Effect of sample matrix on the determination of total petroleum hydrocarbons (TPH) in soil by gas chromatography–flame ionization detection

Research papers in different fields of analytics indicate that the effect of matrix-induced chromatographic response enhancement (matrix effect) is a commonly encountered problem in gas chromatography applications. In this paper, an example of the effect of sample matrix on the quantitative determination of total petroleum hydrocarbons (TPH) by GC–FID in soil is presented. Two types of soil were selected for the evaluation. Extraction and analysis of the soil samples was in accordance with CEN prEN 14039. The relative systematic error resulting from the matrix effect was obtained for three different TPH concentrations by statistical comparison of the slopes of the matrix-matched calibration lines and a pure solvent calibration line. Too high TPH concentrations were obtained when conventional solvent calibration was used for quantitation. This demonstrates that matrix-matched calibration should be exploited in the determination of petroleum hydrocarbons in soil samples. However, there was also significant enhancement of the response due to an interfering matrix with decreasing analyte concentration. Enhancement seems to be especially evident in the quantification of TPH over the concentration range encountered in polluted environments. As a result, even when matrix-matched calibration is used for quantitation, it is still necessary to establish the range over which a linear response can be expected. Otherwise too high results for sample TPH concentrations will be obtained.     

Evaluating the impact of GC operating settings on GC-FID performance for total petroleum hydrocarbon (TPH) determination

Interlaboratory comparisons for the analysis of mineral oil have indicated that many laboratories have problems in producing data of acceptable quality, mainly because of variations in the gas chromatographic settings used in the determination. A D-optimal design was therefore utilized to study the effects of six different GC operating settings on the GC performance criterion proposed by ISO and CEN draft standards ISO/FDIS 16703:2004 and CEN prEN 14039:2004:E for total petroleum hydrocarbon (TPH) determination. Both qualitative and quantitative factors were investigated. The results indicate that the performance criterion can only be achieved if the splitless injection settings are carefully optimized. Otherwise mass discrimination readily affects the validity of the results. The most critical factors affecting GC performance were the inlet liner design, inlet temperature and injection volume. The methods, however, were robust with respect to small changes in split vent time, GC column flow and FID temperature. The results show that non-discriminating splitless injection can only be obtained by optimizing the injector settings with respect to the significant factors. The main conclusion that can be drawn is that, if no further standardization is to be given for TPH determination by GC-FID, then a proper estimate of the expanded uncertainty should be appended to the TPH results. Only then can the reliability of the TPH results be guaranteed and further justification thus gained to support the end-use of the data.     

Connecting pairwise and positional election outcomes

General conclusions relating pairwise tallies with positional (e.g., plurality, antiplurality (“vote-for-two”)) election outcomes were previously known only for the Borda Count. While it has been known since the eighteenth century that the Borda and Condorcet winners need not agree, it had not been known, for instance, in which settings the Condorcet and plurality winners can disagree, or must agree. Results of this type are developed here for all three-alternative positional rules. These relationships are based on an easily used method that connects pairwise tallies with admissible positional outcomes; e.g., a special case provides the first necessary and sufficient conditions ensuring that the Condorcet winner is the plurality winner; another case identifies when there must be a profile whereby each candidate is the “winner” with some positional rule.     

Application of matrix-assisted laser desorption/ionization to on-line aerosol time-of-flight mass spectrometry

Matrix-assisted laser desorption/ionization (MALDI) mass spectra were obtained from single biological aerosol particles using an aerosol time-of-flight mass spectrometer (ATOFMS). The inlet to the ATOFMS was coupled with an evaporation/condensation flow cell that allowed the aerosol to be coated with matrix material as the sampled stream entered the spectrometer. Mass spectra were generated from aerosol composed either of gramicidin-S or erythromycin, two small biological molecules, or from aerosolised spores of Bacillus subtilis var niger. Three different matrices were used: 3-nitrobenzyl alcohol, picolinic acid and sinapinic acid. A spectrum of gramicidin-S was generated from approximately 250 attomoles of material using a molar ratio of 3-nitrobenzyl alcohol to analyte of approximately 20:1. A single peak, located at 1224 Da, was obtained from the bacterial spores. The washing liquid and extract solution from the spores were analyzed using electrospray mass spectrometry and subsequent MS/MS product ion experiments. This independent analysis suggests that the measured species represents part of the B. subtilis peptidoglycan. The on-line addition of matrix allows quasi-real-time chemical analysis of individual, aerodynamically sized particles, with an overall system residence time of less than 5 seconds. These results suggest that a MALDI-ATOFMS can provide nearly real-time identification of biological aerosols. Copyright 2000 John Wiley & Sons, Ltd.     

Variations of antioxidant characteristics and mineral contents in pulp and peel of different apple (Malus domestica Borkh.) cultivars from Pakistan

Variations of phenolics, antioxidant activity, and mineral contents in peel and pulp of five apple (Malus domestica Borkh.) cultivars from Pakistan, namely Red Delicious, Golden Delicious, Kashmiri Amri, Kala Kulu and Sky Spur were appraised. The mean extract yield of antioxidant components obtained with 80:20 methanol-water (v/v), was found to be 22.1 g/100 g for peel and 14.2 g/100 g for pulp on a dry weight basis. The amounts of total phenolics and total flavonoids in peel and pulp of different cultivars of apple ranged from 1,907.5-2,587.9 mg gallic acid equivalent/100 g DW and 1,214.3-1,816.4 mg catechin equivalent/100 g DW and 1,185.2-1,475.5 mg GAE/100 g DW and 711.8-999.3 mg CE/100 g DW, respectively. The inhibition of linoleic acid peroxidation and DPPH scavenging activity of the extracts varied from 71.7-84.9 and 66.6-80.8% in peel, and 43.9-52.8 and 42.9-51.1% in pulp, respectively. Reducing power of the tested fruit part extracts at concentration 12.5 mg/mL ranged from 2.54-2.89 and 1.37-1.73, respectively. With regard to minerals analysis, both fruit parts showed the amount of K to be the highest, followed by Mg, Ca, Fe, Na and Zn. The results revealed that peel of the tested apple cultivars in this study had superior antioxidant capacity and mineral concentration than the pulp, indicating significant variations between the parts tested. Thus, consumption of apple fruits along with peel might be recommended to gaining better nutritive benefits.     

Evaluating the impact of extraction and cleanup parameters on the yield of total petroleum hydrocarbons in soil

Interlaboratory comparisons for the analysis of mineral oil in polluted soil using the GC–FID method indicate that extraction and cleanup conditions have significant effects on the analytical results. In this investigation a ruggedness test was performed on the extraction and cleanup method for the determination of total petroleum hydrocarbons in soil. A two-level Plackett–Burman design was utilized to study the effect of 11 different method parameters on the extraction recovery of total petroleum hydrocarbons (TPH) in soil. Both qualitative and quantitative factors were investigated. The results indicate that total petroleum hydrocarbons can be relatively reliably monitored through strict implementation of the ISO and CEN draft standards. However, variation in certain method parameters readily affects the validity of the results. The most critical factors affecting TPH recovery were the solvent and co-solvent used for extraction, the extraction time, adsorbent and its weight and sample TPH concentration. Because adaptation of the draft standards especially with respect to these factors easily leads to TPH recoveries higher than 200% or lower than 70%, the validity of the adapted method should always be verified. A proper estimate of the expanded uncertainty should also be appended to TPH results, because only then can the reliability of the results be guaranteed and further justification is gained to support the end-use of the data. This also supports the credibility of the analytical services and prevents the data end-users from drawing misleading conclusions concerning the environmental risks and potential remediation requirements.     

A Comprehensive Review on the Techniques for Extraction of Bioactive Compounds from Medicinal Cannabis

Cannabis is well-known for its numerous therapeutic activities, as demonstrated in pre-clinical and clinical studies primarily due to its bioactive compounds. The Cannabis industry is rapidly growing; therefore, product development and extraction methods have become crucial aspects of Cannabis research. The evaluation of the current extraction methods implemented in the Cannabis industry and scientific literature to produce consistent, reliable, and potent medicinal Cannabis extracts is prudent. Furthermore, these processes must be subjected to higher levels of scientific stringency, as Cannabis has been increasingly used for various ailments, and the Cannabis industry is receiving acceptance in different countries. We comprehensively analysed the current literature and drew a critical summary of the extraction methods implemented thus far to recover bioactive compounds from medicinal Cannabis. Moreover, this review outlines the major bioactive compounds in Cannabis, discusses critical factors affecting extraction yields, and proposes future considerations for the effective extraction of bioactive compounds from Cannabis. Overall, research on medicinal marijuana is limited, with most reports on the industrial hemp variety of Cannabis or pure isolates. We also propose the development of sustainable Cannabis extraction methods through the implementation of mathematical prediction models in future studies.     

On the final evolution of the n-body problem

The Newtonian n-body problem is studied. The main result gives the asymptotic properties of the distances between particles as time (t) approaches infinity. It is shown how particles can separate into subsystems between which the distances are asymptotic to constant multiples of time, and within which the mutual distances are at most of the order $\text{t}{}^{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}$. Each subsystem behaves asymptotically like a pure n-body problem in the sense that an energy and an angular momentum relationship are asymptotically satisfied. These techniques allow some three-body results found by Birkhoff and by Sundman to be extended to the n-body problem. Finally, some n-body results are derived for a motion which expands faster than time.     

A global existence theorem for the four-body problem of Newtonian mechanics

It is shown that for the planar or three-dimensional two-, three-, or four-body problems of celestial mechanics, almost all initial conditions (in the sense of Lebesgue measure and Baire category) lead to solutions which exist for all time.