Acknowledgements: A very special thank you to Adirondack Environmental Services for working with us on finding a solution for reducing sample volumes for EPA Method 608.3.
Introduction
Pesticides, including insecticides, fungicides, and herbicides, are used extensively to increase agricultural yield. However, it has since been determined that these pesticides can be detrimental to the health of humans as well as animals. It is important to monitor organochlorine pesticides and polychlorinated biphenyls (PCBs) not just in drinking water (US EPA Method 508), but also in wastewater (US EPA Method 608.3). After the wastewater has gone through the treatment plant, testing needs to be done to ensure that the treated wastewater is safe and will not harm the ecosystems that it flows into.
Some influent wastewater samples can be heavily laden with particulates, sludge, and the like, so it may be difficult to extract an entire liter of this sample when following US EPA Method 608.3. Fortunately, with this method, laboratories have the option of extracting smaller sample volumes, thus reducing the particulates, sludge, etc. that needs to be filtered out of the sample during extraction. This leads to a direct cost savings as smaller solid phase extraction (SPE) disks can be used and less prefilters, filter aids, and solvent are required for each sample extraction. In addition, indirect costs related to shipping can be reduced for all samples types regardless of their particulate content since reduced volumes mean smaller physical sizes and more samples will fit in each shipping container.
The purpose of this application note is to provide a solution for extracting 100 mL of 608.3 wastewater samples utilizing the Biotage® Horizon 5000 to automatically load the sample and rinse the original sample container for solid phase extraction (SPE), DryDisk® Solvent Drying System for drying the residual water from the extracts, and the TurboVap® for concentrating the dried extracts. Samples are extracted in methylene chloride, then solvent exchanged into hexane prior to analysis by Gas Chromatography/Electron Capture Detection (GC/ECD).
Instrumentation
Biotage instruments and consumables
- Biotage® Horizon 5000 (P/N SPE-DEX 5000)
- DryDisk® Solvent Drying System (P/N SDS-101-19/22)
- TurboVap® II (P/N 415001)
- Atlantic® ReadyDisk C18 (P/N 47-6005)
- DryDisk®-R (P/N 40-1000-HT)
- Evaporation Tube TurboVap® II, 200 mL, 1 mL EndPoint (P/N C128506)
Analytical instrument:
- Agilent 6890; HP Micro Dual GC-ECD
- Column 1: Rtx-CLPesticides (30 m, 0.32 mm ID, 0.32 µm film thickness)
- Column 2: Rtx-CLPesticides2 (30 m, 0.32 mm ID, 0.32 µm film thickness)
Method summary
- Purge the Biotage® Horizon 5000 using the method found in Table 1.
- Obtain the 100 mL samples of DI water that will be extracted. Acidify to a pH <2 with HCl. For Matrix Spike (MS) and Matrix Spike Duplicate (MSD) test samples only, 2 mg of oil and grease (hexadecane and stearic acid) was added to the acidified DI water.
- Fortify samples with surrogates decachlorobiphenyl (DCB) and tetrachloro-m-xylene (TCMX).
- Fortify necessary samples with the proper amount of spike mix if analyte retention testing will be determined by this sample.
- Attach the water inlet valve to the sample bottle (and cap adapter if necessary) and place onto the Biotage® Horizon 5000.
- Place an Atlantic® ReadyDisk C18 onto each active station.
- Attach the 19/22 tapered collection vessel to each active station. For the purposes of this application note, the VOA vial adapter with a 40 mL VOA vial was used as the collection vessel.
- Run the extraction method found in Table 2 with the Biotage® Horizon 5000.
- Once the extraction concludes (approximately 30 minutes), remove the collection vessels from the extractor.
- Set up a DryDisk® Solvent Drying System (SDS) with a DryDisk®-R for each extract and attach a collection vessel to the bottom.
- Pour each extract into a glass reservoir over the DryDisk®-R and open the stopcock. Allow the extract to flow through completely before rinsing the collection vessel three times with methylene chloride into the reservoir (approximately 15 mL in total).
- Once all the extract has been transferred, rinse the reservoir and DryDisk®-R once with methylene chloride (approximately 10 mL).
- Transfer the dried extract to a concentration tube and concentrate. For the purposes of this application note, the TurboVap® II, 200 mL, 1 mL EndPoint evaporation tube was used in conjunction with the TurboVap® II. Cover the tube with aluminum foil and using a glass pipette, poke three holes into the foil (one on the left, one in the middle, and one on the right). The nitrogen nozzle should sit in the right hole of the foil.
- Concentrate to endpoint (approximately 0.7 mL) following the concentration protocol found in Table 3.
- Add 10 mL of hexane directly into the tip of the evaporation tube, using a glass pipette, into each concentrated extract. Swirl well for the solvent exchange step.
- Replace the foil on the concentration tubes and bring the sample to an end point of 0.7 mL again using the protocol found in Table 4.
- Once concentration is complete, bring each extract up to 2 mL with hexane.
- Perform any necessary cleanup procedures for PCBs/ Pesticides. For the purposes of this application note, the following cleanups were conducted:
- For PCB extracts only, perform a sulfuric acid cleanup.
- For pesticides and PCB MS extracts, perform a copper cleanup.
- For pesticides and PCB Method Detection Limit (MDL), Laboratory Control Spike (LCS), and MS extracts, perform a florisil cleanup.
- Analyze by GC/ECD following the method protocol found in Table 5.
Table 1. Biotage® Horizon 5000 608.3 purge method.
|
Step |
Step Description |
Solvent |
Volume (mL) |
Purge (s) |
Pump Speed |
Saturate (s) |
Soak (s) |
Drain/Elute (s) |
Done Loading Delay (s) |
|
1 |
Condition SPE Disk |
Reagent Water |
15 |
30 |
4 |
0 |
0 |
30 |
|
|
2 |
Condition SPE Disk |
Methanol |
15 |
30 |
4 |
0 |
0 |
30 |
|
|
3 |
Elute Sample Container |
Acetone |
15 |
15 |
4 |
0 |
0 |
30 |
|
|
4 |
Elute Sample Container |
Methylene Chloride |
15 |
15 |
4 |
0 |
0 |
30 |
|
|
5 |
Elute Sample Container |
Methylene Chloride |
15 |
15 |
6 |
0 |
0 |
30 |
Table 2. Biotage® Horizon 5000 608.3 extraction method.
|
Step |
Step Description |
Solvent |
Volume (mL) |
Purge (s) |
Pump Speed |
Saturate (s) |
Soak (s) |
Drain/Elute (s) |
Done Loading Delay (s) |
|
1 |
Condition SPE Disk |
Methylene Chloride |
20 |
60 |
4 |
1 |
60 |
60 |
|
|
2 |
Condition SPE Disk |
Acetone |
20 |
60 |
2 |
1 |
60 |
30 |
|
|
3 |
Condition SPE Disk |
Methanol |
20 |
60 |
2 |
2 |
60 |
10 |
|
|
4 |
Condition SPE Disk |
Reagent Water |
20 |
60 |
2 |
1 |
45 |
10 |
|
|
5 |
Load Sample |
2 |
45 |
||||||
|
6 |
Wash Sample Container |
Reagent Water |
15 |
60 |
6 |
2 |
20 |
30 |
|
|
7 |
Air Dry |
6 |
360 |
||||||
|
8 |
Elute Sample Container |
Acetone |
3 |
15 |
2 |
1 |
60 |
45 |
|
|
9 |
Elute Sample Container |
Methylene Chloride |
5 |
15 |
2 |
1 |
60 |
45 |
|
|
10 |
Elute Sample Container |
Methylene Chloride |
5 |
15 |
6 |
1 |
60 |
60 |
|
Table 3. TurboVap® II evaporation parameters for methylene chloride (Pre-Solvent Exchange).
|
Settings |
||
|
Gradient Type |
End-Point Detection |
Bath Temperature |
|
Ramp |
||
|
Method Step |
Flow (L/min) |
Time (min) |
|
Step 1 |
3.0 |
9 |
|
Step 2 |
5.0 |
1 |
Table 4. TurboVap® II evaporation parameters for hexane (Post-Solvent Exchange).
