Use of Large-Volume Resin Cartridges for the Determination of

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14 Use of Large-Volume Resin Cartridges for the Determination of Organic Contaminants in Drinking Water Derived from the Great Lakes Guy L. LeBel, David T. Williams, and Frank M. Benoit Monitoring and Criteria Division, Environmental Health Directorate, Health and Welfare Canada, Tunney's Pasture, Ottawa, Ontario, K1A OL2 Canada A large-volume XAD-2 sample approximately to obtain sufficient

resin sampling cartridge was designed to 1500 L of raw and treated drinking

organic water extracts for chemical

water

analysis

and biological testing. The concentration technique was evaluated for the extraction and subsequent target compounds ng/L.

Recoveries

chemical

analysis of

several

in 1500 L of water samples fortified

at 10

were greater than 70%; these recoveries

were

similar to earlier recoveries employing a smaller volume

cartridge.

The cartridges were used to obtain water extracts from six Great Lakes

area

analyzed

drinking

for

hydrocarbon,

and

chromatοgraphy-mass compounds

water

supplies,

organophosphorus, triaryl-alkyl

and

the

organochlorine, phosphate

spectrometry

were found at nanograms-per-liter extracts by two GC-MS

were

polyaromatic

compounds

(GC-MS).

both raw and treated water samples. Analysis field-water

extracts

Some

by

gas

of

the

concentrations in of fortified

laboratories

gave

and

similar

intra- and interlaboratory precision and accuracy data.

IVIACRORETICULAR R E S I N S , particularly the Amberlite XAD series, have been used extensively to isolate and concentrate trace organic com pounds from drinking water (1-8). We have previously reported the use of an X A D cartridge for this purpose and have evaluated the system for the analysis of organophosphorus pesticides (OPs) (4), polynuclear aro matic hydrocarbons (PAHs) (5), phosphate triesters (TAAPs) (6), or0065-2393/87/0214/0309$06.00/0 Published 1987 American Chemical Society

Suffet and Malaiyandi; Organic Pollutants in Water Advances in Chemistry; American Chemical Society: Washington, DC, 1986.


310

ORGANIC POLLUTANTS IN WATER

ganochlorine compounds (OCs) (7), and polychlorinated biphenyls (PCBs) (8). The drinking water extracts were also tested for biological activity b y using the SaimoneZWmammalian-mierosome assay (9, JO). T o provide sufficient material for chemical analysis and an extended battery of biological tests consisting of Sa/mone//a/mammalian-microsome assay, sister-ehromatid exchange ( S C E ) , and micronucleus ( M N ) induction in Chinese hamster ovary ( C H O ) cells (21), it was necessary to m o d i f y and evaluate the X A D resin cartridge for sampling very large volumes (>1000 L) of raw and treated water. This chapter presents the results of studies on cartridge design for evaluation using fortified water samples and the application of the modified cartridge to obtain residual organic compounds for chemical analysis of field samples of drinking water. The biological activity results have already been reported elsewhere (11).

Materials and Methods X A D Resin Cartridge Design. The purification and sources of materials and sampling parameters have been described previously (4, 6) for a small X A D - 2 cartridge used for sampling up to 2000 L of water. A large-volume cartridge for sampling up to 2000 L of water was constructed f r o m stainless steel tubing and fittings and had a b e d volume of approximately 325 m L of X A D - 2 resin. A cross section of the sampling cartridge is illustrated in Figure 1. The dimensions and sampling parameters of the two types of cartridges are shown in Table I. By using a relative f l o w rate similar to that of the small-volume cartridge, that is, 3 bed volume/min, the sampling rate for the largevolume cartridge was approximately 1 L / m i n ; this rate allowed for the collection of a total sample volume of approximately 1500 L during a 24-h period. E v a l u a t i o n of Recovery of Organic C o m p o u n d s w i t h the L V - X A D - 2 Cartridge. The recoveries of selected organic compounds

Table I. Parameters for XAD-2 Sampling Cartridges Parameter Length Outer diameter Inner diameter Bed volume Flow rate (3 bed vol/min) Total volume/24 h Eluent volume

