Johan Dahlén

Determination of low molecular weight organic acids in soil solution by HPLC

An HPLC method employing an ion exclusion column was developed for the determination of low molecular weight organic acids in soil solution. The method includes extensive sample pretreatment using ultrafiltration and cation exchange. The method showed linear calibration graphs (r>0.99) and the limits of detection in the range 0.1-26 muM. The recovery of eleven added acids ranged from 89 to 102%. Soil solutions of five horizons of a podzolised soil were analysed. The results showed that these compounds made up 1-3% of the dissolved organic carbon and 0-14% of the acidity. Identification of the major acids was also carried out by capillary zone electrophoresis.

Determination of nitrate and other water quality parameters in groundwater from UV/Vis spectra employing partial least squares regression

The use of UV/Vis spectroscopy in combination with partial least squares (PLS) regression for the simultaneous prediction of nitrate and non-purgeable organic carbon (NPOC) in groundwaters was evaluated. A model of high quality was obtained using first order derivative spectra in the range 200-300 nm. Inclusion of non-UV-absorbing constituents in the modeling procedure, i.e., chloride, sulfate, fluoride, total carbon (TC), inorganic carbon (IC), alkalinity, pH and conductivity was also evaluated. This model seemed to be useful for prediction of chloride, TC, IC, alkalinity and conductivity, while its ability to predict sulfate, fluoride and pH was poor. In conclusion, application of PLS regression, which requires neither filtration of samples nor addition of chemicals, is a promising alternative for fast interpretation of geochemical patterns of groundwater quality.

Simultaneous analysis of γ-hydroxybutyric acid, γ-butyrolactone, and 1,4-butanediol by micellar electrokinetic chromatography

A micellar electrokinetic chromatography (MEKC) method was optimised for simultaneous analysis of ?-hydroxybutyric acid (GHB), ?-butyrolactone (GBL), and 1,4-butanediol (BD). Best conditions for se ...

Determination of group parameters for organically bound chlorine, bromine and iodine in precipitation

The presence of organically bound halogens in precipitation was studied by first adsorbing organics on activated carbon and then analysing the chloride, bromide and iodide formed during combustion of the carbon. A standard instrument for the group parameter AOX (adsorbable organic halogens) was used for the combustion. The halides formed were trapped in an alkaline solution and analysed by capillary zone electrophoresis. The method described enabled determination of sub-ppb concentrations of the group parameters AOCl, AOBr and AOI (adsorbable organic chlorine, bromine and iodine, respectively). Analysis of rain and snow collected at different sites in Europe showed that organochlorines were responsible for the major part of the AOX content in all samples collected. Organically bound bromine was found in sub-ppb concentrations in all of the samples, whereas organic iodine was detected in only two of the samples.

Application of Capillary Zone Electrophoresis for the Analysis of Low Molecular Weight Organic Acids in Environmental Samples

Abstract The applicability of a recently developed capillary zone electrophoretic (CZE) method for the determination of low molecular weight (LMW) organic acids in water was tested on five types of environmental samples (rainwater, water extract from peat, and soil water from two polluted sites). A full baseline resolved separation of fourteen commonly found LMW carboxylic acids in natural waters (malonic, oxalic, fumaric, maleic, formic, succinic, tartaric, glutaric, adipic, acetic, propionic, butyric, valeric and citric acids), was achieved within eight minutes. The limits of detection (2 X noise) were in the ranges 90–200 μg/l and 0.5 – 5 μg/l for hydrodynamic and electrokinetic injection, respectively. Two different CZE systems, a Waters Quanta 4000 and a Hewlett Packard HP 3DCE system, were used and their performance compared.

Determination of the Molecular Weight of Fulvic Acids By UV/VIS Spectroscopy

Partial least squares (PLS) modeling was applied to investigate number-average molecular weights (Mn) and weight-average molecular weights (Mw) of fulvic acids (FAs) in relation to the corresponding UV/VIS spectra. The Mn and Mw values were determined by size exclusion chromatography (SEC). The impact of pH control, wavelength range and density as well as smoothing and derivation of spectra were tested. It was found that PLS models based on absorbance spectra can be a fast and powerful complement to existing techniques employed for determination of molecular weights of FAs. Control of pH of the FA solutions is important for the performance of the models. The models were also compared with the best univariate alternatives.