|
Settings |
||
|
Gradient Type |
End-Point Detection |
Bath Temperature |
|
Ramp |
On |
60 °C |
|
Method Step |
Flow (L/min) |
Time (min) |
|
Step 1 |
4.2 |
2 |
|
Step 2 |
5.0 |
1 |
Table 5. GC/ECD conditions.
|
Inlet Settings |
|||
|
Pesticides Injection Volume |
PCB Injection Volume |
Injection Mode |
Gas Type |
|
1 µL |
4 µL |
Pulsed Splitless |
Helium |
|
Temperature |
Pulse Pressure |
Pulse Time |
Total Purge Flow |
|
50°C |
28psi |
1 min |
60.4 mL/min |
|
Purge Time Gas Saver Flow Gas Saver Time |
|||
|
0.75 min |
20 mL/min |
2 min |
|
|
Oven Settings |
|||
|
Initial Oven Temperature |
Initial Oven Time |
Post Oven Temperature |
Maximum Oven Temperature |
|
125°C |
0.5 min |
120°C |
325°C |
|
Method Step |
Rate (°C/min) |
Temperature (°C) |
Hold Time (min) |
|
Step 1 |
45 |
200 |
0 |
|
Step 2 |
12.5 |
230 |
0 |
|
Step 3 |
30 |
300 |
1.5 |
Results and discussion
Demonstration of low background
In order to confirm that the instrumentation utilized for the entire preparation workflow was free from background
contamination, a 100 mL laboratory reagent blank (LRB) was processed and analyzed for trace levels of PCBs and Pesticides. The result of this test demonstrated that the instrumentation used was free from PCBs and Pesticides. In addition, the workflow demonstrated excellent extraction performance with surrogate recoveries in the 90% range (Table 6).
Table 6. Blank results (n=1).
|
Analyte |
Lowest Calibration Point (ng/L) |
Blank Results (ng/L) |
Acceptance Criteria |
|
PCB |
1016 |
25 |
N.D |
|
PCB |
1260 |
25 |
N.D |
|
PCB |
1221 |
25 |
N.D |
|
PCB |
1254 |
25 |
N.D |
|
PCB |
1242 |
25 |
N.D |
|
PCB |
1248 |
25 |
N.D |
|
PCB |
1268 |
25 |
N.D |
|
4,4´-DDD |
33 |
N.D |
PASS |
|
4,4´-DDE |
33 |
N.D |
PASS |
|
4,4´-DDT |
33 |
N.D |
PASS |
|
Aldrin |
16 |
N.D |
PASS |
|
alpha-BHC |
16 |
N.D |
PASS |
|
alpha-Chlordane |
16 |
N.D |
PASS |
|
beta-BHC |
16 |
N.D |
PASS |
|
delta-BHC |
16 |
N.D |
PASS |
|
Dieldrin |
33 |
N.D |
PASS |
|
Endosulfan |
I |
16 |
N.D |
|
Endosulfan |
II |
33 |
N.D |
|
Endosulfan |
sulfate |
33 |
N.D |
|
Endrin |
33 |
N.D |
PASS |
|
Endrin |
aldehyde |
33 |
N.D |
|
Endrin |
Ketone |
33 |
N.D |
|
gamma-BHC |
16 |
N.D |
PASS |
|
gamma-Chlordane |
16 |
N.D |
PASS |
|
Heptachlor |
16 |
N.D |
PASS |
|
Heptachlor |
epoxide |
16 |
N.D |
|
Methoxychlor |
16 |
N.D |
PASS |
|
Chlordane |
16 |
N.D |
PASS |
|
Toxaphene |
50 |
N.D |
PASS |
|
DCB |
(Surr.) |
33 |
94% |
|
TCMX |
(Surr.) |
33 |
90% |
Surrogate recovery acceptance criteria is within 60–140%.
N.D. = Not Detected.
Determination of the method detection limits (MDL)
To demonstrate that acceptable method detection limits can be achieved with 100 mL reduced sample volume extractions, laboratory defined practical quantitation limits (PQLs) were utilized as a benchmark for acceptance criteria. Utilizing Adirondack Environmental Services’ PQL values, seven replicate blanks were fortified at low spike levels to demonstrate the reduced sample volume extraction workflow was capable of passing the MDL study for the laboratory’s current limits (Table 7). Results for each individual MDL replicate are provided in the appendix section (Tables 12 and 13). Per EPA Method 608.3 method requirements, acceptance criteria must be met using at least one GC/ECD column. The data here demonstrates that an MDL study was passed on both GC/ECD columns.
Table 7. Calculated method detection limits (n=7).
|
Analyte |
Spike Amount (ng/L) |
Column 1 - MDL (ng/L) |
Column 2 - MDL (ng/L) |
Laboratory Maximum PQL (ng/L) |
Acceptance Criteria |
|
PCB 1016 |
100 |
32 |
60 |
65 |
PASS |
|
PCB 1260 |
100 |
42 |
39 |
65 |
PASS |
|
PCB 1221 |
200 |
68 |
116 |
130 |
PASS |
|
PCB 1254 |
100 |
16 |
22 |
65 |
PASS |
|
PCB 1242 |
100 |
22 |
29 |
65 |
PASS |
|
PCB 1248 |
100 |
12 |
12 |
65 |
PASS |
|
PCB 1268 |
100 |
19 |
23 |
65 |
PASS |
|
4,4´-DDD |
100 |
14 |
29 |
100 |
PASS |
|
4,4´-DDE |
100 |
13 |
17 |
100 |
PASS |
|
4,4´-DDT |
100 |
26 |
21 |
100 |
PASS |
|
Aldrin |
100 |
14 |
12 |
50 |
PASS |
|
alpha-BHC |
100 |
35 |
14 |
50 |
PASS |
|
alpha-Chlordane |
100 |
23 |
14 |
50 |
PASS |
|
beta-BHC |
100 |
33 |
29 |
50 |
PASS |
|
delta-BHC |
100 |
11 |
30 |
50 |
PASS |
|
Dieldrin |
100 |
13 |
11 |
100 |
PASS |
|
Endosulfan I |
100 |
10 |
10 |
50 |
PASS |
|
Endosulfan II |
100 |
22 |
20 |
100 |
PASS |
|
Endosulfan sulfate |
100 |
28 |
13 |
100 |
PASS |
|
Endrin |
100 |
29 |
13 |
100 |
PASS |
|
Endrin aldehyde |
100 |
37 |
31 |
100 |
PASS |
|
Endrin Ketone |
100 |
64 |
11 |
100 |
PASS |
|
gamma-BHC |
100 |
17 |
15 |
50 |
PASS |
|
gamma-Chlordane |
100 |
14 |
36 |
50 |
PASS |
|
Heptachlor |
100 |
21 |
15 |
50 |
PASS |
|
Heptachlor epoxide |
100 |
19 |
10 |
50 |
PASS |
|
Methoxychlor |
100 |
47 |
31 |
500 |
PASS |
|
Chlordane |
200 |
32 |
44 |
50 |
PASS |
|
Toxaphene |
1000 |
281 |
273 |
1000 |
PASS |
Initial demonstration of accuracy and precision
To determine the accuracy and precision of the sample preparation process, four samples were prepared at mid to high level concentrations. The precision and accuracy can be found in Tables 8 and 9, as well as illustrated in Figures 1 and 2. Due to the varying values of acceptance criteria for each analyte, the interim acceptance criteria of 60–140% (Section 8.4.5) was used as the limits on Figure 1 for ease of observation. The lowest %SD limit within 608.3 is 22%. This percent was used as the limit on Figure 2 for ease of observation. The remaining analytes have limits higher than 22%, but it is worth noting that all analytes pass utilizing 22% for the %SD, illustrating the precision with the instrumentation used for conducting this study. Since all analytes recovered within the recovery range of the method, this study also demonstrates that the reduced sample volume (100 mL) extraction provides exceptional precision and accuracy. Results for individual precision and accuracy replicates are provided in the appendix section (Tables 14 and 15). It should be noted here that while the method requires only one GC/ECD column meet the given acceptance criteria, this study yielded data showing that both columns are able to pass the precision and accuracy requirements.
