Concurrent solvent recondensation large sample volume splitless injection

Concurrent Solvent Recondensation Large Sample Volume (CRS‐LV) splitless injection overcomes the limitation of the maximum sample volume to 1–2 μL valid for classical splitless injection. It is based on control of the evaporation rate in the vaporizing chamber, utilization of a strong pressure increase in the injector resulting from solvent evaporation, and greatly accelerated transfer of the sample vapors from the injector into the inlet of an uncoated precolumn by recondensation of the solvent. The sample vapors are transferred into the column as rapidly as they are formed in the injector (concurrent transfer). 20–50 μL of liquid sample is injected with liquid band formation. The sample liquid is received by a small packing of deactivated glass wool positioned slightly above the column entrance at the bottom of the vaporizing chamber. Solvent evaporation strongly increases the pressure in the injector (auto pressure surge), provided the septum purge outlet is closed and the accessible volumes around the vaporizing chamber are small, driving the first vapors into the precolumn. Transfer continues to be fast because of recondensation of the solvent, obtained by keeping the oven temperature below the pressure‐corrected solvent boiling point. The uncoated precolumn must have sufficient capacity to retain most of the sample as a liquid. The experimental data show virtually complete absence of discrimination of volatile or high boiling components as well as high reproducibility.     

Large volume, low discrimination GC injection into a modified splitless injector

Summary A standard GC split/splitless injector was sealed with an airlock. The carrier gas and the sample were introduced through this valve. Such a configuration efficiently prevents an injector overflow. Injections up to 50 μL were made. An almost quantitative analyte and solvent transfer was observed, with only a minimal discrimination, of even volatile analytes. The use of an early vapor exit permitted a high initial liner flow and therefore a fast sample transfer.     

Improving splitless injection with electronic pressure programming

An experimental injection port has been designed for split or splitless sample introduction in capillary gas chromatography; the inlet uses electronic pressure control, in order that the column head pressure may be set from the GC keyboard, and the inlet may be used in the constant flow or constant pressure modes. Alternatively, the column head pressure may be programmed up or down during a GC run in a manner analogous to even temperature programming. Using electronic pressure control, a method was developed which used high column head pressures (high column flow rates) at the time of injection, followed by rapid reduction of the pressure to that required for optimum GC separation. In this way, high flow rates could be used at the time of splitless injection to reduce sample discrimination, while lower flow rates could be used for the separation. Using this method, up to 5 μl of a test sample could be injected in the splitless mode with no discrimination; in another experiment, 2.3 times as much sample was introduced into the column by using electronic pressure programming. Some GC peak broadening was observed in the first experiment.     

Large volume sample introduction using temperature programmable injectors: Implications of liner diameter

Temperature programmable injectors with liner diameters ranging from 1 to 3.5 mm are evaluated and compared for solvent split injection of large volumes in capillary gas chromatography. The liner dimensions determine whether a large sample volume can be introduced rapidly or has to be introduced in a speed controlled manner. The effect of the injection technique used on the recovery of n-alkanes is evaluated. Furthermore the influence of the liner diameter on the occurrence of thermal degradation during splitless transfer to the analytical column is studied. Guidelines are given for the selection of the PTV liner internal diameter best suited for specific applications.     

Direct injection of large sample volumes into capillary columns with packed column injector

A direct injection method for large volume samples which avoids severe tailing of the solvent peak has been developed using a packed column injector (up to 100 μl) leading into an ordinary capillary column (0.3 mm i.d.). Modifications are made to the cooler zones of the inlet port and on the carrier gas flow control system. This injection technique is based on the effective use of phase soaking and cold trapping using a retention gap. The large volume of solvent vapor is rapidly purged out of the injector with a higher flow of carrier gas while the solutes trapped at the head of the column are subsequently analyzed with another optimum flow rate. The proposed carrier gas flow regulation system is also compared with conventional split/splitless injection methods.     

Large volume sample application by a simplified “closed” on-column injector in capillary gas chromatography

Summary A new simplified version of a closed on-column injector is introduced. Because of its design isobaric injection conditions do not have to be followed and a wide range of injection temperatures above the boiling point of the sample solvent can be chosen for on-column injections in capillary gas chromatography. Also, when following certain basic injection rules, injections of large sample volumes (20 l or more) give accurate and reproducible results without further problems.Presented at the 17th International Symposium on Chromatography, September 25–30, 1988, Vienna, Austria.     

