Paal Molander

Temperature-programmed packed capillary liquid chromatography separation with large volume on-column focusing of retinyl esters

Summary A non-aqueous isocratic reversed-phase packed capillary high performance liquid chromatography method for the determination of retinyl esters, utilizing temperature programming and on-column focusing large volume injection, has been developed. The stationary phase material was C30, and the mobile phase consisted of acetonitrile-dichloromethane (70 : 30, v/v). A three-step temperature program, starting at 10 C for 10 min, then 1 /min to 30 C, and finally 2.5 /min to 70 C, was found most appropriate. Compared to an isothermal separation at 25 C, this temperature program provided improved peak resolution, enhanced peak shapes of the last eluting compounds, and a reduction of the overall elution time. A mass limit of detection of 27 pg was found with respect to retinyl palmitate, using UV detection with an “U” shaped flow cell at 327 nm. This corresponds to a concentration limit of detection of 2.7 pg/ L, when utilizing an injection volume of 10 L. The concentration of retinyl palmitate in arctic seal liver samples was estimated to be 62.6 g/g liver.

Occupational Exposure to Airborne Perfluorinated Compounds during Professional Ski Waxing

The concentration levels of 11 perfluorinated carboxylic (PFCA) and eight sulfonic (PFSA) acids were determined in the serum of 13 professional ski waxers. The same components were also determined in workroom aerosols and in fluoro containing solid ski waxes and ski wax powders. The highest median concentration (50 ng/mL) was detected for perfluorooctanoic acid (PFOA), which is around 25 times higher than the background level. For the first time perfluorotetradecanoic acid (PFTeDA) has been found in human serum. Positive statistically significant associations between years exposed as ski waxer and seven different PFCAs were observed. The serum concentrations of the PFCAs with carbon chain lengths from C(8) to C(11) were reduced by around five to 20% on average during the eight month exposure free interval, whereas the reduction was substantially larger when the carbon chain lengths were smaller than C(8) or larger than C(11). This study links for the first time PFCAs in the ski waxers serum to exposure from the work room aerosols. Not only professional ski waxers but also the significant larger group of amateur skiers and waxers are potentially exposed to these compounds.

Separation of polyethylene glycol oligomers using inverse temperature programming in packed capillary liquid chromatography

Inverse temperature programming in packed capillary liquid chromatography coupled to evaporative light-scattering detection has been used to resolve native polyethylene glycol (PEG) oligomers. The model compound, PEG 1000, was separated on a 300 mm x 0.32 mm I.D. capillary column packed with 3 microm Hypersil ODS particles with acetonitrile-water (30:70, v/v) as mobile phase. The retention of the PEG oligomers increased with increasing temperature, different from what is commonly observed in liquid chromatography. The retention times of the oligomers were approximately doubled for each 25 degrees C increment of the column temperature in the temperature range 30-80 degrees C. The oligomers were almost unretained and co-eluted at a column temperature of 30 degrees C. At 80 degrees C a baseline separation of more than 22 peaks was obtained, but the last eluting peaks were severely broadened and all oligomers did not elute. When a negatively sloped temperature ramp from 80 to 25 degrees C at -1.5 degrees C/min was applied, the peak shapes were improved, additional peaks were detected and the analysis time was reduced by 48%. In the temperature programming mode, the intra-day precision of the retention times ranged from 0.5 to 5.8% (n=5).

Aspects and applications of non-aqueous high temperature packed capillary liquid chromatography

The effect of using high isothermal temperatures and temperature programming above ambient in liquid chromatography has been investigated by the use of relatively long packed reversed phase capillary columns and non-aqueous mobile phases. Efficiency measurements have been performed in the temperature interval 50– 175 °C, indicating that the best efficiency was achieved at 100 °C, with a corresponding optimum linear velocity of approximately 0.07 cm s–1. The efficiency measurements revealed that the linear velocity had to be slightly increased in order to operate at the optimum reduced plate height at elevated temperatures. The contribution from extra-column volumes increased the plate height at temperatures above 100 °C where the solute had low retention. This effect was closely examined by introducing larger pre-column dead volumes, demonstrating the need to minimize dead volumes. Temperature programming has successfully been used for partial characterization and for purity testing of different polymer additives. The within and between day precision of retention times for the temperature-programmed separations gave a relative standard deviation of 0.3–2.9%.

Fast and sensitive determination of urinary 1-hydroxypyrene by packed capillary column switching liquid chromatography coupled to micro-electrospray time-of-flight mass spectrometry.

The present work reports capillary liquid chromatographic column switching methodology tailored for fast, sensitive and selective determination of 1-hydroxypyrene (1-OHP) in human urine using micro-electrospray ionization time-of-flight mass spectrometric detection. Samples (100 microl) of deconjugated, water diluted and filtered urine samples were loaded onto a 150 microm I.D.x 30 mm 10 microm Kromasil C(18) pre-column, providing on-line sample clean-up and analyte enrichment, prior to back flushed elution onto a 150 microm I.D.x 100 mm 3.5 microm Kromasil C(18) analytical column. Loading flow rates up to 100 microl/min in addition to the use of isocratic elution by a mobile phase composition of acetonitrile/water (70/30, v/v) containing 5 mM ammonium acetate provided elution of 1-OHP within 5.5 min and a total analysis time of less than 15 min with manual operation. Ionization was performed in the negative mode and 1-OHP was observed as [M-H](-) at m/z 217.08. The method was validated over the concentration range 0.2-40 ng/ml 1-OHP in pre-treated urine, yielding a coefficient of correlation of 0.997. The within-assay (n=6) and between-assay (n=6) precisions were in the range 6.4-7.3 and 7.0-8.1%, respectively, and the recoveries were in the range 96.2-97.5 within the investigated concentration range. The method mass limit of detection was 2 pg, corresponding to a 1-OHP concentration limit of detection of 20 pg/ml (0.09 nmol/l) diluted urine or 0.3 ng/ml (1.35 nmol/l) urine.

