.1OImIal of the Science of Food and Agriculture J Sci Food Agric 80:1798-1804 (online: 2000)

Edward T Urbans~y, 1. Baohua GU,2 Matthew L Magnuson,1 Gilbert M Brown3 and Catherine A Kelty I , Uniled States EnvIrmmen8JProt8Cfon Agency, Offlce of ReseBICh8M ~, Nstiona/Risk ManagementR-m ~, WsW Supplyand WaterR~ DIvisIon,CkJdnnatf, OH 45268, USA 2En~taI Sc/encssDMskJII, Oak Ridge N8tkJn8lL8boratOIy, Oak Ridge, TN 37831, USA* 3Chemic8and AI8Iytk:a/ ScienC8SD;visIon. Oak Ridge NationalLabOIafOIY. Oak Ridge, TN 37831, USA*

Abstract: Perchlorate has been identified in ground and surface around the USA including some that serve as supplies for drinking . Because perchlorate salts are used as solid oxidants in rockets and ordnance, water contamination may occur near military or aerospace installations or defense industry manufacturing facilities. This ion has been added to the Environmental Protection Agency's Contaminant Candidate List and the Unregulated Contaminant Monitoring Rule. Concern over perchlorate has prompted many residents in affected areas to switch to bottled water; however, bottled waters have not previously been examined for perchlorate contamination. Should the EPA promulgate a regulation for municipal water systems, US law requires the Food and Drug Administration to take action on bottled water. Methods will therefore be required to determine perchlorate concentrations not only in tap water, but also in bottled waters. Ion chromatography (IC) is the primary technique used for its analysis in drinking water, but it does not provide a unique identification. Confirmation by electrospray ionization mass spectrometry (ESI-MS) can serve in this capacity. The ESI-MS method can be applied to these products, but it requires an understanding of matrix effects, especially of high ionic strength that can suppress electrospray. When using methyl isobutyl ketone (MIBK) as the extraction solvent, the ESI-MS method can reach lower limits of detection of 6ngml-1 for some bottled waters. However, dilution required to negate ionic strength effects in mineral waters can raise this by a factor of 10 or more, depending on the sample. Decyltrimethylammonium cation (added as the bromide salt) is used to produce an ion pair that is extracted into MIBK. After extraction, the sum of the peak areas of the ions C1oH21NMe3(Br)(CIO4)- (mlz=380) and C1oH21NMe3(CIOJi (mlz=400) is used to quantitate perchlorate. Standard additions are used to account for most of the matrix effects. In this work, eight domestic brands and eight imported brands of bottled water were comparatively analyzed by the two techniques. For comparison, a finished potable water known to contain perchlorate was also tested. None of the bottled waters were found to contain any perchlorate within the lower limit of detection for the IC method. Recoveries on spiked samples subjected to the IC method were ~98%. Published in 2000 for SCI by John Wiley & Sons, Ltd

Keywords: bottled water; perchlorate; ion chromatography; electrospray ionization mass spectrometry; drinking water

INTRODUCTION surface waters at concentrations ranging from 5 ng In 1997, perchlorate ion was found in sources of ml-1 to 3.7mgml-1.1 It is believed that me per- drinking water for much of the south western USA chlorate is largely derived from defense and aerospace including the Colorado River .1-3 Improvements in ion industry practices and military operations mat took chromatography for this moiety have resulted in lower place decades ago. limits of detection on the order of 5 ngml-1 (parts per Perchlorate is a strong oxidant, and this behavior is billion) and made detection possible at these sites.2-10 obvious when hot concentrated perchloric acid Perchlorate has since been found in ground and touches organic matter. Nonemeless, perchlorate

. COITespondence to: Edward T Urbansj(y, United States Environmental Protection Agency, Office of Research and Deyek)pment, National Risk Management Research Laboratory, Water Supply and Water Resources DIvIsion, Cincinnati. OH 45268, USA E-mail: [email protected] t This article is a US Government work and is in the publk: domain in the USA. * Oak Ridge National Laboratory is operated under oontract by University of T ennessee-Battelle LLC for the US Department d Energy. (R8Oeived 24 Febfuaty 2000; revised veIsiCH1received 24 April 2000; scoept8d 31 May 2000)

