|
Step |
Operation |
Solvent |
Solvent Vol. (mL) |
Purge Time (s) |
Pump Rate (#) |
N2 Blanket |
Sat. Time (s) |
Soak Time (s) |
Elute Time (s) |
The US EPA monitors a variety of chemicals in water that may cause harm to humans or wildlife in order to minimize exposure. Method 625 was developed by the Office of Science and Technology in the Clean Water program to monitor a large suite of
semi volatile chemicals in wastewater for compliance with the National Pollution Discharge Elimination System (NPDES). NPDES is a system of permitting that regulates the characteristics of water that is released into a waterway, defined by industrial category. The permitting levels are set depending on the waterway’s use. If the waterway is used for recreation or is an important wildlife habitat, the limit may be set lower.
The original method was developed in the early 1980s and has been updated several times since then to allow for the use of more modern technology. The latest update has taken place over the last few years and was proposed in a Method Update Rule (MUR) in 2015.1 The latest version of the method includes a larger suite of analytes (up to 364) and an extensive set of labelled surrogates to better monitor the method performance throughout sample preparation and analysis steps.2
This note examines the results from an initial demonstration of capability (DOC) with one litre samples utilizing automated disk solid phase extraction (SPE) for US EPA method 625.1. Samples were evaluated and measured against the criteria listed in Table 6 of method 625.1. The analytes chosen for evaluation were from Tables 1, 2 and 3 in Method 625.1. Analytes from Table 3 do not have any acceptance criteria for comparison.
One litre samples were processed as laboratory control samples (LCS), matrix spike (MS), matrix spike duplicate (MSD) and calibration verifications were evaluated. The samples were extracted using an Atlantic® One-pass SPE disk (Biotage) which is a mixed mode disk containing several functionalities. The process was automated with the Biotage® Horizon 5000 (previously known as the SPE-DEX® 5000) extraction system. A carbon cartridge (Max Detect, Biotage) was also used to ensure adequate retention of the light end compounds, such as N-Nitrosodi-n-propylamine.
The Fast Flow Disk Holder (FFSDH) was used with the samples because this method is known for varying levels of particulate matter and the sample size was 1 L. The FFSDH uses a 47 mm disk, but allows larger filters to be placed on top to shield the SPE disk from particulates that may cause clogging and maintain fast flow through the disk.
The particulate material is retained on the filters and washed with solvent during the elution step, so any material that has been absorbed on the surface will be included in the extraction. Figure 1 shows a photo of the Biotage® Horizon 5000 configured with the One Pass kit, Carbon Cartridge and the Fast Flow Disk Holder.
Figure 1. Biotage® Horizon 5000 (Previously known as the SPE-DEX 5000 Extractor).
The resulting extracts were dried using DryDisk® membrane drying system (Biotage) and evaporated to 1 mL with the DryVap™* Automated In-line Drying and Concentration System (Biotage). The DryVap™ was chosen for its ability to in-line dry and concentrate extracts at a very low boiling point. Those two features preserve the extracted compounds concentration throughout the drying and concentration process, compared to traditional multistep processes. Figure 2 shows the DryVap™ system with DryDisk glassware holding the drying membranes in front. The dried extract is drawn into the concentration tube in the back and the evaporation occurs there. Residual water remains in the front reservoirs separated from the extract.
The extraction method used with the Biotage® Horizon 5000 is shown in Table 1. The conditions for operating the DryVap™ are shown in Table 2.
*The DryVap™ system has been discontinued. We recommend using the TurboVap® evaporation systems for achieving equivalent results.
Figure 2. DryVap™ System.
Table 1. Biotage® Horizon 5000 Extraction Method.
|
Step |
Operation |
Message |
Attachment |
|||||
|
1 |
Pause with message |
Part 1 of 3: Neutrals and Acids Elution. Have the Fast Flow Sediment Disk Holder with OnePass Disk, 1 µm filter, 5 µm filter, top screen over the filters, 250 mL collection flask, and carbon cartridge installed. The down spout of the water in valve must push down on the top screen. Click “Continue” to start Part 1. |
None |
|||||
|
Step |
Operation |
Solvent |
Solvent Vol. (mL) |
Purge Time (s) |
Pump Rate (#) |
Sat. Time (s) |
Soak Time (s) |
Drain Time (s) |
|
2 |
Condition SPE |
Acetone |
40 |
60 |
4 |
2 |
60 |
60 |
|
3 |
Condition SPE |
Reagent Water |
20 |
60 |
4 |
2 |
60 |
60 |
|
Step |
Operation |
Sample Flow Rate (#) |
