Biofiltration for removal of BOM and residual ammonia following control of bromate formation.

Nitrification was developed within a biological filter to simultaneously remove biodegradable organic matter (BOM) and residual ammonia added to control bromate formation during the ozonation of drinking water. Testing was performed at pilot-scale using three filters containing sand and anthracite filter media. BOM formed during ozonation (e.g., assimilable organic carbon (396-572 microg/L), formaldehyde (11-20 microg/L), and oxalate (83-145 microg/L)) was up to 70% removed through biofiltration. Dechlorinated backwash water was required to develop the nitrifying bacteria needed to convert the residual ammonia (0.1-0.5 mg/L NH(3)-N) to nitrite and then to nitrate. Chlorinated backwash water resulted in biofiltration without nitrification. Deep-bed filtration (empty-bed contact time (EBCT) = 8.3 min) did not enhance the development of nitrification when compared with shallow-bed filtration (EBCT = 3.2 min). Variable filtration rates between 4.8 and 14.6 m/h (2 and 6 gpm/sf) had minimal impact on BOM removal. However, conversion of ammonia to nitrite was reduced by 60% when increasing the filtration rate from 4.8 to 14.6 m/h. The results provide drinking water utilities practicing ozonation with a cost-effective alternative to remove the residual ammonia added for bromate control.

Broad range analysis of endocrine disruptors and pharmaceuticals using gas chromatography and liquid chromatography tandem mass spectrometry.

Endocrine disrupting compounds (EDCs) and pharmaceuticals and personal care products (PPCPs) have been globally detected in impacted natural waters. The detection of trace quantities of EDCs and PPCPs in the environment is of great concern since some of these compounds have known physiological responses at low concentrations. EDCs can have a wide range of polarities, acidic and basic moieties, and exist in trace quantities, which often requires numerous complex extractions, large sample collection volumes, and multiple instrumental analyses. A comprehensive method has been developed allowing for the analysis of 58 potential EDCs in various water matrices using a single solid-phase extraction (SPE) of a 1L sample with subsequent analyses using both gas chromatography and liquid chromatography, each coupled with tandem mass spectrometry (GC-MS/MS and LC-MS/MS). Instrument detection limits ranged between 0.12-7.5 pg with corresponding method reporting limits of 1-10 ng l(-1) in water. Recoveries for most compounds were between 50% and 112% with good reproducibility (RSD 6-22%).

Trace analysis of bromate, chlorate, iodate, and perchlorate in natural and bottled waters.

A simple and rapid method has been developed to simultaneously measure sub-microg/L quantities of the oxyhalide anions bromate, chlorate, iodate, and perchlorate in water samples. Water samples (10 mL) are passed through barium and hydronium cartridges to remove sulfate and carbonate, respectively. The method utilizes the direct injection of 10 microL volumes of water samples into a liquid chromatography-tandem triple-quadrupole mass spectrometry (LC-MS/MS) system. Ionization is accomplished using electrospray ionization in negative mode. The method detection limits were 0.021 microg/L for perchlorate, 0.045 microg/L for bromate, 0.070 microg/L for iodate, and 0.045 microg/L for chlorate anions in water. The LC-MS/MS method described here was compared to established EPA methods 300.1 and 317.1 for bromate analysis and EPA method 314.0 for perchlorate analysis. Samples collected from sites with known contamination were split and sent to certified laboratories utilizing EPA methods for bromate and perchlorate analysis. At concentrations above the reporting limits for EPA methods, the method described here was always within 20% of the established methods, and generally within 10%. Twenty-one commercially available bottled waters were analyzed for oxyhalides. The majority of bottled waters contained detectable levels of oxyhalides, with perchlorate < or = 0.74 microg/L, bromate < or = 76 microg/L, iodate < or = 25 microg/ L, and chlorate < or = 5.8 microg/L. Perchlorate, iodate, and chlorate were detectable in nearly all natural waters tested, while bromate was only detected in treated waters. Perchlorate was found in several rivers and reservoirs where itwas not found previously using EPA 314.0 (reporting limit of 4 microg/L). This method was also applied to common detergents used for cleaning laboratory glassware and equipmentto evaluate the potential for sample contamination. Only chlorate appeared as a major oxyhalide in the detergents evaluated, with concentrations up to 517 microg/g. Drinking water treatment plants were also evaluated using this method. Significant formations of chlorate and bromate are demonstrated from hypochlorite generation and ozonation. From the limited data set provided here, it appears that perchlorate is a ubiquitous contaminant of natural waters at trace levels.

Analysis of endocrine disruptors, pharmaceuticals, and personal care products in water using liquid chromatography/tandem mass spectrometry.

A method has been developed for the trace analysis of 27 compounds from a diverse group of pharmaceuticals, steroids, pesticides, and personal care products. The method employs solid-phase extraction (SPE) and liquid chromatography/tandem mass spectrometry (LC/MS/MS), using electrospray ionization (ESI) in both positive and negative modes and atmospheric pressure chemical ionization in positive mode. Unlike many previous methods, a single SPE procedure using 1 L of water coupled to a simple LC method is used for all ionization modes. Instrument detection limits for most compounds were below 1.0 pg on column with reporting limits of 1.0 ng/L in water. Recoveries for most compounds in deionized water were greater than 80%. Sulfuric acid was found to be the preferred sample preservative, and structures of all MS/MS product ions are proposed. Matrix effects from waters with a high content of treated municipal effluent were observed in both ESI modes and are discussed in the paper.