Table 8. Initial demonstration of accuracy (n=4).
|
Analyte |
Column 1 - X̅ |
Column 2 - X̅ |
X̅ Recovery Range |
Acceptance Criteria |
|
PCB 1016 |
96.9% |
100.9% |
61–103% |
PASS |
|
PCB 1260 |
117.8% |
117.3% |
37–130% |
PASS |
|
PCB 1221 |
106.5% |
119.8% |
44–150% |
PASS |
|
PCB 1254 |
83.2% |
107.0% |
44–130% |
PASS |
|
PCB 1242 |
72.0% |
104.5% |
50–139% |
PASS |
|
PCB 1248 |
62.8% |
95.2% |
58–140% |
PASS |
|
PCB 1268 |
82.7% |
126.2% |
60–140% |
PASS |
|
4,4´-DDD |
90.0% |
84.5% |
48–130% |
PASS |
|
4,4´-DDE |
98.9% |
93.3% |
58–130% |
PASS |
|
4,4´-DDT |
112.1% |
115.4% |
46–137% |
PASS |
|
Aldrin |
90.1% |
89.1% |
54–130% |
PASS |
|
alpha-BHC |
117.0% |
108.9% |
49–130% |
PASS |
|
alpha-Chlordane |
95.4% |
94.5% |
55–130% |
PASS |
|
beta-BHC |
99.2% |
106.3% |
39–130% |
PASS |
|
delta-BHC |
95.9% |
101.3% |
51–130% |
PASS |
|
Dieldrin |
106.2% |
107.4% |
58–130% |
PASS |
|
Endosulfan I |
85.6% |
90.8% |
57–141% |
PASS |
|
Endosulfan II |
103.8% |
94.7% |
22–171% |
PASS |
|
Endosulfan sulfate |
101.0% |
96.4% |
38–132% |
PASS |
|
Endrin |
102.5% |
102.5% |
51–130% |
PASS |
|
Endrin aldehyde |
109.0% |
117.1% |
60–140% |
PASS |
|
Endrin Ketone |
103.0% |
99.4% |
60–140% |
PASS |
|
gamma-BHC |
104.3% |
103.2% |
43–130% |
PASS |
|
gamma-Chlordane |
98.7% |
98.4% |
55–130% |
PASS |
|
Heptachlor |
98.4% |
97.1% |
43–130% |
PASS |
|
Heptachlor epoxide |
95.5% |
94.4% |
57–132% |
PASS |
|
Methoxychlor |
94.1% |
102.6% |
60–140% |
PASS |
|
Chlordane |
97.1% |
96.6% |
60–140% |
PASS |
|
Toxaphene |
95.2% |
99.4% |
53–130% |
PASS |
|
DCB (Surr.) |
79.9% |
95.9% |
60–140% |
PASS |
|
TCMX (Surr.) |
77.5% |
77.3% |
60–140% |
PASS |
Table 9. Initial demonstration of precision (n=4).
|
Analyte |
Column 1 - %SD |
Column 2 - %SD |
Limit for %SD |
Acceptance Criteria |
|
PCB 1016 |
4.8% |
2.1% |
24% |
PASS |
|
PCB 1260 |
2.0% |
1.2% |
28% |
PASS |
|
PCB 1221 |
5.0% |
5.8% |
50% |
PASS |
|
PCB 1254 |
2.5% |
4.5% |
34% |
PASS |
|
PCB 1242 |
4.5% |
3.4% |
26% |
PASS |
|
PCB 1248 |
5.2% |
7.7% |
32% |
PASS |
|
PCB 1268 |
7.2% |
5.4% |
30% |
PASS |
|
4,4´-DDD |
7.4% |
9.8% |
32% |
PASS |
|
4,4´-DDE |
7.8% |
7.4% |
30% |
PASS |
|
4,4´-DDT |
6.2% |
12.2% |
39% |
PASS |
|
Aldrin |
6.2% |
7.5% |
25% |
PASS |
|
alpha-BHC |
8.1% |
7.6% |
28% |
PASS |
|
alpha-Chlordane |
7.2% |
7.1% |
24% |
PASS |
|
beta-BHC |
6.9% |
8.7% |
38% |
PASS |
|
delta-BHC |
6.7% |
7.6% |
43% |
PASS |
|
Dieldrin |
8.1% |
8.9% |
42% |
PASS |
|
Endosulfan I |
7.7% |
9.5% |
25% |
PASS |
|
Endosulfan II |
7.2% |
13.2% |
63% |
PASS |
|
Endosulfan sulfate |
7.5% |
8.0% |
32% |
PASS |
|
Endrin |
9.0% |
9.4% |
42% |
PASS |
|
Endrin aldehyde |
3.0% |
8.0% |
30% |
PASS |
|
Endrin Ketone |
11.3% |
9.2% |
30% |
PASS |
|
gamma-BHC |
7.2% |
7.3% |
29% |
PASS |
|
gamma-Chlordane |
6.3% |
8.1% |
24% |
PASS |
|
Heptachlor |
6.8% |
6.3% |
28% |
PASS |
|
Heptachlor epoxide |
6.4% |
6.4% |
22% |
PASS |
|
Methoxychlor |
10.9% |
19.1% |
30% |
PASS |
|
Chlordane |
6.7% |
7.8% |
30% |
PASS |
|
Toxaphene |
2.8% |
3.6% |
30% |
PASS |
|
DCB (Surr.) |
8.8% |
11.3% |
30% |
PASS |
|
TCMX (Surr.) |
7.6% |
7.4% |
30% |
PASS |
Figure 1. Initial demonstration of accuracy (n=4).
Figure 2. Initial demonstration of precison (n=4)
Matrix spike and matrix spike duplicate accuracy and precision
To demonstrate the effectiveness of an extraction with matrix interferences (EPA 608.3 - Section 8.1.2.1.2.e) , two duplicate samples were created in-house with 2 mg of oil and grease standard (hexadecane and stearic acid). The results in Table 10 prove that the reduced sample volume (100 mL) provides robust extraction performance of the target analytes. The precision of matrix sample extractions is demonstrated in Table 11 with Relative Percent Differences (RPDs) well within the method requirements for duplicate matrix spikes. Figure 3 provides a visual of the MS/MSD accuracy using acceptance criteria of 60–140% (section 8.4.5). Figure 4 provides a visual of the MS/MSD precision using RPD of 30% (EPA 608.3 section 8.1.2.1.2.e). Results for individual MS/MSD precision and accuracy replicates are provided in the appendix section (Tables 16 and 17). It should be noted here that while the method requires only one GC/ECD column meet the given acceptance criteria, this study yielded data showing that both columns are able to pass the MS/MSD requirements.
Table 10. Matrix duplicate spike (MS/MSD) accuracy (n=2).
