Prenatal Exposure to Tobacco and Cannabis in Six Race/Ethnicity Groups during the First Three Years after Legalization of Cannabis for Recreational Use in California.

There are known health concerns linked to prenatal tobacco and cannabis exposures. This study aims to objectively determine the level of exposure to tobacco and cannabis in pregnant individuals from six race/ethnicity groups (Black, Hispanic, Asian Indian, Native American, Vietnamese, and White) in the first three years following legalization of recreational marijuana use in 2018 in California. We used a cross-sectional sample of prenatal screening program participants (2018-2020) from southern and central California (N = 925). Exposures were estimated by a lab analysis of cotinine (tobacco) and 11-hydroxy-Δ9-tetrahydrocannabinol (OH-THC, cannabis) in banked serum. Disparities in tobacco exposure were evident, with Black subjects experiencing the highest smoking rate (16%) followed by Native American (10%) and White (8%) subjects, and ≤2% among Hispanic, Asian Indian, and Vietnamese subjects. Environmental tobacco exposure generally showed a similar pattern of exposure to tobacco smoking across race/ethnicity groups. Cannabis detection ranged from 5% among Hispanic subjects to 12% and 13% among White and Black subjects, respectively, and was higher among tobacco users and those exposed to environmental tobacco smoke than those with no cotinine detected. Tobacco and cannabis exposure were generally greatest in younger subjects and those with indices of a lower economic status; however, among Black subjects, cannabis exposure was greatest in older subjects and those with a higher socioeconomic status. Race/ethnicity, age, and socioeconomic factors can inform targeting of high-exposure groups for intervention.

The association of in utero tobacco smoke exposure, quantified by serum cotinine, and Autism Spectrum Disorder.

Previous studies on in utero exposure to maternal environmental tobacco smoke (ETS) or maternal active smoking and Autism Spectrum Disorder (ASD) have not been entirely consistent, and no studies have examined in utero cotinine concentrations as an exposure classification method. We measured cotinine in stored second trimester maternal serum for 498 ASD cases and 499 controls born in California in 2011-2012. We also obtained self-reported maternal cigarette smoking during and immediately prior to pregnancy, as well as covariate data, from birth records. Using unconditional logistic regression, we found no association between log10 cotinine concentrations and odds for developing ASD among children of non-smokers (aOR: 0.93 [95% CI: 0.69, 1.25] per ng/ml), which represents exposure to ETS, though there may be a possible interaction with race. We found no association between cotinine-defined smoking (≥3.08 ng/ml vs. <3.08 ng/ml) (adjusted odds ratio [aOR]: 0.73 (95% confidence interval [95% CI]: 0.35, 1.54)) or self-reported smoking (aOR: 1.64 [95% CI: 0.65, 4.16]) and ASD. In one of the few studies of ETS and the first with measured cotinine, our results indicate no overall relationship between in utero exposure to tobacco smoke from maternal ETS exposure or active smoking, and development of ASD. LAY SUMMARY: This study found that women who smoke or are exposed to tobacco smoke during pregnancy are not more likely to have children with Autism Spectrum Disorder (ASD). This is the first ASD study to measure a chemical in the mother's blood during pregnancy to identify exposure to tobacco smoke.

Matrix effects in analysis of dialkyl phosphate metabolites of organophosphate pesticides in urine by gas chromatography/tandem mass spectrometer.

Urinary dialkyl phosphate metabolites (DAPs) are used as biomarkers to evaluate human exposure to organophosphate pesticides. The objective was to evaluate potential artifacts in urinary DAPs analysis during sample preparation and method calibration. Diluted urine pools were commonly used to prepare calibration standards to minimize the effects due to the complexity of urine matrix. Matrix effects on measurements of DAPs were evaluated by spiking known amount of standards into distilled water, synthetic urine and diluted urine pool. Different matrices resulted in similar concentrations detected for all target compounds, except dimethylphosphate (DMP) with the deviation of measurement as large as eight times the spiked amount. In this study, we also found that urinary particles, which usually appeared after thawing frozen human urine samples, could affect the measurements of DAPs, especially DMP and diethylthiophosphate (DETP). Results of DAPs measurements in three types of sample matrices, i.e. urine without particles, urine with particles and particles only were compared. DETP could be subject to large error during this preparation step. The use of deuterated and (13)C(12)-labeled DAPs as internal standards is also evaluated. Overall, these issues can cause misidentification and inaccuracies, which may significantly affect the data quality.

Direct determination of dialkyl phosphates by strong anion-exchange liquid chromatography/atmospheric pressure chemical ionization mass spectrometry using a quadrupole ion trap instrument.

The direct determination of dialkyl phosphates (DAPs) in water by strong anion-exchange (SAX) liquid chromatography/atmospheric pressure chemical ionization (APCI) mass spectrometry was investigated. The SAX high-performance liquid chromatography (HPLC) column was eluted with methanol/water gradients containing ammonium formate (AF) separating the DAPs which included six dimethyl- and diethyl-substituted phosphates, thiophosphates, and dithiophosphates. The high buffer concentrations required for separation were compatible with -ve APCI, but in +ve APCI the DAPs were unstable giving anomalous ions such as [M+15]+ and [M+29]+. These ions are believed to result from ion molecule reactions with CH3OH2+ in the plasma. DAPs are very stable in -ve APCI being detected as abundant [M-H](-) ions, even with 200 mM AF. At higher AF concentration formate clusters ([M+45](-) and [M+91](-)) were seen. Fragmentation by collision-activated dissociation (CAD) was more efficient for deprotonated ethyl-substituted DAPs which lost ethylene followed by ethanol. APCI instrument detection limits were in the low ng/mL range and the response was highly linear. Isotope dilution quantitation using d10-diethyl dithiophosphate (DEDTP) as an internal standard produced an instrument detection limit of 2 ng DEDTP/mL and method detection limit (MDL) of 9.3 ng/mL with accuracy of 99% (spike concentration, 25 ng/mL). DAP mixtures required storage in cold, dry conditions and alcohol solvents should be avoided because of solvolysis reactions.

Atmospheric pressure ionization LC-MS-MS determination of urushiol congeners.

This paper describes atmospheric pressure ionization (API) LC-MS-MS determination of urushiols, 3-n-alkenyl- and -alkyl-substituted catechols responsible for poison oak dermatitis. Urushiol was isolated from Western poison oak according to the method of Elsohly et al. (1) (J. Nat. Prod. 1982, 45, 532-538)-the purified preparation contained C(17)- and C(15)-substituted urushiols with zero, one, two, and three double bonds as determined from GC-MS analysis of trimethylsilyl derivatives. Urushiol mixtures were separated on a C(18) reversed phase HPLC column with a methanol-water gradient with urushiols eluting in 100% methanol. Atmospheric pressure chemical ionization (APCI) produced primarily [M - H](-) and MH(+) molecule ions. Electrospray ionization (ESI) yielded [M - H](-) and adduct ions including [M + Cl](-). Daughter ions of [M - H](-) included quinoid radical anions ([M - H - H(2)](-) and m/z 122(-)) and a benzofuran phenate (m/z 135(-)). A suite of hydrocarbon fragments were produced by collision-induced dissociation of MH(+) directly or via an intermediate [MH - H(2)O](+) daughter ion. Six urushiol congeners, one not previously reported in poison oak, were determined by negative ion API-LC-MS-MS with detection limits of approximately 8 pg/microL (ESI) and approximately 800 pg/microL (APCI). API-LC-MS-MS was used to determine urushiol in surface wipes, air samples, and plant materials.