Detected cyanotoxins by UHPLC MS/MS technique in tropical reservoirs of northeastern Colombia.

This study focused on the detection and quantification of eight cyanotoxins in water samples in three reservoirs located in the eastern department of Antioquia, Colombia. The reservoirs are a source of water supply and hydroelectricity, and also generate economic activities in fishing and recreation. Between May 2015 and October 2016, 8 samplings were carried out at times of high temperatures, which ranged from 20 to 29 °C. This period was selected because of a significant or strong El Niño phenomenon, according to the World Meteorological Organization. For the study, 270 integrated samples were taken from the photic zone (PZ) and the surface of the reservoirs, at each of the three sampling points. The samples were analyzed by the analytical technique of ultra-high-performance liquid chromatography coupled to triple quadrupole mass spectrometry (UHPLC MS/MS). The quantification performed for six microcystins (MCs), a nodularin (NOD) and a cylindrospermopsin (CYN), showed positive results well above 1 µg L-1. In the water of the Abreo Malpaso and Peñol reservoirs, microcystin-LR (MC-LR), microcystin-YR (MC-YR) and [D-Asp3,(E)-Dhb7]- microcystin-RR toxins were detected at levels of considerable concentration, especially between May and September 2015, when there was no rainfall in this region. In the Playas reservoir, positive results for [D-Asp3,(E)-Dhb7]-MC-RR were detected from May to November 2015, with the highest concentrations being reached in dry season. The temperatures reached and the changes in climatic conditions witnessed during the monitoring period of this study were important factors in the production of cyanotoxins. This was evidenced in this work by the high concentrations of detected cyanotoxins and their absence in periods of rain, as happened from the second quarter of 2016 until the end of the study in October. This is the first study of the detection and quantification of cyanotoxins in tropical reservoirs of northeastern Colombia using the UHPLC MS/MS analytical technique, which allowed the toxins to be unequivocally detected and confirmed. A method was developed and validated, proving to be sensitive, reproducible and accurate. For each of the toxins (microcystin-LR (MC-LR), microcystin-RR (MC-RR), microcystin-YR (MC-YR), [D-Asp3,(E)-Dhb7]- microcystin-RR, microcystin-LW (MC-LW), microcystin-LF (MC-LF), nodularin (NOD) and cylindrospermopsina (CYN)) the correlation coefficients (R2) were in a range between 0.9907 and 0.9999. Verification of the accuracy of the method was performed through a calibration curve in solvent. The recovery percentages of the accuracy and precision tests of the method for low level, medium level and high level were in a range between 64% and 115% for all the cyanotoxins. The validation of the cyanotoxin method shows that it is possible to detect them individually in natural water with a quantification limit (LOQ) of approximately 0.05 µg L-1.

Comparative photodegradation study of atrazine and desethylatrazine in water samples containing titanium dioxide/hydrogen peroxide and ferric chloride/hydrogen peroxide.

Results are reported for a comparative photodegradation study of atrazine and desethylatrazine in water using TiO2/H2O2, FeCl3/H2O2, and photolysis. Deionized water and ground water spiked with atrazine or desethylatrazine at 36 micrograms/L were irradiated by using a xenon arc lamp and/or sunlight. After irradiation, the water samples containing the spiked pesticides were preconcentrated by using C18 solid-phase extraction disks and analyzed by gas chromatography with nitrogen-phosphorus and mass spectrometric detection. A relative percentage of 7% desethylatrazine was detected in samples removed after 20 and 4 min of sensitized photodegradation with TiO2 and Fe3+, respectively. Atrazine and desethylatrazine did not degrade when solar irradiation (in winter) and deionized water were used. Atrazine degraded faster than desethylatrazine when a xenon arc lamp or sunlight plus FeCl3 was used, with half-lives varying from 5 to 11 min and from 19 to 26 min, respectively. In other photodegradation experiments, the degradation of atrazine was slightly higher than that of desethylatrazine. This study shows that desethylatrazine has slightly higher stability than atrazine in environmental water samples; this stability accounts for the frequent detection of desethylatrazine together with atrazine in natural waters.

Photodegradation and stability of chlorothalonil in water studied by solid-phase disk extraction, followed by gas chromatographic techniques.

Photodegradation of chlorothalonil was studied in deionized and ground water with sunlight and Suntest apparatus, with and without FeCl3/H2O2 and TiO2/H2O2. After irradiation of the water samples spiked at 28-100 micrograms/l of chlorothalonil, the water solutions were preconcentrated using solid-phase disk extraction with C18 and analyzed by gas chromatography-electron capture and gas chromatography-mass spectrometric detection. The degradation products identified by GC-MS were: trichloro-1,3-dicyanobenzene, dichloro-1,3-dicyanobenzene and chloro-1,3-dicyanobenzene. The degradation kinetics followed a first order reaction and the R.S.D. of rate constants, for n = 3, varied from 2 to 14%. Halflives varied between 0.7 and 101 h. The stability of chlorothalonil on C18 Empore disks was also investigated at 20 degrees C, 4 degrees C and -20 degrees C for periods of up to 3 months. Chlorothalonil was not degraded on C18 Empore disks.

Application of C18 disks followed by gas chromatography techniques to degradation kinetics, stability and monitoring of endosulfan in water.

A comparative degradation study of endosulfan spiked at 35 micrograms/l in water using photocatalysis with (FeCl3/H2O2)/(TiO2/H2O2) and photolysis using either a xenon arc lamp and/or sunlight was performed. After irradiation the water samples were preconcentrated using C18 solid-phase disk extraction and analysis by gas chromatography-electron capture and mass spectrometric detection. Endosulfan sulphate was found in the photodegradation studies. Endosulfan showed high stability in water when it was exposed to sunlight and xenon are lamp, but by means of photocatalysis with FeCl3/H2O2, TiO2/H2O2, the degradation was very fast with half lives varying from 59-98 min. The degradation kinetics followed a first order reaction and the R.S.D. of rate constants, for n = 3, varied from 4-17%. The stability of endosulfan on C18 Empore disks has been determined at 20 degrees C, 4 degrees C and -20 degrees C for periods up to 3 months. Endosulfan was not degraded on C18 Empore disks. Ground water samples from south of Spain (Almeria) were monitored during 1 year. The compounds alpha-, beta- and endosulfan sulphate were detected at concentration values varying from 0.5-540 ng/l.