Phthalates are known endocrine disruptors and associated with decreased fecundity, pregnancy loss, and adverse obstetrical outcomes, however the underlying mechanisms remain to be established. ...Environmental factors can influence gene expression and cell function by modifying epigenetic marks, impacting the developing embryo as well as future generations of offspring. The impact of phthalates on placental gene methylation and expression is largely unknown. We studied the effect of maternal phthalate exposure on the human placental DNA methylome and transcriptome. We determined epigenome-wide DNA methylation marks (Illumina Infinium Human Methylation 850k BeadChip) and gene expression (Agilent whole human genome array) associated with phthalate exposure in first trimester placenta. Integrative genomic analysis of candidate genes was performed to define gene methylation-expression relationships. We identified 39 genes with significantly altered methylation and gene expression in the high phthalate exposure group. Most of these relationships were inversely correlated. This analysis identified epidermal growth factor receptor (EGFR) as a critical candidate gene mediating the effects of phthalates on early placental function. Although additional studies are needed to determine the functional consequences of these changes, our findings are consistent with the model that phthalates impact placental function by modulating the expression of critical placental genes through epigenetic regulation.
Endocrine disruptors like thiocyanate are some of the principal causes of chronic disorders worldwide. Prenatal and postnatal exposure to thiocyanate can interfere with normal neurological ...development in both fetuses and newborns. Currently, little information regarding thiocyanate levels and potential sources of exposure is available. In this study, we evaluated thiocyanate uptake and accumulation in chard and spinach grown under greenhouse conditions. Both chard and spinach are commonly used to produce baby foods. Three thiocyanate concentrations were compared: Control, T1 (30 ng mL−1), and T2 (70 ng mL−1). Thiocyanate accumulation depended on the concentration and exposure time. Chard was found to accumulate more thiocyanate than spinach, with leaf accumulation > stem accumulation (p < 0.0194) and maximum concentrations of 76 ng g−1 (control), 112 ng g−1, (T1), and 134 ng g−1 (T2). The estimated daily intake (EDI) of thiocyanate for chard and spinach (fresh) exceeded the subchronic reference dose of 200 ng−1 kg−1 day−1 and the chronic reference dose of 600 ng−1 kg−1 day−1. In addition, the EDI of thiocyanate for spinach in baby food exceeded twice the chronic reference dose in the vulnerable newborn–1 year age group. However, all EDIs were lower than the lowest observed adverse effect level (LOAEL) of 1.9 × 105 ng kg−1 day−1. Further studies are needed that increase our knowledge of thiocyanate levels and potential environmental sources to reduce opportunities for exposure, especially in vulnerable groups.
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•We evaluated thiocyanate capture and accumulation in chard and spinach.•Thiocyanate accumulation depended on the treatment and culture time.•Chard accumulates more thiocyanate than spinach (T2 > T1): leaves > total aerial fraction•EDI values (0–12 months) for spinach exceeded chronic and subchronic reference doses.
•The uptake and accumulation of perchlorate in spinach and chard under greenhouse conditions were studied.•Spinach accumulates more perchlorate than chard (T2 ˃ T1): ...leaves ˃ shoots ˃ stems ˃ roots.•Chard accumulates half the amount of perchlorate in the shoot than spinach.•The intake of spinach or chard (T2 > T1) represents a significant risk to human health, especially at 1–3 years old.
Very little information is available with regards to the bioavailability of perchlorate in spinach or chard used in the production of baby foods commodities. In the present study, the uptake and accumulation of perchlorate were compared under two different treatments (T1: 1 and T2: 10 mg L−1 ClO4−). Our results indicate that spinach has a higher capacity to accumulate perchlorate than chard (p < 0.0185). Concentrations of perchlorate in leaves, stems and roots (leaves > stem > roots) all gradually increased (p < 0.0001) as vegetable growing and treatment (T2 > T1). No significant differences were found between the control and T1. The daily intake for perchlorate (control) is below the proposed international standard, however, it was exceeded in T1 and T2. The results suggested that perchlorate is actively accumulate in high concentrations in vegetables used in the production of baby food commodities and the exposure of perchlorate via the food consumption (baby foods) was evaluated as not safe.
