Simultaneous detection of perchlorate and bromate using rapid high-performance ion exchange chromatography-tandem mass spectrometry and perchlorate removal in drinking water.

Perchlorate and bromate occurrence in drinking water causes health concerns due to their effects on thyroid function and carcinogenicity, respectively. The purpose of this study was threefold: (1) to advance a sensitive method for simultaneous rapid detection of perchlorate and bromate in drinking water system, (2) to systematically study the occurrence of these two contaminants in Missouri drinking water treatment systems, and (3) to examine effective sorbents for minimizing perchlorate in drinking water. A rapid high-performance ion exchange chromatography-tandem mass spectrometry (HPIC-MS/MS) method was advanced for simultaneous detection of perchlorate and bromate in drinking water. The HPIC-MS/MS method was rapid, required no preconcentration of the water samples, and had detection limits for perchlorate and bromate of 0.04 and 0.01 µg/L, respectively. The method was applied to determine perchlorate and bromate concentrations in total of 23 selected Missouri drinking water treatment systems during differing seasons. The water systems selected include different source waters: groundwater, lake water, river water, and groundwater influenced by surface water. The concentrations of perchlorate and bromate were lower than or near to method detection limits in most of the drinking water samples monitored. The removal of perchlorate by various adsorbents was studied. A cationic organoclay (TC-99) exhibited effective removal of perchlorate from drinking water matrices.

Dermoscopy of black-spot poison ivy.

Black-spot poison ivy is an uncommon presentation of poison ivy (Toxicodendron) allergic contact dermatitis. A 78-year-old sought evaluation of a black spot present on her right hand amid pruritic vesicles. The presentation of a black spot on the skin in a clinical context suggesting poison ivy is indicative of black-spot poison ivy. Dermoscopy revealed a jagged, centrally homogeneous, dark brown lesion with a red rim. A skin sample was obtained and compared against a poison ivy standard using ultra-fast liquid chromatography-tandem mass spectrometry (UFLC-MS/MS). This finding confirmed the presence of multiple urushiol congeners in the skin sample. Black-spot poison ivy may be added to the list of diagnoses that show a specific dermoscopic pattern.

Plant tissue analysis for explosive compounds in phytoremediation and phytoforensics.

Plant tissue analysis methods were evaluated for six explosive compounds to assess uptake and phytoforensic methods development to quantify explosives in plant to obtain the plant data for the evaluation of explosive contamination in soil and groundwater. Four different solvent mixtures containing acetonitrile or methanol were tested at variable extraction ratios to compare the extraction efficiency for six explosive compounds: 2,4,6-trinitrotoluene (TNT), pentaerythritoltetranitrate (PETN), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), 2-amino-4,6-dinitrotoluene (2ADNT), and 2,4-Dinitroanisole (DNAN), in Laurel Willow (Salix pentandra) stem and range grass Big Bluestem (Andropogon gerardii) using LC-MS/MS. Plant tissues were spiked with 500 ng/g of explosives and extracted using ultrasonically-assisted solvent extraction. With the ratio of fresh plant mass to solvent volume of 1:20 for willow and 1:40 for big bluestem grass, results indicated that all explosives in willow except HMX were extracted at higher than 73.3% by using 20 mL of methanol, 50:50 (v/v) methanol:water, or acetonitrile, whereas HMX was extracted with the highest recovery of 61.3% by 20 mL of acetonitrile. In big bluestem grass, the most effective solvents were 20 mL of either methanol or 50:50 (v/v) methanol:water for PETN extraction with a recovery of higher than 101.2% and 20 mL of 50:50 (v/v) methanol:water for HMX, RDX, TNT, 2ADNT, and DNAN extraction with a recovery of 83.8%, 104.4%, 97.5%, 80.7%, and 108.2%, respectively. However, unlike methanol and acetonitrile, 50:50 (v/v) methanol:water provided no problem of leading or split peak in chromatogram; therefore, it was preferred in the test and performed a method validation. Results indicated that 50:50 (v/v) methanol:water provided good repeatability and recovery and method detection limits at 0.5-20 ng/g fresh weight or 8.8-61.3 ng/g dry weight. Overall, results suggested that solvent extraction efficiency of explosives in plant was influenced by plant species and solvent used, and method presented here was believed to provide the preliminary data with respect to the analysis of simultaneous explosives in plants with LC-MS/MS.

Fast separation and quantification method for nitroguanidine and 2,4-dinitroanisole by ultrafast liquid chromatography-tandem mass spectrometry.

Explosives are now persistent environmental pollutants that are targets of remediation and monitoring in a wide array of environmental media. Nitroguanidine (NG) and 2,4-dinitroanisole (DNAN) are two insensitive energetic compounds recently used as munitions explosives. To protect our environment and human health, the levels of these compounds in soils and waters need to be monitored. However, no sensitive analytical methods, such as liquid chromatography-tandem mass spectrometry (LC-MS/MS), have been developed for detecting these new compounds at trace levels and to be concurrently applied to monitor the common explosives. In general, the concentrations of explosives in either soil or water samples are very low and widely distributed. Therefore, a fast and sensitive method is required to monitor those compounds and increase our ability to find and address the threats they pose to human health and ecological receptors. In this study, a fast and sensitive analytical method has been developed to quantitatively determine NG and DNAN in soil, tap water, and river water by using ultrafast LC-MS/MS. To make this method a comprehensive analytical technique for other explosives as well, it has included other commonly used explosives in the method development, such as octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), 1,3,5-trinitroper-hydro-1,3,5-triazine (RDX), 2,4,6-trinitrotoluene (TNT), 2-amino-4,6-dinitrotoluene (ADNT), and pentaerythritol tetranitrate (PETN). The method detection limits (MDLs) of these compounds in soil ranged from 0.2 to 5 ppb, and a good linearity was obtained over a concentration range of 0.5-200 ppb. The recoveries of some compounds are equal to or better than the current EPA methods but with much higher sensitivities.