Polybrominated diphenyl ethers and organochloride pesticides in the organic matter of air suspended particles in Mexico valley: A diagnostic to evaluate public policies.

The presence of organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs) was analysed in air particulate matter ≤ 2.5 µm (PM2.5) and ≤10 µm (PM10) collected in the Metropolitan Zone of Mexico Valley (MZMV), during 2013 and 2014, respectively. Spatial and seasonal distributions of PM and their organic content named solvent extracted organic matter (SEOM) were determined. PM mass concentration and SEOM/PM ratios were compared with previous studies in 2006 in Mexico City. PM2.5 concentration was like found in 2006, however, PM10 decreased ∼43%. The SEOM/PM10 ratio was kept constant, suggesting a decrease in SEOM as well as PM10 emitted from natural sources, probably as a result of changes in the land use due to urban growth. A decrease ∼50% SEOM/PM2.5 ratio was observed in the same period, linked to adequate strategies and public policies applied by the local and federal governments to control the organic matter emitted from anthropogenic sources. Seven out of sixteen OCPs and five out of six PBDEs were found. The most common POPs were endosulfan I, endosulfan II, endosulfan sulfate, BDE-47 and BDE-99, present on >90% of the sampling days. OCPs in PM2.5 and PBDEs in PM10 showed seasonal variability. Higher PBDEs concentration in both particle sizes were observed at east and southeast of the MZMV, where one of the biggest landfills and wastewater treatment plants are located. OCPs in PM10 were mainly emitted from agricultural areas located to the southwest, southeast and east of the MZMV. OCPs in PM2.5 showed a regional contribution from the north and introduced into the valley. OCP degradation products were dominant over native OCPs, indicating no fresh OCP use. POPs comparison with other cities was made. Agreements and commissions created by the Mexican government reduced OCPs emissions, however, more effort must be made to control PBDE emission sources.

An innovative ultrasound assisted extraction micro-scale cell combined with gas chromatography/mass spectrometry in negative chemical ionization to determine persistent organic pollutants in air particulate matter.

New clean technologies are needed to determine concentration of organic pollutants without generating more pollution. A method to extract Persistent Organic Pollutants (POPs) from airborne particulate matter was developed using a novel technology recently patented called ultrasound assisted extraction micro-scale cell (UAE-MSC). This technology extracts, filters, collects the sample, and evaporates the solvent, on-line. No sample transfer is needed. The cell minimizes sample manipulation, solvent consumption, waste generation, time, and energy; fulfilling most of the analytical green chemistry protocol. The methodology was optimized applying a centred 23 factorial experimental design. Optimum conditions were used to validate and determine concentration of 16 organochlorine pesticides (OCls) and 6 polybrominated diphenyl ethers (PBDEs). The best conditions achieved were 2 extractions with 5mL (each) of dichloromethane over 5min (each) at 60°C and 80% ultrasound potency. POPs were determined by gas chromatography/mass spectrometry in negative chemical ionization (GC/MS-NCI). Analytical method validation was carried out on airborne particles spiked with POPs at seven concentration levels between 0.5 and 26.9pgm-3. This procedure was done by triplicate (N=21). Recovery, ranged between 65.5±2.3% and 107.5±3.0% for OCls and between 79.1±6.5% and 105.2±3.8% for PBDEs. Linearity (r2) was ≥0.94 for all compounds. Method detection limits, ranged from 0.5 to 2.7pgm-3, while limits of quantification (LOQ), ranged from 1.7 to 9.0pgm-3. A Bias from -18.6% to 9% for PBDEs was observed in the Standard Reference Material (SRM) 2787. SRM 2787 did not contain OCls. OCls recoveries were equivalent by UAE-MSC and Soxhlet methods UAE-MSC optimized extraction conditions reduced 30 times less solvent and decreased the extraction time from several hours to ten minutes, respect to Soxhlet. UAE-MSC was applied to 15 samples of particles less than 2.5µm (PM2.5) from three seasons (warm dry, rainy, and cold dry) collected in five sites around Mexico City. OCls (4,4'-DDE and endrin aldehyde) concentrations ranged from

Temporal variation of nitro-polycyclic aromatic hydrocarbons in PM10 and PM2.5 collected in Northern Mexico City.