Small-Volume Cartridge 40.5 1.6 1.4 45 140 200 300

cm cm cm mL mL/min L mL

Large-Volume Cartridge 40.5 3.8 3.2 325 1000 1450 1000

cm cm cm mL mL/min L mL



Figure 1. Cross section of sampling cartridge: 1, stainless steel swagelok nut, 0.64 cm (~ in.), no. SS-402-1; 2, stainless steel swagelok male connector, 0.95 cm (fin.), NPT no. SS-400-1-6; 3, Teflon O-ring, 2.664 cm i.d., wall thickness 0.262 cm; 4, stainless steel screen, 40 mesh; 5, stainless steel swagelok cap ( modified with female § in. NPT through end ), no. SS-2400-C; 6, Pyrex brand glass wool; 7, XAD-2 Amberlite resin; and 8, 304 stainless steel tube, 3.81 X 0.305 cm (1.5 X 0.120 in.), ASTM A269.


r


312


were determined b y the direct fortification technique (6). F o r this technique, a known amount of organic compounds was added directly to the X A D resin column. A second cartridge was attached in series to the fortified cartridge to determine whether l o w recoveries of specific compounds were due to breakthrough. After 1500 L of tap water had passed through the cartridges, the residual water was drained f r o m the cartridges, which were then eluted with 1 L of 152 acetone/hexane (v/v). The organic phase f r o m the eluate was dried b y filtration through purified anhydrous sodium sulfate and was then concentrated to a small volume. The aqueous phase of the eluate was extracted with methylene chloride to determine the loss of the more polar organic compounds. F o r organochlorine determinations, the extracts were further purified b y Florisil (magnesium silicate) column chromatography (12) before analysis b y capillary gas chromatography with an electron capture detector ( G C - E C D ) . Field Samples. Duplicate cartridges were connected in parallel to both raw and finished water outlets at each water processing plant after the taps were flushed for at least 15 m i n (10). The flow rate of water through each cartridge was set at 1 L / m i n , monitored, and, if necessary, adjusted at set intervals. After 24 h, the cartridges were disconnected, sealed with swagelok nuts, and brought back to the laboratory. The adsorbed organic compounds were eluted f r o m the resin with 1 L of 152 acetone/hexane f o l l o w e d b y acetone (350 m L ) . The eluates were each concentrated to 10 m L and stored at 4 °C. Blank extracts were obtained b y elution of regenerated X A D - 2 cartridges (4). T w o aliquots (102 extract-aliquot) of the acetone/hexane eluates were used for gas chromatographic-mass spectrometric ( G C - M S ) and gas chromatographic ( G C ) analyses by two different laboratories. The remaining extracts were retained for biological testing (II). C h e m i c a l Analysis of Extracts. The extracts were analyzed b y capillary column G C - M S for O C s , T A A P s , and P A H s (see the list on page 313). The G C - M S parameters used at the two laboratories are shown in Table II. The identification and quantitation were all done b y using automatic routines based on a mass spectra library created f r o m authentic standards of the selected compounds. C o m p o u n d s were located b y searching the reconstructed ion chromatogram for each library entry within a narrow retention time w i n d o w relative to the internal standard (anthracene-dio or phenanthrene-dio). Quantitation was achieved b y comparison of characteristic ion areas in the field samples with ion areas of the internal standard. These ion areas were normalized by response factors established b y comparison of ion ratios of a standard mixture of all 66 analytes at a concentration of 2.5 n g ^ L . The extracts were also analyzed for OPs and T A A P s b y capillary G C equipped with a nitrogen-phosphorus selective detector ( G C - N P D ) (6, 8). Suffet and Malaiyandi; Organic Pollutants in Water Advances in Chemistry; American Chemical Society: Washington, DC, 1986.

14.

LEBEL E T AL.

313

Large-Volume Resin Cartridges

List of Organic Compounds Analyzed in X A D - 2 Extracts PAHs

TAAPs

Naphthalene 2-Methylnaphthalene 1-Methylnaphthalene Biphenyl 1 -Ethylnaphthalene 2-Ethylnaphthalene 2,6-Dimethylnaphthalene 1,3-Dimethylnaphthalene 1,4-Dimethylnaphthalene 1,5-Dimethylnaphthalene 2,3-Dimethylnaphthalene 1,2-Dimethylnaphthalene Bibenzyl cis-Stilbene /rans-Stilbene 2,3,6-Trimethylnaphthalene 2,3,5-Trimethylnaphthalene Fluorene 3,3'-Dimethylbiphenyl 4,4'-Dimethylbiphenyl 9-Fluorenone Phenanthrene Anthracene 2-Methylanthracene 9-Methylanthracene Anthraquinone Fluoranthene Pyrene