Done Loading SampleDelay (s) |
|
|||||
|
4 |
Load Sample |
5 |
45 |
|
|
|
|
|
|
|
Step |
Operation |
Solvent |
Solvent Vol. (mL) |
Purge Time (s) |
Pump Rate (#) |
N2 Blanket |
Sat. Time (s) |
Soak Time (s) |
Drain Time (s) |
|
5 |
Wash Sample Container |
Reagent Water |
20 |
30 |
4 |
Off |
2 |
5 |
30 |
|
Step |
Operation |
|
Dry Time (s) |
Pump Rate (#) |
N2 Blanket |
|
|
|
|
|
6 |
Air Dry Disk Timer |
|
360 |
6 |
Off |
||||
|
Step |
Operation |
Solvent |
Solvent Vol. (mL) |
Purge Time (s) |
Pump Rate (#) |
N2 Blanket |
Sat. Time (s) |
Soak Time (s) |
Elute Time (s) |
|
7 |
Elute Sample Container |
Acetone |
20 |
20 |
4 |
Off |
2 |
180 |
180 |
|
8 |
Elute Sample Container |
MeCl2 |
17 |
15 |
4 |
Off |
2 |
180 |
180 |
|
9 |
Elute Sample Container |
MeCl2 |
17 |
15 |
4 |
Off |
2 |
120 |
120 |
|
10 |
Elute Sample Container |
MeCl2 |
17 |
15 |
4 |
Off |
2 |
120 |
120 |
|
11 |
Elute Sample Container |
MeCl2 |
17 |
15 |
6 |
Off |
2 |
120 |
180 |
|
Step |
Operation |
Message |
Attachment |
||||||
|
12 |
Pause with Message |
Part 2 of 3: Ion Exchange Elution. Remove the 250 mL collection flask containing the neutrals and acids elution. Stopper the flask and set aside for part 3. Then install a clean 125 mL flask to collect the ion exchange elution. Click “Continue” to Start Part 2. |
None |
||||||
|
Step |
Operation |
Solvent |
Solvent Vol. (mL) |
Purge Time (s) |
Pump Rate (#) |
N2 Blanket |
Sat. Time (s) |
Soak Time (s) |
Elute Time (s) |
|
13 |
Elute Sample Container |
Acetone |
20 |
20 |
4 |
Off |
2 |
0 |
180 |
|
14 |
Elute Sample Container |
1% NH4OH |
20 |
30 |
4 |
Off |
2 |
120 |
120 |
|
15 |
Elute Sample Container |
Acetone |
20 |
20 |
4 |
Off |
2 |
180 |
120 |
|
16 |
Elute Sample Container |
MeCl2 |
17 |
15 |
4 |
Off |
2 |
180 |
180 |
|
17 |
Elute Sample Container |
MeCl2 |
16 |
15 |
4 |
Off |
2 |
120 |
180 |
|
18 |
Elute Sample Container |
MeCl2 |
16 |
15 |
4 |
Off |
2 |
120 |
180 |
|
19 |
Elute Sample Container |
MeCl2 |
16 |
15 |
6 |
Off |
2 |
120 |
180 |
|
Step |
Operation |
Message |
Attachment |
||||||
|
20 |
Pause with Message |
Part 3 of 3: Carbon Cartridge Elution. Remove the carbon cartridge from the tubing lines. Connect the tubing ends together. Using a 20 cc syringe, plunge the carbon cartridge with air through the cap adapter to reseat the carbon bed on the frit. Replace the cap adapter with the funnel cartridge. Replace the disk holder with the cartridge. Replace the 125 mL flask with the 250 mL flask containing the neutrals and acids elution from Part 1. Stopper the 125 mL flask. Click “Continue” to start part 3. |
None |
||||||
|
Step |
Operation |
Dry Time (s) |
Pump Rate (#) |
N2 Blanket |
|
|
|
|
|
|
21 |
Air Dry Disk Timer |
60 |
6 |
Off |
|
|
|
|
|
|
Step |
Operation |
Solvent |
Solvent Vol. (mL) |
Purge Time (s) |
Pump Rate (#) |
N2 Blanket |
Sat. Time (s) |
Soak Time (s) |
Elute Time (s) |
|
22 |
Elute Sample Container |
Acetone |
25 |
20 |
4 |
Off |
3 |
60 |
60 |
|
23 |
Elute Sample Container |
MeCl2 |
17 |
15 |
4 |
Off |
3 |
60 |
20 |
|
24 |
Elute Sample Container |
MeCl2 |
17 |
15 |
4 |
Off |
3 |
60 |
20 |
|
25 |
Elute Sample Container |
MeCl2 |
17 |
15 |
4 |
Off |
3 |
60 |
20 |
|
26 |
Elute Sample Container |
MeCl2 |
17 |
15 |
4 |
Off |
3 |
60 |
20 |
|
27 |
Elute Sample Container |
MeCl2 |
17 |
15 |
6 |
Off |
3 |
60 |
60 |
The samples were measured using GC/MS (6890GC/5975CMS, Agilent Technologies). The operational conditions are shown in Table 3.
All spiking standards used were from (Supelco, Bellefonte, PA). The surrogate mixes were from (Restek Corp, Bellefonte, PA.).
Table 2. DryVap™ System Conditions.
|
Parameter |
Setting |
|---|---|
|
Dry Volume |
200 mL |
|
Heat Power |
5 |
|
Heat Timer |
OFF |
|
Auto Rinse Mode |
OFF |
|
Nitrogen Sparge |
20 psi |
|
Vacuum |
-7 in. Hg |
Table 3. GC/MS Conditions.
|
Injection |
|
|---|---|
|
Volume |
1 µL |
|
Inlet Temperature |
280 °C |
|
Mode |
Splitless |
|
Gas Type |
Helium |
|
Cartridge |
Zebron™ ZB-Semi volatiles (Phenomenex) |
|
Mode |
Consistent Flow |
|
Oven Program |
45 °C hold for 1 min to 270 °C at 15 °C/min then to 318 °C at 6 °C/min |
|
MS Ions Monitored |
Scan masses 35–550 |
Table 6 in US EPA Method 625.1 (December 2014) lists criterion by analytes for a variety of characteristics to validate that the method applied with changes will meet the requirements of the original method for a variety of challenging matrices; representative of those that may be encountered in a commercial laboratory. This table is included in Appendix 1 for easy reference.
The first cartridge of Table 6 in Method 625.1 is range in % for recovery of the calibration verification standard. The results for this standard during the testing of the extracts is shown in Table 4 and meets the criteria listed in Method 625.1
for compliance.
Table 4. Calibration Verification over the Course of Operation.