Organophosphates in aircraft cabin and cockpit air—method development and measurements of contaminants

Methods for measurements and the potential for occupational exposure to organophosphates (OPs) originating from turbine and hydraulic oils among flying personnel in the aviation industry are described. Different sampling methods were applied, including active within-day methods for OPs and VOCs, newly developed passive long-term sample methods (deposition of OPs to wipe surface areas and to activated charcoal cloths), and measurements of OPs in high-efficiency particulate air (HEPA) recirculation filters (n = 6). In total, 95 and 72 within-day OP and VOC samples, respectively, have been collected during 47 flights in six different models of turbine jet engine, propeller and helicopter aircrafts (n = 40). In general, the OP air levels from the within-day samples were low. The most relevant OP in this regard originating from turbine and engine oils, tricresyl phosphate (TCP), was detected in only 4% of the samples (min-max <LOQ-0.29 µg m(-3)). TCP was however detected in 39% of the wipe samples (n = 56) and in all HEPA-filters. Other OPs, as dibutylphenyl phosphate (DBPP) and tri-n-butyl phosphate (TnBP) originating from hydraulic oils were more prominent in the samples, illustrated by determination of TnBP in all of the within-day samples collected from airplanes (n = 76, min-max 0.02-4.1 µg m(-3)). All samples were collected under normal flight conditions. However, the TCP concentration during ground testing in an airplane that had experienced leakage of turbine oil with subsequent contamination of the cabin and cockpit air, was an order of magnitude higher as compared to after engine replacement (p = 0.02).

High temperature injection in capillary high temperature liquid chromatography

A new high temperature sample introduction device for use in packed capillary high temperature liquid chromatography has been developed. In combina- tion with a commercially available high temperature injection valve, samples with little solubility in any solvent at ambient temperature could be analyzed. Injections of synthetic high molecular weight hydrocarbon waxes were feasible at elevated temperatures with the high temperature sample introduction device. Compared to injection with a preheated conventional liquid chromatography syringe, problems of precipitation and plugging were removed, the injection time was reduced, and the relative standard deviation of area measurements was improved. The synthetic waxes could be separated with temperature programming and isocratic mobile phases, with packed capillary columns and evaporative light scattering detection. Q 1999 John Wiley & Sons, Inc. J Micro Sep 11: 612)619, 1999

Occupational exposure to airborne solvents during nail sculpturing.

This study describes occupational exposure to acrylates and other solvents during nail sculpturing, including comparative measurements of the exposure using four different sculpturing methods: The acrylic method, the UV-gel method, the acrylic powder method and the resin method. Thirty-two nail technicians working in 22 different salons participated in the study. In total, 92 measurements were performed, comprising 70 solvent measurements and 22 measurements of ethyl 2-cyanoacrylate. The solvents most frequently present in all samples were acetone, ethyl acetate, toluene and n-butyl acetate, measured in 96%, 94%, 91% and 81% of the samples, respectively. The study shows that the overall solvent exposure was low, with all measurements calculated as the additive effect (n = 70) below 20% of the OEL (arithmetic mean 0.06 and range 0.01-0.19). No statistically significant difference between sculpturing methods were observed (p = 0.05).

Separation of technical waxes by temperature-programmed packed-capillary liquid chromatography

SummaryA high-melting saturated hydrocarbon wax in the carbon range C28 to C90, with an average molecular mass of 785, and a saponified, oxidized Fisher-Tropsch wax of average molecular mass 745 have been characterized by reversed-phase packed-capillary liquid chromatography with isocratic nonaqueous mobile phases. High-temperature injection, temperature-programming, and miniaturized evaporative light-scattering detection were successfully employed for these separations. The injection of the wax samples, of low solubility at ambient temperature, was achieved by use of a high-temperature sample-introduction device. Temperature programming was required to achieve satisfactory resolution between the numerous components of the complex was samples.

Temperature-programmed packed capillary liquid chromatography coupled to fourier-transform infrared spectroscopy

Temperature-programmed packed capillary liquid chromatography has been coupled off-line to Fourier-transform infrared spectroscopy, utilizing a commercially available interface with a pheumatic nebulizer rebuilt to handle low flow rates at elevated temperatures. The modified interface showed excellent performance with regard to nonaqueous reversed phase separations of polymer additives, resulting in constructed Gram-Schmidt chromatograms comparable to chromatograms obtained using UV detection. The spray of the in-house constructed nebulizer was not influenced by temperature changes of the column effluent, and hence temperature-programmed gradient separations could be used successfully. The relative standard deviation of peak height was 4.4% (n = 5) and the mass limit of detection was determined to be about 40 ng, using a polymer antioxidant as model compound. The present instrumental coupling has been used for characterization of the antioxidant Irgafos P-EPQ