Env-Or 600 Contaminated Site Management Rule

Update

Waste Management Division Updates

September 12, 2008

Env-Or 600 Update

Effective July 23, 2008 Ambient Ground Water Quality Standards Soil Remediation Standards Groundwater Management Permit

Procedures Expedited Review Fees

Env-Or 600 Update

AMBIENT GROUNDWATER QUALITY STANDARDS

Chemical NameOld

AGQSug/L (ppb)

NewAGQS

ug/L (ppb)

Aldrin 0.04 0.1

Benzo(a)anthracene 0.05 0.1

Benzo(b)fluoranthene 0.05 0.1

Dibenzo(a,h)anthracene 0.005 0.1

Dichloropropene, 1,3- 0.4 0.5

Dieldrin 0.002 0.1

Hexachlorocyclohexane, alpha 0.006 0.1

Hexachlorocyclohexane, beta 0.02 0.1

Hexachlorocyclohexane, gamma (Lindane) 0.02 0.2

Indeno(1,2,3-cd)pyrene 0.05 0.1

Env-Or 600 UpdateSOIL REMEDIATION STANDARDS

Chemical NameOld

Standard(mg/kg).

NewStandard(mg/kg)

Benzidine 0.002 0.004

Benzo(a)anthracene 0.7 1

Benzo(b)fluoranthene 0.7 1

Benzo(k)fluoranthene 4 12

Chlordane 2 4

Chlorotrifluoroethylene (CFC1113) 0.1 NA

Chrysene 44 120

2,4-D (Dichlorophenooxy acetic acid, 2,4-) 4 300

DDD (Dichlorodiphenyl dichloroethane, p,p’) 4 6

DDE (Dichlorodiphenyl dichloroethylene, p,p’) 2 4

DDT (Dichlorodiphenyl trichloroethane, p,p’) 2 4

Dichlorobenzidine, 3,3’- 0.2 0.7

Di-(2-ethylhexyl)phthalate (DEHP) 30 72

Env-Or 600 Update

SOIL REMEDIATION STANDARDS

Chemical NameOld

Standard(mg/kg).

NewStandard(mg/kg)

Dinitrophenol, 2,4- 3 0.7

Diphenylhydrazine, 1,2- 0.5 1

Diquat (dibromide) 0.2 0.3

Ethylene glycol 86 91

Formaldehyde 2 1

Heptachlor 0.09 0.2

Hexachlorobenzene 0.7 0.8

Hexachlorodibenzodioxin, 2,3,7,8- 0.0001 0.00007

Indeno(1,2,3-cd)pyrene 0.7 1

Toxaphene 0.8 1

2,4,5-TP (Silvex) 260 60

Trichloropropane, 1,2,3- 0.1 0.2

Env-Or 600 Update

Env-Or 607.02 Groundwater Management Permit Procedures.

(2) Provide notification on a form provided by the department by certified mail, return receipt requested, to all owners of properties specified in Env-Or 607.03(a)(20) that their property is proposed for inclusion within the GMZ;

http://www.des.nh.gov/orcb/doclist/prop_gd_ma_permit.doc

Env-Or 600 Update

Env-Or 607.03 Groundwater Management Permit Application.

(16) Certification that notification has been provided to all owners of lots proposed for inclusion in the GMZ as required by Env-Or 607.02(b)(2);

Env-Or 600 Update

Env-Or 607.08 Permit Notification. (a) Within 3030 15 days after the department

issues the groundwater management permit, the permittee shall provide notice of the permit by certified mail, return receipt requested, to all owners of lots of record within the GMZ.

(b) Within 6060 45 days after the department issues the groundwater management permit, the permittee shall submit documentation of the notification required by (a), above, to the department.