|
Analyte |
Recovery (%) |
Recovery (%) |
Recovery (%) |
Recovery (%) |
Recovery (%) |
Recovery (%) |
Range for Q (%) |
Pass/Fail |
|
NDMA |
102.9 |
94.4 |
96.9 |
97.8 |
97.6 |
94.1 |
60-140 |
Pass |
|
1,2,4,5- Tetrachlorobenzene |
98.0 |
97.5 |
95.0 |
101.9 |
100.8 |
97.2 |
60-140 |
Pass |
|
1,2,4-Trichlorobenzene |
97.7 |
98.4 |
95.0 |
101.2 |
100.9 |
97.2 |
61-130 |
Pass |
|
1,3,5,-Trinitrobenzene |
95.5 |
94.7 |
92.1 |
97.1 |
94.6 |
92.8 |
60-140 |
Pass |
|
1,4-Naphthoquinone |
94.8 |
94.7 |
92.6 |
97.9 |
95.4 |
92.0 |
60-140 |
Pass |
|
1-Naphthylamine |
85.5 |
82.6 |
82.8 |
87.8 |
82.6 |
82.4 |
60-140 |
Pass |
|
2,3,4,6- Tetrachlorophenol |
93.9 |
93.5 |
93.5 |
98.1 |
96.3 |
93.6 |
60-140 |
Pass |
|
2,4,5-Trichlorophenol |
95.1 |
94.8 |
93.9 |
99.2 |
95.9 |
93.0 |
60-140 |
Pass |
|
2,4-Dichlorophenol |
96.7 |
96.2 |
94.4 |
99.5 |
96.3 |
93.1 |
64-130 |
Pass |
|
2,4-Dimethylphenol |
98.0 |
97.9 |
95.2 |
99.9 |
97.2 |
93.8 |
58-130 |
Pass |
|
2,4-Dinitrophenol |
80.2 |
81.2 |
85.7 |
87.9 |
85.6 |
82.1 |
39-173 |
Pass |
|
2,4-Dinitrotoluene |
93.5 |
94.2 |
94.0 |
98.6 |
96.9 |
93.9 |
53-130 |
Pass |
|
2,6-Dichlorophenol |
95.8 |
96.5 |
94.9 |
99.2 |
96.3 |
93.7 |
60-140 |
Pass |
|
2,6-Dinitrotoluene |
94.5 |
94.3 |
92.6 |
98.9 |
96.3 |
93.5 |
68-137 |
Pass |
|
2-Chloronaphthalene |
97.8 |
97.4 |
94.7 |
100.2 |
99.6 |
96.0 |
70-130 |
Pass |
|
2-Chlorophenol |
97.4 |
96.6 |
94.6 |
98.9 |
99.2 |
94.7 |
55-130 |
Pass |
|
2-Fluorobiphenyl |
99.0 |
97.9 |
97.3 |
100.0 |
92.5 |
91.0 |
60-140 |
Pass |
|
2-Fluorophenol |
99.9 |
95.8 |
97.8 |
95.4 |
96.3 |
94.3 |
60-140 |
Pass |
|
2-Methylnaphthalene |
96.7 |
98.4 |
95.3 |
100.5 |
98.8 |
95.3 |
60-140 |
Pass |
|
2-Naphthylamine |
68.6 |
70.4 |
66.2 |
71.8 |
65.5 |
66.7 |
60-140 |
Pass |
|
2-Nitroaniline |
95.1 |
94.3 |
93.4 |
98.1 |
94.9 |
92.5 |
60-140 |
Pass |
|
2-Nitrophenol |
95.2 |
96.5 |
93.7 |
98.2 |
96.1 |
93.7 |
61-163 |
Pass |
|
3,3'-Dichlorobenzidine |
107.2 |
106.0 |
100.4 |
108.2 |
102.7 |
102.2 |
18-213 |
Pass |
|
3,3'-Dimethylbenzidine |
80.2 |
84.5 |
80.1 |
92.8 |
86.1 |
88.0 |
60-140 |
Pass |
|
3-Methylcholanthrene |
95.0 |
96.1 |
92.4 |
99.4 |
95.9 |
94.4 |
60-140 |
Pass |
|
3-Nitroaniline |
99.2 |
96.0 |
96.2 |
100.6 |
97.8 |
96.1 |
60-140 |
Pass |
|
4 Aminobiphenyl |
87.9 |
88.2 |
79.6 |
86.2 |
79.9 |
80.4 |
60-140 |
Pass |
|
4,6-Dinitro-2- methylphenol |
89.0 |
90.5 |
90.9 |
96.2 |
94.0 |
90.7 |
56-130 |
Pass |
|
4-Bromophenyl phenyl ether |
96.6 |
99.8 |
96.0 |
103.5 |
100.8 |
98.1 |
70-130 |
Pass |
|
4-Chloro-3- methylphenol |
94.8 |
96.5 |
95.2 |
97.7 |
96.0 |
91.9 |
68-130 |
Pass |
|
4-Chloroaniline |
74.7 |
86.9 |
75.3 |
87.5 |
85.3 |
82.5 |
60-140 |
Pass |
|
4-Chlorophenyl phenyl ether |
95.3 |
97.9 |
94.9 |
101.0 |
98.8 |
97.5 |
57-145 |
Pass |
|
4-Nitroaniline |
96.3 |
92.4 |
94.9 |
94.6 |
94.6 |
89.9 |
60-140 |
Pass |
|
4-Nitrophenol |
96.4 |
89.3 |
91.5 |
91.7 |
90.0 |
86.8 |
35-130 |
Pass |
|
4-Nitroquinoline-1- oxide |
89.7 |
95.9 |
87.2 |
104.1 |
94.4 |
101.0 |
60-140 |
Pass |
|
5-nitro-o-toluidine |
94.3 |
92.9 |
92.7 |
98.6 |
96.3 |
93.5 |
60-140 |
Pass |
|
Analyte |
Recovery (%) |
Recovery (%) |
Recovery (%) |
Recovery (%) |
Recovery (%) |
Recovery (%) |
Range for Q (%) |
Pass/Fail |
|
7,12-Dimethylbenz(a)- anthracene |
94.6 |
98.2 |
95.0 |
100.2 |
98.8 |
95.1 |
60-140 |
Pass |
|
Acenaphthene |
97.1 |
96.7 |
94.6 |
100.4 |
97.7 |
95.0 |
70-130 |
Pass |
|
Acenaphthylene |
96.9 |
96.5 |
94.6 |
100.5 |
97.2 |
94.6 |
60-130 |
Pass |
|
Acetophenone |
96.7 |
96.7 |
94.2 |
100.0 |
99.0 |
95.2 |
60-140 |
Pass |
|
Acetylaminofluorene |
97.0 |
95.8 |
92.1 |
98.5 |
94.4 |
93.7 |
60-140 |
Pass |
|
Aniline |
90.6 |
90.6 |