Cold on-column – solvent split injection with a three-way press-fit device

In a previous paper we described the possibilities of cold on-column – sample split injection achieved by means of an inexpensive and simple three way press-fit device [1]. The same arrangement is proposed here for cold on-column – solvent split injection in which specific elimination of the solvent, without loss of any other sample components, is achieved by opening the splitting tube (or better, in this case, the early solvent vapor exit) during solvent elution, and then closing it during elution of the sample's other components. Discrimination between solvent and other sample components is achieved by means of a retention gap, a retaining precolumn, and an early vapor exit. The technique enables both selective enrichment of a sample, in order to record satisfactory mass and infrared spectra of minor components, and injection of large volumes (up to 100 μl) of dilute solutions which cannot be concentrated because of component volatility. Details of the assembly and tuning the system are given, together with some examples.     

Multiresidue determination of thermolabile insecticides in cereal products by gas chromatography-mass spectrometry: evaluation with on-column injection and conventional hot splitless injection

This communication presents a study on the simultaneous determination of thermolabile N-methylcarbamate and organophosphorus insecticides in cereal products by gas chromatography-mass spectrometry. The thermal stability of the multiple insecticides was evaluated with conventional hot splitless injection and on-column injection. The results obtained by GC-MS with these two injection techniques were compared in terms of the recovery, the limit of detection, the limit of qualification, and the reproducibility. With on-column injection, the pesticide recoveries in cereal samples were better than 82%, with relative standard deviations lower than 5.4%. The limits of qualification for most insecticides were in the range of 0.009-0.08 mg/kg, i. e. lower than the maximum residue limits established for insecticides in cereal products by the European Union. The long-term stability using on-column injection for analysis of insecticides in real samples was evaluated and normal chromatographic performance could be obtained within 50 analyses. The results revealed that it was possible for application of on-column injection in the analysis of thermolabile multiple insecticides in food sample after comprehensive sample clean-up, despite the highly contaminated nature of the column system.     

Novel pressurized solvent extraction vessels for the analysis of polychlorinated biphenyl congeners in avian whole blood

Persistent organic pollutants remain a serious threat to many food-chain systems. New pollutants continue to emerge. The present study has created novel extraction vessels which are compatible with readily available commercial instrumentation to validate the analysis of one class of persistent organic pollutants, polychlorinated biphenyls (PCBs), in avian blood. The volumes used can be reasonably sampled without sacrificing individuals, or comprising breeding or migratorial success. The procedure consists of the pressurized solvent extraction (PSE) of analytes in a novel PSE extraction vessel. The new extraction cell contains a 38-cm long, coiled, re-packable, in situ clean-up column. Lipid elimination, using Florisil, occurs within the coiled region of the extraction vessel, eliminating the requirement for post extraction clean-up. For development, 0.2 g samples of chicken whole blood have been used. Extract volumes are reduced from (30 to 10) cm³, compared to unmodified systems. The new PSE vessel with its integrated clean-up method showed satisfactory performance for the analysis of ten environmentally relevant PCB congeners in chicken whole blood samples with recoveries in the range of (70-130)%. Detection limits using gas chromatography coupled with large volume injection ion-trap mass spectrometry (GC-LVI-ITMS-MS) were in the range of (0.05-0.5) ng g⁻¹. The relative standard deviations for all congeners investigated were better than 5%. This is the first PSE validation to have been conducted on unaltered whole blood samples.     

Automated sample treatment with the injection of large sample volumes for the determination of contaminants and metabolites in urine

This work reports the development of a simple and automated method for the quantitative determination of several contaminants (triazine, phenylurea, and phenoxyacid herbicides; carbamate insecticides and industrial chemicals) and their metabolites in human urine with a simplified sample treatment. The method is based on the online coupling of an extraction column with RP LC separation–UV detection; this coupling enabled fast online cleanup of the urine samples, efficiently eliminating matrix components and providing appropriate selectivity for the determination of such compounds. The variables affecting the automated method were optimized: sorbent type, washing solvent and time, and the sample volume injected. The optimized sample treatment reported here allowed the direct injection of large volumes of urine (1500 μL) into the online system as a way to improve the sensitivity of the method; limits of detection in the 1–10 ng/mL range were achieved for an injected volume of 1500 μL of urine, precision being 10% or better at a concentration level of 20 ng/mL. The online configuration proposed has advantages such as automation (all the steps involved in the analysis – injection of the urine, sample cleanup, analyte enrichment, separation and detection – are carried out automatically) with high precision and sensitivity, reducing manual sample manipulation to freezing and sample filtration.     

