DECABROMODIPHENYL OXIDE
C12 Br10 O
MW: 959.12
METHOD: 2559, Issue 1
CAS: 1163-19-5
RTECS: KN3525000
EVALUATION: PARTIAL
OSHA : no PEL NIOSH: no REL ACGIH: WEEL: 5.0 mg/m3
PROPERTIES:
2559
Issue 1: 15 March 2003
solid, white powder; MP 300 °C; sp gr 3.0; decomposes @ ca. 425 °C
SYNONYMS: DBDPO; Pentabromophenyl ether; bis(pentabromophenyl)ether; decabromodiphenyl ether; decabromobiphenyl ether.
SAMPLING SAMPLER:
Filter (Quartz fiber filter, 37-mm)
FLOW RATE:
2.0 L/min
VOL-MIN: -MAX:
48 L 960 L
SHIPMENT:
Ship at ambient temperature.
SAMPLE STABILITY:
At least 30 days @ room temp.
BLANKS:
2 to 10 field blanks per set.
MEASUREMENT TECHNIQUE:
HPLC, UV DETECTION
ANALYTE:
Decabromodiphenyl oxide (DBDPO)
DESORPTION:
1.5 mL DMSO; place on a rotary shaker for minimum of 2 hours.
INJECTION VOLUME:
5 µL
MOBILE PHASE:
98% methanol/2% pH 7 buffer of KH2 PO4 and Na2 HPO4 @ 0.225 mL/min; ambient temperature.
COLUMN:
C-18, 5 µm, 150 cm x 2.1 mm ID or equivalent .
ACCURACY DETECTOR:
UV absorption @ 228 nm.
RANGE STUDIED:
Generated atmospheres not studied.
CALIBRATION:
DBDPO dissolved in DMSO.
BIAS:
Not determined
RANGE:
2 to 240 µg per sample.
OVERALL PRECISION (Ö r T ): Not determined ACCURACY:
Not determined
ESTIMATED LOD: 1.0 µg per sample. PRECISION ( þ r ):
0.038 @ 2.6 to 240 µg per sample. [1]
APPLICABILITY: The working range is 0.002 to 5.0 mg/m3 . An appropriate range of calibration standards should be used to bracket the expected analyte concentration range. To prevent the need to switch detector sensitivity settings for field samples with higher levels of DBDPO, a calibration curve made from standards containing greater levels of DBDPO may be appropriate. This method was developed to analyze DBDPO in an air sample.
INTERFERENCES: None identified - however, compounds with a similar retention time may interfere. Positive identification may be confirmed by dual column chromatography using an appropriate alternative LC column. Identification can also be confirmed by mass spectrometry.
OTHER METHODS: None identified.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition DEC ABR OM OD IPHEN YL OX IDE: ME TH OD 2559, Issue 1, dated 1 5 Ma rch 2003 - Page 2 of 4 REAGENTS:
EQUIPMENT:
1. Me than ol, HP LC grad e.* 2. Dim ethyl Su lfoxide (DM SO ), HP LC grad e.* 3. Decabromodiphenyl oxide, 98%. Sold as Pentabromophenyl ether (Sigma-Aldrich, Milwa ukee, W I., or equivalen t).* 4. Potassium dihydrogen phosphate (KH 2PO 4). (Sigm a-Aldrich, Milwaukee, W I., or equivalent). 5. Disodium hydrogen phosphate (Na 2HPO 4). (Sigm a-Aldrich, Milwaukee, W I., or equivalent). 6. Mobile phase buffer: 1.509 g KH 2PO 4 and 2.477 g Na2HPO 4 in 1 L deionized water.
1. Sam pler: quartz fiber filter, 37-m m diame ter, 0.45 mm thick (SKC, Eighty Four, PA, or equivalent), backed by a cellulose support pad 37-mm OD, in a two part, 37-mm cassette filter holder. 2. For calibration and QC sam ples, filter spacer rings are u sed instea d of a sup port p ad. Space r Ring, 37 m m (SKC , Eighty Four, PA). 3. Personal sampling pump capable of operating for 8 hr at 2 L/min., with flexible connecting tube. 4. Lab qua ke rotary shak er or equ ivalent. 5. Vials, Autosampler, glass with PTFE lined crimp or screw top cap. 6. Forceps. 7. Syringes, glass: 5-µL, 10-µL, 1-mL, other sizes as needed. 8. Liquid Chromatograph: Shimadzu LC-10ADvp pum p, SIL-10AD vp auto injector, and SPD 10AVvp UV detector (or equivalent), Alltech Alltima C -18 5µ, 150 X 2.1 m m colum n (or equivalent).
- See SPECIAL PRECAUTIONS
SPECIAL PRECAUTIONS: Decabromodiphenyl Oxide is a cancer suspect agent and irritant. Methanol is a flamm able liquid, toxic. DMSO is an irritant, wear protective clothing as it can penetrate the skin.
SAMPLING: 1. Calibrate each personal sampling pump with a representative sampler in line. 2. Sam ple at an accurately known flow rate of 1.0 to 2.0 L/min for a volume of 48 to 960 L. 3. After the sa m ple is c olle cte d, p lace the plastic plugs in the tubing connector stubs on the sampling cassette.