Triethyl phosphate Tributyl phosphate Tris(2-chloroethyl) phosphate Tris(l,3-dichloropropyl) phosphate Triphenyl phosphate Tributoxyethyl phosphate 2-Ethylhexyldiphenyl phosphate ο -Isopropylphenyldiphenyl phosphate Tri-o-tolyl phosphate Tri-m-tolyl phosphate p-terf-Butylphenyldiphenyl phosphate Tri-2,4-xylyl phosphate


OCs 1,4-Dichlorobenzene 1,2-Dichlorobenzene 1,3,5-Trichlorobenzene 1,2,3-Trichlorobenzene 2,4,5-Trichlorotoluene 1,2,3,5-Tetrachlorobenzene 1,2,3,4-Tetrachlorobenzene Pentachlorobenzene Hexachlorobenzene 7-BHC a-BHC

β-mc

Aldrin Dieldrin Octachlorostyrene ρ,ρ'-ΌΌΕ ρ,ρ'-DDT Photomirex Mirex Hexabromobiphenyl Heptachlor epoxide Oxychlordane 7-Chlordane a-Chlordane ûf-Endosulfan β-Endosulfan

OPs Dimethoate Diazinon Phosphamidon Methylparathion Ronnel Fenitrothion Malathion Dursban Parathion Ruelene Supracide Ethion Trithion Imidan EPN Azinphos-methyl Phosalone

N O T E : O C S and PAHs were analyzed by G C - M S ; TAAPs were analyzed by G C - M S and G C - N P D ; and OPs were analyzed by G C - N P D .

Results and Discussion Large quantities of organic extracts of Great Lakes raw and treated water were required for chemical analysis and for biological testing. T o provide a sufficient amount of material for these tests, an X A D - 2 cartridge was designed to allow the sampling of 1500 L of water, about 7 times the volume of our earlier studies (10). Water samples were collected during a 24-h period at a flow rate of 1 L / m i n , that is, 3 b e d volume/min. Suffet and Malaiyandi; Organic Pollutants in Water Advances in Chemistry; American Chemical Society: Washington, DC, 1986.

314


Table II. GC-MS Parameters for Analysis of L V - X A D Extracts Lab A

Lab Β

Finnigan 4100-INCOS DB-5 15 m X 0.25 mm i.d. 10" A/V 0.3 A 1350 V 3 μ ι splitless 250 °C

Finnigan 4500-INCOS DB-1 30 m X 0.25 mm i.d. 10~ A/V 0.5 A 1350 - > 1450 V 2 μία splitless 250 °C

50 °C 0.1 min 100 °C 15 °C/min 270 °C 5 °C/min 60 min total run anthracene-dio 4 (average)

50 °C 0.1 min 180 °C 8 °C/min 285 °C 10 °C/min 10 min phenanthrene-dio 2 (average)

Parameter


System Column Sensitivity Filament current Electrometer voltage Injection volume Injection temperature Oven temperature program Initial temperature Hold time Final temperature (level 1) Rate (level 1) Final temperature (level 2) Rate (level 2) Hold time Internal standard Quantitation (number of ions)

7

8

The recovery of selected O P and O C compounds was determined b y fortifying the X A D - 2 resin at a level equivalent to 10 ng/L, and 1500 L passed through the cartridge. T h e concentrated extracts f r o m the fortified samples were analyzed b y G C - N P D (Table III) and G C - E C D (Table I V ) . T h e results i n Tables III and I V show similar recoveries for the small and the large cartridges. This finding indicates that propor tional increases i n the volumes of X A D - 2 resin and water samples d i d not cause significant changes i n recovery of the organic compounds. N o O C s and only a small percentage of the more polar T A A P s (Table III) broke through the first column onto the second X A D - 2 cartridge. Only tris(2-chloroethyl) phosphate (13.92) was detected i n the extract of the aqueous phase derived f r o m solvent elution of the X A D - 2 cartridge. Although the percentage recoveries were not determined for other organic compounds (i.e., P A H s , O C and O P pesticides, and P C B s ) , w e believe f r o m our previous studies (4-8) that the percentage recoveries w o u l d be similar for these other classes of compounds. T o field test the large-volume cartridges, the cartridges were used to accumulate the waterborne organic compounds i n drinking water supplies f r o m five selected Great Lakes areas: Sault Ste. Marie, A m herstburg, Fort E r i e , Burlington, and C o r n w a l l . Barrie, which is about 25 k m f r o m the Great Lakes and has ground water supply, was chosen as a control site. Duplicate organic concentrates from raw and treated water were obtained f r o m each site once during the summer of 1982 and once during the winter of 1983. Aliquots of the extracts were


14.