|
Analyte |
Column 1 - MS/MSD % R |
Column 2 - MS/MSD % R |
Range for Recovery (P) |
Acceptance Criteria |
|
PCB 1016 |
106.0% |
103.0% |
50–140% |
PASS |
|
PCB 1260 |
117.0% |
122.5% |
8–140% |
PASS |
|
PCB 1221 |
96.5% |
107.5% |
15–178% |
PASS |
|
PCB 1254 |
93.5% |
97.5% |
29–140% |
PASS |
|
PCB 1242 |
66.5% |
94.0% |
39–150% |
PASS |
|
PCB 1248 |
91.5% |
93.0% |
38–158% |
PASS |
|
PCB 1268 |
81.0% |
123.5% |
60–140% |
PASS |
|
4,4´-DDD |
77.0% |
77.4% |
31–141% |
PASS |
|
4,4´-DDE |
81.4% |
82.0% |
30–145% |
PASS |
|
4,4´-DDT |
104.0% |
108.4% |
25–160% |
PASS |
|
Aldrin |
87.0% |
87.2% |
42–140% |
PASS |
|
alpha-BHC |
107.0% |
101.6% |
37–140% |
PASS |
|
alpha-Chlordane |
95.2% |
76.8% |
45–140% |
PASS |
|
beta-BHC |
94.2% |
97.8% |
17–147% |
PASS |
|
delta-BHC |
90.2% |
96.0% |
19–140% |
PASS |
|
Dieldrin |
88.2% |
90.4% |
36–140% |
PASS |
|
Endosulfan I |
64.0% |
76.4% |
45–153% |
PASS |
|
Endosulfan II |
89.6% |
80.0% |
D–202% |
PASS |
|
Endosulfan sulfate |
86.4% |
87.0% |
26–144% |
PASS |
|
Endrin |
90.2% |
89.6% |
30–147% |
PASS |
|
Endrin aldehyde |
108.2% |
92.2% |
60–140% |
PASS |
|
Endrin Ketone |
97.4% |
89.2% |
60-140% |
PASS |
|
gamma-BHC |
98.4% |
96.6% |
32–140% |
PASS |
|
gamma-Chlordane |
79.6% |
75.4% |
45–140% |
PASS |
|
Heptachlor |
96.4% |
98.4% |
34–140% |
PASS |
|
Heptachlor epoxide |
84.4% |
59.8% |
37–140% |
PASS |
|
Methoxychlor |
92.2% |
96.4% |
60–140% |
PASS |
|
Chlordane |
87.4% |
76.1% |
60–140% |
PASS |
|
Toxaphene |
90.5% |
116.9% |
41–140% |
PASS |
|
DCB (Surr.) |
79.3% |
90.8% |
60–140% |
PASS |
|
TCMX (Surr.) |
82.9% |
81.6% |
60–140% |
PASS |
Table 11. Matrix duplicate spike (MS/MSD) relative percent difference (n=2).
|
Analyte |
Column 1 - RPD (%) |
Column 2 - RPD (%) |
Maximum MS/MSD RPD (%) |
Acceptance Criteria |
|
PCB 1016 |
1.4% |
4.1% |
36% |
PASS |
|
PCB 1260 |
8.6% |
9.1% |
38% |
PASS |
|
PCB 1221 |
1.1% |
17.2% |
48% |
PASS |
|
PCB 1254 |
7.7% |
5.2% |
45% |
PASS |
|
PCB 1242 |
2.1% |
6.3% |
29% |
PASS |
|
PCB 1248 |
5.5% |
6.5% |
35% |
PASS |
|
PCB 1268 |
8.4% |
10.7% |
30% |
PASS |
|
4,4´-DDD |
3.6% |
3.6% |
39% |
PASS |
|
4,4´-DDE |
16.2% |
7.8% |
35% |
PASS |
|
4,4´-DDT |
6.9% |
9.6% |
42% |
PASS |
|
Aldrin |
2.3% |
0.9% |
35% |
PASS |
|
alpha-BHC |
1.1% |
2.4% |
36% |
PASS |
|
alpha-Chlordane |
7.6% |
2.1% |
35% |
PASS |
|
beta-BHC |
2.1% |
9.4% |
44% |
PASS |
|
delta-BHC |
4.0% |
1.7% |
52% |
PASS |
|
Dieldrin |
3.2% |
3.5% |
49% |
PASS |
|
Endosulfan I |
12.5% |
2.1% |
28% |
PASS |
|
Endosulfan II |
4.5% |
3.0% |
53% |
PASS |
|
Endosulfan sulfate |
3.7% |
1.4% |
38% |
PASS |
|
Endrin |
3.1% |
3.6% |
48% |
PASS |
|
Endrin aldehyde |
9.2% |
4.8% |
30% |
PASS |
|
Endrin Ketone |
6.2% |
5.4% |
30% |
PASS |
|
gamma-BHC |
1.6% |
5.4% |
39% |
PASS |
|
gamma-Chlordane |
2.0% |
2.7% |
35% |
PASS |
|
Heptachlor |
3.3% |
0.8% |
43% |
PASS |
|
Heptachlor epoxide |
0.9% |
12.7% |
26% |
PASS |
|
Methoxychlor |
27.3% |
5.8% |
30% |
PASS |
|
Chlordane |
5.0% |
0.3% |
30% |
PASS |
|
Toxaphene |
2.6% |
3.0% |
41% |
PASS |
|
DCB (Surr.) |
14.4% |
8.4% |
30% |
PASS |
|
TCMX (Surr.) |
14.7% |
15.7% |
30% |
PASS |
Figure 3. Matrix duplicate spike (MS/MSD) accuracy (n=2).
Figure 4. Matrix duplicate spike (MS/MSD) relative percent difference. (n=2).
This application note demonstrates the ability to extract and analyze 100 mL samples of PCBs and pesticides for EPA Method 608.3 with the automated SPE format of the Biotage® Horizon 5000, the DryDisk® Solvent Drying System, and the TurboVap® II. When reducing sample volumes from 1 L to 100 mL, the extraction and concentration time is reduced and most importantly the amount of methylene chloride used for extraction is significantly reduced. See Figures 5 and 6 illustrating the differences in time and volume between extracting 1 L and 100 mL samples.
Additional information
Due to the lingering nature of the pesticides and PCBs within this method, it is very important that good cleaning practices are performed not only for quality control samples, but also is most important for when a laboratory adopts the method for real sample extractions. Conducting the purge method found in Table 1 at the start of the day, between samples, and at the end of the day is very important to ensure the cleanliness of the Biotage® Horizon 5000 and its supporting components.
When utilizing a reusable disk holder or collection vessel, it is very important that they are cleaned well. The best practice for cleaning these components is to use warm, soapy water to remove any remaining residue, followed by three rinses with acetone, and three rinses with methylene chloride. Since the Atlantic® ReadyDisk C18 and VOA vials were used for this application note, time and solvent were saved, as this manual cleaning procedure was not required.
For extract drying, a new DryDisk®-R was used for each sample and all the parts of the SDS were rinsed three times with acetone and three times with methylene chloride. Lastly, the TurboVap® II, 200 mL, 1 mL EndPoint evaporation tubes were rinsed three times with acetone and three times with methylene chloride as well to prevent cross contamination. Following these cleaning procedures will help to reduce the chance of contamination from sample to sample for PCBs and Pesticides.
Another tip when working in implement this extraction procedure in the laboratory is to eliminate solvent squeeze bottles entirely. It is recommended that any rinsing or transferring action within the process be replaced with glass. For example, 10 mL glass pipettes were used in the production of this application note.
Figure 5. Total extraction and concentration time.
Figure 6. Total methylene chloride extraction volume.
Appendix
This section provides all the additional raw data for each sample extracted within this application note.
Table 12. Method Detection Limit (MDL) Results - Column 1.