SAMPLE PREPARATION: 4. Extract Filters: a. Re m ove the filter fro m the cass ette with a pair of forceps, discard the support pad, fold the filter and transfer to an autos am pler vial. b. Add 1.5 mL of DMSO and cap the vial with the appropriate top. c. Place the vial on the labquak e rotary shaker (VW R Sc ientific, Batavia, IL). Rotate the samples for a m inim um of 2 h ours . Place sam ples in an ultrasonic ba th for 3 0 m inutes . NOTE: Decabrom odiphenyl oxide is not a highly soluble com pound. T o insure com plete s olubility, both m anual agitation and sonication are used on the samples to solubilize the decabromodiphenyl oxide. 5. Prepare the filter extract for analysis. a. Carefully remove the septum cap from the vial containing the extracted filter. b. Using a transfer pipette, remove as m uch liquid extract from the extraction vial as possible and trans fer to a n au tosa m pler vial. Cap the vial with an app ropriate se ptum cap .
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition DEC ABR OM OD IPHEN YL OX IDE: ME TH OD 2559, Issue 1, dated 1 5 Ma rch 2003 - Page 3 of 4
CALIBRATION AND QUALITY CONTRO L: 6. Ca librate daily with at least six ca libration standards to cover the concentration range of the samples. A typical liquid chromatogram of a DBDPO standard is shown in Figure 1. a. Prepare calibration standards by adding kno wn am ounts of the DB DPO standard solution or a secon dary stock solution prepared from the standard solution to an au tosa m pler vial conta ining 1.5 mL DMSO. b. Analyze with samp les and blanks (steps 9 & 10 ). c. Prepare a calibration graph (pe ak area vs. µg DB DPO ). 7. Determine the recovery (R) of the an alyte fro m the sa m plin g m edia using the quartz fiber filters with analyte spikes in the concentration range of the samples (see step 6). Prepare three filters at each of five levels plus two media blanks. a. Place a filter spacer ring in the bottom section of a two part 37-m m filter cassette. Place a 37-m m quartz fiber filter on top of the spacer ring (do not use a s upport pad). b. Inoc ulate the filter with a known amount of calibration stock solution with a microliter syringe, place the top section of the cassette in place and seal the filter in place by squeezing the two sections together. c. Place the plugs in the inlet and outlet tubing stubs and set the cassettes aside for a minimum of twelve hours. d. Prepare the filter samples (steps 4 & 5) and analyze with the calibration standards. e. Prepare a graph of R vs. µg DBDPO. 8. Analyze three quality control blind spikes and three analyst spikes to ensure that the calibration graph and R gra ph are in control.
MEASUREMENT: 9. Se t the liquid chromatograph according to manufacturer’s recomm endations and to conditions given on page 2559-1. Inject sample with autosampler or by manual injection. NOTE: If peak area is above the linear range of the calibration standards, dilute the sample with DMSO, reanalyze, and app ly the app ropriate dilution facto r in calculation s. O r, prepare a calibration curve with stan dard s of h igher levels of D BD PO . 10. Measure peak area of DBDPO peak and determine µg per sample from calibration graph.
CALCULATIONS: 11. From the calibration graph, determ ine the ma ss, µg (correc ted for R) for the sam ple (W ), and average m edia blank (B). 12. Calculate conce ntration, C, of decabrom odiphenyl oxide in the air volume sam pled, V(L):
NO TE : :g/L = m g/m 3
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition DEC ABR OM OD IPHEN YL OX IDE: ME TH OD 2559, Issue 1, dated 1 5 Ma rch 2003 - Page 4 of 4 EVALUATION OF METHOD: This method was not evaluated with laboratory generated air sam ples. All of the recovery and storage study determinations have been performed with laboratory spiked filters in the development of this method. Air was not pulled throug h the filters prior to analysis. The LO D/LO Q values are 1.0 µg/sa m ple and 3.3 µ g/s am ple res pectively, based on a liquid standard calibration curve. Reco very of spiked quartz fiber filters rang ed from 94.5% to 104.2% for an alyte quantities of 2.6 3 to 25.1 µg/filter using liquid standa rds as the sp iking solution. A thirty day storage stability study of DBDPO spiked on quartz fiber filters indicates that the recovery of the ana lyte at a level of 5.01 :g/filter (N=12) is 103.0%. The sam ples were stored in a closed cardboa rd container at roo m tem pera ture fo r the duration of the study.
REFERENCES: [1] [2]
Jaycox LB, May LR [2001]. Backup data report for decabrom odiphen yl oxide m etho d de velop m ent, Cinc innati, OH: Natio nal Institute fo r O ccupatio nal Safety and H ealth, D AR T/NIOSH (un published report). Riess M, van Eldik R [1998]. Identification of Brominated Flame Retardants in Polymeric Materials by Re vers ed-P has e Liqu id Ch rom atog raph y with Ultraviolet D etec tion. J C hrom atog raph y, 827 65-71.
AUTHORS: Larry B. Jaycox, Ph.D., NIOSH/ DART. Leroy R. May, NIOSH/ PRL.
FIGURE 1: This chrom atogram shows a standard of decabromodiphenyl oxide at 22.0 ug/sample. The m ajor pea k at approximately 12.2 m inutes is DB DP O.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition