Analysis of cocaine and benzoylecgonine in urine by using multisyringe flow injection analysis‐gas chromatography‐mass spectrometry system

In this paper, a method was described to determine cocaine (COC) and benzoylecgonine (BZE) in human urine samples by GC‐MS detection. The extraction of analytes from urine samples was achieved in an Oasis hydrophilic–lipophilic balance column (20 mm×3.9 mm id, dp=25 μm; Waters, USA), incorporated in a multisyringe flow injection system, used for the sample treatment. Finally, to improve the volatility of the BZE, an in‐line derivatization reaction with N,O‐bis (trimethylsilyl) trifluoroacetamide with 1% trimethylchlorosilane was made microwave‐assisted in order to reduce the reaction time. The results showed that the proposed method is a good alternative for the analysis of COC and BZE in urine samples because it offers advantages compared with those described in the literature, which include simplicity in the sample treatment, the sensitivity and selectivity necessary to determine the analytes of interest at low levels in the urine and high sample throughput.     

Crustal fraction of cattle feedlot particulate matter emissions using neutron activation analysis: method development

Neutron activation analysis (NAA), along with multivariate statistical methods, were employed as a proposed method to measure concentrations of some 30 elements in filtered air particulates and to estimate the fraction of particulate matter originating from crustal sources. The new method may provide a means for certain agricultural industries, in particular cattle feedlots, to take advantage of the proposed crustal credit in emission regulations, if such a credit is implemented by the US Environment Protection Agency (EPA). Chemical composition of particulate source materials as well as environmental air particulate samples were determined and results compared using computer modelling techniques to determine contribution from each potential source.     

Validated, non-destructive and environmentally friendly determination of cocaine in euro bank notes

A non-destructive, fast and environmentally friendly procedure has been developed for cocaine determination in euro bank notes. Cocaine was extracted with 15 ml methanol by vortex agitation during 5 min. The extract was evaporated and reconstituted in 0.5 ml methanol. GC-MS-MS analysis was performed using as precursor ion m/z 182.2, with an excitation energy voltage of 1.60 eV, being the product ions measured m/z 150.2 and 82.0. A limit of detection of 0.15 ng per note and a repeatability of 6%, established from the relative standard deviation, of a 1 ng ml(-1) level, were achieved. Recoveries of 101+/-2 and 98+/-3% were obtained for samples spiked with 100 and 10 microg respectively. Results show that all the euro bank notes measured (16 samples) were contaminated with cocaine in the range between 1.25 and 889 microg. Two different contamination levels, high level (150-889 microg) and low one (1.25-77 microg) were found and it could be related with the direct or indirect contact with the drug.     

层析净化-气相色谱-质谱法测定大气颗粒物中7种有机磷酸酯阻燃剂

采用层析净化-气相色谱-质谱法测定大气颗粒物中7种有机磷酸酯阻燃剂的含量。大气颗粒物样品经乙酸乙酯-丙酮(3+2)溶液提取,硅胶∶氧化铝(3∶1)层析柱分离纯化。以RTI-5MS色谱柱为固定相,在质谱分析中采用选择离子监测模式。7种有机磷酸酯阻燃剂在一定的质量浓度范围内与其峰面积呈线性关系,方法的检出限(3S/N)在1.01~8.74pg·m-3之间。加标回收率在51.9%~89.3%之间,测定值的相对标准偏差(n=3)在3.2%~11%之间。     

Determination of cocaine and its metabolites using cation-selective exhaustive injection and sweeping-MEKC

We have employed a high-sensitivity on-line preconcentration method, cation-selective exhaustive injection (CSEI) and sweeping MEKC, for the analysis of cocaine, benzoylecgonine, norcocaine, and cocaethylene. We monitored the effects of several of the CSEI-sweeping-MEKC parameters - including the pH, the concentrations of SDS and organic modifier, the injection length of the high-conductivity buffer, and the injection time of the sample - to optimize the separation process. The optimal BGE was 100 mM phosphoric acid (pH 1.8) containing 75 mM SDS with 10% 2-propanol and 10% tetrahydrofuran as the organic modifier. In addition, electrokinetic injection of the sample at 15 kV for 900 s provided both high separation efficiency and enhanced sweeping sensitivity. The sensitivity enhancements for cocaine, norcocaine, and cocaethylene ranged from 2.06 x 10(4) to 3.96 x 10(4); for benzoylecgonine it was 1.75 x 10(3); the coefficients of determination exceeded 0.9958. The LODs, based on an S/N ratio of 3:1, of sweeping-MEKC ranged from 33.5 to 52.8 ng/mL; in contrast, when using CSEI-sweeping-MEKC the sensitivity increased to range from 29.7 to 236 pg/mL. Under the optimal conditions, we analyzed cocaine in a human urine sample prepared using off-line SPE to minimize the influence of the matrix. The recovery of the SPE efficiency was satisfactory (ca. 74.9-87.6%). Our experimental results suggest that, under the optimal conditions, the CSEI-sweeping-MEKC method can be used to determine cocaine and its metabolites with high sensitivity in human urine.     

Peptides trapping cocaine: docking simulation and experimental screening by solid phase extraction followed by liquid chromatography mass spectrometry in plasma samples

Two different hexapeptides were computationally designed and tested as selective SPE sorbent for cocaine. The amino acid residues used for designing the two hexapeptides, tested in SPE experiments, were, according to chemical function and interatomic distances, the most (QHWWDW) and the lowest (ESSIDH) preserved sequences in 4 proteins binding cocaine. The hexapeptide–cocaine complex was docked with different scoring functions combinations and resulting binding scores were compared with the SPE results. The extraction procedure for SPE was optimized considering volume loading, pH effect, and human plasma matrix interferences. Cocaine was loaded onto the modified resin cartridge at 10 ng mL⁻¹ and the peptide QHWWDW was found to have the highest recovery with the best retention at pH 7.5, in agreement with docking simulation. Retention experiments were carried out also on cocaine metabolites nor-cocaine, benzoylecgonine and ecgonine methyl ester. Except for nor-cocaine the retention of metabolites on resin modified with peptide QHWWDW decreased drastically confirming the peptide selectivity, and validating the simulation data. Compared to standard solutions, only a slight decrease in cocaine recovery was observed loading human plasma samples after a partial protein precipitation.     

A review of monitoring of airborne polycyclic aromatic hydrocarbons: An African perspective

In this review, we focus on the status of the monitoring of polycyclic aromatic hydrocarbons (PAHs) in ambient air as well as in living (indoor) and working environments in Africa from 2000 to 2018. This is important as PAHs are ubiquitous in the environment and are known to be potentially carcinogenic. Aspects of sampling such as collection media for particle bound and gaseous PAHs are discussed. The efficiency and basic quality assurance data of commonly employed extraction techniques for separating target PAHs from sampling media using conventional solvent-based and emerging solvent-free approaches were also evaluated. Polyurethane foam and quartz fiber filters are generally the most commonly used collection media for gaseous and particle bound PAHs, respectively. A wide range of total PAH concentrations in ambient air has been reported across the continent of Africa, with the highest levels found at sampling sites close to high density traffic and industrial areas. A rapidly increasing population, commercial and industrial development, poor urban transportation infrastructure and the use of low quality oil products were the main causes of high total gas and particulate PAH concentrations (1.6–103 μg/m³) in West African port cities such as Cotonou, Benin. With regards to indoor environments, gas phase PAHs were detected at the highest total concentrations in rural areas ranging from 1 to 43 μg/m³ in Burundi with naphthalene being the most prevalent. Firewood burning was the major emission source in most developing countries and resulted in benzo[a]pyrene concentrations above the European permissible risk level of 1 ng/m³.     