|
Analyte |
Spike Level (µg/L) |
MDL 1 (µg/L) |
MDL 2 (µg/L) |
MDL 3 (µg/L) |
MDL 4 (µg/L) |
MDL 5 (µg/L) |
MDL 6 (µg/L) |
MDL 7 (µg/L) |
Standard Deviation (µg/L) |
Calculated MDL (µg/L) |
Calculated MDL (ng/L) |
|
PCB-1016 |
0.10 |
0.130 |
0.128 |
0.106 |
0.134 |
0.116 |
0.128 |
0.114 |
0.01001 |
0.0315 |
31.5 |
|
PCB-1260 |
0.10 |
0.103 |
0.107 |
0.098 |
0.119 |
0.108 |
0.128 |
0.088 |
0.01332 |
0.0419 |
41.9 |
|
PCB-1221 |
0.20 |
0.230 |
0.215 |
0.262 |
0.256 |
0.255 |
0.281 |
0.244 |
0.02158 |
0.0678 |
67.8 |
|
PCB-1254 |
0.10 |
0.089 |
0.086 |
0.091 |
0.099 |
0.095 |
0.099 |
0.095 |
0.00519 |
0.0163 |
16.3 |
|
PCB-1242 |
0.10 |
0.126 |
0.114 |
0.125 |
0.125 |
0.124 |
0.137 |
0.120 |
0.00683 |
0.0215 |
21.5 |
|
PCB-1248 |
0.10 |
0.047 |
0.049 |
0.054 |
0.046 |
0.045 |
0.055 |
0.048 |
0.00377 |
0.0118 |
11.8 |
|
PCB-1268 |
0.10 |
0.059 |
0.066 |
0.071 |
0.064 |
0.059 |
0.075 |
0.071 |
0.00597 |
0.0188 |
18.8 |
|
4,4´-DDD |
0.10 |
0.072 |
0.076 |
0.084 |
0.082 |
0.080 |
0.080 |
0.084 |
0.00439 |
0.0138 |
13.8 |
|
4,4´-DDE |
0.10 |
0.100 |
0.092 |
0.092 |
0.098 |
0.098 |
0.102 |
0.092 |
0.00423 |
0.0133 |
13.3 |
|
4,4´-DDT |
0.10 |
0.104 |
0.096 |
0.094 |
0.096 |
0.082 |
0.108 |
0.094 |
0.00828 |
0.0260 |
26.0 |
|
Aldrin |
0.10 |
0.072 |
0.072 |
0.074 |
0.076 |
0.078 |
0.084 |
0.080 |
0.00443 |
0.0139 |
13.9 |
|
alpha-BHC |
0.10 |
0.098 |
0.096 |
0.096 |
0.074 |
0.070 |
0.088 |
0.090 |
0.01810 |
0.0569 |
56.9 |
|
alpha-Chlordane |
0.10 |
0.094 |
0.102 |
0.112 |
0.106 |
0.112 |
0.108 |
0.096 |
0.00725 |
0.0228 |
22.8 |
|
beta-BHC |
0.10 |
0.136 |
0.126 |
0.114 |
0.140 |
0.112 |
0.120 |
0.120 |
0.01065 |
0.0335 |
33.5 |
|
delta-BHC |
0.10 |
0.080 |
0.082 |
0.078 |
0.088 |
0.080 |
0.086 |
0.080 |
0.00365 |
0.0115 |
11.5 |
|
Dieldrin |
0.10 |
0.106 |
0.104 |
0.104 |
0.112 |
0.108 |
0.114 |
0.104 |
0.00412 |
0.0129 |
12.9 |
|
Endosulfan I |
0.10 |
0.084 |
0.084 |
0.086 |
0.090 |
0.088 |
0.090 |
0.082 |
0.00315 |
0.0099 |
9.9 |
|
Endosulfan II |
0.10 |
0.092 |
0.092 |
0.102 |
0.110 |
0.108 |
0.100 |
0.102 |
0.00701 |
0.0220 |
22.0 |
|
Endosulfan sulfate |
0.10 |
0.102 |
0.094 |
0.098 |
0.106 |
0.088 |
0.116 |
0.098 |
0.00898 |
0.0282 |
28.2 |
|
Endrin |
0.10 |
0.086 |
0.110 |
0.104 |
0.110 |
0.106 |
0.114 |
0.104 |
0.00908 |
0.0285 |
28.5 |
|
Endrin aldehyde |
0.10 |
0.138 |
0.114 |
0.120 |
0.136 |
0.116 |
0.144 |
0.132 |
0.01182 |
0.0372 |
37.2 |
|
Endrin Ketone |
0.10 |
0.054 |
0.072 |
0.070 |
0.102 |
0.100 |
0.102 |
0.104 |
0.02044 |
0.0642 |
64.2 |
|
gamma-BHC |
0.10 |
0.106 |
0.104 |
0.104 |
0.118 |
0.106 |
0.114 |
0.106 |
0.00547 |
0.0172 |
17.2 |
|
gamma-Chlordane |
0.10 |
0.122 |
0.120 |
0.122 |
0.126 |
0.122 |
0.130 |
0.116 |
0.00443 |
0.0139 |
13.9 |
|
Heptachlor |
0.10 |
0.104 |
0.104 |
0.104 |
0.112 |
0.114 |
0.122 |
0.112 |
0.00678 |
0.0213 |
21.3 |
|
Heptachlor epoxide |
0.10 |
0.112 |
0.112 |
0.116 |
0.120 |
0.114 |
0.122 |
0.104 |
0.00594 |
0.0187 |
18.7 |
|
Methoxychlor |
0.10 |
0.070 |
0.064 |
0.084 |
0.104 |
0.080 |
0.102 |
0.082 |
0.01494 |
0.0470 |
47.0 |
|
Chlordane |
0.20 |
0.216 |
0.222 |
0.234 |
0.232 |
0.234 |
0.238 |
0.212 |
0.01012 |
0.0318 |
31.8 |
|
Toxaphene |
1.00 |
1.174 |
1.238 |
1.136 |
1.022 |
1.294 |
1.221 |
1.238 |
0.08923 |
0.2805 |
280.5 |
Table 13. Method Detection Limit (MDL) Results - Column 2.
|
Analyte |
Spike Level (µg/L) |
MDL 1 (µg/L) |
MDL 2 (µg/L) |
MDL 3 (µg/L) |
MDL 4 (µg/L) |
MDL 5 (µg/L) |
MDL 6 (µg/L) |
MDL 7 (µg/L) |
Standard Deviation (µg/L) |
Calculated MDL (µg/L) |
Calculated MDL (ng/L) |
|
PCB-1016 |
0.10 |
0.0953 |
0.1057 |
0.0904 |
0.1251 |
0.1183 |
0.1303 |
0.0792 |
0.01907 |
0.05994 |
59.9 |
|
PCB-1260 |
0.10 |
0.1031 |
0.1139 |
0.1004 |
0.1125 |
0.1144 |
0.1312 |
0.0927 |
0.01244 |
0.03911 |
39.1 |
|
PCB-1221 |
0.20 |
0.2796 |
0.1968 |
0.1928 |
0.2549 |
0.2086 |
0.2715 |
0.2597 |
0.03700 |
0.11629 |
116.3 |
|
PCB-1254 |
0.10 |
0.075 |
0.0756 |
0.0831 |
0.08 |
0.0816 |
0.0959 |
0.0816 |
0.00693 |
0.02179 |
21.8 |
|
PCB-1242 |
0.10 |
0.0951 |
0.0849 |
0.106 |
0.1139 |
0.0933 |
0.101 |
0.0985 |
0.00933 |
0.02931 |
29.3 |
|
PCB-1248 |
0.10 |
0.0639 |
0.0691 |
0.0706 |
0.0646 |
0.0633 |
0.0739 |
0.0669 |
0.00393 |
0.01234 |
12.3 |
|
PCB-1268 |
0.10 |
0.0864 |
0.0946 |
0.102 |
0.094 |
0.0857 |
0.1035 |
0.1006 |
0.00723 |
0.02273 |
22.7 |
|
4,4´-DDD |
0.10 |
0.074 |
0.062 |
0.086 |
0.086 |
0.084 |
0.088 |
0.08 |
0.00924 |
0.02904 |
29.0 |
|
4,4´-DDE |
0.10 |
0.094 |
0.086 |
0.084 |
0.09 |
0.092 |
0.1 |
0.088 |
0.00538 |
0.01691 |
16.9 |
|
4,4´-DDT |
0.10 |
0.096 |
0.09 |
0.086 |
0.096 |
0.09 |
0.102 |
0.082 |
0.00678 |
0.02131 |
21.3 |
|
Aldrin |
0.10 |
0.086 |
0.076 |
0.078 |
0.082 |
0.08 |
0.086 |
0.084 |
0.00390 |
0.01226 |
12.3 |
|
alpha-BHC |
0.10 |
0.078 |
0.068 |
0.07 |
0.076 |
0.078 |
0.08 |
0.076 |
0.00445 |
0.01399 |
14.0 |
|
alpha-Chlordane |
0.10 |
0.096 |
0.09 |
0.094 |
0.096 |
0.098 |
0.104 |
0.092 |
0.00454 |
0.01427 |
14.3 |
|
beta-BHC |
0.10 |
0.082 |
0.076 |
0.1 |
0.08 |
0.08 |
0.078 |
