Trace-Level Semivolatiles Analysis: An Evaluation of the RMX-5Sil MS Column

Published in Collaboration with Shimadzu Corporation

21 Nov 2025

Yoshiro Hiramatsu

Ramkumar Dhandapani, PhD

Erica Pack, PhD

Key Highlights

Highly effective GC column deactivation produces an exceptionally inert sample flow path.
Maximum inertness results in sharp, symmetrical peaks and single or sub-picogram instrument detection limits (IDL) for a wide range of challenging semivolatiles.
Data quality objectives for calibration were easily met with ≤20% relative standard error (RSE) for all semivolatiles and lowest calibration points of 1-10 ppb for all compounds, except benzoic acid (50 ppb).

Abstract

This application note evaluates the performance of an RMX-5Sil MS column for trace-level GC-MS/MS analysis of semivolatile organic compounds. Single or sub-picogram instrument detection limits were achieved for all compounds, except benzoic acid (14.70 pg) and 2,4-dinitrophenol (11.53 pg). Calibration curve %RSE was ≤20% for all compounds, and curves ranged from 1-1000 ppb to 10-1000 ppb for all compounds, except benzoic acid, which was 50-1000 ppb.

Introduction

Environmental testing laboratories routinely analyze semivolatile organic compounds (SVOCs) by GC-MS or GC-MS/MS using methods such as EPA Method 8270E. Labs are increasingly adopting GC-MS/MS methods because the improved selectivity of the detector allows for more sensitive analyses, such as those needed for EPA Method 3511 microextraction, which saves time and reduces solvent consumption compared to traditional sample preparation methods that can use up to a liter of sample. To achieve the full benefits of MS/MS sensitivity, the analytical column must be highly inert to maximize peak signal-to-noise ratios. A broadly effective column deactivation is essential for ensuring good overall method performance across a wide range of compound chemistries that interact via different mechanisms with any active sites present on the column surface. In this study, an RMX-5Sil MS column was independently evaluated for analytical performance across a wide range of trace-level semivolatiles, including compounds that are known to be very challenging. Chromatographic performance and calibration ranges were assessed to evaluate the column’s suitability for achieving picogram-level detection.

Experimental

Standard Preparation

Multicomponent calibration standards were prepared in methylene chloride across a range of 1-1000 ppb (11 points) from commercially available reference standards.

Instrument Conditions

Samples were run on an RMX-5Sil MS column in a 30 m, 0.25 mm ID, 0.25 μm format (cat.# 17323). A Shimadzu Nexis GC-2030 GC paired with a Shimadzu GCMS-TQ8050 NX ultra-fast mass spectrometer with EI source and UFsweeper high-efficiency collision cell was used for GC-MS/MS semivolatiles analysis under the conditions listed below.

Table I: GC-MS/MS Method Conditions for Trace-Level Semivolatiles Analysis

Gas Chromatograph	Shimadzu Nexis GC-2030
Column	RMX-5Sil MS, 30 m x 0.25 mm ID x 0.25 µm (cat.# 17323)
Flow mode	Constant linear velocity (39.5 cm/s)
Injector mode	Split (5:1)
Injector liner	Topaz 3.5 mm ID single taper inlet liner w/wool (cat.# 23336)
Injection volume	1 µL
Injector temperature	275 °C
Oven program	40 °C (hold 1.5 min) to 280 °C at 20 °C /min to 320 °C at 5 °C /min (hold 1 min)
MS system	Shimadzu GCMS-TQ8050 NX ultra-fast mass spectrometer with EI source and UFsweeper high-efficiency collision cell
Ionization	Electron impact
Ionization energy	70 eV
Emission current	60 mA
Acquisition mode	MRM
Collision gas	Argon
Source temperature	230 °C
GC interface temperature	300 °C

Results and Discussion

Chromatographic Performance

Overall, the RMX-5Sil MS column produced excellent peak shapes and separations for 86 semivolatiles at 50 ppb across the chromatographic space with the last compound eluting in just under 21 minutes (Figure 1). To evaluate column inertness, peak tailing was measured at or near the low and high ends of the linear calibration range for acidic and basic compounds that are known to be particularly problematic. As shown in Figure 2, the inert surface minimized surface activity at low levels and maximized peak symmetry for easy, accurate integration, even when difficult compounds were being integrated at low concentrations. In addition, the surface did not show any negative effects on polymer selectivity, as demonstrated by good separation of the closely eluting polycyclic aromatic hydrocarbon (PAH) pair, benzo(b)fluoranthene and benzo(k)fluoranthene at 1 ppb.