LEBEL ET AL.


Table III. Τ ΑΑΡ Percent Recoveries at 10-ng/L Fortification Level Large Volume (1500 L) 1st Cartridge


TAAP Tributyl phosphate Tris(2-chloroethyl) phosphate Tris(l,3-dichloropropyl) phosphate Triphenyl phosphate Tributoxyethyl phosphate 2-Ethylhexyldiphenyl phosphate ο -Isopropy lphenyldiphenyl phosphate Tri-o-tolyl phosphate Tri-m-tolyl phosphate p-tert- Butylphenyldiphenyl phosphate Tri-2,4-xylyl phosphate

112.9 81.8 (13.9) 96.8 97.8 101.6 95.5 b

c

2nd Cartridge

Low Volume (200 L)

0.3 5.5 (1.6)

101.2 95.5 nd 107.4 141.0 nd

c

— —

1.8 —

97.0 94.6 92.2

— — —

95.9 90.7

— —

a

nd 97.0 (cresyl) nd nd nd

N O T E : —means not found; nd means not determined. Data are taken from reference 6. Value is from a single determination. Value is for the aqueous phase (see text).

a

b c

analyzed b y two laboratories b y G C - M S for 66 analytes (listed on page 313), which were selected on the basis of the results of earlier studies. The results of analyses of the extracts b y G C - M S are presented i n Tables V - V I I where the analytes detected are listed. T h e results presented i n the tables are the average results of the duplicate samples and both laboratories when a compound was detected b y both analysts. Table IV. Percent Recoveries for OC Compounds at 10-ng/L Fortification Level OC

Large Volume (1500 L)

Low Volume (200 L)

1,4-Dichlorobenzene 1,2-Dichlorobenzene 1,3,5-Trichlorobenzene 1,2,3-Trichlorobenzene 2,4,5-Trichlorotoluene 1,2,3,5-Tetrachlorobenzene 1,2,3,4-Tetrachlorobenzene Pentachlorobenzene Hexachlorobenzene Octachlorostyrene Photomirex Mirex Hexabromobiphenyl

70.0 80.7 70.0 86.0 81.3 103.3 88.7 76.7 76.0 74.7 79.3 72.0 74.0

67.0 68.3 69.6 79.7 79.4 87.5 86.9 90.8 89.7 89.0 79.8 68.4 61.9

N O T E : No O C s were found in the backup cartridge.