0.07 |
0.00930 |
0.02923 |
29.2 |
|
delta-BHC |
0.10 |
0.082 |
0.076 |
0.064 |
0.088 |
0.09 |
0.09 |
0.078 |
0.00944 |
0.02967 |
29.7 |
|
Dieldrin |
0.10 |
0.106 |
0.104 |
0.106 |
0.112 |
0.108 |
0.112 |
0.104 |
0.00341 |
0.01072 |
10.7 |
|
Endosulfan I |
0.10 |
0.096 |
0.088 |
0.094 |
0.094 |
0.092 |
0.088 |
0.092 |
0.00306 |
0.00962 |
9.6 |
|
Endosulfan II |
0.10 |
0.088 |
0.08 |
0.086 |
0.098 |
0.094 |
0.096 |
0.09 |
0.00626 |
0.01968 |
19.7 |
|
Endosulfan sulfate |
0.10 |
0.096 |
0.092 |
0.09 |
0.098 |
0.094 |
0.086 |
0.09 |
0.00407 |
0.01279 |
12.8 |
|
Endrin |
0.10 |
0.102 |
0.102 |
0.102 |
0.108 |
0.106 |
0.11 |
0.098 |
0.00416 |
0.01307 |
13.1 |
|
Endrin aldehyde |
0.10 |
0.08 |
0.086 |
0.106 |
0.098 |
0.098 |
0.098 |
0.082 |
0.00985 |
0.03096 |
31.0 |
|
Endrin Ketone |
0.10 |
0.096 |
0.096 |
0.098 |
0.102 |
0.1 |
0.102 |
0.092 |
0.00365 |
0.01147 |
11.5 |
|
gamma-BHC |
0.10 |
0.092 |
0.092 |
0.092 |
0.1 |
0.096 |
0.104 |
0.092 |
0.00486 |
0.01527 |
15.3 |
|
gamma-Chlordane |
0.10 |
0.08 |
0.082 |
0.078 |
0.106 |
0.09 |
0.102 |
0.098 |
0.01131 |
0.03555 |
35.5 |
|
Heptachlor |
0.10 |
0.072 |
0.076 |
0.068 |
0.072 |
0.074 |
0.082 |
0.068 |
0.00488 |
0.01534 |
15.3 |
|
Heptachlor epoxide |
0.10 |
0.098 |
0.094 |
0.096 |
0.102 |
0.096 |
0.102 |
0.096 |
0.00315 |
0.00990 |
9.9 |
|
Methoxychlor |
0.10 |
0.088 |
0.09 |
0.102 |
0.112 |
0.102 |
0.108 |
0.088 |
0.00991 |
0.03115 |
31.1 |
|
Chlordane |
0.20 |
0.176 |
0.172 |
0.172 |
0.202 |
0.188 |
0.206 |
0.19 |
0.01394 |
0.04381 |
43.8 |
|
Toxaphene |
1.00 |
1.206 |
1.25 |
1.186 |
1.106 |
1.168 |
1.37 |
1.29 |
0.08676 |
0.27270 |
272.7 |
Table 14. Initial Demonstration of Capability (DOC) Results - Column 1.
|
Analyte |
Spike Level (µg/L) |
LCS 1 (µg/L) |
Recovery |
LCS 2 |
Recover |
LCS 3 |
Recovery |
LCS 4 |
Recovery |
Average Recovery |
Standard Deviation |
|
(%) |
(µg/L) |
(%) |
(µg/L) |
(%) |
(µg/L) |
(%) |
(%) |
(%) |
|||
|
PCB-1016 |
1.0 |
0.998 |
99.8 |
1.02 |
102.0 |
0.918 |
91.8 |
0.938 |
93.8 |
96.9 |
4.8 |
|
PCB-1260 |
1.0 |
1.154 |
115.4 |
1.198 |
119.8 |
1.168 |
116.8 |
1.19 |
119.0 |
117.8 |
2.0 |
|
PCB-1221 |
1.0 |
1.0542 |
105.4 |
1.0642 |
106.4 |
1.1312 |
113.1 |
1.0115 |
101.2 |
106.5 |
5.0 |
|
PCB-1254 |
0.5 |
0.412 |
82.4 |
0.421 |
84.2 |
0.4308 |
86.2 |
0.401 |
80.2 |
83.2 |
2.5 |
|
PCB-1242 |
0.5 |
0.3579 |
71.6 |
0.3628 |
72.6 |
0.3319 |
66.4 |
0.3864 |
77.3 |
72.0 |
4.5 |
|
PCB-1248 |
0.5 |
0.3023 |
60.5 |
0.2882 |
57.6 |
0.3157 |
63.1 |
0.3489 |
69.8 |
62.8 |
5.2 |
|
PCB-1268 |
0.5 |
0.3868 |
77.4 |
0.3874 |
77.5 |
0.4168 |
83.4 |
0.4634 |
92.7 |
82.7 |
7.2 |
|
4,4´-DDD |
0.5 |
0.42 |
84.0 |
0.438 |
87.6 |
0.438 |
87.6 |
0.504 |
100.8 |
90.0 |
7.4 |
|
4,4´-DDE |
0.5 |
0.466 |
93.2 |
0.48 |
96.0 |
0.48 |
96.0 |
0.552 |
110.4 |
98.9 |
7.8 |
|
4,4´-DDT |
0.5 |
0.53 |
106.0 |
0.554 |
110.8 |
0.554 |
110.8 |
0.604 |
120.8 |
112.1 |
6.2 |
|
Aldrin |
0.5 |
0.426 |
85.2 |
0.44 |
88.0 |
0.44 |
88.0 |
0.496 |
99.2 |
90.1 |
6.2 |
|
alpha-BHC |
0.5 |
0.552 |
110.4 |
0.572 |
114.4 |
0.572 |
114.4 |
0.644 |
128.8 |
117.0 |
8.1 |
|
alpha-Chlordane |
0.5 |
0.45 |
90.0 |
0.464 |
92.8 |
0.464 |
92.8 |
0.53 |
106.0 |
95.4 |
7.2 |
|
beta-BHC |
0.5 |
0.466 |
93.2 |
0.486 |
97.2 |
0.486 |
97.2 |
0.546 |
109.2 |
99.2 |
6.9 |
|
delta-BHC |
0.5 |
0.45 |
90.0 |
0.47 |
94.0 |
0.47 |
94.0 |
0.528 |
105.6 |
95.9 |
6.7 |
|
Dieldrin |
0.5 |
0.498 |
99.6 |
0.518 |
103.6 |
0.518 |
103.6 |
0.59 |
118.0 |
106.2 |
8.1 |
|
Endosulfan I |
0.5 |
0.396 |
79.2 |
0.416 |
83.2 |
0.416 |
83.2 |
0.484 |
96.8 |
85.6 |
7.7 |
|
Endosulfan II |
0.5 |
0.486 |
97.2 |
0.51 |
102.0 |
0.51 |
102.0 |
0.57 |
114.0 |
103.8 |
7.2 |
|
Endosulfan sulfate |
0.5 |
0.458 |
91.6 |
0.506 |
101.2 |
0.506 |
101.2 |
0.55 |
110.0 |
101.0 |
7.5 |
|
Endrin |
0.5 |
0.476 |
95.2 |
0.498 |
99.6 |
0.498 |
99.6 |
0.578 |
115.6 |
102.5 |
9.0 |
|
Endrin aldehyde |
0.5 |
0.546 |
109.2 |
0.534 |
106.8 |
0.534 |
106.8 |
0.566 |
113.2 |
109.0 |
3.0 |
|
Endrin Ketone |
0.5 |
0.47 |
94.0 |
0.496 |
99.2 |
0.496 |
99.2 |
0.598 |
119.6 |
103.0 |
11.3 |
|
gamma-BHC |
0.5 |
0.492 |
98.4 |
0.51 |
102.0 |
0.51 |
102.0 |
0.574 |
114.8 |
104.3 |
7.2 |
|
gamma-Chlordane |
0.5 |
0.47 |
94.0 |
0.482 |
96.4 |
0.482 |
96.4 |
0.54 |
108.0 |
98.7 |
6.3 |
|
Heptachlor |
0.5 |
0.466 |
93.2 |
0.48 |
96.0 |
0.48 |
96.0 |
0.542 |
108.4 |
98.4 |
6.8 |
|
Heptachlor epoxide |
0.5 |
0.45 |
90.0 |
0.468 |
93.6 |
0.468 |
93.6 |
0.524 |
104.8 |
95.5 |
6.4 |
|
Methoxychlor |
0.5 |
0.394 |
78.8 |
0.482 |
96.4 |
0.482 |
96.4 |
0.524 |
104.8 |
94.1 |
10.9 |
|
Chlordane |
1.0 |
0.92 |
92.0 |
0.946 |
94.6 |
0.946 |
94.6 |
1.07 |
107.0 |
97.1 |
6.7 |
|
Toxaphene |
10.0 |
9.468 |
94.7 |
9.178 |
91.8 |
9.844 |
98.4 |
9.598 |
96.0 |
95.2 |
2.8 |
|
DCB (Surr.) |
1.0 |
0.82 |
82.0 |
0.73 |
73.0 |
0.73 |
73.0 |
0.914 |
91.4 |
79.9 |
8.8 |
|
TCMX (Surr.) |
1.0 |
0.776 |
77.6 |
0.72 |
72.0 |
0.72 |
72.0 |
0.882 |
88.2 |
77.5 |
7.6 |
Table 15. Initial Demonstration of Capability (DOC) Results - Column 1.