Development of a screening method for cocaine and cocaine metabolites in saliva using hollow fiber membrane solvent microextraction

Hollow fiber membrane solvent microextraction (HFMSME) has been applied as a simple and efficient means of sample preparation for the screening of drugs of abuse in saliva. Extraction of cocaine and its metabolites from a 2 ml saliva solution was achieved in 10 min. This was followed by fast GC separation allowing complete analysis to be achieved in 15 min. Using HFMSME, detection limits ranged between 6 and 28 ng ml⁻¹ with average relative standard deviations of 9.0%. The effect of the presence of various foodstuffs was also investigated.     

Development of a method for the monitoring of odor‐causing compounds in atmospheres surrounding wastewater treatment plants

This study describes the development of an analytical method based on active collection in a multisorbent Tenax TA/Carbograph 1TD tube, followed by thermal desorption and GC‐MS for the determination of 16 volatile organic compounds in air samples. The analyzed compounds include ozone precursors and odor‐causing compounds belonging to different chemical families (sulfur‐ and nitrogen‐containing compounds, aldehydes, and terpenes). Two types of sorbents were tested and desorption conditions (temperature, time, and sampling, and desorption flow) were evaluated. External calibration was carried out using the multisorbent bed. Method detection limits in the range 0.2–2.0 μg m^?3 for 1 L samples were obtained. The method was applied for determining the target compounds in air samples from two different wastewater treatment plants. Most compounds were detected and toluene, limonene, and nonanal were found in particularly high concentrations with maximum values of 438, 233, and 382 μg m^?3, respectively.     

Determination of cocaine contamination on banknotes using tandem mass spectrometry and pattern recognition

Tandem mass spectrometry is used to monitor the contamination of banknotes by cocaine. By introducing a series of banknotes into an instrument a distribution of contamination can be obtained. The distribution of samples arising from defendants where the banknotes have been in close proximity to cocaine should differ from the distribution from the general background population. Peak picking and integration is used to produce a series of intensity readings for a batch of banknotes. By visually inspecting these distribution, and applying a variety of chemometric methods (principal components analysis, cluster analysis and class modelling via Mahalanobis distance) it is possible to discriminate effectively between the two classes of distribution (7157 background notes and 4826 case notes alleged to be from drug dealers). By calculating the Mahalonobis distance over 100 bootstrap iterations, background samples were correctly classified 96.48% of the time, while case samples were correctly classified 89.37% of the time.     

Detection and validated quantification of toxic alkaloids in human blood plasma--comparison of LC-APCI-MS with LC-ESI-MS/MS

Poisonings with toxic plants may occur after abuse, intentional or accidental ingestion of plants. For diagnosis of such poisonings, multianalyte procedures were developed for detection and validated quantification of the toxic alkaloids aconitine, atropine, colchicine, coniine, cytisine, nicotine and its metabolite cotinine, physostigmine, and scopolamine in plasma using LC-APCI-MS and LC-ESI-MS/MS. After mixed-mode solid-phase extraction of 1 ml of plasma, the analytes were separated using a C8 base select separation column and gradient elution (acetonitrile/ammonium formate, pH 3.5). Calibration curves were used for quantification with cotinine-d(3), benzoylecgonine-d(3), and trimipramine-d(3) as internal standards. The method was validated according to international guidelines. Both assays were selective for the tested compounds. No instability was observed after repeated freezing and thawing or in processed samples. The assays were linear for coniine, cytisine, nicotine and its metabolite cotinine, from 50 to 1000 ng/ml using LC-APCI-MS and 1 to 1000 ng/ml using LC-ESI-MS/MS, respectively, and for aconitine, atropine, colchicine, physostigmine, and scopolamine from 5 to 100 ng/ml for LC-APCI-MS and 0.1 to 100 ng/ml for LC-ESI-MS/MS, respectively. Accuracy ranged from -38.6 to 14.0%, repeatability from 2.5 to 13.5%, and intermediate precision from 4.8 to 13.5% using LC-APCI-MS and from -38.3 to 8.3% for accuracy, from 3.5 to 13.8%, for repeatability, and from 4.3 to 14.7% for intermediate precision using LC-ESI-MS/MS. The lower limit of quantification was fixed at the lowest calibrator in the linearity experiments. With the exception of the greater sensitivity and higher identification power, LC-ESI-MS/MS had no major advantages over LC-APCI-MS. Both presented assays were applicable for sensitive detection of all studied analytes and for accurate and precise quantification, with the exception of the rather volatile nicotine. The applicability of the assays was demonstrated by analysis of plasma samples from suspected poisoning cases.     