With the aim to determine the presence of individual nitro-PAH contained in particles in the atmosphere of Mexico City, a monitoring campaign for particulate matter (PM(10) and PM(2.5)) was carried out in Northern Mexico City, from April 2006 to February 2007. The PM(10) annual median concentration was 65.2µgm(-3) associated to 7.6µgm(-3) of solvent-extractable organic matter (SEOM) corresponding to 11.4% of the PM(10) concentration and 38.6µgm(-3) with 5.9µgm(-3) SEOM corresponding to 15.2% for PM(2.5). PM concentration and SEOM varied with the season and the particle size. The quantification of nitro-polycyclic aromatic hydrocarbons (nitro-PAH) was developed through the standards addition method under two schemes: reference standard with and without matrix, the former giving the best results. The recovery percentages varied with the extraction method within the 52 to 97% range depending on each nitro-PAH. The determination of the latter was effected with and without sample purification, also termed fractioning, giving similar results. 8 nitro-PAH were quantified, and their sum ranged from 111 to 819pgm(-3) for PM(10) and from 58 to 383pgm(-3) for PM(2.5), depending on the season. The greatest concentration was for 9-Nitroanthracene in PM(10) and PM(2.5), detected during the cold-dry season, with a median (10th-90th percentiles) concentration in 235pgm(-3) (66-449pgm(-3)) for PM(10) and 73pgm(-3) (18-117pgm(-3)) for PM(2.5). The correlation among mass concentrations of the nitro-PAH and criteria pollutants was statistically significant for some nitro-PAH with PM(10), SEOM in PM(10), SEOM in PM(2.5), NO(X), NO(2) and CO, suggesting either sources, primary or secondary origin. The measured concentrations of nitro-PAH were higher than those reported in other countries, but lower than those from Chinese cities. Knowledge of nitro-PAH atmospheric concentrations can aid during the surveillance of diseases (cardiovascular and cancer risk) associated with these exposures.

Cell proliferation kinetics and genotoxicity in lymphocytes of smokers living in Mexico City.

Genotoxicity caused by tobacco smoke was assessed in peripheral blood lymphocytes of smokers living in Mexico City by determining sister chromatid exchange (SCE), cell proliferation kinetics (CPK), replication index (RI) and mitotic index (MI). Nicotine levels, and its major metabolite cotinine, were also estimated in urine samples using gas-chromatography-mass spectrometry to quantify smoking intensity. The outcome of the analysis and the comparison of the 77-smoker group with a non-smoking control group showed that moderate and heavy smokers exhibited significant differences (P < 0.001 and P < 0.05, respectively) in CPK, with an underlying delay in the cellular cycle; similarly, RI was significantly different in these groups (P < 0.001 and P < 0.0001, respectively). There were significant correlations (P < 0.05) between age and number of years the subject had been smoking, as well as between RI and nicotine and cotinine levels and between CPK (M1, M2 and M3) and nicotine and cotinine levels. Smokers were classified for the analysis according to the nicotine levels (it is in relation to number of cigarettes smoked per day) found in urine (ng/mL) as: light (10-250), moderate (251-850) and heavy (851-4110). Significant differences in CPK were found (P < 0.05) between moderate and heavy smokers and non-smokers. Significant differences in RI were found between moderate (P < 0.001) and heavy smokers (P < 0.0001) and non-smokers, but not for the light smoking group. MI was determined in 57 of the smokers, whereas SCE frequency was only recorded in 34 smokers. Both parameters yielded no significant differences, nor correlations with any of the assessed variables. In conclusion, cytokinetic and cytostatic effects were mainly detected in heavy and moderate smokers. Cell cycle delay and RI decrease were found in all ;healthy' smokers. The nicotine and cotinine exposure (causing oxidative damage to DNA) may have implications in the decrease in cell replication due to direct damage to DNA and/or a decrease in the DNA repair mechanisms. Alternatively, nicotine and cotinine may possibly induce apoptosis.

Persistent organochlorine pesticides in Mexican butter.