Rapid detection and identification of chemical warfare agents and related precursors/degradation products in various environmental matrices is of paramount importance for verification of standards ...set by the chemical weapons convention (CWC). Nitrogen mustards, N,N-dialkylaminoethyl-2-chlorides, N,N-dialkylaminoethanols, N-alkyldiethanolamines, and triethanolamine, which are listed CWC scheduled chemicals, are prone to undergo N-oxidation in environmental matrices or during decontamination process. Thus, screening of the oxidized products of these compounds is also an important task in the verification process because the presence of these products reveals alleged use of nitrogen mustards or precursors of VX compounds. The N-oxides of aminoethanols and aminoethylchlorides easily produce M + H
+
ions under electrospray ionization conditions, and their collision-induced dissociation spectra include a specific neutral loss of 48 u (OH + CH
2
OH) and 66 u (OH + CH
2
Cl), respectively. Based on this specific fragmentation, a rapid screening method was developed for screening of the N-oxides by applying neutral loss scan technique. The method was validated and the applicability of the method was demonstrated by analyzing positive and negative samples. The method was useful in the detection of N-oxides of aminoethanols and aminoethylchlorides in environmental matrices at trace levels (LOD, up to 500 ppb), even in the presence of complex masking agents, without the use of time-consuming sample preparation methods and chromatographic steps. This method is advantageous for the off-site verification program and also for participation in official proficiency tests conducted by the Organization for the Prohibition of Chemical Weapons (OPCW), the Netherlands. The structure of N-oxides can be confirmed by the MS/MS experiments on the detected peaks. A liquid chromatography-mass spectrometry (LC-MS) method was developed for the separation of isomeric N-oxides of aminoethanols and aminoethylchlorides using a C18 Hilic column. Critical isomeric compounds can be confirmed by LC-MS/MS experiments, after detecting the N-oxides from the neutral loss scanning method.
Figure
Rapid screening of N-oxides of aminoethanols and aminoethylchlorides by neutral loss scan method
Most of the precursors and/or degradation products related to the Chemical Weapons Convention (CWC) are polar. Identification of these molecules in environmental samples provides clues regarding the ...alleged usage and/or synthesis of the parent toxic chemicals. Such polar compounds need to be derivatized in order to analyze them by gas chromatography–mass spectrometry (GC–MS). In this study, we developed a new derivatizing reagent,
para
-tolyl isocyanate (PTI), for derivatization of polar CWC-related compounds. The PTI reagent selectively derivatizes the –OH and/or−SH functional groups with high efficiency, but does not react with carboxylic acid (−COOH) or phosphonic acid (−(O)P(OH)
2
) groups. The PTI derivatives of dialkyl aminoethanols, dialkyl aminoethanol-
N
-oxides, and 3-quinuclidinol were successfully eluted through GC, and their electron ionization (EI) mass spectra were distinct and provided the structure information by which the isomeric compounds can be easily distinguished. We also calculated the GC-retention index values that can be used for further confirmation of the target compounds. All the studied PTI derivatives can be analyzed by EI-MS with direct insertion probe and/or by direct electrospray ionization mass spectrometry (ESI-MS) together with the MS–MS data; both sets of data provide full structure information. The PTI reagent was found to be better in some respects than the conventional bistrimethylsilyl trifluoroacetamide (BSTFA), a trimethyl silylating reagent. The PTI reagent is commercially available, and the PTI derivatives are highly stable for months and are not sensitive to moisture. The applicability of the PTI derivatization for trace-level determination of the target CWC-related polar compounds in environmental matrices and in human plasma samples is also evaluated.
Fig. a
ᅟ
Sulfur mustards are a class of vesicant chemical warfare agents that rapidly degrade in environmental samples. The most feasible degradation products of sulfur mustards are chloroethyl vinylic ...compounds and divinylic compounds, which are formed by the elimination of one and two HCl molecules from sulfur mustards, respectively. The detection and characterization of these degradation products in environmental samples are an important proof for the verification of sulfur mustard usage. In this study, we synthesized a set of sulfur mustard degradation products, i.e., divinylic compounds (1–7) and chloroethyl vinylic compounds (8–14), and characterized using gas chromatography/mass spectrometry (GC/MS) under electron ionization (EI) and chemical ionization (CI) (methane) conditions. The EI mass spectra of the studied compounds mainly included the fragment ions that resulted from homolytic cleavages with or without hydrogen migrations. The divinylic compounds (1–7) showed M – SH+ ions, whereas the chloroethylvinyl compounds (8–14) showed M – Cl+ and M – CH2CH2Cl+ ions. Methane/CI mass spectra showed M + H+ ions and provided molecular weight information. The GC retention index (RI) values were also calculated for the studied compounds. The EI and CI mass spectral data together with RI values are extremely useful for off-site analysis for the verification of the chemical weapons convention and also to participate in official Organization for the Prohibition of Chemical Weapons proficiency tests.
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