Published in 2000 for SCI by John Wiley &: Sons, ud 1798 SunJey of boulBd waun for /)I1f:h/orQteby ESI-MS reduction is encumbered by a high activation energy, natural springs. Both brands are then purified by which precludes reaction under cold and dilute reverse osmosis. Other bottled waters, such as conditions. The chemistry of perchlorate has been Grayson Mountain Springs, Dannon, Polar Mountain reviewed previously. 1 As a consequence of this Water, , San Pellegrino, Naya and are activation barrier, perchlorate is quite unreactive and taken from specific natural springs. Both Perrier and thus long-lived under the dilute and relatively cold San Pellegrino are naturally carbonated. Some inter- conditions encountered in natural bodies of water, nationally distributed bottled waters are taken from finished potable water supplies, and in biophysiology specific springs and therefore represent widespread (as when water is consumed by people or animals). In geographical exposure for North American and tenus of public health, perchlorate interferes with European nations, even if the products are consumed iodide uptake in the thyroid gland because the tWo by a relatively small fraction of the population. anions are similar in size.1,3,11,12The BPA National Consumption of this nature presents cha1Iengesfor Center for Environmental Assessmenthas undertaken risk assessmentand management. Products such as studies to determine safe levels for exposure to this Dasani and Aquafina represent a local bottler's water contaminant. Meanwhile, tWo provisional action levels source and thus a localized geographical zone of of 4 and 18ngml-1, based on different assumptions exposure. Of course, they must be tested on a local used in the original toxicology studies, remain in force. scale as they represent the specific source for a bottler At present, the BPA Office of Water has not and not for the brand overall. established a national primary drinking water standard for perchlorate; however, this ion has been added to the Contaminant Candidate List (CCL)13.14 and the Unregulated Contaminants Monitoring Rule (UCMR).15 If the BPA promulgates a drinking water EXPERIMENTALPROCEDURE regulation, the Food and Drug Administration (FDA), Sample procurement and custody will be required to act on bottled water, pursuant to 21 Bottled waters were obtained by EPA staff. Manufac- USC 349. Newspaper accounts have suggested that turer seals were broken by EPA staff in the laboratory; many people in areas with perchlorate-contaminated 1.2-dl portions were decanted into new polypropylene drinking water have switched to bottled water, or high-density polyethylene bottles, placed in sealed although bottled waters have not so far been tested packages to ensure chain of custody, and sent to the to our knowledge. Oak Ridge National Laboratory (ORNL) by overnight Previously, we reported on the determination of carrier, where they were opened exclusively by ORNL perchlorate in drinking water using electrospray staff. Perrier and San Pellegrino were allowed to ionization mass spectrometry (ESI-MS).16-19 Per- de-gas CO2 prior to use. For comparison, a perchlo- chlorate anion may be extracted into organic solvents rate-tainted potable water sample (Southern Nevada using surfactant cations, especially aikyltrimethylam- Water Authority) was also subjected to the experi- monium ions (eg decyl, lauryl, myristyl or cetyl).17-19 mental procedure. Tested waters are listed in Table 1. Other investigators also report quantitation of per- chlorate by mass spectrometric methods.20-23In this Electrospray Ionization mass spectrometric work, we examine the application of this approach as analyses well as the ion chromatographic method to ten brands Reagents of bottled water. Ion chromatography can be a useful High purity deionized water (HP DI water) was screening tool. If a sample is chromatographed and no prepared by polishing house deionized water (reverse peak is observed, a fortified sample can be tested. If osmosis/UV-irradiation) with a Barnstead EasyPure recovery of the spike is satisfactory, there is reasonable system with organic-removal and deionizing cartridges assurance that the analyte is not present. One of the to obtain a resistivity ~18MQcm. The cationic weaknessesof any chromatographic method is that surfactant, decyltrimethylammonium bromide identification by retention time is not necessarily (CI~INMe3Br), was obtained from Fluka (Buchs, unique. Confirmatory testing can be accomplished Switzerland) and prepared at O.20M (5.6gdl-l) by effectively by mass spectrometry because of the mass dissolving the solid in HP DI water. The choice of of the ion and the resulting m/z ratio. Isotopic ratios surfactant involves striking a balance among three based on relative abundance (in this case 35CI vs 37CI main factors: the ability form extractable ion pairs, with a 3:1 ratio) provide additional evidence that the availability of the reagent in high purity, and resistance identification is correct. to forming intractable emulsions, as descnoed pre- Bottled waters can vary significantly in ionic viously.IS HPLC grade 4-methyl-2-pentanone strength, salt composition and dissolved gas content (methyl isobutyl ketone, MIBK) was obtained from (mainly dioxide). Like municipal potable water Spectrum Quality Chemicals (San Rafael, CA, USA) supplies, bottled waters vary in treatment techniques, and used as the extraction solvent. Ammonium including disinfection. Some bottled waters, such as perchlorate (Aldrich, Milwaukee, WI, USA) was Pepsi's Aquafina or Coca-Cola's Dasani are derived prepared at 1.OOgl-1 CIO:; in HP DI water and from local sources - either municipal tap water or serially diluted as necessary.