|
Analyte |
Spike Level (µg/L) |
LCS 1 (µg/L) |
Recovery |
LCS 2 |
Recovery |
LCS 3 |
Recovery |
LCS 4 |
Recovery |
Average Recovery |
Standard Deviation |
|
(%) |
(µg/L) |
(%) |
(µg/L) |
(%) |
(µg/L) |
(%) |
(%) |
(%) |
|||
|
PCB-1016 |
1.00 |
0.978 |
97.8 |
1.01 |
101.0 |
1.026 |
102.6 |
1.02 |
102.0 |
100.9 |
2.1 |
|
PCB-1260 |
1.00 |
1.178 |
117.8 |
1.156 |
115.6 |
1.172 |
117.2 |
1.184 |
118.4 |
117.3 |
1.2 |
|
PCB-1221 |
1.00 |
1.1341 |
113.4 |
1.1682 |
116.8 |
1.2265 |
122.7 |
1.2644 |
126.4 |
119.8 |
5.8 |
|
PCB-1254 |
0.50 |
0.5138 |
102.8 |
0.5477 |
109.5 |
0.5602 |
112.0 |
0.5177 |
103.5 |
107.0 |
4.5 |
|
PCB-1242 |
0.50 |
0.5288 |
105.8 |
0.5255 |
105.1 |
0.4978 |
99.6 |
0.5369 |
107.4 |
104.5 |
3.4 |
|
PCB-1248 |
0.50 |
0.458 |
91.6 |
0.4382 |
87.6 |
0.4794 |
95.9 |
0.5282 |
105.6 |
95.2 |
7.7 |
|
PCB-1268 |
0.50 |
0.6085 |
121.7 |
0.6072 |
121.4 |
0.6479 |
129.6 |
0.6612 |
132.2 |
126.2 |
5.5 |
|
4,4´-DDD |
0.50 |
0.398 |
79.6 |
0.396 |
79.2 |
0.4 |
80.0 |
0.496 |
99.2 |
84.5 |
9.8 |
|
4,4´-DDE |
0.50 |
0.45 |
90.0 |
0.436 |
87.2 |
0.46 |
92.0 |
0.52 |
104.0 |
93.3 |
7.4 |
|
4,4´-DDT |
0.50 |
0.53 |
106.0 |
0.562 |
112.4 |
0.55 |
110.0 |
0.666 |
133.2 |
115.4 |
12.2 |
|
Aldrin |
0.50 |
0.418 |
83.6 |
0.424 |
84.8 |
0.44 |
88.0 |
0.5 |
100.0 |
89.1 |
7.5 |
|
alpha-BHC |
0.50 |
0.526 |
105.2 |
0.516 |
103.2 |
0.536 |
107.2 |
0.6 |
120.0 |
108.9 |
7.6 |
|
alpha-Chlordane |
0.50 |
0.446 |
89.2 |
0.454 |
90.8 |
0.466 |
93.2 |
0.524 |
104.8 |
94.5 |
7.1 |
|
beta-BHC |
0.50 |
0.496 |
99.2 |
0.504 |
100.8 |
0.534 |
106.8 |
0.592 |
118.4 |
106.3 |
8.7 |
|
delta-BHC |
0.50 |
0.484 |
96.8 |
0.48 |
96.0 |
0.5 |
100.0 |
0.562 |
112.4 |
101.3 |
7.6 |
|
Dieldrin |
0.50 |
0.51 |
102.0 |
0.506 |
101.2 |
0.53 |
106.0 |
0.602 |
120.4 |
107.4 |
8.9 |
|
Endosulfan I |
0.50 |
0.442 |
88.4 |
0.424 |
84.8 |
0.426 |
85.2 |
0.524 |
104.8 |
90.8 |
9.5 |
|
Endosulfan II |
0.50 |
0.436 |
87.2 |
0.434 |
86.8 |
0.452 |
90.4 |
0.572 |
114.4 |
94.7 |
13.2 |
|
Endosulfan sulfate |
0.50 |
0.456 |
91.2 |
0.454 |
90.8 |
0.478 |
95.6 |
0.54 |
108.0 |
96.4 |
8.0 |
|
Endrin |
0.50 |
0.482 |
96.4 |
0.484 |
96.8 |
0.502 |
100.4 |
0.582 |
116.4 |
102.5 |
9.4 |
|
Endrin aldehyde |
0.50 |
0.56 |
112.0 |
0.544 |
108.8 |
0.61 |
122.0 |
0.628 |
125.6 |
117.1 |
8.0 |
|
Endrin Ketone |
0.50 |
0.464 |
92.8 |
0.47 |
94.0 |
0.49 |
98.0 |
0.564 |
112.8 |
99.4 |
9.2 |
|
gamma-BHC |
0.50 |
0.488 |
97.6 |
0.494 |
98.8 |
0.514 |
102.8 |
0.568 |
113.6 |
103.2 |
7.3 |
|
gamma-Chlordane |
0.50 |
0.468 |
93.6 |
0.466 |
93.2 |
0.482 |
96.4 |
0.552 |
110.4 |
98.4 |
8.1 |
|
Heptachlor |
0.50 |
0.448 |
89.6 |
0.48 |
96.0 |
0.49 |
98.0 |
0.524 |
104.8 |
97.1 |
6.3 |
|
Heptachlor epoxide |
0.50 |
0.452 |
90.4 |
0.448 |
89.6 |
0.47 |
94.0 |
0.518 |
103.6 |
94.4 |
6.4 |
|
Methoxychlor |
0.50 |
0.496 |
99.2 |
0.516 |
103.2 |
0.404 |
80.8 |
0.636 |
127.2 |
102.6 |
19.1 |
|
Chlordane |
1.00 |
0.914 |
91.4 |
0.92 |
92.0 |
0.948 |
94.8 |
1.08 |
108.0 |
96.6 |
7.8 |
|
Toxaphene |
10.00 |
9.692 |
96.9 |
9.642 |
96.4 |
10.434 |
104.3 |
9.994 |
99.9 |
99.4 |
3.6 |
|
DCB (Surr.) |
1.00 |
0.868 |
86.8 |
0.95 |
95.0 |
0.896 |
89.6 |
1.12 |
112.0 |
95.9 |
11.3 |
|
TCMX (Surr.) |
1.00 |
0.72 |
72.0 |
0.77 |
77.0 |
0.724 |
72.4 |
0.878 |
87.8 |
77.3 |
7.4 |
Table 16. Matrix Spike and Matrix Spike Duplicate (MS/MSD) Results - Column 1.
