The Occurrence, Health Effects & Regulation of Perchlorate in Massachusetts

Tsedash Zewdie Office of Research & Standards Massachusetts Department of Environmental Protection tsedash [email protected]

http://mass.gov/dep/water/drinking/percinfo.htm

Massachusetts Department

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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 Massachusetts Department

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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 Massachusetts Department

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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 Massachusetts Department

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Uses of Perchlorate

Most Familiar Uses:

Rocket Fuel Military Weapons Fireworks Flares Blasting Agents Massachusetts Department

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•

In The Beginning, There Was MMR...

2000 – Perchlorate detected on-base (500



g/L)

•

2002- 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) Massachusetts Department

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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 Massachusetts Department

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Federal and State Activities on Perchlorate (2003 –2005)

• 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 10 -4 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 Massachusetts Department

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Health Effects Assessment

Massachusetts Department

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Perchlorate Mode of Action Stroma Thyroid cell Colloid I vs ClO4 NIS I -

PO

I TG

Pendrin

IE ClO 4 I odinated thyroglobulin

Enzymes

T4,T3 T4, T3

Essential for metabolism, growth and development NIS =Sodium Iodide Symporter PO =Peroxidase enzyme TG = Thyroglobulin IE = Iodinase enzyme Enzymes = lysozymes and proteases

Massachusetts Department

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• • • •

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 Massachusetts Department

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Standard Setting

Massachusetts Department

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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) RfD = 0.007 mg/kg/d (LOAEL human IUI ) 100 (Uncertainty Factor) =

7 x 10 -5 mg/kg/d

Massachusetts Department

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• • • • • •

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

Massachusetts Department

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Known Sources of Perchlorate Exposure

• • • Emerging Information (2003) Research is Ongoing Lettuce Cow’s Milk Breast Milk 0 - 6,900  g/kg 0 - 11  g/L 1.4 - 92  g/L Massachusetts Department

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Comparison of Perchlorate Drinking Water Levels (DWL)

State/ Agency MA POD (mg/kg/d) 0.007 (LOAEL) Basis Greer et al., 2002 UF 100 10 = Hum. Var.

3 = LOAEL Adj.

3 = Dbase def RSC (%) 20 RfD (mg/kg/d) 7 x 10 -5 USEPA 0.007 (NOEL) Greer et al., 2002 10 7 x 10 -4 DWL (



g/L) 0.4* 24.5

CA NJ 0.0037 (BMDL) 0.0037 (BMDL) Greer et al., 2002 Greer et al., 2002 10 10 60 20 3.7 x 10 3.7 x 10 -4 -4 6 5 *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 )

Massachusetts Department

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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 Massachusetts Department

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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 2001-2002 Change in Urine Perchlorate (0.19  g/L is minimum level measured ) Change in thyroxin (  gdL) Change in TSH (IU/L) Depends on initial TSH level 0.19 to 0.65 mg/L (5 th percentile) 0.19 to 0.92 mg/L (10 th percentile) 0.19 to 1.6 mg/L (25 th percentile) 0.19 to 2.9 mg/L (50 th percentile) 0.19 to 5.2 mg/L (75 th percentile) 0.19 to 9.0 mg/L (90 th percentile) 0.19 to 13 mg/L (95 th percentile) 0.19 to 100 mg/L (maximum) a Normal range for thyroxin 5-12  g/dl b Normal range for TSH: 0.3-4.5 IU/L 0.48

0.61

0.83

1.06

1.28

1.49

1.64

2.43

Initial TSH of 1.40 IU/L (50 th percentile) 0.23

0.30

0.42

0.56

0.70

0.85

0.95

1.63

Initial TSH of 3.11 IU/L (90 th percentile) 0.51

0.67

0.93

1.24

1.56

1.89

2.21

3.61

Massachusetts Department

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Perchlorate Exposure and Thyroid Function in California Neonates; Infant Characteristics versus Perchlorate Levels in Drinking Water (Schwartz, 2001)