1SdPO()(lAgric 80:1798-1804 (online: 2000) 1799 ET UrlJansky et al

Table 1. Waters ex8ninecl in this study Brand CaIf'BrIy, address ScxNce Apoilinaris Naturally Sparkling Spring Water Liberty Richter (distributor), Saddle Brook, NJ 07663, USA Germany Aquafina PepsiCo bottler was Warrenton Products Inc, Warrenk)n, Varies by location MO 63383, USA Crystal Geyser Natural Spring Water CG Roxane LP, POBox 249, Benton, TN 37307, USA CG Roxane Dannon Danoon National Spring Water, 208 Harbor Drive, Stamford, Spring Piedmont, CT 06902, USA Quebec, Canada Dasani The Coca-Goia Co. Atlanta, GA, USA Varies by location Eureka Springs All Natural Spring Water SaegertONnBeverages, Saegertown, PA 16433, USA Municipal tap Evian SA Evian Co, Evian-les-Bains, France Cachet Spring FountainheadNatural Spring Water Fountainhead,White Water Falls Rd, Oconee,SC, USA SumterNatural Forest Gerolsteiner Natural Gerolsteiner Brunnen GmbH & Co, GerOisteinspring D-54567 GerolsteinNulkaneifel, Germany (near Rhine, Moselle) Grayson Mountains Grayson MountainWater Co, Independence,VA, USA Localspring Naya NoraBeverages Inc, Mirabel, Quebec, JOV1Z0, Canada Localspring S Pellegrino San Pellegrino, Italy Localspring Perrier Perrier, Vergeze, France Local spring PolandSpring Natural Spring Water PolandSpring Water Co, Poland,ME 04274, USA Local spring Polar Mountain Spring Water CrystalSprings Water Co, Mableton,GA 30059,USA Crystal Spring, Blue Ridge, GA Southem Nevada8Water Authority Las Vegas, NV, USA Lake Mead on Colorado River Volvic Natural Spring Water Danone Group, Ste VoMc, at VoMc 63500. France Clairvic Spring .5I'tNA.. fiIWh8d/X)1ab18 water ~ a mIIk:ipai~-~ 8 boWed~. It. UI8db"~ _It 18~ tI coIUin perc~al8 m.