Figure 1: GC-MS/MS Analysis of 86 Semivolatiles on an RMX-5Sil MS Column (50 ppb, TIC)

EPA 8270E Semivolatiles on RMX-5Sil MS by GC-MS/MS (Shimadzu Chromatogram)

GC_EV1534

Peaks

	Peaks	t_R (min)	Transition 1	Collision energy 1	Transition 2	Collision energy 2
1.	N-Nitrosodimethylamine	3.173	74.00>44.10	6	74.00>42.10	18
2.	Pyridine	3.276	79.10>50.10	21	79.10>52.10	15
3.	2-Fluorophenol	4.532	112.00>64.10	18	112.00>92.10	9
4.	Phenol	5.514	94.00>66.00	9	66.00>40.00	12
5.	Phenol-d5 Surr	5.5	99.00>71.10	12	99.00>69.10	27
6.	Aniline	5.554	93.00>66.10	18	93.00>51.10	30
7.	Bis(2-chloroethyl) ether	5.619	93.00>63.10	9	95.00>65.00	6
8.	2-Chlorophenol	5.688	128.00>64.00	18	128.00>91.90	15
9.	1,3-Dichlorobenzene	5.863	146.00>111.10	21	146.00>75.20	30
10.	1,4-Dichlorobenzene	5.944	146.00>111.10	21	146.00>75.20	30
11.	Benzyl alcohol	6.069	79.00>77.10	12	107.00>79.10	9
12.	1,2-Dichlorobenzene	6.116	146.00>111.10	21	146.00>75.20	30
13.	2-Methylphenol	6.194	108.00>77.00	27	108.00>79.00	18
14.	2,2′-oxybis(1-chloropropane)	6.229	121.05>77.00	9	121.05>45.00	6
15.	3 and 4-Methylphenol	6.369	107.10>77.10	15	107.10>79.10	6
16.	N-Nitrosodi-N-propylamine	6.374	130.10>113.10	4	130.10>88.10	4
17.	Hexachloroethane	6.511	117.00>81.90	30	119.00>83.80	33
18.	Nitrobenzene	6.563	77.05>51.00	21	123.05>77.00	15
19.	Nitrobenzene-d5	6.541	82.00>54.10	18	128.00>82.10	18
20.	Isophorone	6.846	82.00>54.00	9	138.00>82.00	18
21.	2-Nitrophenol	6.941	139.00>109.10	9	139.00>81.00	12
22.	2,4-Dimethylphenol	6.99	107.00>77.10	18	122.00>107.10	18
23.	Benzoic Acid	7.019	122.10>105.10	9	105.10>77.10	15
24.	Bis(2-chloroethoxy)methane	7.102	93.00>63.10	9	95.00>65.00	6
25.	2,4-Dichlorophenol	7.223	162.00>63.10	33	164.00>63.10	30
26.	1,2,4-Trichlorobenzene	7.333	180.00>109.00	30	180.00>145.10	18
27.	Naphthalene	7.424	128.10>102.10	20	128.10>78.00	20
28.	2,6-Dichlorophenol	7.223	136.00>108.10	27	136.00>134.10	27
29.	4-Chloroaniline	7.484	127.00>65.10	27	127.00>92.10	18
30.	Hexachlorobutadiene	7.59	225.00>189.80	21	225.00>155.00	30
31.	4-Chloro-3-methylphenol	8.072	107.00>77.10	18	142.00>107.00	18
32.	2-Methylnaphthalene	8.268	142.10>115.10	28	115.10>89.00	16
33.	1-Methylnaphthalene	8.388	142.10>115.10	28	115.10>89.00	16
34.	Hexachlorocyclopentadiene	8.474	237.00>141.00	27	237.00>143.00	27
35.	2,4,6-Trichlorophenol	8.613	196.00>97.00	33	198.00>97.00	30
36.	2,4,5-Trichlorophenol	8.651	196.00>97.00	33	198.00>97.00	30
37.	2-Fluorobiphenyl	8.721	172.00>151.20	27	172.00>146.10	27
38.	2-Chloronaphthalene	8.862	162.00>127.10	18	162.00>77.10	33
39.	2-Nitroaniline	8.979	138.00>92.00	15	138.00>65.10	33
40.	1,4-Dinitrobenzene	9.143	168.00>75.10	30	168.00>92.00	15
41.	Dimethylphthalate	9.216	163.00>77.20	15	163.00>133.10	15
