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of Massachusetts Department ENVIRONMENTAL PROTECTION The Occurrence, Health Effects & Regulation of Perchlorate in Massachusetts Tsedash Zewdie Office.

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Presentation on theme: "of Massachusetts Department ENVIRONMENTAL PROTECTION The Occurrence, Health Effects & Regulation of Perchlorate in Massachusetts Tsedash Zewdie Office."— Presentation transcript:

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2 of Massachusetts Department ENVIRONMENTAL PROTECTION The Occurrence, Health Effects & Regulation of Perchlorate in Massachusetts Tsedash Zewdie Office of Research & Standards Massachusetts Department of Environmental Protection tsedash

3 of Massachusetts Department ENVIRONMENTAL PROTECTION Acknowledgments ORS: Carol Rowan West, C. Mark Smith, Michael S. Hutcheson, Diane Manganaro MassDEP/MADPH Advisory Committee On Health Effects Staff of MassDEP’s Drinking Water Program and Bureau of Waste Site Cleanup

4 of Massachusetts Department ENVIRONMENTAL PROTECTION Topics I 1.Background information 2.Health effects and standard setting 3.Differences in standard setting between regulatory agencies 4.Conclusions II 1.Occurrence of perchlorate in MA drinking water supplies –Sources –Case studies 2.Conclusions

5 of Massachusetts Department ENVIRONMENTAL PROTECTION What is Perchlorate? Anion consisting of chlorine and oxygen (ClO 4 - ) Most common form is ammonium perchlorate Highly soluble and dissociates to give ClO 4 - Migrates to groundwater & stable in water for years

6 of Massachusetts Department ENVIRONMENTAL PROTECTION Rocket Fuel Uses of Perchlorate Flares Fireworks Military Weapons Blasting Agents Most Familiar Uses:

7 of Massachusetts Department ENVIRONMENTAL PROTECTION In The Beginning, There Was MMR – Perchlorate detected on-base (500  g/L) Perchlorate detected in Town of Bourne production wells at low (< 1 µg/L) No federal or state drinking water standard MassDEP set an interim drinking water guideline (www.mmr.org)

8 of Massachusetts Department ENVIRONMENTAL PROTECTION MADEP Drinking Water Guideline 1 µg/L for sensitive subgroups: pregnant and nursing women fetus, infant and young children individuals with hypothyroidism Showering at low concentrations OK

9 of Massachusetts Department ENVIRONMENTAL PROTECTION MassDEP decided to establish MCL in 2003 MassDEP issued its draft report for public review in 2004 (1  g/L). NAS Panel established RfD of 7 x mg/kg/d (2005) US EPA used NAS RfD and derived a DWEL of 24.5  g/L (2005) CA EPA and NJ proposed to set DWLs at 6, and 5  g/L respectively National drinking water standard is years away, if ever MassDEP took NAS results into account to to derive RfD and MCL Federal and State Activities on Perchlorate (2003 –2005)

10 of Massachusetts Department ENVIRONMENTAL PROTECTION Health Effects Assessment

11 of Massachusetts Department ENVIRONMENTAL PROTECTION NIS Perchlorate Mode of Action I-I- vs ClO4 - I-I- PO I TG I odinated thyroglobulin Enzymes T4,T3 Stroma Thyroid cellColloid NIS =Sodium Iodide Symporter PO =Peroxidase enzyme TG = Thyroglobulin IE = Iodinase enzyme Enzymes = lysozymes and proteases Pendrin Essential for metabolism, growth and development IE

12 of Massachusetts Department ENVIRONMENTAL PROTECTION Observed Downstream Effects Altered Thyroid and Pituitary Hormones Thyroid Histopathy – colloid depletion, hypertrophy and hyperplasia, goiter Developmental Effects – brain morphometry changes, behavioral effects Tumors and tumor promotion

13 of Massachusetts Department ENVIRONMENTAL PROTECTION Standard Setting

14 of Massachusetts Department ENVIRONMENTAL PROTECTION MA Perchlorate Reference Dose (RfD) MassDEP evaluated available animal and human data, and put more emphasis on a human iodide uptake inhibition study (Greer et al. 2002) mg/kg/d (LOAEL human IUI ) 100 (Uncertainty Factor) = 7 x mg/kg/d RfD =