Extraction quadrupole mass spectrometer (Q3) with a Finnegan- The following were quantitatively added to a 100-ml Mat electrospray interface apparatus was used for volumetric flask: 96.0ml of the test water sample, analysis. A Waters (Milford, MA, USA) MS-600 1.0ml ofO.20M C1O~INMe3Br (aquesus), and 5.0ml pump delivered pesticide residue analysis grade of MIBK. The rationale for this procedure is fairly methanol (Burdick & Jackson, Baxter Healthcare, straightforward. The presence of small water droplets Muskegon, MI, USA) as the carrier; sheathing gas cannot be tolerated in the ESI-MS analysis. A pressure was 480kPa (70 psi); capillary temperature separatory funnel will not work because MIBK is less was 200°C; spray potential was 4.0kV. dense than water (coming out second); thus, residual water droplets left on the funnel will be carried along in Ion chromatographic analyses the MIBK layer. Becauseof the large volume of water Samples were analyzed at ORNL as received from to MIBK, a 40-ml vial, such as that used for many EPA following the method reported by Jackson et aL 8 EPA drinking water methods also will not work. The Dionex (Sunnyvale, CA, USA) AG 11 guard and ASII advantage to a 100-ml volumetric flask is that the analyrical columns were used on a Dionex DX-500 ion solvent is constrained to the neck, where it is readily chromatograph for these analyses. In addition to the drawn off once the extraction is complete. We test water samples, spiked samples containing 10 and emphasize that the flask is not used in its volumetric 20ngml-1 CIO; were run to verify performance. capacity, but merely as a convenient vessel for recovering the extraction solvent. Duplicate samples were run with the following fortifications (spikes): 0 RESULTS AND DISCUSSION (unspiked), 10, or 20ngml-1 CIOi. As a blank, ESI-MS data analysis unspiked samples of the bottled waters were extracted To correct for od1er species that form ions wid1 m/z without the surfactant. The blank correction proce- equal to d1at of d1e analyte ions, d1e peak areas dure has been explained previously.lS,19 Due to obtained for an MIBK extract wid1out detergent were limited sample volume of the first lot, Perrier and S subtracted from d1ose extracted wid1 d1e cationic Pellegrino were not run in duplicate; however, another surfactant. Perchlorate forms complexes wid1 d1e lot was tested in duplicate. surfactant cation of d1e form C1O~INMe3(Br) (CIO4)- (m/z =380) and C10H21NMe3(CIO~2 Instrumentation (m/z =400). When extracted wid1 dichloromethane, A Finnigan-Mat (San Rafael, CA, USA) TSQ 700 municipal potable water samples showed linear

