11 10-50 ng g -1 155 PFOS, PFOA, PFBS, PFOSA, PFHS Dust (0.5 g) from vacuum cleaners passed through a 150 µm mesh sieve US with 5 mL ACN 5 min (x2) Clean-up of a 2 mL aliquot on a SPE cartridge (C18 Waters), elution with 7 mL ACN, concentration to dryness, reconstitution in 0.2 mL ACN, and addition of 13 C-labled IS LC/ESI-MS (MS/MS) 46-101 1.7- 6.3 0.99-4.56 ng g - 1 129 MeFOSE, EtFOSE, EtFOSA, MeFOSEA Dust (0.25 g) from vacuum cleaners passed through a 150 µm mesh sieve Soxhlet with DCM, 24 h Concentration to 0.5 mL and addition of IS (Mirex) GC/EI-MS (SIM) NR NR NR 156 MBT, DBT, TBT, MOT, DOT, TPT Dust (0.5-1.0 g) from vacuum cleaners US with ethanol Buffering with sodium acetate (pH 4.5), derivatization with sodium tetraethylborate (STEB) and LLE with hexane GC/EI-MS (SIM) > 70 NR 10 ng g -1 Page 67 of 69 Accepted Manuscript 26 157 41 PCBs and 7 pesticides Dust collection from the filters of air conditioning units or the blades of ceiling fan using a small pair of steel tweezers rinsed with n-hexane Addition of IS (0.2 g dust), MAE with 25 mL nhexane-DCM (1:1) in the presence of sodium sulfate (2 g) Acid silica gel column, elution with 100 mL n-hexane and subsequently with 50 mL nhexane-DCM (2:3). GPC packed with Biobeads (6 g) per column using n-hexane- DCM (1:1) as a mobile phase. Concentration to 0.5 mL (N 2 ). Further concentration to 25 µL after addition of IS. GC-MS/EI (SIM) 70-126 <19 0.2-1.0 ng mL -1 (on column) 80 Pentachlrophen ol, bisphenol- A, nonylphenol HVS3 vacuum sampler ASE with acetone Concentration, addition of IS (dicamba-d 3 ), followed by methylation or silylation. Cleanup by SPE with Florisil and final concentration GC/MS NR NR 2.0 ng g -1 108 Biocides Manual wiping with Soxhlet-extracted paper towels (20 h toluene and 20 h acetone). Also, collection in a cleaned glass vial using metallic spoons. Soxhlet or US with acetone-hexane 50:50 NR GC/ECD, GC/MS NR NR LOQ < 1 µg g -1 158 4 pyrethroids Dust collected using a modified vacuum cleaner where the usual dust bag was replaced by a Soxhlet filter tube Soxhlet with EtAcO, 15 h Concentration, solvent exchange into hexane, clean-up with silica gel and elution with DCM-hexane 30:70. Solvent exchange to EtAcO GC/EI-MS NR NR 0.5 µg g -1 159 6 PCDDs, 9 PCDFs, 12 PCBs NR ASE (150ºC, 12 min, 2000 psi) Concentration (N2) using a Turbovap. Cleanup with multi-layered silica chromatography column and microcolumns packed with Florisil. Elution with DCM-hexane (1:49) for PCBs and with DCM for PCDD/Fs. Solvent exchanged with nonane and addition of IS. For PCB fractions collected after Florisil clean-up, concentration to 0.5 mL, additional clean-up on alumnia (16 h, 200ºC), elution with 25 mL DCM-hexane (3:7), solvent exchanged with nonane and addition of IS GC/LRMS (SIM), HRGC/HRMS/po sitive ion mode (SIM) 58-112 ≤41 1.0-12 pg g -1 Page 68 of 69 Accepted Manuscript 27 89 8 Organophosph orous pesticides Hi-vol Surface Sampler HVS3 with a Teflon catch bottle, sieving through a 150-µm stainless steel mesh US with 50 mL acetone, 1 min Concentration, solvent exchange into cyclohexane, filtration through PTFE membrane filters, GPC, and elution with cyclohexane. Final concentration to 2 mL GC/MS (SIM) NR NR 0.18-0.56 µg g - 1 11 15 pesticides Vacuum cleaner modified to collect dust into a cellulose extraction thimble (45-90 min, 4g/sample) Addition of a SS (pterphenyl-d 14 ) and/or matrix spike solutions in hexane. Equilibration for 30 min, and Soxhlet with 6% DE in hexane, 16 h Concentration to 10 mL, clean-up in a Florisil column, elution with 20 mL acetone-hexane (10%), concentration and elution with 2 mL DE-hexane (10%) GC/MS (SIM) NR NR 0.2-1 µg g -1 160 2 insecticides: permethrin and cyfluthrin Dust collected with a vacuum cleaner (10- 770 g) and sieved into two fractions; a fine fraction (<2 mm) and a coarse fraction (> 2 mm) Soxhlet with EtAcO, 15 h Concentration, solvent exchange into hexane, clean-up with silica gel and elution with DCM-hexane 30:70. Solvent exchange to EtAcO GC/EI-MS 93.9- 109.1 3.0- 5.8 0.5 µg g -1 97 Insecticides: pyrethrins, pyrethroids and a synergist Dust collected using a modified vacuum cleaner where the usual dust bag was replaced by a Soxhlet filter tube Soxhlet with 250 mL EtAcO, 15 h Concentration, clean-up on a silica gel minicolumn. Elution with 12 mL DCM-hexane 20:80 for 2 pyrethroids, elution with 13 mL EtAcO-hexane 15:85, solvent exchange to ACN (HPLC) or EtAcO (GC) GC/ECD, GC/FID, HPLC/UV 95.3- 116.8 1.6- 6.3 LOQ = 0.05- 0.5 µg g -1 124 24 pesticides: 18 insecticides, 2 herbicides, 1 fungicide HVS3 vacuum cleaner (high volume small surface sampler, 4-180 g), sieving to a size fraction < 53 µm, and resuspension using a fluidized bed generator (FBG). Addition of a SS (pterphenyl-d 14 ). Soxhlet with DE in hexane (6%, 16-18 h) Concentration to 20 mL by rotary evaporation (40ºC, N 2 ) GC/MS (SIM) NR NR NR Page 69 of 69 Accepted Manuscript 28 161 4 organophospho rous pesticides HSV3 sampler (cyclone-equipped vacuum sampler, which collects small particles in a Teflon catch bottle, 5 g). Particles sieved through a 150-µm stainless steel mesh US with 50 mL acetone, 1 min Concentration (N 2 ), solvent exchange into cyclohexane, filtration through PTFE membrane filters, GPC, and elution with cyclohexane. Concentration with K.D. and final concentration to 2 mL (N 2 ) GC/MS 72-106 ≤20 LOQ = 11-40 ng g -1 100 23 pesticides Dust collected using a vacuum cleaner and homogenizated in a food processor SE with 5 mL acetone by shaking, 45 min Filtration through a funnel containing glass wool and concentration to 1 mL (N 2 ). Addition of IS GC/CI (with isobutene)-MS 60.7-135 1.4- 18.3 25-100 ng g -1