Detecting N-nitrosamines in drinking water at nanogram per liter levels using ammonia positive chemical ionization.

Detection of N-nitrosamines in water supplies is an environmental and public health issue because many N-nitrosamines are classified as probable human carcinogens. Some analytical methods are inadequate for detecting N-nitrosodimethylamine (NDMA) at low ng/L concentrations in water due to poor extraction efficiencies and nonselective and nondistinctive GC/MS electron ionization techniques. Development of a selective, sensitive, and affordable benchtop analytical method for eight N-nitrosamines, at relevant drinking water concentrations was the primary objective of this project. A solid-phase extraction method using Ambersorb 572 and LiChrolut EN was developed in conjunction with GC/MS ammonia positive chemical ionization (PCI). Ammonia PCI shows excellent sensitivity and selectivity for N-nitrosamines, which were quantified using both isotope dilution/surrogate standard and internal standard procedures. Method detection limits for all investigated N-nitrosamines ranged from 0.4 to 1.6 ng/L. Applying our extraction method to authentic drinking water samples with dissolved organic carbon concentrations of 9 mg/L, we were able to detect N-nitrosodimethylamine (2-180 ng/L) as well as N-nitrosopyrrolidine (2-4 ng/L) and N-nitrosomorpholine (1 ng/L), two N-nitrosamines that have not been reported in drinking water to date. With high recoveries of standards and analytes, the described internal standard method offers a valuable new approach for investigating several N-nitroso compounds at ultratrace levels in drinking water.

Characterization of naphthenic acids by electrospray ionization high-field asymmetric waveform ion mobility spectrometry mass spectrometry.

Electrospray ionization (ESI) high-field asymmetric waveform ion mobility spectrometry (FAIMS) was combined with quadrupole, time-of-flight, and tandem mass spectrometry to characterize commercial and naturally occurring naphthenic acids (NA) mixtures. This new method provides quantitatively reliable mass and isomer distributions of NA components in approximately 3 min without extensive sample preparation. ESI-FAIMS-MS seems to be especially useful for characterization of fragile ions that cannot be detected by other methods. A unique part of this technique is separation of structural isomers that proved to be critical in determination of elemental composition and in structure elucidation. Tandem mass spectrometry of NA ions separated by FAIMS provides more information about the structure of NA than other methods in the field of NA analysis.

Comparison of high-field asymmetric waveform ion mobility spectrometry with GC methods in analysis of haloacetic acids in drinking water.

Haloacetic acids (HAAs) are major byproducts of chlorination of drinking water. Electrospray ionization high-field asymmetric waveform ion mobility spectrometry mass spectrometry (ESI-FAIMS-MS) provides a tool for direct monitoring of these compounds. However, treated drinking water samples can be challenging to analyze due to the large number of chemicals present and due to matrix effects that can hinder quantitation of analytes. We developed a standard addition ESI-FAIMS-MS method that permits submicrogram per liter detection of haloacetic acids and overcomes matrix effects. An advantage of FAIMS is increased selectivity through a significant reduction in the chemical background from ESI. Moreover, detection limits with this method are much lower than with previously existing GC and GC/MS methods, and quantitation results compare favorably with other existing methods. This new method does not require sample preparation or chromatographic separation and provides a fast, simple, sensitive, and selective method for monitoring HAAs.

Rapid and sensitive differentiation of anomers, linkage, and position isomers of disaccharides using High-Field Asymmetric Waveform Ion Mobility Spectrometry (FAIMS).

A challenging aspect of structural elucidation of carbohydrates is gaining unambiguous information for anomers, linkage, and position isomers. Such isomers with identical mass can't be easily distinguished in mass spectrometry and a separation step is required prior to mass spectrometry identification. In our laboratory, gas-phase separation and differentiation of anomers, linkage, and position isomers of disaccharides was achieved using High-Field Asymmetric Waveform Ion Mobility Spectrometry (FAIMS). The FAIMS method responds to changes in ion mobility at high field rather than absolute values of ion mobility, and was shown to provide efficient separation and identification of disaccharide isomers at high sensitivity. Separation of analyzed disaccharide isomers can be accomplished at low nM level in a matter of seconds without sample purification or fractionation. Capability for examining a large population of ionic species of disaccharides by this method allowed for correlating structural details of disaccharide isomers with their separation properties in FAIMS. Results for disaccharide isomers indicate that this method could be applied to a larger group of carbohydrates.