1100 J SdFoodAgric 80:1798-1804 (online: 2000) Surwy of /)ottJ.J V1QU1ffor P'7'I:/I/orrIteby ESI-MS

25

20

i15

8 0 010 Flgu" 1. Negativeion ESI-MSinjectk)n peaks ffX SoothemNevada Water Au~ty finished~. a s~plY knCPNnto contain perdiklr8le. The ~ank } val~ is ootained~ surfactant(no C1aH21NMe;).Along wiIh the (niz=380) arxl 0 C1oH21NMe,(ClOJ2(niz-400). Nd8 that perchlorale~ntration is reIaEd to peek 8'88 aid not paek haighl The refatk)nshipbetween -10 -5 0 5 10 15 20 25 90%) of the ~ is 8Xb'ad8dinto Fig... 2. StarKlard~ition p~ for (0) Aquaflna.(6) Naya. and (V) thesolvent tII8 first time as shown by ~ ~. SNWAtaT! ESI-MSanalysis. The sum of the blank~ pe8t'- for ntzs380 and 400 88 p~ against the added peroN«* ~Iration (~ic8e spikes at 10 and 2Ong~~I). The ~ increase in peak area with perchlorate concentra- r8Pf888nIsthe conc:enIr8lion~ ~ in the S8nple. tion.18,19For this work, however, MIBK was chosen as the solvent to minimi7.e exposure of laboratory personnel to chlorinated solvents in keeping with shows chromatograms for SNW A finished water EPA's goals of laboratory safety in test method unspiked and spiked with 10ngml-1 CIO;. development. Partitioning and ionization of the ion Least squaresparameters for the standard additions pairs in MIBK is reduced relative to methylene used in the ~I-MS method are summarized for chloride. This proceduce is sufficient for the purposes bottled waters in Table 2. The ESI-MS method of quantitation, but it requires more careful treatment corroborates the IC result obtained for the SNW A of the raw data. The difference in partitioning is sample. For the non-carbonated bottled waters, the heightened in waters of higher ionic strength because ESI-MS results are consistent with the IC findings that there is more competition for the decyltrimethyl- perchlorate is below the lower limit of detection, of ammonium ion. The best results are obtained by approxilnately 5 ngml-1. The two naturally carbo- summing the areas of the two ions, C1~lNM~(Br) nated waters show a curious effect: positive abscissal (ClOJ- and C1oH21NMe3(ClO4)2. While it may be intercepts, which correspond to negative analyte possible to mitigate the effect by using more surfac- concentrations. This non-sensical result is caused by tant, there is a significant risk of forming emulsions the high ionic strength of these waters. Although they and the latter approach was not explored. were de-gassedprior to analysis to remove CO2, they Figure 1 shows the flow injection peaks observed for contain high levels of dissolved inorganic salts. High a water known to contain perchlorate (SNWA). ionic strength interferes with electrospray iomzation; Making standard additions and monitoring the sum accordingly, signal intensity is diminished. This of the peak areas at m/z=380 and 400, we then produces a negative peak relative to the background extrapolated to the abscissa.This gives the concentra- signal of the methanol carrier, which has an ionic tion of perchlorate in the sample in a reasonably strength approaching zero. In some cases,the problem straightforward fashion (Fig 2). can be eliminated by diluting the sample; however, the lower limit of detection is raised by a factor equal to the Analytical results dilution factor. Consequently, there is a trade-off to be Perchlorate was found only in the water sample from made, and thorough characterization of the matrix