91.0 |
96.9 |
93.3 |
93.1 |
60-140 |
Pass |
|
Anthracene |
98.1 |
98.0 |
94.5 |
100.1 |
98.6 |
95.0 |
58-130 |
Pass |
|
Benz(a)anthracene |
96.6 |
95.1 |
94.1 |
98.2 |
97.2 |
94.3 |
42-133 |
Pass |
|
Benzidine |
81.9 |
84.7 |
76.3 |
87.4 |
82.0 |
85.3 |
60-140 |
Pass |
|
Benzo(a)pyrene |
96.5 |
96.0 |
93.7 |
99.3 |
97.1 |
94.7 |
32-148 |
Pass |
|
Benzo(b)fluoranthene |
93.7 |
94.6 |
92.2 |
98.2 |
96.2 |
93.2 |
42-140 |
Pass |
|
Benzo(ghi)perylene |
96.4 |
93.8 |
91.3 |
97.1 |
92.8 |
91.1 |
13-195 |
Pass |
|
Benzo(k)fluoranthene |
97.5 |
99.3 |
97.7 |
101.1 |
100.2 |
96.6 |
25-146 |
Pass |
|
Benzoic acid |
93.6 |
89.8 |
92.1 |
92.9 |
87.5 |
86.7 |
60-140 |
Pass |
|
Benzyl alcohol |
97.1 |
96.5 |
94.3 |
99.1 |
97.4 |
94.6 |
60-140 |
Pass |
|
Bis(2- chlorethoxy)methane |
96.7 |
98.9 |
94.3 |
100.6 |
98.4 |
95.5 |
52-164 |
Pass |
|
Bis(2-chloroethyl)ether |
99.6 |
99.8 |
94.7 |
100.1 |
99.1 |
96.5 |
60-140 |
Pass |
|
Bis(2chloroisopropyl)et her |
95.7 |
98.8 |
94.0 |
102.1 |
99.7 |
98.4 |
63-139 |
Pass |
|
Bis(2-ethylhexyl) phthalate |
85.3 |
98.6 |
91.0 |
102.3 |
99.9 |
98.4 |
43-137 |
Pass |
|
Carbazole |
100.0 |
96.6 |
95.1 |
98.2 |
97.6 |
93.5 |
60-140 |
Pass |
|
Chrysene |
97.4 |
96.1 |
94.8 |
98.1 |
97.6 |
93.9 |
44-140 |
Pass |
|
Dibenz(ah)anthracene |
91.2 |
93.5 |
91.1 |
98.2 |
94.2 |
92.5 |
13-200 |
Pass |
|
Dibenzofuran |
97.0 |
96.4 |
94.8 |
100.7 |
98.4 |
95.1 |
60-140 |
Pass |
|
Diethyl phthalate |
92.5 |
96.3 |
93.3 |
101.4 |
98.5 |
97.0 |
47-130 |
Pass |
|
Dimethyl phthalate |
93.7 |
95.7 |
93.3 |
99.4 |
97.4 |
94.4 |
50-130 |
Pass |
|
Dimethylaminoazoben- zene |
90.2 |
97.7 |
93.3 |
99.5 |
97.9 |
95.5 |
60-140 |
Pass |
|
Di-n-butyl phthalate |
90.9 |
100.1 |
91.1 |
101.8 |
100.8 |
98.7 |
52-130 |
Pass |
|
Di-n-octyl phthalate |
89.3 |
99.2 |
92.2 |
102.3 |
99.4 |
98.4 |
21-132 |
Pass |
|
Dinoseb |
89.8 |
94.1 |
90.0 |
98.5 |
97.1 |
94.2 |
60-140 |
Pass |
|
Diphenylamine |
96.2 |
96.3 |
95.3 |
99.4 |
97.9 |
95.3 |
60-140 |
Pass |
|
Ethylmethane Sul- fonate |
96.8 |
95.2 |
94.8 |
98.6 |
97.9 |
95.9 |
60-140 |
Pass |
|
Fluoranthene |
98.4 |
96.9 |
94.8 |
97.4 |
97.7 |
95.1 |
47-130 |
Pass |
|
Fluorene |
95.6 |
96.5 |
93.9 |
99.4 |
98.5 |
94.8 |
70-130 |
Pass |
|
Hexachlorobenzene |
96.1 |
99.6 |
94.4 |
101.3 |
99.4 |
96.2 |
38-142 |
Pass |
|
Hexachlorobutadiene |
97.9 |
101.3 |
95.5 |
104.7 |
103.5 |
100.3 |
68-130 |
Pass |
|
Hexachlorocyclopenta- diene |
89.9 |
92.4 |
88.2 |
99.4 |
96.7 |
94.2 |
60-140 |
Pass |
|
Analyte |
Recovery (%) |
Recovery (%) |
Recovery (%) |
Recovery (%) |
Recovery (%) |
Recovery (%) |
Range for Q (%) |
Pass/Fail |
|
Hexachloroethane |
97.9 |
100.3 |
93.8 |
102.9 |
102.9 |
100.7 |
55-130 |
Pass |
|
Hexachloropropene |
97.5 |
98.9 |
93.8 |
101.4 |
100.6 |
97.1 |
60-140 |
Pass |
|
Indeno(1,2,3-cd)pyrene |
94.3 |
93.3 |
89.6 |
95.2 |
90.8 |
88.6 |
13-151 |
Pass |
|
Isophorone |
95.6 |
98.8 |
93.8 |
100.1 |
98.0 |
95.1 |
52-180 |
Pass |
|
Methapyrilene |
90.2 |
94.0 |
89.5 |
97.1 |
94.8 |
92.9 |
60-140 |
Pass |
|
Naphthalene |
98.5 |
97.9 |
95.0 |
100.2 |
98.8 |
95.6 |
70-130 |
Pass |
Before running samples, the laboratory must first demonstrate their capability to use a method with an initial DOC, running four spiked reagent water samples through the complete sample preparation and analysis step. The results for recovery accuracy and precision are compared with the range specified for compliance. The range is included in Table 5 for easy comparison. Analytes with a * indicate that they are from Table 3 and do not have acceptance criteria in Table 6 within Method 625.1. It is up to the laboratory to generate their own acceptance criteria for Table 3 analytes.