Assessment and characterization of polychlorinated biphenyls near a hazardous waste incinerator: analysis of vegetation, snow, and sediments.

Samples of spruce needles, snowpack, and sediment were analyzed in the area around the Alberta Special Waste Treatment Centre (ASWTC) near Swan Hills, Canada, in 1997 and 1998, following a major accidental release of polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) in October 1996. The PCB concentrations in spruce needles and snow were mostly elevated to the east of the plant and contained congeners that were not present at upwind or distant sites. Several years of annual vegetation monitoring data indicated that PCB emissions increased prior to the reported accident. Within 3 km of the plant, there was a predominance of higher chlorinated congeners penta-, hexa-, hepta-, and octachlorobiphenyls in white spruce (Picea glauca) needles and snow. Polychlorinated biphenyl congener patterns varied seasonally in spruce needles, likely influenced by temperature effects on the volatilization and of particle-bound and vapor phase PCBs in the forest canopy. The similarity of deposition patterns in snow and needles in 1997 and 1998 suggested the PCBs in the surrounding area were derived by long-term fugitive releases of PCBs rather than an accidental release. In addition, hexachlorobenzene, a combustion by-product of chlorinated organics in waste incinerators, was not measured at elevated concentrations in spruce needles or snow east of the facility and, when detected, was not correlated with PCB concentrations. A radiometrically dated sediment core from nearby Chrystina Lake (AB, Canada) showed a gradual increase in annual PCB flux during the early years of operation of the ASWTC, followed by a higher PCB flux in 1997, indicating that the lake may have been directly contaminated by the accidental release.

Trichloroacetic acid as a biomarker of exposure to disinfection by-products in drinking water: a human exposure trial in Adelaide, Australia.

We addressed the need for a biomarker of ingestion exposure to drinking water disinfection by-products by performing a human exposure trial. We evaluated urinary excretion of trichloroacetic acid (TCAA) as an exposure biomarker using 10 volunteers who normally consume their domestic tap water. We recruited the volunteers at a water quality research laboratory in Adelaide, Australia. Participants maintained a detailed consumption and exposure diary over the 5-week study. We also analyzed tap water and first morning urine (FMU) samples for TCAA, and tap water for chloral hydrate (CH). We documented both interindividual and intraindividual variability in TCAA ingestion and urinary excretion, and both were substantial. With a TCAA-free bottled water intervention, we used creatinine-adjusted urinary TCAA levels to estimate urinary TCAA excretion half-lives for three of the participants. We observed correspondence over time between estimated TCAA excretion, calculated from TCAA + CH ingestion levels, and measured TCAA urinary excretion. This study demonstrates the merits and feasibility of using TCAA in FMU as an exposure biomarker, and reveals remaining concerns about possible alternate sources of TCAA exposure for individuals with low drinking water ingestion exposure.

Assessing exposure in epidemiologic studies to disinfection by-products in drinking water: report from an international workshop.

The inability to accurately assess exposure has been one of the major shortcomings of epidemiologic studies of disinfection by-products (DBPs) in drinking water. A number of contributing factors include a) limited information on the identity, occurrence, toxicity, and pharmacokinetics of the many DBPs that can be formed from chlorine, chloramine, ozone, and chlorine dioxide disinfection; b) the complex chemical interrelationships between DBPs and other parameters within a municipal water distribution system; and c) difficulties obtaining accurate and reliable information on personal activity and water consumption patterns. In May 2000, an international workshop was held to bring together various disciplines to develop better approaches for measuring DBP exposure for epidemiologic studies. The workshop reached consensus about the clear need to involve relevant disciplines (e.g., chemists, engineers, toxicologists, biostatisticians and epidemiologists) as partners in developing epidemiologic studies of DBPs in drinking water. The workshop concluded that greater collaboration of epidemiologists with water utilities and regulators should be encouraged in order to make regulatory monitoring data more useful for epidemiologic studies. Similarly, exposure classification categories in epidemiologic studies should be chosen to make results useful for regulatory or policy decision making.