|
Analyte |
Spike Level (µg/L) |
MS (µg/L) |
Recovery (%) |
MSD (µg/L) |
Recovery (%) |
Average Recovery (%) |
Relative Percent Difference (%) |
|
PCB-1016 |
0.5 |
0.534 |
106.8 |
0.5267 |
105.3 |
106.1 |
1.4 |
|
PCB-1260 |
0.5 |
0.559 |
111.8 |
0.6096 |
121.9 |
116.9 |
8.6 |
|
PCB-1221 |
1 |
0.964 |
96.4 |
0.9748 |
97.5 |
96.9 |
1.1 |
|
PCB-1254 |
0.5 |
0.450 |
90.0 |
0.486 |
97.2 |
93.6 |
7.7 |
|
PCB-1242 |
0.5 |
0.328 |
65.6 |
0.335 |
67.0 |
66.3 |
2.1 |
|
PCB-1248 |
0.5 |
0.444 |
88.8 |
0.4692 |
93.8 |
91.3 |
5.5 |
|
PCB-1268 |
0.5 |
0.388 |
77.6 |
0.4221 |
84.4 |
81.0 |
8.4 |
|
4,4´-DDD |
0.5 |
0.378 |
75.6 |
0.392 |
78.4 |
77.0 |
3.6 |
|
4,4´-DDE |
0.5 |
0.374 |
74.8 |
0.44 |
88.0 |
81.4 |
16.2 |
|
4,4´-DDT |
0.5 |
0.502 |
100.4 |
0.538 |
107.6 |
104.0 |
6.9 |
|
Aldrin |
0.5 |
0.43 |
86.0 |
0.44 |
88.0 |
87.0 |
2.3 |
|
alpha-BHC |
0.5 |
0.532 |
106.4 |
0.538 |
107.6 |
107.0 |
1.1 |
|
alpha-Chlordane |
0.5 |
0.458 |
91.6 |
0.494 |
98.8 |
95.2 |
7.6 |
|
beta-BHC |
0.5 |
0.466 |
93.2 |
0.476 |
95.2 |
94.2 |
2.1 |
|
delta-BHC |
0.5 |
0.442 |
88.4 |
0.46 |
92.0 |
90.2 |
4.0 |
|
Dieldrin |
0.5 |
0.434 |
86.8 |
0.448 |
89.6 |
88.2 |
3.2 |
|
Endosulfan I |
0.5 |
0.3 |
60.0 |
0.34 |
68.0 |
64.0 |
12.5 |
|
Endosulfan II |
0.5 |
0.438 |
87.6 |
0.458 |
91.6 |
89.6 |
4.5 |
|
Endosulfan sulfate |
0.5 |
0.44 |
88.0 |
0.424 |
84.8 |
86.4 |
3.7 |
|
Endrin |
0.5 |
0.444 |
88.8 |
0.458 |
91.6 |
90.2 |
3.1 |
|
Endrin aldehyde |
0.5 |
0.566 |
113.2 |
0.516 |
103.2 |
108.2 |
9.2 |
|
Endrin Ketone |
0.5 |
0.472 |
94.4 |
0.502 |
100.4 |
97.4 |
6.2 |
|
gamma-BHC |
0.5 |
0.488 |
97.6 |
0.496 |
99.2 |
98.4 |
1.6 |
|
gamma-Chlordane |
0.5 |
0.394 |
78.8 |
0.402 |
80.4 |
79.6 |
2.0 |
|
Heptachlor |
0.5 |
0.474 |
94.8 |
0.49 |
98.0 |
96.4 |
3.3 |
|
Heptachlor epoxide |
0.5 |
0.424 |
84.8 |
0.42 |
84.0 |
84.4 |
0.9 |
|
Methoxychlor |
0.5 |
0.398 |
79.6 |
0.524 |
104.8 |
92.2 |
27.3 |
|
Chlordane |
1 |
0.852 |
85.2 |
0.896 |
89.6 |
87.4 |
5.0 |
|
Toxaphene |
10 |
9.162 |
91.6 |
8.93 |
89.3 |
90.5 |
2.6 |
|
DCB (Surr.) |
1 |
0.85 |
85.0 |
0.736 |
73.6 |
79.3 |
14.4 |
|
TCMX (Surr.) |
1 |
0.89 |
89.0 |
0.768 |
76.8 |
82.9 |
14.7 |
Table 17. Matrix Spike and Matrix Spike Duplicate (MS/MSD) Results - Column 1.
|
Analyte |
Spike Level (µg/L) |
MS (µg/L) |
Recovery (%) |
MSD (µg/L) |
Recovery (%) |
Average Recovery (%) |
Relative Percent Difference (%) |
|
PCB-1016 |
0.5 |
0.503 |
100.6 |
0.5243 |
104.9 |
102.7 |
4.1 |
|
PCB-1260 |
0.5 |
0.585 |
117.0 |
0.6408 |
128.2 |
122.6 |
9.1 |
|
PCB-1221 |
1 |
1.169 |
116.9 |
0.9839 |
98.4 |
107.6 |
17.2 |
|
PCB-1254 |
0.5 |
0.501 |
100.2 |
0.4752 |
95.0 |
97.6 |
5.2 |
|
PCB-1242 |
0.5 |
0.456 |
91.1 |
0.4849 |
97.0 |
94.0 |
6.3 |
|
PCB-1248 |
0.5 |
0.448 |
89.6 |
0.4782 |
95.6 |
92.6 |
6.5 |
|
PCB-1268 |
0.5 |
0.583 |
116.7 |
0.649 |
129.8 |
123.2 |
10.7 |
|
4,4´-DDD |
0.5 |
0.38 |
76.0 |
0.394 |
78.8 |
77.4 |
3.6 |
|
4,4´-DDE |
0.5 |
0.394 |
78.8 |
0.426 |
85.2 |
82.0 |
7.8 |
|
4,4´-DDT |
0.5 |
0.516 |
103.2 |
0.568 |
113.6 |
108.4 |
9.6 |
|
Aldrin |
0.5 |
0.434 |
86.8 |
0.438 |
87.6 |
87.2 |
0.9 |
|
alpha-BHC |
0.5 |
0.502 |
100.4 |
0.514 |
102.8 |
101.6 |
2.4 |
|
alpha-Chlordane |
0.5 |
0.388 |
77.6 |
0.38 |
76.0 |
76.8 |
2.1 |
|
beta-BHC |
0.5 |
0.466 |
93.2 |
0.512 |
102.4 |
97.8 |
9.4 |
|
delta-BHC |
0.5 |
0.476 |
95.2 |
0.484 |
96.8 |
96.0 |
1.7 |
|
Dieldrin |
0.5 |
0.444 |
88.8 |
0.46 |
92.0 |
90.4 |
3.5 |
|
Endosulfan I |
0.5 |
0.378 |
75.6 |
0.386 |
77.2 |
76.4 |
2.1 |
|
Endosulfan II |
0.5 |
0.394 |
78.8 |
0.406 |
81.2 |
80.0 |
3.0 |
|
Endosulfan sulfate |
0.5 |
0.432 |
86.4 |
0.438 |
87.6 |
87.0 |
1.4 |
|
Endrin |
0.5 |
0.44 |
88.0 |
0.456 |
91.2 |
89.6 |
3.6 |
|
Endrin aldehyde |
0.5 |
0.472 |
94.4 |
0.45 |
90.0 |
92.2 |
4.8 |
|
Endrin Ketone |
0.5 |
0.434 |
86.8 |
0.458 |
91.6 |
89.2 |
5.4 |
|
gamma-BHC |
0.5 |
0.47 |
94.0 |
0.496 |
99.2 |
96.6 |
5.4 |
|
gamma-Chlordane |
0.5 |
0.372 |
74.4 |
0.382 |
76.4 |
75.4 |
2.7 |
|
Heptachlor |
0.5 |
0.49 |
98.0 |
0.494 |
98.8 |
98.4 |
0.8 |
|
Heptachlor epoxide |
0.5 |
0.28 |
56.0 |
0.318 |
63.6 |
59.8 |
12.7 |
|
Methoxychlor |
0.5 |
0.496 |
99.2 |
0.468 |
93.6 |
96.4 |
5.8 |
|
Chlordane |
1 |
0.76 |
76.0 |
0.762 |
76.2 |
76.1 |
0.3 |
|
Toxaphene |
10 |
11.868 |
118.7 |
11.52 |
115.2 |
116.9 |
3.0 |
|
DCB (Surr.) |
1 |
0.946 |
94.6 |
0.87 |
87.0 |
90.8 |
8.4 |
|
TCMX (Surr.) |
1 |
0.88 |
88.0 |
0.752 |
75.2 |
81.6 |
15.7 |
Literature number: AN974