4,4'-Dimethylbiphenyl

3,3'-Dimethylbiphenyl

Biphenyl

Trimethylnaphthalene

Dimethylnaphthalene

Methylnaphthalene

Naphthalene

Compound

— — — — — — — — —

14.5 16.8

S

—

— — — — — — — —

W 9.4 8.4

Barrie

— — —

— — —

3.4 40.5 0.9* 1.5

S

—

—

— —

— — —

1.3

5.9 4.2

W

Cornwall

fe

— — —

1.6

15.1 9.8 61.9 5.3 63.1 0.2 23.2

S

b

5.7

5.7

—

4.0

12.8 4.1 72.2 2.9 232.4 2.3 99.8

W

Burlington

—

— —

— — —

3.5 5.2 2.2 3.1

S

—

—

— —

—

b

0.3

6.6 9.9 1.8 4.4

W

Fort Erie

—

b

0.3* 0.3

— —

3.9 5.2 4.7 1.1 1.8

S

—

1.8 1.3

23.2 20.0 32.3 17.5 19.5 3.9 2.7

W

Amherstburg

Table V. P A H Levels (ng/L) in Great Lakes Water as Determined by GC-MS


—

—

b

0.8 2.4

—

5.0

—

48.9 101.0 9.4 14.7

S

— —

— — —

95.7 23.7 10.4 2.6

W

Sault Ste. Marie


—

—

—

Anthracene Methylanthracene

0.3* 0.2*

—

0.6* 0.4*

—

—

—

0.8* 0.3 0.3*

—

0.6* 1.1 0.5 0.7 0.3*

— — —

—

1.0* 0.8* 0.7* 0.3*

—

14.0

— 0.3* 0.8* 0.4* 0.7*

—

1.3 13.1 1.5

5.4 0.8

—

0.6

—

0.4*

— — —

0.5* 0.6 0.6* 0.3*

— e

b

1.1 1.0 0.2

1.0* 0.6 4.2 0.7 8.5 0.8*

— 2.4

— 0.3* 1.3* 0.7 0.8* 0.7

— —

b

0.2 2.6 0.6 3.4 0.5

—

—

— —

—

1.9 1.6 1.6 2.5 2.4 2.1

—

20.5

—

2.1 0.7 2.2

0.4* 0.7

—

1.7

—

0.7* 1.4

— —

—

1.6 1.3 3.0

—

—

0.9

—

33.7 0.5 1.2

— — —

18.9

2.7 4.9 9.8 1.4 3.1

3.0

04 v».*x

3.1 6.5 23.1

—

2.4 5.6

fe

1.2 2.2 1.2* 1.1*

— —

—

—

5.3

—

0.3

—

— 0.9

a

N O T E : S indicates summer, and W indicates winter. For each compound, the first row gives levels for raw samples, and the second row gives levels for treated samples. Laboratory A. * Laboratory B.

Pyrene

Fluoranthene

Anthraquinone

—

_

1.0 0.9

9-Fluorenone Phenanthrene

0.4 0.4

— — — —

0.6 0.1

—

Fluorene



-

0.4

W

9.8 0.2

14.3 7.0 8.3 4.3 3.7 1.7 11.9 5.3 4.5 2.1 0.8 0.6

W

Cornwall

b

54.4 11.0

2.2 12.9

2.6

7.8 11.6 2.3 3.0

b

16.6 6.4

3.4 8.2 2.8 4.9 1.6* 1.6

W

Burlington

1.4 1.9 1.3* 1.3*

0.9 1.3 1.7* 1.0

W

Fort Erie

5.9 6.0

1.5 1.2

6.1 6.5 10.7 3.6

0.4

W

Amherstburg

N O T E : S indicates summer, and W indicates winter. For each compound, the first row gives levels for raw samples, and the second row gives levels for treated samples. None of the T A A P compounds were detected in Sault Ste. Marie samples, ο-Isopropylphenyldiphenyl phosphate was only detected by laboratory Β in the treated, summer, Amherstburg sample at a concentration of 1.2 ng/L. £ Laboratory A (not shown). Laboratory B.

Tributoxyethyl phosphate

Triphenyl phosphate

Tris ( 1,3-dichloropropy1) phosphate

Tris(2~chloroethyl) phosphate

Tributyl phosphate

Triethyl phosphate

Compound

BarHe

Table V I . Τ ΑΑΡ Concentrations (ng/L) in Great Lakes Water As Determined by G C - M S



—

W

0.8 0.8

—

— 2.5

2.1

0.3

— 0.2

—

0.2 1.9 1.6 1.9

— — —

W

S

W

0.4 0.2 0.6 0.9 2.2 2.5

S

Burlington

Cornwall

0.8 2.6

—

— — — —

1.4 1.5

— —

0.4

W S

Fort Erie

— 1.8 3.8

b

0.4 0.6 0.6

S

b b

1.6 1.0 0.4 0.5 1.4 2.0

W

Amherstburg

b

a

N O T E : S indicates summer, and W indicates winter. For each compound, the first row gives levels for raw samples, and the second row gives levels for treated samples. None of the O C compounds were detected in Sault Ste. Marie samples. Dieldrin was only detected by laboratory A in the raw, winter, Cornwall sample at a concentration of 13.8 ng/L. Laboratory A (not shown). Laboratory B.

