Progress report. Nov 2013 Apr 2014

Transcription

1 Progress report Nov 2013 Apr 2014 Alin Ionas (ESR 1) Supervisor: Adrian Covaci

2 Projects 1. Analysis of textile samples (carpets & curtains) for FRs (secondment IVM + ToxLab) 2. Leaching/migration experiments of PBDEs from hard plastics & toys (Secondment IVM) 3. Participated (ToxLab) at the NORMAN Collaborative Trial 4. Other adjacent activities 2

3 1. Analysis of textile samples for FRs Sample collection: - Curtains (47 samples, from 3 stores) - Carpets (14 samples, from 2 stores) Instrumental analysis: - Screening: Direct probe-tof (IVM, secondment) - GC-MS (EI and ECNI ToxLab) - LC-QqQ (if HBCD is detected) 3

4 1. Analysis of textile samples for FRs Screening: Direct probe-tof (worked with Ana on it) - First: checked detection limit in textiles Un-complicated matrix: ~0.025% Complex matrix: ~0.1% - Next: created an adequate vaporizer temperature gradient Start: 225 C End: 300 C Run-time: 5 min 4

5 1. Analysis of textile samples for FRs Typically, most analytes would desorb from the matrix within 1.5 min e.g. textile sample spiked with PBDE standards At too high temperature, samples can get carbonised high noise + possibly source contamination Hepta BDE Hexa BDE Octa BDE Penta BDE 5

6 1. Analysis of textile samples for FRs Above: un-complicated matrix/best-case scenario (textile spiked with PBDEs) Not many brominated clusters observed (DP) perhaps low amounts or other FR systems used (N- or inorganic FRs, inherently FR fabrics e.g. polyester) trace analysis (GC-MS or ToxLab Data analysis ongoing 6

7 2. FR leaching into saliva from toys Saliva simulant used: British Standard Specification BS 6684 / 1987 (adjusted to ph=6.8) Preliminary tests: CRM EC-591 used (for PBDEs in polypropylene) significant leaching for 24h test (at the limits of solubility of the PBDE congeners in water) Extraction: LLE with n-hexane/dcm (1:1) (2 5 ml) Experimental setup: - VWR Incubating Orbital shaker used at 250 rpm - Volume and ph of saliva simulant: 30 ml, ph=6.8 - Migration temperature: 37 ºC 7

8 2. FR leaching into saliva from toys To study the leaching process (using the CRM): different time points were considered (15 min, 30 min, 1h, 2h, 4h, 8h, 16h) (in triplicate) For real samples: 2 exposure scenarios considered: - Low exposure (15 min) - High exposure (1 h) - favorite toy scenario - Matrices: mainly hard plastic, also textile tested Sample/CRM used: 10 cm 2 (the approx. corresponding surface area of a child s open mouth/earls et al. 2003/CSTEE 1998) To assess how well real-life conditions are simulated migration experiment with real human saliva (30 ml, from 9 donors) 8

9 2. FR leaching into saliva from toys (Shorter) analysis method prepared for this on GC- ECNI/MS (nona BDEs included) Column: Agilent J&W DB-5HT 15m 0.25mm 0.1 µm i.d. 9

10 2. FR leaching into saliva from toys New internal standards used: F-BDE 47 & F-BDE 183 All samples injected Data analysis ongoing 10

11 3. NORMAN Collaborative Trial (ToxLab) Non-target screening of organic substances in river water - Sampling point: downstream Ruse (BG)/Giurgiu (RO) - Sample initial volume: 1000 L after sample prep. 1.5 ml Instruments used: - LC-QToF (AJS ESI) - GC-EI/MS 10 analytes identified & reported (e.g. Tributylphosphate, Metformin, Tramadol, Venlafaxine, Carbamazepine, Telmisartan, Terbutylazine, Acesulfame, Atrazine, DEET) 11

12 4. Other adjacent activities Started compiling the information about my screening / identification experiments for halogenated chemicals using (Q)ToF type detectors into a publication Submitted 2 abstracts for the SETAC Europe 24th Annual Meeting (posters): - Ionas AC, Ballesteros Gómez AM, Leonards PEG and Covaci A. Identification strategies for halogenated flame retardants and related chemicals - Ionas AC, Dirtu AC, Anthonissen T, Neels H, Covaci A. Harmful organic chemicals in children s toys due to use of recycled materials 12

13 4. Other adjacent activities Worked on three publications which are in preparation (as a result of previous collaborations) Set up a powerful data analysis workstation to be used by remote access - Advantages: Data available from anywhere in the world (workstation =centralised data hub) Data processing possible from anywhere in the world Multiple users can run demanding data processing simultaneously Only one software licence required for multiple users (reduced costs) 13

14 Other future work Analyse all data generated during 2 nd part of my secondment Analyse textile samples by GC-MS (or LC-MS/MS, if required) Prepare abstracts for Dioxin 2014 Prepare posters for SETAC Europe 2014 Prepare secondments (Japan and Australia) within INTERFLAME 14

15 Thank you for your attention 15

16 Direct Probe The capillary used for the direct probe is similar to a tube used to take the melting point of a chemical. 16

17 Saliva simulant solution Saliva simulant of choice: BS 6684 according to the British Standard Specification for Safety Harnesses g sodium chloride 0.3 g potassium chloride 0.3 g sodium sulphate 0.4 g ammonium chloride 0.2 g urea 3.0 g lactic acid dissolved in 1000 ml distilled water adjusted to ph 6.8 BS 6684:1987 Specification for safety harnesses (including detachable walking reins) for restraining children when in perambulators (baby carriages), pushchairs and high chairs and when walking 17