Table 5. Initial demonstration of compliance.
|
Analyte |
Average DOC |
DOC Range |
Pass/ Fail |
SD |
Limit for s (%) |
Pass/ Fail |
|
1,2,4,5-Tetrachlorobenzene* |
61.89 |
|
|
5.24 |
|
|
|
1,2,4-Trichlorobenzene |
57.69 |
57-130 |
Pass |
5.08 |
30 |
Pass |
|
1,2-Dichlorobenzene* |
51.60 |
|
|
4.49 |
|
|
|
1,3,5,-Trinitrobenzene* |
83.54 |
|
|
6.65 |
|
|
|
1,3-Dichlorobenzene* |
46.37 |
|
|
4.58 |
|
|
|
1,3-Dinitrobenzene* |
88.29 |
|
|
5.80 |
|
|
|
1,4-Dichlorobenzene* |
48.39 |
|
|
4.84 |
|
|
|
1,4-Naphthoquinone* |
77.21 |
|
|
2.15 |
|
|
|
1-Naphthylamine* |
89.88 |
|
|
1.58 |
|
|
|
2,3,4,6-Tetrachlorophenol* |
87.10 |
|
|
5.02 |
|
|
|
2,4,5-Trichlorophenol* |
84.55 |
|
|
4.56 |
|
|
|
2,4-Dichlorophenol |
86.09 |
53-122 |
Pass |
4.45 |
30 |
Pass |
|
2,4-Dimethylphenol |
85.77 |
42-120 |
Pass |
4.31 |
35 |
Pass |
|
2,4-Dinitrophenol |
83.62 |
D-173 |
Pass |
5.97 |
79 |
Pass |
|
2,4-Dinitrotoluene |
88.97 |
48-127 |
Pass |
4.91 |
25 |
Pass |
|
2,6-Dichlorophenol* |
85.58 |
|
|
4.19 |
|
|
|
2,6-Dinitrotoluene |
89.83 |
68-137 |
Pass |
5.49 |
29 |
Pass |
|
2-Chloronaphthalene |
70.88 |
65-120 |
Pass |
5.97 |
15 |
Pass |
|
2-Chlorophenol |
77.07 |
36-120 |
Pass |
5.10 |
37 |
Pass |
|
2-Fluorobiphenyl* |
83.45 |
|
|
2.46 |
|
|
|
2-Fluorophenol* |
55.75 |
|
|
6.09 |
|
|
|
2-Methyl phenol* |
80.66 |
|
|
5.19 |
|
|
|
2-Methylnaphthalene* |
68.80 |
|
|
5.49 |
|
|
|
2-Naphthylamine* |
109.87 |
|
|
6.08 |
|
|
|
Analyte |
Average DOC |
DOC Range |
Pass/ Fail |
SD |
Limit for s (%) |
Pass/ Fail |
|
2-Nitroaniline* |
87.96 |
|
|
6.80 |
|
|
|
2-Nitrophenol |
75.83 |
45-167 |
Pass |
3.66 |
79 |
Pass |
|
2-Picoline* |
47.44 |
|
|
2.09 |
|
|
|
3,3'-Dichlorobenzidine |
88.90 |
8-213 |
Pass |
3.25 |
65 |
Pass |
|
3,3'-Dimethylbenzidine* |
94.17 |
|
|
2.61 |
|
|
|
3+4 Methyl phenol* |
82.47 |
|
|
6.41 |
|
|
|
3-Methylcholanthrene* |
84.77 |
|
|
5.18 |
|
|
|
3-Nitroaniline* |
91.89 |
|
|
4.77 |
|
|
|
4 Aminobiphenyl* |
112.58 |
|
|
6.89 |
|
|
|
2-methyl-4,6-Dinitrophenol |
87.21 |
53-130 |
Pass |
5.66 |
122 |
Pass |
|
4-Bromophenyl phenyl ether |
82.74 |
65-120 |
Pass |
4.84 |
26 |
Pass |
|
4-Chloro-3-methylphenol |
89.01 |
41-128 |
Pass |
4.86 |
44 |
Pass |
|
4-Chloroaniline* |
118.22 |
|
|
8.03 |
|
|
|
4-Chlorophenyl phenyl ether |
79.56 |
38-145 |
Pass |
4.55 |
36 |
Pass |
|
4-Nitroaniline* |
86.93 |
|
Pass |
4.82 |
|
|
|
4-Nitrophenol |
92.06 |
13-129 |
Pass |
4.99 |
79 |
Pass |
|
4-Nitroquinoline-1-oxide* |
90.69 |
|
|
7.66 |
|
|
|
5-nitro-o-toluidine* |
93.58 |
|
|
5.44 |
|
|
|
7,12-Dimethylbenz(a)-anthracene* |
84.98 |
|
|
4.36 |
|
|
|
Acenaphthene |
76.24 |
60-132 |
Pass |
5.58 |
29 |
Pass |
|
Acenaphthylene |
77.33 |
54-126 |
Pass |
5.81 |
45 |
Pass |
|
Acetophenone* |
75.52 |
|
|
3.75 |
|
|
|
Acetylaminofluorene* |
90.49 |
|
|
6.10 |
|
|
|
Aniline* |
80.22 |
|
|
6.18 |
|
|
|
Anthracene* |
85.84 |
43-120 |
Pass |
6.38 |
40 |
Pass |
|
Azobenzene* |
82.72 |
|
|
4.95 |
|
|
|
Benz(a)anthracene |
86.41 |
42-133 |
Pass |
5.20 |
32 |
Pass |
|
Benzidine* |
99.72 |
|
|
4.45 |
|
|
|
Benzo(a)pyrene |
86.46 |
32-148 |
Pass |
5.17 |
43 |
Pass |
|
Benzo(b)fluoranthene |
87.03 |
42-140 |
Pass |
4.62 |
43 |
Pass |
|
Benzo(ghi)perylene |
87.07 |
D-195 |
Pass |
6.09 |
61 |
Pass |
|
Benzo(k)fluoranthene |
86.62 |
25-146 |
Pass |
4.91 |
38 |
Pass |
|
Benzoic acid* |
57.15 |
|
|
6.57 |
|
|
|
Benzyl alcohol* |
78.97 |
|
|
3.41 |
|
|
|
Bis(2-chlorethoxy)methane |
82.26 |
49-165 |
Pass |
3.42 |
32 |
Pass |
|
Bis(2-chloroethyl)ether |
68.31 |
43-126 |
Pass |
2.05 |
65 |
Pass |
|
Bis(2chloroisopropyl)ether |
68.10 |
63-139 |
Pass |
3.03 |
46 |
Pass |
|
Bis(2-ethylhexyl) phthalate |
91.34 |
29-137 |
Pass |
6.66 |
50 |
Pass |
|