«-BHC

—

0.2 0.4

1,4-Dichlorobenzene 1,2-Dichlorobenzene

S

Compound

Barrie

Table VII. OC Concentrations (ng/L) in Great Lakes Water as Determined by GC-MS



320


However, when one laboratory reported detection of a compound in both replicates and that compound was not reported b y the other laboratory, only the average for the one laboratory was reported. Single occurrences were not reported. The field-sample extracts were also analyzed for T A A P s and O P pesticides b y capillary G C - N P D ; however, no O P pesticides were detected. T h e T A A P results are shown in Table VIII. The use of the N P D - s p e c i f i c detector permitted lower detection limits than G C - M S for the T A A P (8); however, all of the higher concentrations were in agreement with results obtained b y G C - M S . Similar to our earlier surveys, triethyl phosphate levels were highest in the eastern section of the Great Lakes system. T o estimate the validity of the results obtained b y G C - M S analysis of X A D extracts, eight fortified drinking water extracts were analyzed b y two G C - M S laboratories. Several target-compound mixture solutions were prepared, and fortified extract was made b y spiking various aliquots of the mixture solutions into analyte-free L V - X A D extracts. T h e extracts were fortified with at least t w o concentrations of target com pounds (see the list below). B y assuming a 150-L representative water extract, the analyte amounts w o u l d be equivalent to approximately 1-100 ng/L of water. The results f r o m the t w o laboratories (Tables I X and X ) show an overall percentage deviation of 43.32 f r o m the fortified values. N o strong trends related to the parameters tested were evident, although laboratory A experienced poorer accuracy at the lower spiking levels.

Organics and Fortification Levels (^/μ^ in G C - M S Accuracy Study

Used

OCs

TAAPs

1,2,3-Trichlorobenzene (6.0, 1.6) 2,4,5-Trichlorotoluene (6.0, 1.8) 1,2,3,4-Tetrachlorobenzene (3.0, 0.6) Pentachlorobenzene (4.5, 1.2) Hexachlorobenzene (1.5, 0.8) 7 - B H C (4.5, 0.6) Octachlorostyrene (1.5, 0.4) Heptachlor epoxide (12.0, 1.6) 7-Chlordane (4.5, 0.9) a-Chlordane (3.0, 0.8) a-Endosulfan (6.0, 3.2) p , p ' - D D E (7.5, 1.5) Dieldrin (1.5, 0.8) Mirex (15.0, 2.0)

Triethyl phosphate (7.5, 4.0) Tris(l,3-dichloropropyl) phosphate (30.0, 6.0) Triphenyl phosphate (3.0 [ 4 X ] , 0.8, 1.6, 0.4, 0.6) o-Isopropylphenyldiphenyl phosphate (7.5, 1.0) Tri-o-tolyl phosphate (4.5, 1.2) PAHs Naphthalene (1.5, 0.4) 2-Methyinaphthalene (4.5, 2.4) Fluorene (9.0, 1.2) 9-Fluorenone (6.0, 1.2)

N O T E : Fortified extracts were 0.5 mL.



— — — — — —

_

—

0.4 0.4

— — —

— — — — — — — — — — —

1.8 1.3

0.1

W

S

— —

11.8 11.2 9.5 7.8 9.6 6.3 2.5 1.2 1.1 0.9 16.4 4.1

S

— —

9.9 10.1 4.1 2.2 6.2 3.2 1.7 0.9 0.6 1.1 4.4 1.8

W

Cornwall

— —

9.5 11.2 5.3 7.4 4.2 6.2 1.5 2.1 20.4 1.2 73.8 16.4

— —

5.2 7.0 3.5 4.8 3.0 4.4 0.7 1.5 2.7 0.9 19.8 8.8

— —

1.0 3.3 1.6 3.3 5.7 9.1 1.3 2.2 0.3 1.3 3.5 8.0

— —

0.9 0.6 0.3 1.2 6.0 4.6 1.3 1.2 0.2 0.3 2.8 2.1

W

S

S

W

Fort Erie

Burlingt on

0.1 1.1 1.6 1.2 3.0 6.5 0.3 0.5 8.4 8.6 5.8 5.5 1.8 1.3

S

0.8 4.0 4.9 0.4 0.4 4.5 8.0 8.1 7.8 0.7 0.6

_

0.3

—

W

Amherstburg

N O T E : S indicates summer, and W indicates winter. For each compound, the first row gives levels for raw samples, and the second row gives levels for treated samples. None of the T A A P compounds were detected in Sault Ste. Marie samples except for triphenyl phosphate, which was detected in the raw, summer sample at a concentration of 0.1 ng/L. All values are the mean of two replicate extracts.