42.	1,3-Dinitrobenzene	9.14	168.00>75.00	30	168.00>122.00	12
43.	2,6-Dinitrotoluene	9.281	165.00>90.00	15	165.00>63.10	33
44.	Acenapthylene	9.374	152.10>150.10	28	152.10>126.10	28
45.	3-Nitroaniline	9.484	92.05>65.00	12	138.05>65.00	27
46.	Acenaphthene	9.592	152.10>150.10	28	152.10>126.10	28
47.	2,4-Dinitrophenol	9.617	184.05>107.00	12	154.05>107.00	6
48.	4-Nitrophenol	9.689	109.05>81.00	12	109.05>53.10	18
49.	2,4-Dinitrotoluene	9.778	89.05>63.10	18	165.05>119.00	6
50.	Dibenzofuran	9.805	168.00>139.10	24	139.00>89.10	21
51.	2,3,5,6-Tetrachlorophenol	9.904	230.00>130.90	36	232.00>132.90	36
52.	2,3,4,6-Tetrachlorophenol	9.958	230.00>130.90	36	232.00>132.90	36
53.	Diethylphthalate	10.093	149.00>65.00	30	177.00>149.10	12
54.	4-Chlorophenyl phenyl ether	10.234	141.00>115.20	21	204.00>141.20	21
55.	Fluorene	10.23	165.10>163.10	28	165.10>115.10	28
56.	4-Nitroaniline	10.234	138.00>108.10	12	108.00>80.00	12
57.	4,6-Dinitro-2-methylphenol	10.283	198.05>121.00	12	198.05>53.00	27
58.	N-Nitrosodiphenylamine (Diphenylamine)	10.376	169.00>167.20	27	168.00>139.00	39
59.	Diphenylhydrazine	10.429	77.00>51.20	15	77.00>74.10	33
60.	2,4,6-Tribromophenol	10.524	329.80>141.00	36	331.80>142.90	36
61.	4-Bromophenyl phenyl ether	10.839	250.00>141.10	21	248.00>141.10	18
62.	Hexachlorobenzene	10.922	283.80>248.80	24	283.80>213.80	28
63.	Pentachlorophenol	11.159	265.90>164.90	26	265.90>166.90	26
64.	Phenanthrene	11.421	178.10>176.10	28	178.10>152.10	20
65.	Anthracene	11.484	178.10>176.10	28	178.10>152.10	20
66.	Carbazole	11.68	167.00>139.20	27	166.00>140.00	18
67.	Di-n-butylphthalate	12.131	149.00>93.10	18	149.00>65.10	24
68.	Fluoranthene	12.9	202.10>200.10	30	200.10>198.10	30
69.	Benzidine	13.062	184.00>156.10	24	184.00>167.10	24
70.	Pyrene	13.18	202.10>200.10	30	200.10>198.10	30
71.	o-Terphenyl-D14	13.377	244.00>240.10	30	244.00>226.20	18
72.	Butylbenzylphthalate	14.012	149.00>65.10	24	149.00>93.10	18
73.	Bis(2-ethylhexyl)adipate	14.129	129.00>55.10	21	129.00>101.10	9
74.	3’3-Dichlorobenzidine	14.769	212.00>180.10	24	212.00>196.20	21
75.	Benz[a]anthracene	14.805	228.10>226.10	32	226.10>224.10	32
76.	Bis(2-ethylhexyl)phthalate	14.875	149.00>65.10	24	167.00>149.10	15
77.	Chrysene	14.861	228.10>226.10	32	226.10>224.10	32
78.	Di-n-octylphthalate	16	149.00>65.10	24	149.00>93.20	18
79.	Benzo[b]fluoranthene	16.691	252.10>250.10	36	250.10>248.10	36
80.	Benzo[k]fluoranthene	16.746	252.10>250.10	36	250.10>248.10	36
81.	Benzo[a]pyrene	17.338	252.10>250.10	36	250.10>248.10	36
82.	Dibenz[a,j]acridine	19.26	279.00>277.10	33	279.00>250.00	45
83.	Indeno[1,2,3-cd]pyrene	19.754	276.10>274.10	36	274.10>272.10	36
84.	Dibenz[a,h]anthracene	19.813	278.10>276.10	36	278.10>274.10	60
85.	Benzo[g,h,i]perylene	20.339	276.10>274.10	36	274.10>272.10	36