is the Southern Nevada Water Authority. The concen- required to apply this method optimally to waters with tration of the ion obtained using IC and ESI-MS high ionic content. Even with 10% v/v dilutions, we methods agreed within the limits of experimental were unable to successfully quantitate trace perchlo- error. None of the bottled waters tested contained rate in Perrier, Pellegrino, or several other sparkling perchlorate above the lower limit of detection reported mineral waters that contain high levels of dissolved for the IC method, 5ngtnI-1. The IC method is well inorganic salts (positive x-intercepts were obtained for established8and straightforward. Chromatograms for all). Although perchlorate concentrations ?200ng Aquafina and Naya are shown in Fig 3; recovery is ml-1 can be quantitated in mineral waters, this has excellent as shown by the chromatograms of the little practical application. fortified samples. For all of the waters, recovery of The lower limit of detection (il..OD) for the ~I- the spike by IC was >98%. Perchlorate was not MS method using MIBK is 6ngml-1, based on DI detected in any brand of water. For comparison, Fig 4 water standards run at 0, 1.0, 2.0, 4.0, 6.0, 8.0 and

J sa FoodAgric 80:1798-1804 (online: 2000) 180] ET U7baJU}y et al

Figure 3. Ion chromatQ9'8nsfa" OOtIJedwater samplesthat oontain00 perchk>late:(a) AquafinawwJ (b) Naya. Ch~rams fa" the -.TIe S8mpIe8

fortified with 10 ng ml ~ 1 perci1k1rae:

(c) Aquafina and (d) Naya.

10.Ongml-l. Eight replicates at 6.0ngml-1 gave an samples.However, the ESI-MS method cannot readily estimated standard deviation of 0.2ngml-l. This be used for beveragessuch as fruit juices or wines or for leads to an EPA method detection limit (MDL) of seawater. 0.7 ngml-1 (using Student's t = 3.500 for the 99% confidence interval and seven degrees of freedom). Applicability and conclusions However, a threshold signal distinguishable from the While IC is likely to be the predominant technique for blank does not occur below 5ngml-l, and so we feel a determining perchlorate ion concentration in raw and minimum reporting level of 5-6ngml-1 is the most finished drinking waters (including bottled waters), appropriate. ESI-MS provides a useful means of confirming the IC In addition to the possloility of electrospray sup- identification, which is based on retention time alone. pression, it is worth noting that samples of very high Capillary electrophoresis or Raman scattering spectra- ionic strength may suffer from a limiting reagent me~4,25 may one day playa similar role, but these problem. The post-mixing concentration of the techniques are currently not sensitive enough without cationic surfactant is 2.0D1M;thus, competition among pre-concentration (eg with an anion exchange resin or anions for the surfactant must be considered. This is sample stacking). ESI-MS may be applied to a variety particularly true for less-hydrated anions, such as of drinking water matrices as a confirmatory technique nitrate or bromide, which are extracted into the to support identifications made by IC. It is reasonably MIBK, paired wim the surfactant cation. Competition rugged and reproducible while requiring a minimum for me surfactant - to the point of adversely affecting of sample preparation and no separation step prior to the analysis - is uncommon with potable water analysis. As with the IC method, high levels of