Benzyl butyl phthalate |
90.69 |
D-140 |
Pass |
5.14 |
36 |
Pass |
|
Carbazole* |
89.33 |
|
|
7.42 |
|
|
|
Chrysene |
87.54 |
44-140 |
Pass |
5.42 |
53 |
Pass |
|
cis-Isosafrole* |
75.74 |
|
|
4.98 |
|
|
|
Analyte |
Average DOC |
DOC Range |
Pass/ Fail |
SD |
Limit for s (%) |
Pass/ Fail |
|
Dibenz(ah)anthracene |
87.88 |
D-200 |
Pass |
4.85 |
75 |
Pass |
|
Dibenzofuran* |
78.22 |
|
|
5.60 |
|
|
|
Diethyl phthalate |
90.84 |
D-120 |
Pass |
4.45 |
60 |
Pass |
|
Dimethyl phthalate |
89.80 |
D-120 |
Pass |
4.36 |
110 |
Pass |
|
Dimethylaminoazobenzene* |
91.85 |
|
|
4.54 |
|
|
|
Di-n-butyl phthalate |
90.70 |
8-120 |
Pass |
6.31 |
28 |
Pass |
|
Di-n-octyl phthalate |
89.40 |
19-132 |
Pass |
5.25 |
42 |
Pass |
|
Dinoseb* |
87.13 |
|
|
6.29 |
|
|
|
Diphenylamine* |
87.58 |
|
|
5.24 |
|
|
|
Ethylmethane Sulfonate* |
75.62 |
|
|
3.61 |
|
|
|
Fluoranthene |
87.77 |
43-121 |
Pass |
6.82 |
40 |
Pass |
|
Fluorene |
81.07 |
70-120 |
Pass |
5.80 |
23 |
Pass |
|
Hexachlorobenzene |
83.49 |
8-142 |
Pass |
5.44 |
33 |
Pass |
|
Hexachlorobutadiene |
44.63 |
38-120 |
Pass |
4.47 |
38 |
Pass |
|
Hexachlorocyclopentadiene* |
41.53 |
|
|
4.33 |
|
|
|
Hexachloropropene* |
45.64 |
|
|
4.68 |
|
|
|
Indeno(1,2,3-cd)pyrene |
85.73 |
D-151 |
Pass |
5.28 |
60 |
Pass |
|
Isophorone |
82.02 |
47-180 |
Pass |
3.88 |
56 |
Pass |
|
Methapyrilene* |
89.82 |
|
|
4.64 |
|
|
|
Methyl Methane Sulfonate* |
49.04 |
|
|
2.10 |
|
|
|
Naphthalene |
66.73 |
36-120 |
Pass |
5.59 |
39 |
Pass |
|
NDMA* |
36.34 |
|
|
0.68 |
|
|
|
Nitrobenzene |
72.65 |
54-158 |
Pass |
3.72 |
37 |
Pass |
|
Nitrobenzene-d5 |
77.26 |
15-314 |
Pass |
4.08 |
|
|
|
N-Nitroso-diethylamine* |
67.44 |
|
|
2.70 |
|
|
|
N-nitroso-di-n-butylamine* |
85.87 |
|
|
4.26 |
|
|
|
N-nitroso-di-n-propylamine |
79.49 |
14-198 |
Pass |
4.52 |
52 |
Pass |
|
N-Nitrosomethyl ethylamine |
58.95 |
|
|
1.50 |
|
|
|
N-Nitroso-morpholine* |
78.99 |
|
|
7.92 |
|
|
|
N-Nitroso-piperidine* |
82.98 |
|
|
3.96 |
|
|
|
N-Nitroso-pyrrolidine* |
83.07 |
|
|
4.02 |
|
|
|
o-toluidine* |
95.47 |
|
|
6.77 |
|
|
|
Pentachlorobenzene* |
74.93 |
|
|
5.07 |
|
|
|
Pentachloroethane* |
49.71 |
|
|
4.29 |
|
|
|
Pentachloronitrobenzene* |
85.84 |
|
|
5.93 |
|
|
|
Pentachlorophenol |
88.93 |
38-152 |
Pass |
7.50 |
52 |
Pass |
|
Phenacetin* |
89.68 |
|
|
6.07 |
|
|
|
Phenanthrene |
86.11 |
65-120 |
Pass |
6.78 |
24 |
Pass |
|
Phenol |
57.80 |
17-120 |
Pass |
4.35 |
39 |
Pass |
|
Analyte |
Average DOC |
DOC Range |
Pass/ Fail |
SD |
Limit for s (%) |
Pass/ Fail |
|
Phenol-d5 |
57.80 |
8-424 |
Pass |
4.35 |
|
|
|
p-Terphenyl-d14* |
91.52 |
|
|
4.98 |
|
|
|
Pyrene |
87.34 |
70-120 |
Pass |
7.55 |
30 |
Pass |
|
Pyridine* |
32.13 |
|
|
2.96 |
|
|
|
Safrole* |
78.46 |
|
|
5.28 |
|
|
|
trans-Isosafrole* |
77.99 |
|
|
5.67 |
|
|
The criteria were met in all cases within the demonstrated Table 6 analytes in Method 625.1, indicating the analyte list is under control and further analysis can proceed.
Table 6 demonstrates the results for the matrix spike (MS) and matrix spike duplicate (MSD). The spike recovery data from the sample is shown in the second cartridge, where the range criteria shown in Table 6 of Method 625.1 is presented. The spike and surrogates were added at 100 µg/mL in each litre of sample. The relative percent difference between the spike recovery and spike recovery duplicate is calculated using the equation in Method 625.1. If the data meets the criterion, a pass is indicated in the Pass/Fail. Analytes with a * indicate that they are from Table 3 and do not have acceptance criteria in Table 6 within Method 625.1. It is up to the laboratory to generate their own acceptance criteria for Table 3 analytes.
