Dual-Element Isotope Analysis of Desphenylchloridazon to Investigate Its Environmental Fate in a Systematic Field Study: A Long-Term Lysimeter Experiment.

Desphenylchloridazon (DPC), the main metabolite of the herbicide chloridazon (CLZ), is more water soluble and persistent than CLZ and frequently detected in water bodies. When assessing DPC transformation in the environment, results can be nonconclusive if based on concentration analysis alone because estimates may be confounded by simultaneous DPC formation from CLZ. This study investigated the fate of DPC by combining concentration-based methods with compound-specific C and N stable isotope analysis (CSIA). Additionally, DPC formation and transformation processes were experimentally deconvolved in a dedicated lysimeter study considering three scenarios. First, surface application of DPC enabled studying its degradation in the absence of CLZ. Here, CSIA provided evidence of two distinct DPC transformation processes: one shows significant changes only in 13C/12C, whereas the other involves changes in both 13C/12C and 15N/14N isotope ratios. Second, surface application of CLZ mimicked a realistic field scenario, showing that during DPC formation, 13C/12C ratios of DPC were depleted in 13C relative to CLZ, while 15N/14N ratios remained constant. Finally, CLZ depth injection simulated preferential flow and demonstrated the importance of the topsoil for retaining DPC. The combination of the lysimeter study with CSIA enabled insights into DPC transformation in the field that are superior to those of studies of concentration trends.

Sensitive and selective quantification of free and total malondialdehyde in plasma using UHPLC-HRMS.

Quantification of malondialdehyde (MDA) as a marker of lipid peroxidation is relevant for many research fields. We describe a new sensitive and selective method to measure free and total plasmatic MDA using derivatization with 2,4-dinitrophenylhydrazine (DNPH) and ultra-HPLC-high-resolution MS. Free and total MDA were extracted from minute sample amounts (10 µl) using acidic precipitation and alkaline hydrolysis followed by acidic precipitation, respectively. Derivatization was completed within 10 min at room temperature, and the excess DNPH discarded by liquid-liquid extraction. Quantification was achieved by internal standardization using dideuterated MDA as internal standard. The method's lowest limit of quantification was 100 nM and linearity spanned greater than three orders of magnitude. Intra- and inter-day precisions for total MDA were 2.9% and 3.0%, respectively, and those for free MDA were 12.8% and 24.9%, respectively. Accuracy was 101% and 107% at low and high concentrations, respectively. In human plasma, free MDA levels were 120 nM (SD 36.26) and total MDA levels were 6.7 µM (SD 0.46). In addition, we show the applicability of this method to measure MDA plasma levels from a variety of animal species, making it invaluable to scientists in various fields.

Development and Validation of an Ultra-Sensitive UHPLC-MS/MS Method for Neonicotinoid Analysis in Milk.

A very sensitive ultrahigh performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method was developed and validated for the quantitation of the most common neonicotinoids (thiamethoxam, clothianidin, imidacloprid, acetamiprid, and thiacloprid) at trace levels in milk. Using fast and selective liquid-liquid extraction (LLE) starting from 0.5 mL of milk, lowest limits of quantitation (LLOQ) equal or lower than 10 pg/mL for all analytes were achieved. Precision and accuracy were evaluated at four different concentrations (5, 10, 500, and 10000 pg/mL) and ranged between 2 and 16% (RSD) and 77-125%, respectively. Extraction recoveries and matrix effects ranged between 64 and 76% and 88-98%, respectively. The method was applied to measure neonicotinoid levels in a series of conventional and organic Swiss milks as well as in human breast milk and commercial powdered milk. More than 90% of the samples tested positive for at least one neonicotinoid. However, all animal samples were far below the maximum residue limits authorized for human consumption with average total neonicotinoid levels of 16.1 ± 13.1 pg/mL. Human breast milks and powdered milks contained similar amounts of neonicotinoids. Taken together, our results demonstrate the high prevalence of neonicotinoids in milk from all origins, albeit at levels considered to be safe for human consumption.