15 of Massachusetts Department ENVIRONMENTAL PROTECTION MA MCL Development Used RfD and considered: Exposure parameters: 70 kg person drinking 2 L of H 2 0 RSCF of (0.2) (food being major source) Calculated drinking water level = 0.49  g/L Considered other factors (occurrence and level in water supplies and source, ability and costs to treat, health impacts) to determine MCL First in the Nation MA MCL (2006) = 2  g/L NSF (2006) study indicated levels of perchlorate in treated drinking water could be 2  g/L or higher

16 of Massachusetts Department ENVIRONMENTAL PROTECTION Known Sources of Perchlorate Exposure Emerging Information (2003) Research is Ongoing Lettuce 0 - 6,900  g/kg Cow’s Milk  g/L Breast Milk  g/L

17 of Massachusetts Department ENVIRONMENTAL PROTECTION State/ Agency POD (mg/kg/d) BasisUFRSC (%) RfD (mg/kg/d) DWL (  g/L) MA0.007 (LOAEL)Greer et al., = Hum. Var. 3 = LOAEL Adj. 3 = Dbase def 207 x * USEPA0.007 (NOEL)Greer et al., x CA (BMDL)Greer et al., x NJ (BMDL)Greer et al., x Comparison of Perchlorate Drinking Water Levels (DWL) *MA final drinking water standard (MCL) was 2  g/L after consideration of other factors (occurrence and level in water supplies, ability and costs to treat, health impacts)

18 of Massachusetts Department ENVIRONMENTAL PROTECTION Urinary Perchlorate and Thyroid Hormone Levels in Adolescent and Adult men and women Living in the USA (Blount et al., 2006) Performed one of a kind study correlating urine perchlorate with serum T4 and TSH Perchlorate was a significant predictor of T4 and TSH levels in iodine deficient women Perchlorate was a significant predictor of TSH in iodine sufficient women Perchlorate was not a significant predictor of T4 and TSH in men

19 of Massachusetts Department ENVIRONMENTAL PROTECTION Predicted Change in Serum Thyroxin a and Serum TSH b levels from changes in urinary perchlorate levels, women aged 12 and older, with urine iodine < 100  g/L, NHANES

20 of Massachusetts Department ENVIRONMENTAL PROTECTION Perchlorate Exposure and Thyroid Function in California Neonates; Infant Characteristics versus Perchlorate Levels in Drinking Water (Schwartz, 2001) Perchlorate Concentration None (0 ppb) Low (1-2 ppb) Medium (3-12 ppb) High  13 ppb Test stat p Value (df) No. of infants255,382 (49.5) 127,041 (24.6) 131,483 (25.5) 1,945 (0.4) Female, % T4 mg/dL) Mean (SD) (50.9) (48.7) (48.3) (44.0) F = P <0.001 (3) TSH, (  U/mL) Mean (SD) 7.6 (18.8) 7.6 (19.8) 7.7 (19.4) 7.9 (4.6) F = 0.05 P = 0.9 (3) SD = Standard deviation; df = degree of freedom

21 of Massachusetts Department ENVIRONMENTAL PROTECTION Conclusions MassDEP: took the weight of evidence approach in evaluating the toxicity of perchlorate used human data accounting for all possible uncertainties in the database for standard setting considered various factors and set the MCL at 2  g/L

22 of Massachusetts Department ENVIRONMENTAL PROTECTION Perchlorate Occurrence in MA Drinking water, Sources, and Case Studies

23 of Massachusetts Department ENVIRONMENTAL PROTECTION Perchlorate Occurrence Monitoring Detections (> 1 µ g/L) March 2004 – February 2005 (approximately 700 systems)

24 of Massachusetts Department ENVIRONMENTAL PROTECTION MA DEP Follow-Up Investigations Site specific investigations private well sampling conducted by MADEP near contaminated public supply wells... Testing and evaluation of suspected source materials and activities.