ο-Isopropylphenyldiphenyl phosphate

Tributoxyethyl phosphate

Triphenyl phosphate

Tris ( 1,3-dichloropropyl) phosphate

Tris(2-chloroethyl) phosphate

Tributyl phosphate

Triethyl phosphate

Compound

Barrie

Table VIII. Τ ΑΑΡ Concentrations (ng/L) in Great Lakes Water As Determined by GC-NPD


322



Table I X . Accuracy of GC-MS Analysis of Fortified Extracts by Compound Groups Mean Percent Deviation from Fortified Concentration

Compound

No. of Determi nations per Lab

All

Lab A

Lab Β

All PAHs TAAPs OCs

52 8 16 28

43.3 25.0 45.8 47.1

50.1 17.1 49.4 59.8

36.5 32.9 42.1 34.3

Poorer accuracy is to be expected at the l o w levels because the uncer tainty of the measurement rises as the m i n i m u m detection limit is approached. Laboratory Β reported better overall accuracy than laboratory A , particularly for the O C s . T o estimate the precision of the analysis, five of the field-sample extracts were analyzed b y G C - M S i n duplicate at laboratory A . T h e results, gathered b y compound classes, are shown in Table X I . The table also includes the results of a single analysis f r o m laboratory B . T h e average percent deviation of the duplicate analyses f r o m the mean value was 162, whereas the average percent deviation between the results from laboratory Β and the mean value from laboratory A was 222. A comparison of the results f r o m a single analysis of the treated water extracts (summer and winter) for class aggregate concentration i n laboratories A and Β (Table XII) showed an average percent deviation of 202. Hence, the intra- and interlaboratory uncertainties in the results are comparable. T o examine the effect of seasons or water types on the concentra tions of organic compounds, the aggregate sums for the summer and winter water extracts were tabulated (Tables XIII and X I V ) for each water type. O n the basis of the uncertainty data just presented, and with one exception (see Tables XIII and X I V , Burlington P A H s results), no apparent differences or trends i n aggregate organic compound Table X . Accuracy of GC-MS Analysis of Fortified Extracts by Level of Fortification Mean Percent Deviation from Fortified Concentration

Level (ng/extract)

No. of Determi nations per Lab

AU

Lab A

Lab Β

5000

12 37 3

47.8 39.8 62.6

65.3 44.7 55.4

30.3 35.9 69.8


14.

LEBEL ET AL.

323


Table XI. Aggregate Concentrations (ng/L) in Great Lakes Water by GC-MS Lab

Injection No.

PAHs

TAAPs

OCs

Cornwall (R, S)

A

—

Cornwall (T, W)

Β A

1 2

Β A

—

Fort Erie (T, W) Amherstburg (T, S)

Β A

_

Β A

—

Amherstburg (R, W)

Β

—

8.8 3.6 5.8 12.9 14.5 5.3 22.3 32.4 22.6 15.0 8.2 13.1 125.1 119.9 106.1

35.6 35.3 35.1 10.2 10.8 6.1 2.0 .7 2.1 10.7 7.9 9.4 22.3 11.0 15.4

3.4 3.5 4.0 2.0 1.8 .5 1.8 2.5 2.8 4.2 2.8 3.9 5.4 5.0 3.5


Sample*

1 2

1 2 1 2 1 2

S indicates summer, and W indicates winter; R means raw sample, and Τ means treated sample.

a

concentrations could be found for the water types and seasonal varia tion. The aggregate organic compound concentrations for the treated water were also of the same magnitude as those found in our 1980 survey of Great Lakes water quality (JO). A l l the results have been corrected for blank contribution. The X A D - 2 cartridge blanks for the evaluation stage and the field cartridge blanks were essentially free of all of the compounds analyzed. However, the field samples, as w e l l as the field blanks, had significant amounts Table XII. Comparison of Results (ng/L) from Two GC-MS Laboratories TAAPs City Barrie

0

S

Cornwall Burlington Fort Erie Amherstburg Sault Ste. Marie a

Season W

S w s w s w s w s w

Lab A

Lab Β

0.7 7.6 7.8 27.6 19.4 2.6 2.7 7.2 9.0

0.2 16.3 8.2 31.2 21.5 5.2 2.1 10.2 12.0 1.6 0.4

— —

OCs

PAHs

Lab A

Lab Β

Lab A

Lab Β

0.5

0.3

20.0 6.0 45.7 5.0 20.1 10.0 14.2 16.2 15.1 40.5 157.9 26.7

16.2 11.7 43.5 4.3 18.3 12.9 15.8 22.7 14.2 60.6 190.2 44.9

—

2.4 0.4 5.1 5.5 2.5 1.4 4.6 2.0 —

1.7

—

5.0 1.2 4.3 3.1 2.8 2.4 4.1 4.6 3.8 2.1

S indicates summer, and W indicates winter.