Conditions

Oven
Column	RMX-5Sil MS, 30 m, 0.25 mm ID, 0.25 µm (cat.# 17323)

Injection
Inj. Vol.:	1 µL split (split ratio 5:1)
Liner:	Topaz 3.5 mm ID single taper inlet liner w/wool (cat.# 23336)
Inj. Temp.:	275 °C
Oven Temp.:	40 °C (hold 1.5 min) to 280 °C at 20 °C/min to 320 °C at 5 °C/min (hold 1 min)
Carrier Gas	He, constant flow
Linear Velocity:	39.5 cm/sec @ 40 °C

Detector	SRM/MRM
Acquisition Type:	SRM/MRM
Source Temp.:	230 °C
Transfer Line Temp.:	300 °C
Analyzer Type:	Triple Quadrupole
Ionization Mode:	EI
Collision Gas:	Ar
Tune Type:	PFTBA
Tune Emission Current:	60 μA
Notes	Shimadzu Nexis GC-2030 with Shimadzu GCMS-TQ8050 NX ultra-fast mass spectrometer with EI source and UFsweeper high-efficiency collision cell
Acknowledgement	Shimadzu

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Figure 2: The highly effective deactivation used in RMX-5Sil MS columns creates an exceptionally inert surface that produces symmetrical peaks for a wide range of semivolatiles, including acidic compounds (pentachlorophenol); basic compounds (benzidine); and closely eluting PAHs.

Select EPA 8270E Semivolatiles on RMX-5Sil MS by GC-MS/MS (Shimazu Chromatogram)

GC_EV1535

Peaks

	Peaks	t_R (min)	Transition 1	Collision energy 1	Transition 2	Collision energy 2
1.	Benzidine	13.062	184.00>156.10	24	184.00>167.10	24
2.	Benzo[b]fluoranthene	16.691	252.10>250.10	36	250.10>248.10	36
3.	Benzo[k]fluoranthene	16.746	252.10>250.10	36	250.10>248.10	36
4.	Pentachlorophenol	11.159	265.90>164.90	26	265.90>166.90	26

Conditions

Oven
Column	RMX-5Sil MS, 30 m, 0.25 mm ID, 0.25 µm (cat.# 17323)

Injection
Inj. Vol.:	1 µL split (split ratio 5:1)
Liner:	Topaz 3.5 mm ID single taper inlet liner w/wool (cat.# 23336)
Inj. Temp.:	275 °C
Oven Temp.:	40 °C (hold 1.5 min) to 280 °C at 20 °C/min to 320 °C at 5 °C/min (hold 1 min)
Carrier Gas	He, constant flow
Linear Velocity:	39.5 cm/sec @ 40 °C

Detector	SRM/MRM
Acquisition Type:	SRM/MRM
Source Temp.:	230 °C
Transfer Line Temp.:	300 °C
Analyzer Type:	Triple Quadrupole
Ionization Mode:	EI
Collision Gas:	Ar
Tune Type:	PFTBA
Tune Emission Current:	60 μA
Notes	Shimadzu Nexis GC-2030 with Shimadzu GCMS-TQ8050 NX ultra-fast mass spectrometer with EI source and UFsweeper high-efficiency collision cell
Acknowledgement	Shimadzu

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Calibration Performance

As demonstrated in Table II, the combination of the Shimadzu GC-MS/MS system and the highly inert RMX-5Sil MS analytical column allowed for outstanding trace-level sensitivity for a broad range of semivolatile compound classes. The calibration curve %RSE was ≤20% for all compounds, which met data quality objectives for calibration. In addition, R² was determined for a subset of representative semivolatiles and was found to be ≥0.99 for all compounds that were assessed. For all semivolatiles, the calibration curves ranged from 1-1000 ppb to 10-1000 ppb, except benzoic acid which was 50-1000 ppb. A slightly higher linear range for benzoic acid was not surprising because it does not solubilize well in 5-type phases. Finally, very low instrument detection limits were achieved and were single or sub-picogram levels for all semivolatiles, except benzoic acid (14.70 pg) and 2,4-dinitrophenol (11.53 pg).