25 of Massachusetts Department ENVIRONMENTAL PROTECTION Source Discovery Fireworks Blasting Sodium Hypochlorite Industrial Discharges

26 of Massachusetts Department ENVIRONMENTAL PROTECTION Fireworks Perchlorate use and content has increased over time Primary uses are to produce color effects and loud bang/flash Potential Environmental Release Pathways  Atmospheric fallout  Duds  Misfires Sodium Hypochlorite

27 of Massachusetts Department ENVIRONMENTAL PROTECTION Water Supply Wells 0.44 to 8.9  g/L Chesterfield, MA Perchlorate in Public Water Supply Well, Private Wells, and Fireworks Display Location

28 of Massachusetts Department ENVIRONMENTAL PROTECTION ANFO 95,000 LBS Slurran XLS (SEC) 9,500 LBS % Ammonium Perchlorate Westford, Mass

29 of Massachusetts Department ENVIRONMENTAL PROTECTION Westford, MA Construction of new municipal highway garage Perchlorate in Public Water Supply Well

30 of Massachusetts Department ENVIRONMENTAL PROTECTION Westford, MA Perchlorate in Public Water Supply Well and Fireworks Display Locations

31 of Massachusetts Department ENVIRONMENTAL PROTECTION Westford, MA Perchlorate in Public Water Supply Well, Fireworks Display Locations and Blasting Site

32 of Massachusetts Department ENVIRONMENTAL PROTECTION Blasting Blasting is locally regulated (harder to get handle on state-wide activities) DEP worked with Department of Fire Services and Fire Marshall (http://mass.gov/dfs) to draft a letter to blasting contractors and interested parties (http://www.mass.gov/dep/bwsc/files/blasting.htm) Perchlorates used as a sensitizer in a relatively small percentage of blasting agents and explosives; primarily water gel and emulsion formulations

33 of Massachusetts Department ENVIRONMENTAL PROTECTION ANFO: 621,000 LBS Detagel: 360 LBS (?) “< 7% Ammonium Perchlorate” Blasting Caps: EZ-Det 0.5% Potassium Perchlorate (?) Millbury, MA

34 of Massachusetts Department ENVIRONMENTAL PROTECTION The Merrimac River Hits greater than 1 µg/L in Surface Water Supply (Tewksbury) DEP conducted source investigation: –Ambient sampling of Merrimac and Concord Rivers –Influent, Process & Effluent sampling of WWTPs –Mapping & sampling of sites, facilities and other sources along the rivers –Concurrent sampling using IC and LC/MS/MS

35 of Massachusetts Department ENVIRONMENTAL PROTECTION Perchloric Acid Discharge Concord and Merrimack Rivers, MA Tewksbury, MA 1-3  g/L in the public water supply system in Tewksbury Public water supply system draws water from the Merrimack river

36 of Massachusetts Department ENVIRONMENTAL PROTECTION Industrial Discharges and Hypochlorite Perchloric acid is a powerful oxidizing agent Industrial-scale discharges of process wastewater have the potential to create significant impacts to groundwater and surface water Perchlorate is present in hypochlorite solutions used in commercial and household applications

37 of Massachusetts Department ENVIRONMENTAL PROTECTION Commercial Hypochlorite Products PlantBrand Perchlorate (  g/L) LC/MS/MS Lowell WWTPUnivar3400 Lowell WWTPJones260 Billerica WWTPUnivar4600 Tewksbury WTPUnivar4100

38 of Massachusetts Department ENVIRONMENTAL PROTECTION Commercial Hypochlorite Product – Storage Study AgeStorage Perchlorate (  g/L) LC/MS/MS NewJust DeliveredN.D. 26 Days Cool (5  C) 995/ Days Filtered (5  C) DaysRoom Temp6750

39 of Massachusetts Department ENVIRONMENTAL PROTECTION BrandBrand Info Perchlorate  g/L LC/MS/MS Chlorox6% NaOCl370 Shaws2.5 years old8000 Market Basket 6% NaOCl390 Walmart6% NaOCl89 Household Bleach

40 of Massachusetts Department ENVIRONMENTAL PROTECTION Perchlorate Occurrence Monitoring March – October Public Water Supply Data Only (693 systems) Town Maximum (µg/L)Source? Boxboro1,300Blasting Chesterfield8.9Fireworks Hadley3.8Unknown Millbury45Blasting Southbridge3.1Unknown Tewksbury3.3Industry Westford3.7Blasting Westport3Fireworks Williamstown10Fireworks

41 of Massachusetts Department ENVIRONMENTAL PROTECTION Conclusions Occurrence monitoring data may prompt regulation of disinfecting products nationally Perchlorate contamination is not pervasive in Massachusetts Localized impacts exist and present risks Most significant Sources of GW contamination: –Military use (hundreds of µg/L) –Blasting (tens-to-hundreds of µg/L) –Fireworks (up-to-tens of µg/L)

42 of Massachusetts Department ENVIRONMENTAL PROTECTION For More Information…


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