Spontaneous formation of γ-hydroxybutyric acid from γ-butyrolactone in tap water solutions

The spontaneous conversion of γ-butyrolactone (GBL) to γ-hydroxybutyric acid (GHB) in seven different Swedish tap waters was investigated. The waters used in the study were selected to represent the diversity among Swedish tap waters as well as possible, which was enabled by principal component analysis (PCA) of a number of water quality parameters. GBL solutions (5, 25 and 50% v/v) were prepared in each of the tap waters and in deionized water and the formation of GHB was followed over time. The GHB quantifications were made using a CZE method, employing a carrier electrolyte consisting of 25mM benzoic acid, 54mM tris(hydroxymethyl)aminomethane (Tris) and 1.7mM tetradecyltrimethylammonium bromide (TTAB), which was developed as a part of the current study. Data evaluation showed that the formation of GHB was largely dependent on the type of tap water. For example, there was a negative correlation between the kinetics of the GHB formation and the alkalinity of the tap waters (r(2)=0.990). This could be explained by a faster decrease in pH in the waters with low buffering capacity (i.e. low alkalinity), which catalysed the hydrolysis of GBL. Equilibrium was reached after 40-250 days depending on the initial GBL concentration and the type of tap water. The level of the equilibrium appeared to be dependent on the initial GBL concentration and ranged from 26 to 37%. Gained knowledge on the levels of the GHB/GBL equilibrium and the kinetics of the formation of GHB in tap water solutions of GBL, including the influence of the tap water quality, may be useful information for casework with the GHB/GBL problem in focus.

Analysis of Explosives by GC-UV

A mixture of explosives was analyzed by gas chromatography (GC) linked to ultraviolet (UV) spectrophotometry that enabled detection in the range of 178–330 nm. The gas‐phase UV spectra of 2,4,6‐trinitrotoluene (TNT), 2,4‐dinitrotoluene (DNT), ethylene glycol dinitrate (EGDN), glycerine trinitrate (NG, nitroglycerine), triacetone triperoxide (TATP), and pentaerythritol tetranitrate (PETN) were successfully recorded. The most interesting aspect of the current application is that it enabled simultaneous detection of both the target analyte and its decomposition products. At suitable elevated temperatures of the transfer line between the GC instrument and the UV detector, a partial decomposition was accomplished. Detection was made in real time and resulted in overlaid spectra of the mother compound and its decomposition product. Hence, the presented approach added another level to the qualitative identification of the explosives in comparison with traditional methods that relies only on the detection of the target analyte. As expected, the decomposition product of EGDN, NG, and PETN was NO, while TATP degraded to acetone. DNT and TNT did not exhibit any decomposition at the temperatures used.

Prediction of designer drugs: Synthesis and spectroscopic analysis of synthetic cathinone analogs that may appear on the Swedish drug market

The use of hyphenated analytical techniques in forensic drug screening enables simultaneous identification of a wide range of different compounds. However, the appearance of drug seizures containing new substances, mainly new psychoactive substances (NPS), is steadily increasing. These new and other already known substances often possess structural similarities and consequently they exhibit spectral data with slight differences. This situation has made the criteria that ensure indubitable identification of compounds increasingly important. In this work, 6 new synthetic cathinones that have not yet appeared in any Swedish drug seizures were synthesized. Their chemical structures were similar to those of already known cathinone analogs of which 42 were also included in the study. Hence, a total of 48 synthetic cathinones making up sets of homologous and regioisomeric compounds were used to challenge the capabilities of various analytical techniques commonly applied in forensic drug screening, ie, gas chromatography-mass spectrometry (GC-MS), gas chromatography-Fourier transform infrared spectroscopy (GC-FTIR), nuclear magnetic resonance (NMR), and liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS). Special attention was paid to the capabilities of GC-MS and GC-FTIR to distinguish between the synthetic cathinones and the results showed that neither GC-MS nor GC-FTIR alone can successfully differentiate between all synthetic cathinones. However, the 2 techniques proved to be complementary and their combined use is therefore beneficial. For example, the structural homologs were better differentiated by GC-MS, while GC-FTIR performed better for the regioisomers. Further, new spectroscopic data of the synthesized cathinone analogs is hereby presented for the forensic community. The synthetic work also showed that cathinone reference compounds can be produced in few reaction steps.