Table 6. Recovery Data: Matrix spike (MS) and matrix spike duplicate (MSD).
|
Analyte |
Average MS, MSD Recovery % |
Range P,Ps % |
Pass/Fail |
RPD % |
(%) Limit |
Pass/Fail |
|
1,2,4,5-Tetrachlorobenzene* |
67.1 |
|
|
9.11 |
|
|
|
1,2,4-Trichlorobenzene |
62.1 |
44-142 |
Pass |
4.96 |
50 |
Pass |
|
1,2-Dichlorobenzene* |
56.5 |
|
|
5.31 |
|
|
|
1,3,5,-Trinitrobenzene* |
87.7 |
|
|
1.85 |
|
|
|
1,3-Dichlorobenzene* |
51.1 |
|
|
5.58 |
|
|
|
1,3-Dinitrobenzene* |
92.9 |
|
|
0.52 |
|
|
|
1,4-Dichlorobenzene* |
53.1 |
|
|
5.14 |
|
|
|
1,4-Naphthoquinone* |
82.5 |
|
|
4.89 |
|
|
|
1-Naphthylamine* |
92.3 |
|
|
5.45 |
|
|
|
2,3,4,6-Tetrachlorophenol* |
90.5 |
|
|
0.74 |
|
|
|
2,4,5-Trichlorophenol* |
87.5 |
|
|
1.04 |
|
|
|
2,4-Dichlorophenol |
89.0 |
39-135 |
Pass |
0.47 |
50 |
Pass |
|
2,4-Dimethylphenol |
87.9 |
32-120 |
Pass |
0.38 |
58 |
Pass |
|
2,4-Dinitrophenol |
87.5 |
D-191 |
Pass |
7.00 |
132 |
Pass |
|
2,4-Dinitrotoluene |
92.9 |
39-139 |
Pass |
1.44 |
42 |
Pass |
|
2,6-Dichlorophenol* |
87.8 |
|
|
1.90 |
|
|
|
2,6-Dinitrotoluene |
93.6 |
50-158 |
Pass |
3.18 |
48 |
Pass |
|
2-Chloronaphthalene |
75.9 |
60-120 |
Pass |
7.87 |
24 |
Pass |
|
2-Chlorophenol |
81.7 |
23-134 |
Pass |
3.08 |
61 |
Pass |
|
2-Fluorobiphenyl* |
86.9 |
|
|
3.43 |
|
|
|
2-Fluorophenol* |
61.8 |
|
|
5.05 |
|
|
|
2-Methyl phenol* |
84.8 |
|
|
0.68 |
|
|
|
2-Methylnaphthalene* |
72.7 |
|
|
4.62 |
|
|
|
2-Naphthylamine* |
113.0 |
|
|
2.93 |
|
|
|
2-Nitroaniline* |
92.9 |
|
|
1.41 |
|
|
|
2-Nitrophenol |
80.7 |
29-182 |
Pass |
4.36 |
55 |
Pass |
|
2-Picoline* |
49.2 |
|
|
6.96 |
|
|
|
3,3'-Dichlorobenzidine |
93.3 |
D-262 |
Pass |
7.92 |
108 |
Pass |
|
3,3'-Dimethylbenzidine* |
99.3 |
|
|
0.90 |
|
|
|
3+4 Methyl phenol* |
86.4 |
|
|
1.17 |
|
|
|
3-Methylcholanthrene* |
87.9 |
|
|
8.34 |
|
|
|
3-Nitroaniline* |
95.4 |
|
|
4.75 |
|
|
|
4 Aminobiphenyl* |
114.6 |
|
|
2.36 |
|
|
|
2-methyl-4,6-Dinitrophenol |
91.9 |
D-181 |
Pass |
1.83 |
203 |
Pass |
|
4-Bromophenyl phenyl ether |
85.0 |
53-127 |
Pass |
3.90 |
43 |
Pass |
|
4-Chloro-3-methylphenol |
91.1 |
22-147 |
Pass |
3.06 |
73 |
Pass |
|
4-Chloroaniline* |
120.7 |
|
|
0.11 |
|
|
|
4-Chlorophenyl phenyl ether |
82.3 |
25-158 |
Pass |
4.57 |
61 |
Pass |
|
4-Nitroaniline* |
90.7 |
|
|
2.92 |
|
|
|
4-Nitrophenol |
97.3 |
D-132 |
Pass |
4.31 |
131 |
Pass |
|
4-Nitroquinoline-1-oxide* |
95.8 |
|
|
1.99 |
|
|
|
5-nitro-o-toluidine* |
96.8 |
|
|
3.00 |
|
|
|
7,12-Dimethylbenz(a)-anthracene* |
86.9 |
|
|
5.42 |
|
|
|
Acenaphthene |
80.1 |
47-145 |
Pass |
6.28 |
48 |
Pass |
|
Acenaphthylene |
81.3 |
33-145 |
Pass |
4.75 |
74 |
Pass |
|
Acetophenone* |
80.2 |
|
|
5.11 |
|
|
|
Acetylaminofluorene* |
94.7 |
|
|
6.09 |
|
|
|
Aniline* |
84.0 |
|
|
7.85 |
|
|
|
Anthracene* |
89.2 |
27-133 |
Pass |
7.17 |
66 |
Pass |
|
Azobenzene* |
86.6 |
|
|
3.64 |
|
|
|
Benz(a)anthracene |
89.2 |
33-143 |
Pass |
8.15 |
53 |
Pass |
|
Benzidine* |
105.5 |
|
|
9.38 |
|
|
|
Benzo(a)pyrene |
88.8 |
17-163 |
Pass |
9.10 |
72 |
Pass |
|
Benzo(b)fluoranthene |
89.2 |
24-159 |
Pass |
6.83 |
71 |
Pass |
|
Benzo(ghi)perylene |
90.1 |
D-219 |
Pass |
11.44 |
97 |
Pass |
|
Benzo(k)fluoranthene |
89.2 |
11-162 |
Pass |
7.01 |
63 |
Pass |
|
Benzoic acid* |
58.7 |
|
|
6.47 |
|
|
|
Benzyl alcohol* |
81.3 |
|
|
2.07 |
|
|
|
Bis(2-chlorethoxy)methane |
85.4 |
33-184 |
Pass |
0.19 |
54 |
Pass |
|
Bis(2-chloroethyl)ether |
74.6 |
12-158 |
Pass |
6.50 |
108 |
Pass |
|
Bis(2chloroisopropyl)ether |
73.7 |
36-166 |
Pass |
8.23 |
76 |
Pass |
|
Bis(2-ethylhexyl) phthalate |
92.3 |
8-158 |
Pass |
0.81 |
82 |
Pass |
|
Analyte |
Average MS, MSD Recovery % |
Range P,Ps % |
Pass/Fail |
RPD % |
(%) Limit |
Pass/Fail |
|
Benzyl butyl phthalate |
91.7 |
D-152 |
Pass |
1.99 |
60 |
Pass |
|
Carbazole* |
93.1 |
|
|
5.94 |
|
|
|
Chrysene |
89.4 |
17-168 |
Pass |
10.27 |
87 |
Pass |
|
cis-Isosafrole* |
79.9 |
|
|
3.64 |
|
|
|
Dibenz(ah)anthracene |
91.2 |
D-227 |
Pass |
6.46 |
126 |
Pass |
|
Dibenzofuran* |
82.7 |
|
|
6.37 |
|
|
|
Diethyl phthalate |
94.3 |
D-120 |
Pass |
1.07 |
100 |
Pass |
|
Dimethyl phthalate |
93.2 |
D-120 |
Pass |
0.97 |
183 |
Pass |
|
Dimethylaminoazobenzene* |
93.4 |
|
|
4.06 |
|
|
|
Di-n-butyl phthalate |
93.9 |
1-120 |
Pass |
5.12 |
47 |