Env-Or 600 Update

Fees for Expedited Reviews as specified in RSA 485:3-b, I

Equalized Assessed Valuation

Fee

$0 to $250,000 $1,800

$250,001 to $500,000 $2,250

$500,001 to $1,000,000 $3,750

greater than $1,000,000 $7,500

Env-Or 600 Update Summary

Effective July 23, 2008 Ambient Ground Water Quality Standards Soil Remediation Standards Groundwater Management Permit

Procedures Expedited Review Fees

Env-Or 600NHDES Contact

Robin Mongeon, P.E.Waste Management Division29 Hazen DriveConcord, NH 03301Tel: (603) 271-7378Fax: (603) 271-2181E-mail: Robin.Mongeon@des.nh.gov

Env-Or 607.09, Recordation

Groundwater Management Recordation Procedures

Env-Or 607.09, Recordation Updates - Private Sector Feedback Registry Index - Grantor/Grantee New Notice & Release of Notice Forms Links Contact Info

Grantor/Grantee Index

Grantor/Grantee Search

NOTICE OF GROUNDWATER MANAGEMENT PERMITGWP-_________-A-001

TO BE RECORDED AGAINST:

[IDENTIFY OWNER OF PARCEL AND BOOK AND PAGE OF DEED IN TO THAT PARTY]

NOTICE IS HEREBY GIVEN THAT: The New Hampshire Department of Environmental Services (Department) has issued Groundwater Management Permit #GWP-_________-A-001 (“Permit”) to [Permittee]. Pursuant to Env-Or 607.09(a) this notice is recorded for each property located within the groundwater management zone identified in the Permit at the Registry of Deeds for the county in which the property is located.

The Permit establishes a Groundwater Management Zone (“GMZ”), an area within which groundwater use must be controlled and monitored due to the presence of groundwater contaminants that exceed the State’s Ambient Groundwater Quality Standards (“AGQS”). The Permit may include conditions to and restrictions upon the use of the properties within the GMZ, including restrictions on the use of groundwater.

The Permit was issued on [Date] and expires on [Date], unless renewed for subsequent five-year period(s). This Notice will remain in effect until such time as the AGQS are restored within the GMZ and the Department issues a Release of Recordation to the Permittee. The Permit is available for review at the New Hampshire Department of Environmental Services, 29 Hazen Drive, Concord, NH 03301 or can be viewed by searching under our OneStop Data Retrieval Site at http://www2.des.nh.gov/OneStop/ORCB_Query.aspx?Project+CCST .

The following properties are located within the GMZ:

Property Owner/Property Address Tax Map/Lot Deed Reference Book/Page

/s/ [Permittee Name], Permittee ______________[Company Name] Date

Form

DISCHARGE AND RELEASE OF NOTICE OF GROUNDWATER MANAGEMENT PERMIT

TO BE RECORDED IN FAVOR OF [CURRENT OWNER OF PARCEL IDENTIFIED IN ORIGINAL OR AMENDED

NOTICE]at [BOOK /PAGE OF DEED IN TO THAT PARTY]

For value received, the State of New Hampshire Department of Environmental Services, issuer of a groundwater management permit GWP-_________-A-_ to [name of Permittee] and recorded by Notice of Groundwater Management Permit, dated ____, against the real property of [name of property owner], in __________ County Registry of Deeds at Book __________, Page __________, hereby discharges and releases the said Notice of Groundwater Management Permit.

Subscribed, sworn to and acknowledged before me by ______________, the issuer, this __________ day of __________, 20__________.

____________________________Carl W. Baxter, P.E., AdministratorHazardous Waste Remediation BureauWaste Management Division_________________________Printed Name_______________Notary Public/Justice of the PeaceMy commission expires_________

Form

Env-OR 607.09 RecordationLink to Notice Forms:http://www.des.state.nh.us/ORCB/DOCLIST/notice_of_gmp.dochttp://www.des.state.nh.us/ORCB/DOCLIST/landfill_notice_of_gmp.doc

Env-Or 607.09 RecordationNHDES ContactKarlee Kenison, P.G.Waste Management Division29 Hazen Drive Concord, NH 03301-0095Tel: (603) 271-6542Fax: (603) 271-2181Email: karlee.kenison@des.nh.gov

Low-Level Ethylene Dibromide (EDB)

Screening Program Update

Kenneth Richards, P.G.

NH Department of Environmental Services

Low-Level Ethylene Dibromide (EDB)

Screening Program Update

Kenneth Richards, P.G.