12.0 3.7 44.6

TAAPs OCs PAHs 8.0 0.8 4.6

W

1.5 0.2 16.5

TAAPs OCs PAHs 10.2

—

W 36.5 3.2 5.4

S

18.8 0.8 7.1

W

Cornwall

N O T E : S indicates summer, and W indicates winter.

S

Compond

Barne

29.4 4.7 19.2

S 20.5 4.3 11.5·

W

Burlington

3.9 2.7 15.0

S 2.4 1.9 19.5

W

Fort Erie

8.7 4.4 14.7

S

77.4 1.6 202.4

S

23.6 0.6 518.4

W

Burlington

2.7 0.9 8.0

S

1.8 1.5 10.1

W

Fort Erie

9.2 2.6 13.1

S

16.9 3.2 99.7

W

Amherstburg

10.5 3.3 50.5

W

Amherstburg

Table XIV. Aggregate Results (ng/L) for Raw Water (GC-MS)

N O T E : S indicates summer, and W indicates winter.

8.9

—

0.5

—

0.4 18.1

S

W

S

Cornwall

Compond

Barrie

Table XIII. Aggregate Results (ng/L) for Treated Water (GC-MS)


0.2 2.0 35.8

W

74.4

S

110.1

W

Sault Ste. Marie

0.8 1.9 174.1

S

Sault Ste. Mane


14. LEBEL ET AL.


325

of diethylhexyl phthalate ( D E H P ) ( 0 . 5 - 2 0 μg/L of D E H P for an equiv alent 1 5 0 - L aliquot). This finding was traced to the inadvertent use of a short piece of T y g o n tubing b y the analyst during the extract prepara tion stage, although the protocol required the avoidance of all plas tic/rubber components. This interference d i d not cause serious dif ficulties during the G C - M S analysis because the resolving power of the capillary column allowed the isolation of D E H P from the other analytes, and/or the data system could ignore the ions due to D E H P when generating reconstructed ion chromatograms.

Acknowledgments The collection of samples and preparation of the X A D extracts were carried out under contract ( H & W no. 8 8 5 ) b y C o n c o r d Scientific Corporation, D o w n s v i e w , Ontario. Part of the G C - M S analysis was performed under contract ( H & W no. 1084) b y Mann Testing Lab oratories, Mississauga, Ontario.

Literature Cited 1. Junk, G. Α.; Richard, J. J.; Greiser, M. D.; Witiak, D.; Witiak, J. L.; Arguello, M. D.; Vick, R.; Svec, H. J.; Fritz, J. S.; Calder, G. V. J. Chromatogr. 1974, 99, 745-762. 2. Burnham, A. K.; Calder, G V.; Fritz, J. S.; Junk, G Α.; Svec, H. J.; Willis, R. Anal. Chem. 1972, 44, 139-142. 3. Van Rossum, P.; Webb, R. G. J. Chromatgr. 1978,150,381-392. 4. LeBel, G. L.; Williams, D. T.; Griffith, G.; Benoit, F. M. J. Assoc. Off. Anal. Chem. 1969, 62, 241-249. 5. Benoit, F. M.; LeBel, G. L.; Williams, D. T. Int. J. Environ. Anal. Chem. 1979, 6, 277-287. 6. LeBel, G. L.; Williams, D. T.; Benoit, F. M. J. Assoc. Off. Anal. Chem. 1981, 64, 991-998. 7. McNeil, Ε.; Otson, R.; Miles, W.; Rajabalee, F. J. M. J. Chromatogr. 1977, 132, 277-286. 8. LeBel, G. L.; Williams, D. T. Bull. Environ. Contam. Toxicol. 1980, 24, 397-403. 9. Nestmann, E. R.; LeBel, G. L.; Williams, D. T.; Kowbel, D. J. Environ. Mutagenesis 1979, 1, 337-345. 10. Williams, D. T.; Nestmann, E. R.; LeBel, G. L.; Benoit, F.M.; Otson, R. Chemosphere 1982, 11, 263-276. 11. Douglas, G. R.; Nestmann, E. R.; LeBel, G. L. Environ. Health Perspect. in press. 12. LeBel, G. L.; Williams, D. T. J. Assoc. Off. Anal. Chem. 1983, 66, 691-699. RECEIVED for review August 14, 1985. ACCEPTED February 10, 1986.


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