1802 , &;i FoodAgric 80:1798-1804 (online: 2000) Sun;rcyof boaW -.n for pen;hlorauby ESI-MS

Slope- y-intercept csIcd [C/Oilb Water (counts mlng-1) (counts) (nJIng-1) Aquafina 11500%400 15000%9000 1.3:'0.&0 Cannon 7200%300 29 % 6000 0.1*1° Casani 88X>%200 2000%4000 0.2*°.5" EurekaSprings 7400%100 9000%2000 12:.0.~ Evian ~%600 11 % 13 1.3:.1.~ GraysonMountains 9800%800 7% 15 O.7~1.~ Naya 9700%500 3Q% 10 3~1c Polar 10CXX>% 700 15 % 15 1.4~1.4c SNWA 5!XX>%200 54 % 5(XX) 9.2:'0.8 . ~ were caclAaIed based 00 the SIm of the - b' rrtz - ~ Md 400. Each~ is based on duplicale Jx)jrD at 0, 10, ~ngm-1 added perchlaoate. b The perc~e caw:en1ralionis ~ 86 !he addiliw imlelSe01 the x-interceptin the method01

Table 2. ESI-MS results obtained fa' amenab8 sl8ndard addllklns. I888d balded wMers and SNWA water c~LLODof6.0ngml-1. dissolved salts also affect me ESI-MS method, reduction of perchlorate has beep observed in the primarily by reducing the eleCtroSpray efficiency. laboratory,29,30 it has not yet been definitively ob- Almough we did not specifically try to overcome me served in me environment. Consequently, contami- problems posed by high CO2/HCO; concentrations, nated sites may remain in that condition for decades. we suspect that careful acidification could help reduce Until such time as natural attenuation can be demon- these. Previously, we have found mat moderate acetic strated or source water protection can be assured, it acid concentrations (~O.l mM) did not advsersely will be necessary continually to assessnatural water affect ionization or detection.l~lS sources and finished potable water for this ion. Once me matrix effects have been dealt with, it is possible to run a large number of samples quickly, as each sample requires only a few minutes of instrument ACKNOWLEDGEMENTS time. Although the drinking water industry has We thank Peggy Roefer and Kay Brothers of the characteristically relied on ion chromatography for Southern Nevada Water Authority for providing measurement the concentration of ions, many labora- samples of finished potable water from their facility. tories (especially research laboratories) have quadru- pole mass spectrometers and electrospray introduction is increasingly popular. ESI-MS thus becomes one more technique in the arsenal of analytical weapons to REFERENCES be used with d~ water matrices. This is 1 Urbansky ET, Perd11orate chemimy: implications for analysis and remediation. Bior8m J 2:81-95 (1998) and references particularly important because IC is the only other therein. technique that can be readily applied to low-level 2 Urbansky ET and Schock MR, Issues in managing the risks contamination. It is particularly significant that ESI- associated with perchlorate in drinkina water. J EmJiron Manag MS and IC are fundamentally different techniques. 56:79-95 (1999) 8nd references therein. Accordingly, one can have higher confidence in a 3 Damian P and Pontius FW, From rockets to remediation: the perd11orate problem. EmJiron 1+ot 10:24-31 (1999). measured concentration when results from dissimilar 4 California Department of Health Services, Sanitation and techniques agree than in the agreement of retention Radiation Laboratories Branch, DetemIinaIiOII of Perchlorate time on different chromatography columns. In the by Ion Chromatography, Rev O. Jun 3, 1997. case of a particularly problematical sample, eluate 5 Harrington P and Shen Y, Improved analysis of perd1lorate in fractions can be collected from me IC and then water, Proc Water Qual TechnolCo1!/; A WW A, San Dicao, CA, Nov 1--4, 1998, 1405-1412 (CD-ROM). subjected to ESI-MS; however, this requires collecting 6 Win K. Laikhtman M, Robm J and Jackson FE, Low level the peak from a considerable number of runs. In perchlorate analysis in drinking water 8nd ground water by ion matrices with higil concentrations of interfering chromatography. Am EmI Lab 10:1 (1998). anions, the collected fractions can be reinjected. We 7 Eaton A, Hagbani A, Cox N and Wong E, Proc Water Qual have applied such a process to the measurement of TechnolCon!, AWWA, San Diego, CA, Nov 1--4,1998,1413- 1423 (CD-ROM). perchlorate in the wood of salt cedar growing in 8 Jackson FE, Laikhtman M and Rohrer JS, Determination of trace perchlorate-contaminated regions.26 level perchlorate in drinking 8nd ground water by ion With the popularity and worldwide availability of chromatography. J ChromatogrA 850:131-135 (1999). many brands of bottled water, purity is a global 9 Jackson FE, Gokhale S and Robm JS, Chapter 2. Recent concern. With any source water, there is a possibility of devel~ents in the analysis of perchlorate by ion chroma- tography, in Perchlorate m the Envinmmmt, Urbansky ET, exposure to perchlorate through run-off from ord- Kluwer/Plenum, New York, NY, USA (2000). nance installations or agricultural fields fertilized with 10 Tsui DT, Clewell RE, Eldridge IE and Mattie DR, Chapter 7. natural Chile saltpeter?7.2SAlthough microbiological Perd11orate analysis with the AS 16 separation eolumn, in