Organochlorine pesticides have been used in Mexico in malaria control programmes against ectoparasites and as seed dresser. Owing to their chemical stability, they tend to accumulate in the lipid part of the organisms. The stored pesticides are excreted with the endogenous fat during milk production. The aim was to monitor the organochlorine pesticide levels in butter manufactured in Mexico. From the pesticides, only HCB, beta-HCH, pp'-DDT, op'-DDT and pp'-DDE with major frequency and levels were detected. The HCB mean level was low at 0.008 mg kg(-1) on a fat basis. From the HCH isomer, only the beta-HCH at 0.065 mg kg(-1) on a fat basis was determined, remaining as the main contaminant of the monitored butters. Among DDTs, pp'-DDE was the major constituent (0.043 mg kg(-1) on a fat basis) followed by pp'-DDT (0.036 mg kg(-1)) and op'-DDT (0.009 mg kg(-1)). Comparing the previous study (1994) and this one (2001), all organochlorine pesticides had a descendent tendency; beta-HCH decreased from 0.095 to 0.065 mg kg(-1) on a fat basis, whereas the total DDT decreased from 0.056 to 0.047 mg kg(-1), pp'-DDT from 0.050 to 0.036 mg kg(-1), op'-DDT from 0.018 to 0.009 mg kg(-1), while pp'-DDE increased from 0.032 to 0.043 mg kg(-1). The decreased DDT levels in Mexican butters is caused by the substitution of organochlorine insecticides with pyrethroids used by the Mexican Ministry of Health since 1999 in sanitary programmes.

Cytogenetic biomonitoring in a Mexican floriculture worker group exposed to pesticides.

The cytogenetic damage in floriculturists of Morelos State, Mexico, exposed to pesticides, was evaluated by mean of biological tests based on sister chromatid exchanges (SCE) in lymphocytes of peripheral blood and micronuclei (MN) in exfoliated cells of the buccal mucosa. Besides the cytogenetic analysis, the effects of pesticides exposure on the cell proliferation kinetics (CPK) by the replication index (RI) were also studied. The mitotic index (MI) to detect cytotoxic effects was also determined. Greenhouses of the towns of Santa Catarina, Jiutepec and Yecapixtla were selected for the study, because the application of chemicals to the flowers is uncontrolled. As non-exposed group, people of the town of Temisco were chosen; their activity was not related to pesticides. The SCE were analyzed in the peripheral blood of 30 persons, 22 women and 8 men, with 10 and 1.5 years of exposure to pesticides, respectively, and of 30 persons, 28 women and 2 men, that were considered as the non-exposed group. Samples of buccal mucosa were also taken from each person. Significant differences between exposed and non-exposed groups were found in SCE, CKP and MI. Besides, the MN frequencies in the exposed group were three times higher than in the non-exposed group.

Sister-chromatid exchange analysis in a rural population of Mexico exposed to pesticides.

Cytogenetic damage was evaluated by means of the analysis of sister-chromatid exchange (SCE) in a rural population of Tlaxcala, Mexico, in occupational contact with pesticides. We studied 170 men, 94 exposed and 76 not exposed. It was shown that SCE followed a normal distribution and Student's t test did not present differences between the two groups (P = 0.4). The frequency of SCE was not correlated with the duration of exposure of the rural workers (r = -0.06), the multiple covariance analysis applied to the data of duration of exposure, tobacco intake and alcohol ingestion demonstrated a lack of statistical significance. In the exposed people we observed no symptoms provoked by these compounds.

Cytogenetic effects of cadmium accumulation on water hyacinth (Eichhornia crassipes).

Cadmium was bioassayed to observe cytogenetic effects in the water hyacinth (Eichhornia crassipes). Plants were exposed for 96 hr to freshwater containing 0.01, 0.05, 0.10, 1.5, and 10 mg/liter of cadmium. Metal concentrations in tissues were determined by atomic absorption spectrophotometry. The highest level was found in roots, thus root-tip cells were used for cytogenetic studies; after 24 hr of exposure, micronuclei, c-mitotic effects, and pycnosis were detected and after 48 hr polyploidy was observed. A linear relationship between frequencies of micronuclei and cadmium concentrations was found: at 1.5, and 10 mg/liter micronuclei numbers were always the lowest. The inhibition of cell proliferation. shown by the low mitotic index, was proportional to the concentration and time of exposure. From the results presented in this paper it may be concluded that water hyacinth is a good sensor, due to its fast rate of metal accumulation, which allows an easy way to determine the presence of potential mutagenic compounds in water.