Pass |
|
Di-n-octyl phthalate |
90.7 |
4-146 |
Pass |
2.69 |
69 |
Pass |
|
Dinoseb* |
91.0 |
|
|
1.83 |
|
|
|
Diphenylamine* |
91.3 |
|
|
2.03 |
|
|
|
Ethylmethane Sulfonate* |
79.1 |
|
|
3.34 |
|
|
|
Fluoranthene |
91.6 |
26-137 |
Pass |
6.57 |
66 |
Pass |
|
Fluorene |
85.1 |
59-121 |
Pass |
5.18 |
38 |
Pass |
|
Hexachlorobenzene |
86.1 |
D-152 |
Pass |
6.56 |
55 |
Pass |
|
Hexachlorobutadiene |
48.8 |
24-120 |
Pass |
5.56 |
62 |
Pass |
|
Hexachlorocyclopentadiene* |
46.5 |
|
|
4.15 |
|
|
|
Hexachloropropene* |
49.9 |
|
|
5.69 |
|
|
|
Indeno(1,2,3-cd)pyrene |
89.6 |
D-171 |
Pass |
11.95 |
99 |
Pass |
|
Isophorone |
85.0 |
21-196 |
Pass |
0.36 |
93 |
Pass |
|
Methapyrilene* |
92.8 |
|
|
3.99 |
|
|
|
Methyl Methane Sulfonate* |
53.4 |
|
|
8.39 |
|
|
|
Naphthalene |
71.4 |
21-133 |
Pass |
4.06 |
65 |
Pass |
|
NDMA* |
38.6 |
|
|
17.34 |
|
|
|
Nitrobenzene |
77.4 |
35-180 |
Pass |
5.18 |
62 |
Pass |
|
Nitrobenzene-d5 |
82.0 |
|
|
5.54 |
|
|
|
N-Nitroso-diethylamine* |
71.4 |
|
|
6.09 |
|
|
|
N-nitroso-di-n-butylamine* |
88.2 |
|
|
0.45 |
|
|
|
N-nitroso-di-n-propylamine |
83.6 |
D-230 |
Pass |
3.64 |
87 |
Pass |
|
N-Nitrosomethyl ethylamine |
62.8 |
|
|
11.95 |
|
|
|
N-Nitroso-morpholine* |
82.3 |
|
|
13.96 |
|
|
|
N-Nitroso-piperidine* |
85.7 |
|
|
2.10 |
|
|
|
N-Nitroso-pyrrolidine* |
85.7 |
|
|
0.86 |
|
|
|
o-toluidine* |
100.1 |
|
|
1.58 |
|
|
|
Pentachlorobenzene* |
78.8 |
|
|
7.32 |
|
|
|
Pentachloroethane* |
55.3 |
|
|
7.13 |
|
|
|
Pentachloronitrobenzene* |
89.1 |
|
|
5.28 |
|
|
|
Pentachlorophenol |
93.5 |
14-176 |
Pass |
3.03 |
86 |
Pass |
|
Analyte |
Average MS, MSD Recovery % |
Range P,Ps % |
Pass/Fail |
RPD % |
(%) Limit |
Pass/Fail |
|
|
Phenacetin* |
92.7 |
|
|
3.73 |
|
|
|
|
Phenanthrene |
88.8 |
54-120 |
Pass |
6.07 |
39 |
Pass |
|
|
Phenol |
62.2 |
5-120 |
Pass |
5.59 |
64 |
Pass |
|
|
Phenol-d5 |
61.8 |
|
|
6.61 |
|
|
|
|
p-Terphenyl-d14* |
89.1 |
|
|
6.72 |
|
|
|
|
Pyrene |
90.8 |
52-120 |
Pass |
7.51 |
49 |
Pass |
|
|
Pyridine* |
32.3 |
|
|
4.49 |
|
|
|
|
Safrole* |
83.0 |
|
|
3.83 |
|
|
|
|
trans-Isosafrole* |
82.8 |
|
|
1.56 |
|
|
|
The matrix spike (MS) and matrix spike duplicate (MSD) were successfully spiked and measured recoveries were within the range specified in Table 6 in Method 625.1. The relative percent difference (RPD) between the matrix spike and duplicate sample showed excellent agreement when compared to the limit allowed. The agreement was generally well below the limit, sometimes more than an order of magnitude better.
US EPA Method 625 is an important method for evaluation of water pollution or clean-up. It allows a full suite of analytes to be evaluated at one time using GC/MS. Sample preparation is an important part of the process and disk solid phase extraction can provide advantages in using less solvent, eliminating emulsions and providing good extraction across the suite of analytes considered while minimizing exposure. A number of analytes within Tables 1-3 were extracted simultaneously with a 1 litre sample volume. This was to challenge the extraction method and matrix components that may interfere with good adsorption and release of the analytes. The results show excellent performance of the One-Pass disk coupled with a Carbon Cartridge for capture of the analytes.
Reduced sample volumes can be used for this method to improve method performance as long as all Method Detection Limits (MDLs) and reporting limits are met. Solid phase extraction disks are another tool for the environmental laboratory to consider when evaluating their workflow for increased efficiency and safety. Other things can be considered once analytical performance is demonstrated, such as the ability to use less solvent, and reducing the need for evaporation and subsequent solvent recollection. Automation can also enhance reproducibility. Excellent duplicate agreement was shown here, even for the more difficult samples. Overall, the demonstrated analytical performance meets the criteria required and other favourable factors can be included in the decision making process to bring newer technology into today’s modern laboratory.
Table 6 from US EPA Method 625.1, December 2014
Literature number: AN123-HOR