ENVIRONMENTAL MASS SPECTROMETRY: EMERGING ENVIRONMENTAL CONTAMINANTS AND CURRENT ISSUES

S.D. Richardson U.S. Environmental Protection Agency, National Exposure Research Laboratory, Athens, GA 30605 Much has been achieved in the way of environmental protection over the last 30 years. However, as we learn more, new concerns arise (including potential adverse health effects, bioaccumulation, and widespread distribution). This presentation will discuss emerging environmental contaminants that the U.S. Environmental Protection Agency (EPA) and other agencies are currently concerned about. Emerging contaminants include pharmaceuticals, perfluorooctanoic acid (PFOA) and other perfluorinated compounds, nanomaterials, drinking water disinfection by-products (DBPs), polybrominated diphenyl ether (PBDE) flame retardants, pesticide degradation/reaction products, perchlorate, hormones, algal toxins, sunscreens/UV filters, benzotriazoles, dioxane, gasoline additives, naphthenic acids, and pathogens. In addition, a recent study of the finding of a new artificial sweetener, sucralose, in surface waters from 27 countries in Europe (up to ppb levels) will be discussed. Pharmaceuticals are of concern due to antibiotic resistance and potential endocrine disrupting effects. A recent study by researchers in Canada and the U.S. EPA will be highlighted, where ethinylestradiol (EE2, a contraceptive) was dosed at low ng/L levels in a natural lake, and significant reproductive effects were observed in the wild fish population. Regarding pharmaceuticals, there is also new research showing reduced microbial decomposition of leaf litter in rivers and streams, which could ultimately affect the availability of organic carbon to aquatic organisms, including fish. Concerns with PFOA and PBDEs include widespread global distribution in the blood of the general population and in wildlife, as well as potential health effects, including cancer and developmental toxicity. Nanomaterials are of concern because of their unique properties and potential for toxicity. Currently, the U.S. EPA is investigating fullerenes, ZnO, and nano-silver to understand their fate and transport and potential aquatic toxicity effects. Emerging drinking water DBPs include iodo-acids, iodo-trihalomethanes, bromonitromethanes, haloamides, and nitrosamines (including nitrosodimethylamine, NDMA). New toxicological research is revealing that some of these emerging DBPs are more genotoxic and cytotoxic than DBPs currently regulated, and the use of newer alternative disinfectants (chloramines, ozone, chlorine dioxide) can increase their formation. Perchlorate is of concern due to its widespread presence in the environment and its potential to affect the thyroid function. It is used in solid rocket propellants (including fire works) and can also be introduced through the use of fertilizers that are contaminated with natural perchlorate that is sometimes found in nitrate deposits mined for fertilizer. A recent study of perchlorate measurements in 350 foods and beverages from more than 50 countries will be highlighted, which demonstrates the widespread presence of perchlorate and accumulation in plants and foods. Algal toxins of interest include microcystin-LR, anatoxin-a, and cylindrospermopsin, which have been found in many environmental waters and have been responsible for large fish kills and illness in people. Some of the emerging contaminants (e.g., nitrosamines, PBDE flame retardants, and pesticide degradation products) are currently listed on the proposed Unregulated Contaminants Monitoring Rule (UCMR-2), which requires EPA to select five or more contaminants every five years to consider for regulation. Other emerging rd contaminants are listed on the 3 draft Contaminant Candidate List (CCL-3), which identifies priority drinking water contaminants that might be regulated by the U.S. EPA at a future date. A new ambient water quality criteria is also currently under development that would establish criteria for emerging contaminants in environmental waters. The status and health/environmental issues with these emerging environmental contaminants will be discussed, as well as analytical methods used to measure them. Because mass spectrometry is a key technology for nearly all of these emerging contaminants, its use will be highlighted, along with a few examples of specific methods used for emerging contaminants. Both gas chromatography (GC)/mass spectrometry (MS)(/MS) and liquid chromatography (LC)/MS/MS are key technologies for identifying and measuring these emerging contaminants, and the recent development of high resolution mass spectrometers with LC/MS (especially time-of-flight and quadrupole-time-of-flight mass spectrometers) has enabled structural identification of environmental transformation products of many emerging contaminants. Examples in this regard will be presented for X-ray contrast media microbial transformation products and pesticide transformation products. In past years, many fate studies have simply focused on the disappearance of the parent contaminant in the environment (or in wastewater or drinking water treatment), but new work is revealing that these contaminants are often not mineralizedthat they are degraded to stable transformation

products that can often retain the same biological (or pharmaceutical) activity as the parent compound or are as toxic or more toxic than the parent compound.