Co-solvent effects for preventing broadening or loss of early eluted peaks when using concurrent solvent evaporation in capillary GC. Part 1: Concept of the technique

The concept and some first results of a method are described for evaporating large volumes of solvent in a relatively short pre-column (retention gap) in such a way that solvent trapping retains volatile components in the inlet up to completion of solvent evaporation. The method was developed for transferring large volumes (easily exceeding 1 ml) of HPLC eluent to GC when using on-line coupled HPLC-GC, but is equally suited for injecting large sample volumes (at least some 50 μl) and could be particularly useful for introducing aqueous solutions. Concurrent solvent evaporation allows introduction of very large volumes of liquid into GC. However, peaks eluted up to some 40–80° above the column temperature during introduction of the liquid are strongly broadened due to the absence of solvent trapping. On the other hand, previous retention gap techniques involving solvent trapping were not suited for transferring very large volumes of liquid into GC. Using a relatively high boiling co-solvent added to the sample or the HPLC eluent, advantages of concurrent solvent evaporation can be combined with solute reconcentration by solvent effects, allowing elution of sharp peaks starting at the column temperature during introduction of the sample.     

Phase transfer membrane supported liquid-liquid-liquid microextraction combined with large volume sample injection capillary electrophoresis-ultraviolet detection for the speciation of inorganic and organic mercury

In this paper, a novel sample pretreatment technique termed phase transfer based liquid-liquid-liquid microextraction (PT-LLLME) was proposed for the simultaneous extraction of inorganic and organic mercury species. In PT-LLLME, an intermediate solvent (acetonitrile) was added into the donor phase to improve the contacting between target mercury species and complexing reagent. Meanwhile, a membrane supported (MS)-LLLME unit was designed to realize the PT-LLLME procedure. By using nylon membrane as supporting carrier, larger than 50 μL of acceptor solution could be hung up. Following PT/MS-LLLME, the acceptor solutions were directly analyzed by large volume sample stacking capillary electrophoresis/ultraviolet detection (LVSS-CE/UV). Accordingly, a new method of PT/MS-LLLME combined with LVSS-CE/UV was developed for the simultaneous speciation of inorganic and organic mercury species. Parameters affecting the extraction efficiency of PT/MS-LLLME were investigated in details. Under the optimized conditions, enrichment factors (EFs) ranging from 160- to 478-fold were obtained for the extraction of target mercury species by PT/MS-LLLME. By combining PT/MS-LLLME with LVSS-CE/UV, EFs were magnified up to 12,138-fold and the limits of detection (at a signal-to-noise ratio of 3) were at sub ppb level. The established approach of PT/MS-LLLME-LVSS-CE/UV was successfully applied to simultaneous determination of inorganic and organic mercury species in biological samples and environmental water samples.     

在线样品前处理大体积进样离子色谱法直接测定海水中亚硝酸盐、硝酸盐和磷酸盐

采用戴安公司谱睿(Pre)在线样品除氯技术,结合OnGuard Ba柱去除硫酸盐,建立了离子色谱直接测定海水中亚硝酸盐、硝酸盐和磷酸盐的方法。该方法以IonPac AG23为富集柱,高容量IonPac AS23为分离柱,淋洗液自动发生装置在线产生KOH溶液进行梯度淋洗,抑制电导检测。实验结果表明: 样品稀释5～10倍时,直接进样不会干扰目标物测定。当流速为1 mL/min、进样量为500 μL时,海水中NO~2-N、NO~3-N、PO3~4-P的方法检出限分别为0.3、0.4、0.2 μg/L,线性范围分别为10～500 μg/L、14～680 μg/L、3.4～170 μg/L,线性相关系数r均大于0.9990。测得人工海水样品中目标物的加标回收率为92%～106%,相对标准偏差(RSD, n=6)为1.2%～7.7%。该方法一次进样可在13 min内完成分析,具有操作简单快捷、无污染等优点,能满足近海海水中NO~2、NO~3、PO3~4的定量分析要求。