Table II: Calibration Performance for Trace-Level Semivolatiles Analysis on an RMX-5Sil MS Column

Compound Name	Retention Time (min)	Calibration Curve %RSE	R²	Low Point (ppb)	High Point (ppb)	IDL (pg)
N-Nitrosodimethylamine	3.173	16.82		5	1000	2.14
Pyridine	3.276	8.69	0.994	10	1000	3.23
2-Fluorophenol	4.532	15.24		5	1000	0.28
Phenol	5.514	19.25		1	1000	0.70
Phenol-d5	5.5	17.86		1	1000	0.29
Aniline	5.554	9.52	0.993	10	1000	1.43
Bis(2-chloroethyl) ether	5.619	14.33		1	1000	0.42
2-Chlorophenol	5.688	19.78		1	1000	1.28
1,3-Dichlorobenzene	5.863	16.96		1	1000	0.36
1,4-Dichlorobenzene	5.944	17.90		1	1000	0.77
Benzyl alcohol	6.069	17.06		1	1000	0.98
1,2-Dichlorobenzene	6.116	17.32		1	1000	1.13
2-Methylphenol	6.194	19.48		10	1000	1.95
2,2′-oxybis(1-chloropropane)	6.229	19.32		10	1000	4.04
3- and 4-Methylphenol	6.369	19.71		1	1000	1.01
N-Nitrosodi-N-propylamine	6.374	5.38	0.997	10	1000	3.10
Hexachloroethane	6.511	15.67		5	1000	1.36
Nitrobenzene	6.563	12.10	0.996	5	1000	0.81
Nitrobenzene-d5	6.541	17.81		1	1000	0.96
Isophorone	6.846	18.92		1	1000	0.56
2-Nitrophenol	6.941	13.56	0.996	10	1000	1.26
2,4-Dimethylphenol	6.99	19.63		1	1000	0.36
Benzoic acid	7.019	3.84	0.998	50	1000	14.70
Bis(2-chloroethoxy)methane	7.102	14.01		1	1000	0.26
2,4-Dichlorophenol	7.223	18.99		1	1000	0.83
1,2,4-Trichlorobenzene	7.333	10.67		1	1000	0.46
Naphthalene	7.424	8.68		1	1000	0.73
2,6-Dichlorophenol	7.223	18.18		1	1000	0.62
4-Chloroaniline	7.484	13.85	0.998	5	1000	1.34
Hexachlorobutadiene	7.59	13.96		1	1000	0.65
4-Chloro-3-methylphenol	8.072	16.99		1	1000	0.30
2-Methylnaphthalene	8.268	10.57		1	1000	0.63
1-Methylnaphthalene	8.388	18.50		1	1000	0.64
Hexachlorocyclopentadiene	8.474	16.59	0.998	5	1000	2.72
2,4,6-Trichlorophenol	8.613	16.69		5	1000	1.55
2,4,5-Trichlorophenol	8.651	16.98		5	1000	0.76
2-Fluorobiphenyl	8.721	16.31		1	1000	1.05
2-Chloronaphthalene	8.862	14.23		1	1000	0.43
2-Nitroaniline	8.979	17.82	0.996	10	1000	1.33
1,4-Dinitrobenzene	9.143	12.76	0.996	10	1000	8.63
Dimethylphthalate	9.216	18.60		1	1000	0.60
1,3-Dinitrobenzene	9.14	18.88	0.991	10	1000	6.97
2,6-Dinitrotoluene	9.281	19.86	0.997	5	1000	2.06
Acenapthylene	9.374	11.73		1	1000	0.37
3-Nitroaniline	9.484	18.30	0.995	10	1000	2.89
Acenaphthene	9.592	9.44	0.991	1	1000	2.61
2,4-Dinitrophenol	9.617	7.79	0.995	10	1000	11.53
4-Nitrophenol	9.689	14.01	0.998	10	1000	4.39
2,4-Dinitrotoluene	9.778	14.84	0.999	10	1000	4.30
Dibenzofuran	9.805	9.94		1	1000	0.38
2,3,5,6-Tetrachlorophenol	9.904	16.86		5	1000	2.37
2,3,4,6-Tetrachlorophenol	9.958	17.72	0.997	5	1000	1.74
Diethylphthalate	10.093	15.97		1	1000	0.67
4-Chlorophenyl phenyl ether	10.234	7.21		1	1000	0.57
Fluorene	10.23	14.54		1	1000	0.37
4-Nitroaniline	10.234	18.81	0.993	10	1000	2.33
4,6-Dinitro-2-methylphenol	10.283	19.99	0.996	10	1000	7.99
N-Nitrosodiphenylamine	10.376	18.03		1	1000	0.53
Diphenylamine	10.376	18.03		1	1000	0.53
Diphenylhydrazine	10.429	14.83		10	1000	3.39
2,4,6-Tribromophenol	10.524	18.55	0.997	5	1000	4.15
4-Bromophenyl phenyl ether	10.839	15.84		1	1000	0.74
Hexachlorobenzene	10.922	12.99		1	1000	0.96
Pentachlorophenol	11.159	16.75	0.997	5	1000	1.14
Phenanthrene	11.421	13.06		1	1000	0.18
Anthracene	11.484	15.30		1	1000	0.92
Carbazole	11.68	14.68		1	1000	0.52
Di-n-butylphthalate	12.131	15.80		5	1000	0.25
Fluoranthene	12.9	10.80		1	1000	0.26
Benzidine	13.062	19.24	0.998	10	1000	1.43
Pyrene	13.18	10.13		1	1000	0.54
o-Terphenyl-D14	13.377	13.45		1	1000	0.62
Butylbenzylphthalate	14.012	15.67		5	1000	0.76
Bis(2-ethylhexyl)adipate	14.129	18.95	0.994	10	1000	1.15
3’3-Dichlorobenzidine	14.769	17.70	0.996	10	1000	1.76
Benz[a]anthracene	14.805	11.61		1	1000	0.38
Bis(2-ethylhexyl)phthalate	14.875	19.67		5	1000	0.58
Chrysene	14.861	8.91		1	1000	0.34
Di-n-octylphthalate	16	18.78	0.998	5	1000	0.49
Benzo[b]fluoranthene	16.691	11.15		1	1000	0.41
Benzo[k]fluoranthene	16.746	13.09		1	1000	0.50
Benzo[a]pyrene	17.338	12.32		1	1000	0.24
Dibenz[a,j]acridine	19.26	19.92		1	1000	0.60
Indeno[1,2,3-cd]pyrene	19.754	15.17		1	1000	0.71
Dibenz[a,h]anthracene	19.813	13.06		1	1000	0.56
Benzo[g,h,i]perylene	20.339	10.79		1	1000	0.50