No. of infants None (0 ppb) 255,382 (49.5) Perchlorate Concentration Low (1-2 ppb) 127,041 (24.6) Medium (3-12 ppb) 131,483 (25.5) High  13 ppb 1,945 (0.4) Test stat p Value (df) Female, % T4 mg/dL) Mean (SD) 48 179.9

(50.9) 48.8

162.1

(48.7) TSH, (  U/mL) Mean (SD) 7.6 (18.8) 7.6 (19.8)

SD = Standard deviation; df = degree of freedom

49 160.6

(48.3) 7.7 (19.4) 49 150.5

(44.0) 7.9 (4.6) F = 1649.6

P <0.001 (3) F = 0.05

P = 0.9 (3) Massachusetts Department

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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 Massachusetts Department

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Perchlorate Occurrence in MA Drinking water, Sources, and Case Studies

Massachusetts Department

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Perchlorate Occurrence Monitoring

Detections (> 1 µ g/L) March 2004 – February 2005 (approximately 700 systems)

Massachusetts Department

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• •

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 .

Massachusetts Department

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Source Discovery

• Fireworks • Blasting • Sodium Hypochlorite • Industrial Discharges Massachusetts Department

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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 Massachusetts Department

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Chesterfield, MA Water Supply Wells 0.44 to 8.9



g/L Perchlorate in Public Water Supply Well, Private Wells, and Fireworks Display Location

Massachusetts Department

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Westford, Mass ANFO 95,000 LBS Slurran XLS (SEC) 9,500 LBS 20-30 % Ammonium Perchlorate

Massachusetts Department

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Westford, MA Construction of new municipal highway garage Perchlorate in Public Water Supply Well

Massachusetts Department

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Westford, MA Perchlorate in Public Water Supply Well and Fireworks Display Locations

Massachusetts Department

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Westford, MA Perchlorate in Public Water Supply Well, Fireworks Display Locations and Blasting Site

Massachusetts Department

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Blasting

Perchlorates used as a sensitizer in a relatively small percentage of blasting agents and explosives; primarily water gel and emulsion formulations 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) Massachusetts Department

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Millbury, MA ANFO: 621,000 LBS Detagel: 360 LBS (?)

“< 7% Ammonium Perchlorate”

Blasting Caps: EZ-Det

0.5% Potassium Perchlorate (?) Massachusetts Department

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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

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Influent, Process & Effluent sampling of WWTPs

–

Mapping & sampling of sites, facilities and other sources along the rivers

Massachusetts Department –

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Concurrent sampling using IC and LC/MS/MS

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 Massachusetts Department

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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 Massachusetts Department

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Commercial Hypochlorite Products

Plant

Lowell WWTP

Brand

Univar

Perchlorate (



g/L) LC/MS/MS

3400 Lowell WWTP Jones 260 Billerica WWTP Univar 4600 Tewksbury WTP Univar 4100 Massachusetts Department

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Age

New

Commercial Hypochlorite Product – Storage Study

Perchlorate (



g/L) LC/MS/MS Storage

Just Delivered N.D.

26 Days 26 Days Cool (5  C) Filtered (5  C) 995/1020 490 26 Days Room Temp 6750 Massachusetts Department

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Brand

Chlorox

Household Bleach

Brand Info

6% NaOCl

Perchlorate



g/L LC/MS/MS

370 Shaws Market Basket Walmart 2.5 years old 6% NaOCl 6% NaOCl 8000 390 89 Massachusetts Department

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Perchlorate Occurrence Monitoring

March – October 2004 - Public Water Supply Data Only (693 systems)

Town

Boxboro Chesterfield Hadley Millbury Southbridge Tewksbury Westford Westport Williamstown

Maximum (µg/L)

1,300 8.9

3.8

45 3.1

3.3

3.7

3 10

Source?

Blasting Fireworks Unknown Blasting Unknown Industry Blasting Fireworks Fireworks Massachusetts Department

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Conclusions

• Occurrence monitoring data may prompt regulation of disinfecting products nationally • Perchlorate contamination is

not

Massachusetts pervasive in • 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) Massachusetts Department

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For More Information…

http://Mass.Gov/dep Massachusetts Department

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