Environmental and biological monitoring of organochlorine pesticides in the city of Salamanca, Mexico.

The former Tekchem Industrial Unit located in the city of Salamanca, Mexico, constitutes an environmental liability in which the presence of high levels of organochlorine pesticides (OCPs) has been reported. In the present study, levels of OCPs were quantified using gas chromatography-mass spectrometry in 52 soil samples and in 88 blood samples from school-age children in the city of Salamanca. A median concentration of 70.6 ng/g (6.93-3299) was obtained for total OCPs in soil, while for the total sum of dichlorodiphenyltrichloroethane (DDT) the value was 49.6 ng/g (6.93-3276). In children, the median level of the total sum of OCPs was 390 ng/g lipid (7.34-14,895), and for the total sum of DDT was 175 ng/g lipid (< LOD-14,802). The OCPs that resulted in highest concentrations in soil were DDT and its metabolites, as well as aldrin and heptachlor epoxide, while in blood the highest levels corresponded to 4,4'-dichlorodiphenyltrichloroethane (4,4'-DDT) and its metabolites, followed by heptachlor and heptachlor epoxide. The spatial distribution of the concentrations of OCPs in soil shows that the facilities of Tekchem may be a significant potential source for the dispersion of these compounds toward the metropolitan area of Salamanca. The results obtained in the present study demonstrate the presence of OCPs in soil and in child population, providing important bases to study the problem from a broader perspective, while reiterating the importance of continuing efforts to generate resolute and precautionary measures with respect to the environmental liability of Tekchem.

Determination of chromium(III) picolinate in dietary supplements by flow injection - electrospray ionization - tandem mass spectrometry, using cobalt(II) picolinate as internal standard.

In this work, a principle of flow injection analysis (FIA) was applied for sample introduction to an electrospray ionization - ion trap mass spectrometer (ESI-ITMS) with the aim to quantify chromium(III) picolinate (CrPic3) in commercial supplements by multiple reaction monitoring, and using cobalt(II) picolinate as internal standard (IS). FIA system was operated with ammonium formate 10 mmol L-1 in methanol-water (1:1, v/v) as a carrier solution at a flow rate 200 µL min-1; 100 µL injections were performed in 2-min intervals. Setting ion transitions m/z 419 â†’ 270 and 304 â†’ 260 for the analyte and IS, respectively, and 100 ms integration time, the method detection and quantification limits 12 ng g-1 and 40 ng g-1 of Cr (as CrPic3) in the air-dried powder. Acetonitrile extracts of the real-world samples presented varying from sample-to-sample chemical composition and IS efficiently compensated for ionization interferences. Mean results from triplicate analysis of four different supplements were obtained with relative standard deviation 0.1-4.0%, indicating acceptable precision. Trueness of the proposed FIA-ESI-ITMS/MS procedure was demonstrated by 95.8-108% percentage recoveries attained in the analysis of the CrPic3-spiked samples. For comparative purposes, total Cr was determined by ICP-MS. The quantitative results obtained indicate the necessity of analytical control of Cr(III) supplements commercially available and demonstrate that the proposed FIA-ESI-ITMS/MS procedure is well-suited for the determination of CrPic3 in such products.

Mass spectrometry-based identification of bacteria isolated from industrially contaminated site in Salamanca (Mexico) and evaluation of their potential for DDT degradation.

Longstanding industrial deposits of 1-chloro-4-[2,2,2-trichloro-1-(4-chlorophenyl)ethyl]benzene (DDT) impose environmental threat in Salamanca city, located in central Mexico. Native bacteria from this location were isolated and identified, and their potential utility for DDT biodegradation was examined. Twenty-five isolates were obtained, and cell lysates were analyzed by matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF MS) with BiotyperTR; twenty-one organisms were identified at species level, and the other four were assigned to genus. The most abundant species corresponded to Bacillus (44%) and Pseudomonas genera (20%). Eight bacteria could grow in the presence of 200 mg/L of DDT. Two-week exposure of Lysinibacillus fusiformis, Bacillus mycoides, Bacillus pumilus, and Bacillus cereus to DDT 50 mg/L and 200 mg/L, caused percentage pesticide degradation in the range 41-48% and 26-31%, respectively. Other four bacteria presented lower degradation rates. Gas chromatography-mass spectrometry (GC-MS) analysis of the spent media revealed that eight isolates assisted the conversion of DDT, DDD (1,1-dichloro-2,2-bis-(4-chlorophenyl)ethane), and DDE (1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene) to DDMU (1,1-(2-chloro-1,1-ethenediyl)-bis-(4-chlorobenzene)); however, DDNU (2,2-bis(4-chlorophenyl)ethylene), DBP (4,4'-dichlorobenzophenone(bis(4-chlorophenyl)methanone)) and DBH (bis(4-chlorophenyl)methanol) were found only for L. fusiformis, B. mycoides, B. cereus, B. marisflavi, and B. megaterium. Within the context of DDT biodegradation, the first three were the most promising isolates and further studies will be aimed at setting the experimental conditions for efficient mineralization of DDT congeners.

