Ultra-trace level speciated isotope dilution measurement of Cr(VI) using ion chromatography tandem mass spectrometry in environmental waters.

The reliable analysis of highly toxic hexavalent chromium, Cr(VI), at ultra-trace levels remains challenging, given its easy conversion to non-toxic trivalent chromium. This work demonstrates a novel analytical method to quantify Cr(VI) at low ngL(-1) concentration levels in environmental water samples by using speciated isotope dilution (SID) analysis and double-spiking with Cr(III) and Cr(VI) enriched for different isotopes. Ion chromatography tandem mass spectrometry (IC-MS/MS) was used for the analysis of Cr(VI) as HCrO4(-) → CrO3(-). Whereas the classical linear multipoint calibration (MPC) curve approach obtained a method detection limit (MDL) of 7ngL(-1) Cr(VI), the modified SID-MS method adapted from U. S. EPA 6800 allowed for the quantification of Cr(VI) with an MDL of 2ngL(-1) and provided results corrected for Cr(VI) loss occurred after sample collection. The adapted SID-MS approach proved to yield more accurate and precise results than the MPC method, allowed for compensation of Cr(VI) reduction during sample transportation and storage while eliminating the need for frequent external calibration. The developed method is a complementary tool to routinely used inductively-coupled plasma (ICP) MS and circumvents typically experienced interferences.

Lithium an emerging contaminant: bioavailability, effects on protein expression, and homeostasis disruption in short-term exposure of rainbow trout.

Worldwide production of lithium (Li) has increased dramatically during the past decade, driven by the demand for high charge density batteries. Information about Li in the aquatic environment is limited. The present study was designed to explore the effects of Li in rainbow trout (Oncorhynchus mykiss). Juvenile trout were exposed to a nominal concentration of 1.0mg Li/L in three separate exposures. Major ion concentrations were measured in brain and plasma by ion chromatography. Plasma proteins and fatty acids were measured by HPLC-MS/MS. Lithium accumulated in the brain and plasma. Arachidonic acid was elevated in plasma after 48h. Elevated concentrations of Li in brain were associated with depressed concentrations of sodium, magnesium, potassium and ammonium relative to the control. In plasma, sodium and calcium were also depressed. Several changes occurred to plasma proteins corresponding to Li exposure: inhibition of prostaglandin synthase (Ptgs2), increased expression of copper transporting ATP synthases, and Na(+)/K(+) ATPase. To our knowledge, ours is the first study to demonstrate elevated Li concentrations in fish brain, with associated effects on ion regulation.

Twenty-four-hour light exposure and melatonin levels among shift workers.

OBJECTIVES: We sought to measure melatonin levels and 24-hour light intensity exposure in health care workers over a 7-day period in natural occupational and residential settings. METHODS: Five office workers and 17 nurses working either days or rotating night and day shifts wore a device to record light intensity exposure for one or two 7-day periods, completed a questionnaire, and provided three saliva samples for melatonin. RESULTS: Rotating shift workers had irregular light exposure patterns and abnormal melatonin levels compared with those working days. In addition to lower-than-normal melatonin levels during sleep periods, rotating shift workers exhibited higher-than-normal melatonin levels on arising and during work. Self-reported years of shift work were correlated with measured melatonin and light. CONCLUSIONS: Rotating shift work is supported as a surrogate for exposure to light-at-night and circadian disruption.