J Sci FoodAgric 80:1798-1804 (online: 2000) 1803 ET Ur6ansky et al

Pm:hlorau in the Em7irrmmmr, ed by Urbansky ET, KIuwer/ mobility spectrometry!mass spectrometry. Appl Spearosc Plenwn, New York, NY, USA (2000). 53:1367-1374 (1999). 11 Wolff 1, PerclI)orate and the thyroid gland. J¥JamI &m 50:89- 21 Barnett DA and Horlick G, Quantitative electroapray mass 105 (1998). spectrometry of halides and halogenic anions. J Anal At 12 ClarkJ, Chapter 3. Toxicology of perchlorate, inPercllJOfOauinthe Spearom 12:497-501 (1997). E1If1irl)llJllellt,ed by Urbansky ET, KIuwer/PImum, New York, 22 oewen RE, Olaudhuri S, Dickson S, Cassady RS, Wallner WN, NY, USA (2000). Eldridge IE and Tsui DT, Olapter 6. Analysis of trace level 13 Perciasepe R, Part m. Environmmtal Protection Agency. perchlorate in driDkina water and ground water by elec:ttospray Announcement of the drinking water contaminant candidate mass spectrometry, in Pen:hlomte in the EntIinmmmt, ed by list; notice. Fed &gist 63: 10273-10287 (1998). Urbansky ET, KJuwer/Plenum, New York, NY, USA (2000). 14 Drinking Water Contaminant Candidate List, Feb 1998, EPA 23 Koester CI, Bdler HR and Halden RU, Analysis of perchlorate Doc No 815-F-98-002. in groundwater by electrospray ionization mass spectrometry! 15 Browner C, Part II. Environmental Protection Agency, 40 CPR mass spectrometry. EmJinmSci TechIIOl34:1862-1864 (2000). pans 9, 141 and 142, Revisions to unregulated contaminant 24 Kowalchyk WK. Walker PAm and Morris MS, Rapid normal monitoring regulation for public water systems; final rule. Fed Raman spectroSCOpyof sub-ppm oxy-anion solutions: the role &gist 64:50555-50620 (1999). of elecaophoretic preconcentration. Appl Spectrosc49: 1183- 16 Urbansky ET, Magnuson ML, Freeman D and Jelks C, 1188 (1995). Quantitation of perchlorate ion by electrospray ionization 25 Miller AG and Macklin IA, Matrix effects on the Raman mass spectrometry (ESI-MS) using stable association com- analyticallines of oxyanions.Anal Ghent52:807-812 (1980). plexes with organic cations and bases to enhance selectivity. J 26 Urbansky ET, Magnuson ML, Kelty CA, Brown SK. Per- Ana/At Spearom 14:1861-1866 (1999). chlorate uptake by salt cedar (Tamarix _sissima) in the Las 17 Urbansky ET and Magnuson ML, Chapter 8. Smsitivity and Vegas Wash riparian ecosystem. sci TOt BII!JiMI 256:227-232 selectivity enhancemmt in perchlorate anion quantitation using complexation-eleClrospray ionization-mass SpectroIDe- (2000). 27 Schilt AA, Perchloric Acid and Perchlorates. GFS Chemicals, ny, in Pen;h/onIu in the EmIinmment, ed by Urbansky ET, KIuwer/Plmum, New York, NY, USA (2000). Columbus, OH, USA, pp 3-4 (1979) and references therein. 18 Magnuson ML, Urbansky ET and Kelty CA. Detennination of 28 Susarla S, Collette TW, Garrison A W, Wolfe NL and perchlorate at trace levels in drinking water by ion-pair McCutcheon SC, Perchlorate identification in fertilizers. extraction with eleClrospray ionization mass Spectromeny. BmIiroII sci TechIIOl 33:3469-3472 (1999) and references Anal ChmI 71:25-29 (2000). therein; see also correction EmJiron Sci Technol34:224 (2000). 19 Magnuson ML, Urbansky ET and Kelty CA. Microscale 29 Logan BE, A review of chlorate- and perchlorate-respiring extraction of perchlorate in drinking water with low level microorganisms. B~ J 2:69-78 (1998) and references detection by e1ectrospray-massspectrometry. Talanta SZ:285- therein. 291 (2000). 30 Coates ID, Michaelidou U, Broce RA, O'Connor SM. CrespiJN 20 Barnett DA. Guevremont R and Purves RW, Determination of and Achenbach LA, The ubiquity and diversity of dissim- pans..per-ttiUion levels of chlorate, bromate, and iodate by ilatory (per)chlorate-reducing bacteria. Appi Env Microbiol electrospray ionization/high-field asymmetric wavefonn ion 65:5234-5241 (1999).

1804 , Sci Food Agric 80:1798-1804 (online: 2000) From: Lynne Haber Sent: Thursday, May 01, 2003 11 :58 AM To: Meg Poehlmann Subject: Copper Phase II

Meg, Could you please take care of the rest of getting the paper resubmitted?

All of the files you need are on the server: Project files\copper\Publications Phase II\Resubmitted-post peer review.

This is what I need:

Print out the cover letter (coverlet) on letterhead for me to sign. The package to the publisher includes: Two hard copies of the revised manuscript (Copper phase II-revised) Two hard copies of the response to comment (Copper phase II-response to reviewers) A diskette with the revised manuscript.

Please also print a clean coppy of the revised manuscript for the files (I think you keep submitted papers down there, rather than with project files?) Please send regular mail.

I'd love to get this out today, but it can wait until Friday if you're swamped.

Celebrate when this goes out!!

Scott has cut us off on funding for this, given the history, so this isn't income generating. I'd prefer that you mark it as admin or professional development (you're contributing to a nonprofit - TERA). However, if you feel strongly that this should be billable, you can do the same thing I'm doing - marking to director's developmental reserve (my way of having Mike take some responsibility for the history here.)

Thank you!!

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