Impact of Cr(VI) on the oxidation of polyunsaturated fatty acids in Helianthus annuus roots studied by metabolomic tools.

The impact of Cr(VI) in sunflower roots has been studied, focusing on the oxidation of polyunsaturated fatty acids. Plants were grown hydroponically in the presence of 0, 1.0, 5.0 and 25 mgCr L-1. Methanolic root extracts were analyzed by capillary liquid chromatography coupled through negative electrospray ionization to a quadrupole-time of flight mass spectrometry (capHPLC-ESI-QTOF-MS). Using partial least squares algorithm, eighteen features strongly affected by Cr(VI) were detected and annotated as linoleic acid (LA), alpha-linolenic acid (ALA) and sixteen oxidation products containing hydroperoxy-, epoxy-, keto-, epoxyketo- or hydroxy-functionalities, all of them classified as oxylipins. Inspection of the MS/MS spectra acquired for features eluting at different retention times but assigned as a sole compound, confirmed isomers formation: three hydroperoxy-octadecadienoic acids (HpODE), two oxo-octadecadienoic acids (OxoODE) and four epoxyketo-octadecenoic acids (EKODE). Around 70% of metabolites in sunflower LA metabolic pathway were affected by Cr(VI) stress and additionally, four EKODE isomers not included in this pathway were found in the exposed roots. Among ALA-derived oxylipins, 13-epi-12-oxo-phytodienoic acid (OPDA) is of relevance, because of its participation in the activation of secondary metabolism. The abundances of all oxylipins were directly dependent on the Cr(VI) concentration in medium; furthermore, autooxidation of LA to HpODE isomers was observed after incubation with Cr(VI). These results point to the direct involvement of Cr(VI) in non-enzymatic oxidation of fatty acids; since oxylipins are signaling molecules important in plant defensive response, their synthesis under Cr(VI) exposure sustains the ability of sunflower to grow in Cr(VI)-contaminated environments.

Changes of Metabolomic Profile in Helianthus annuus under Exposure to Chromium(VI) Studied by capHPLC-ESI-QTOF-MS and MS/MS.

The application of capHPLC-ESI-QTOF-MS and MS/MS to study the impact of Cr(VI) on metabolites profile in Helianthus annuus is reported. Germinated seeds were grown hydroponically in the presence of Cr(VI) (25 mgCr/L) and root extracts of the exposed and control plants were analyzed by untargeted metabolomic approach. The main goal was to detect which metabolite groups were mostly affected by Cr(VI) stress; two data analysis tools (ProfileAnalysis, Bruker, and online XCMS) were used under criteria of intensity threshold 5 · 104 cps, fold change ≥ 5, and p ≤ 0.01, yielding precursor ions. Molecular formulas were assigned based on data processing with two computational tools (SIRIUS and MS-Finder); annotation of candidate structures was performed by database search using CSI:FingerID and MS-Finder. Even though ultimate identification has not been achieved, it was demonstrated that secondary metabolism became activated under Cr(VI) stress. Among 42 candidate compounds returned from database search for seven molecular formulas, ten structures corresponded to isocoumarin derivatives and eleven were sesquiterpenes or sesquiterpene lactones; three benzofurans and four glycoside or pyrane derivatives of phenolic compounds were also suggested. To gain further insight on the effect of Cr(VI) in sunflower, isocoumarins and sesquiterpenes were selected as the target compounds for future study.