车载色质-热脱附联用系统及其对恶臭类物质测定的研究

为了应对当今日益突出的环境污染问题,建立了一套车载色质-热脱附联用系统(配有正压系统)及其对恶臭类物质测定的方法。该系统在恶臭物质测定方面既能解决目前应急监测设备所普遍存在的只能半定量的问题,又能解决样品运送到实验室分析过程中所带来的干扰、损失的问题。方法检出限在8~14ng/m3,精密度好(RSD小于4.1%)。     

Use of high-performance liquid chromatography to assess airborne mycotoxins. Aflatoxins and ochratoxin A

An HPLC analytical method combining methanol-deionised water (80:20, v/v) extraction, methanol-acetonitrile (50:50, v/v) extraction and fluorescence detection was implanted to analyse ochratoxin A and aflatoxins B1, B2, G1 and G2 of air samples collected during the usual production process in a number of workplaces of a coffee factory to assess the occupational exposure of the engaged workers. The average levels of airborne ochratoxin A and aflatoxins were less than 1.2 and 0.4 ng/m3, respectively, using 50 L air samples. When 150 L air samples were used, levels lower than 0.04 ng/m3 ochratoxin A and 0.013 ng/m3 for aflatoxins B1, B2, G1 and G2, could be detected.     

Microwave assisted sample preparation for determining water-soluble fraction of trace elements in urban airborne particulate matter: evaluation of bioavailability

The feasibility of using two different microwave-based sample preparation methods was investigated to determine the total and water-soluble trace metal fraction in airborne particulate matter. The extraction techniques were then applied to urban particulate matter of different sizes in order to evaluate their bioavailability of associated trace metals. While a combination of HNO₃-HF-H₂O₂ was used for the total trace metal fraction of particulate matter, water was employed for the microwave-assisted extraction of water-soluble trace metal fractions. Inductively coupled plasma-mass spectrometry (ICP-MS) was used for the analysis of trace elements. The experimental protocol for the microwave assisted digestion was established using two different SRMs (1648, urban particulate matter and 1649a, urban dust). In the case of water-soluble trace metal fraction, the quantities extracted from the SRMs were compared between ultrasonic and microwave-assisted extractions, and there was a good agreement between the two extraction methods. Blanks values and limits of detection (LODs) for total and water-soluble trace metal concentrations were determined for three different filter substrates (Teflon, Zeflour, and Quartz). Subsequently, the proposed digestion method was evaluated for its extraction efficiency with these filter substrates. Finally, the real-world application of the proposed microwave-based sample preparation methods was demonstrated by analyzing trace elements in airborne particulate samples collected from different outdoor environments in Singapore. The solubility of 11 trace elements detected in the particulate samples is quantified.     

Indirect Atomic Absorption Determination of Cocaine via Formation and Liquid‐liquid Extraction of the Iron(III)‐cocaine Complex

The principles of metal‐alkaloid ion‐pair formation and liquid‐liquid extraction are applied to the development of a sensitive and convenient atomic absorption spectrophotometery (AAS) method for the indirect determination of cocaine. In an aqueous medium of 5 M hydrochloric acid, cocaine is protonated and is associated with tetrachloro ferrate (III) anion prior to its extraction into 1,2‐dichloroethane. The critical experimental variables were identified and optimized. The method is simple and reproducible with a detection limit (DL) of 0.1 ng cm^?3 cocaine in water, a relative standard deviation of 0.07 (n = 12), and the calibration graph was linear up to 50 ng cm^?3 cocaine.     