Conclusion

This study confirmed the suitability of RMX-5Sil MS columns for trace-level (single digit ppb) semivolatiles analysis by GC-MS/MS. Overall, the column demonstrated inertness for a broad range of compounds chemistries (acids, bases, and neutrals) and generated excellent linear calibrations. Peak shape and symmetry were intact even at low levels where active compounds are exceptionally difficult to analyze. Nearly all compounds (98%) achieved IDLs at or below single-picogram levels; calibration ranges of 1, 5, or 10 ppb to 1000 ppb; and calibration curves with ≤20% RSE.

References

U.S. Environmental Protection Agency, Method 8270E, Semivolatile organic compounds by gas chromatography/mass spectrometry, June 2018. https://www.epa.gov/sites/default/files/2020-10/documents/method_8270e_update_vi_06-2018_0.pdf
U.S. Environmental Protection Agency, Method 3511 (SW-846), Organic compounds in water by microextraction, July 2014. https://www.epa.gov/hw-sw846/sw-846-test-method-3511-organic-compounds-water-microextraction

Products Mentioned

Catalog No. 17323

17323

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Catalog No. 23336

Topaz Inlet Liner a Cono Singolo, 3,5 mm x 5,0 x 95, per GC Shimadzu 17A, 2010, 2014 e 2030, con Lana di Quarzo nella Parte Inferiore, Deattivazione Premium, 5 pz.