新型除草剂及其杂质的LC-MS和GC-MS分析

High performance liquid chromatography (HPLC) and electrospray ionization mass spectrometry (ESI-MS) have been utilized to analyze the synthesized 2-(2-arylaminomethylphenoxy)pyrimidine derivatives, which are a new kind of environmentally benign herbicides and have passed the temporary pesticide registration. The identification of main product and impurities has been achieved according to the UV and mass spectra. Moreover, one impurity, introduced by the raw material in the last step of the synthetic route, was identified by GC-MS analysis. It can be concluded that the combination of chromatography and mass spectrometry, including LC-MS and GC-MS, provided a vital tool of the pesticide science.     

Comparison of several extraction procedures for the determination of biopesticides in soil samples by ultrahigh pressure LC-MS/MS

A new procedure has been proposed for the determination of biopesticides (nicotine, sabadine, veratridine, rotenone, azadirachtin, cevadine, deguelin, spynosad D, and pyrethrins) and piperonyl butoxide in agricultural soils. Several extraction procedures such as solid-liquid extraction using mechanical shaking, sonication, pressurized liquid extraction, and modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) have been tested, obtaining better results when QuEChERS procedure without further cleanup steps was applied. The determination of the compounds was carried out by ultra high pressure liquid chromatography coupled to tandem mass spectrometry, using methanol and aqueous solution of ammonium formate 5 mM as mobile phase. The method was validated for all compounds at concentrations ranging from 10 to 100 μg/kg and recoveries ranged from 68 to 116%, except for nicotine and sabadine, with recoveries lower than 50%. Precision was estimated through intra- and inter-day studies, obtaining intra-day precision lower than 20% for most of the compounds, and inter-day precision was lower than 25%. Limits of detection and quantification were also estimated, obtaining limits of quantification equal or lower than 10 μg/kg. Finally, the method was applied to the analysis of 20 real agricultural soil samples and no biopesticide residues were found over the limit of quantification.     

Liquid‐phase microextraction based on two immiscible organic solvents followed by gas chromatography with mass spectrometry as an efficient method for the preconcentration and determination of cocaine,ketamine, and lidocaine in human urine samples

A new type of liquid‐phase microextraction based on two immiscible organic solvents was optimized and validated for the quantification of lidocaine, ketamine, and cocaine in human urine samples. A hollow‐fiber based microextraction technique followed by gas chromatography coupled with mass spectrometry detection was used to reduce matrix interferences and improve limits of detection. The analytes were extracted from aqueous sample with pH 11.0, into a thin layer of organic solvent (n‐dodecane) sustained in the pores of a hollow fiber, and then into a second organic acceptor (acetonitrile) located inside the lumen of the hollow fiber. With the application of optimized values, good linearity was obtained in the range of 1–500 μg/L for lidocaine and ketamine and 2–500 μg/L for cocaine with the determination coefficient values (r²) >0.9943. The preconcentration factors and limits of detection (S/N > 3) were 250–350 and 0.01–0.05 μg/L, respectively. Intra and interassay precision values were <7.3 and 9.3%, respectively. The method was successfully applied for the determination and quantification of target analytes in human urine samples.     

Extractability of dioxins from soil: I. Extractability of dioxins from airborne particulates and humic acid fraction in soil

The extractability of dioxins (polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and coplanar polychlorinated biphenyls) from airborne particulates (APs) and humic acid (HA) in soil was evaluated. APs collected from ambient atmosphere and dioxins-associated precipitated HA fraction (PHA) were extracted by pressurized liquid extraction with either toluene or acetone. Native dioxins were equivalently extracted from APs with both solvents, whereas only acetone could satisfactorily recover the ¹³C-labelled compounds from metal-free PHA. The recovery rates of dioxins by toluene extraction from metal-free PHA varied with the organic carbon content of the PHA. However, even with acetone, the recovery of dioxins from metal-bound HA was poor (11–40%). These results suggest that PHA prevented the solvents from accessing sequestered dioxins. This characteristic of solid HA may influence the extractability of dioxins from humus-rich soil.