NH Department of Environmental Services

Ethylene Dibromide (EDB) Also known as 1,2-dibromomethane and numerous trade

names and acronyms

Used in the past as a leaded gas additive (phased out in 1985) and soil fumigant (banned in 1984) for crops and turf (golf courses). Also as a solvent, waterproofing agent, in dyes & pharmaceuticals

Still used in aviation and racing fuels and chemical formulations

Released to the environment by leaded gasoline spills and land applications as a pesticide

Ethylene Dibromide (EDB) (cont.)

EDB is a volatile organic compound (VOC) and is included on the U.S. EPA SW-846 Method 8260 list of analytes

The Method 8260 detection limit for EDB in relatively clean samples is generally 0.5 – 1.0 ug/l

The Federal Maximum Contaminant Level (MCL) and New Hampshire AGQS for EDB is 0.05 ug/l

Program Goals Identify EDB presence/absence at NH Sites

Identify potential EDB impacts to drinking water wells

Provide basis to formulate modified monitoring programs at identified EDB sites to include low-level EDB analysis

Site & Sampling Point Selection

Release sites with known gasoline storage in 1985 or earlier

Sampling points selected along transect of contaminant plume

In general, samples collected from one source area well, one mid-plume well & one distal well

Analytical Methods For Low-Level EDB Detection

US EPA SW-846 Method 8011

US EPA SW-846 Method 504.1

US EPA SW-846 Method 8260 SIM (Selective Ion Method)

Preliminary Results

200 sites during Spring, 2008 groundwater sampling rounds; 700 groundwater samples analyzed

EDB positively detected at 15% of sites sampled

Detections ranged up to 650 ug/l

45% of the EDB detections were <1.0 ug/l

Preliminary Results (cont.)

EDB detections primarily found at sampling points within or immediately downgradient of source areas

EDB not identified in water supply wells included in program

U.S. EPA LNAPL Screening Study EPA analyzed LNAPL collected from 28 older

release sites in 8 states

DES coordinated the submittal of 23 LNAPL samples from 8 NH sites

EDB identified in LNAPL samples from 4 of the 8 NH sites

EDB detected at levels ranging from 0.15mg/l to 255.28 mg/l

Path Forward

Second round of low-level EDB screening to be conducted during the Fall 2008 groundwater sampling rounds

DES has been requesting field pH measurements on wells included in Fall screening round

Individual EDB site strategy should be developed in consultation with DES project managers

1,4-Dioxane and 1,2-1,4-Dioxane and 1,2-Dibromoethane (EDB)Dibromoethane (EDB)

Analytical Methods ReviewAnalytical Methods Review

Lou Barinelli, Assistant Director, Lou Barinelli, Assistant Director, NHDES LaboratoryNHDES Laboratory

1,4-Dioxane 1,4-Dioxane

• MW=88.11MW=88.11

• Density=1.03Density=1.03

• BP=101.1BP=101.1

• Soluble in waterSoluble in water

Available MethodsAvailable Methods

• EPA Method 8260B (C)EPA Method 8260B (C)– Purge and Trap-GC/MSPurge and Trap-GC/MS

• EPA Method 8270C (D)EPA Method 8270C (D)– Liquid/Liquid Extraction-GC/MSLiquid/Liquid Extraction-GC/MS

• EPA Method 8261AEPA Method 8261A– Vacuum Distillation-GC/MSVacuum Distillation-GC/MS

EPA Method 8260EPA Method 8260

• In order to meet low level reporting In order to meet low level reporting limits on the order of 3 ppb, must limits on the order of 3 ppb, must make modificationsmake modifications

• Heat sample during purge cycle (80-Heat sample during purge cycle (80-90 90 ooC)C)

• Acquire data in SIM Acquisition Mode Acquire data in SIM Acquisition Mode

• Use 1,4-dioxane-d8 as an internal or Use 1,4-dioxane-d8 as an internal or surrogate standardsurrogate standard

EPA Method 8270CEPA Method 8270C

• Extract 1L of waterExtract 1L of water

• Concentrate ExtractConcentrate Extract

• Use Isotope Dilution (1,4-dioxane-d8)Use Isotope Dilution (1,4-dioxane-d8)

• Acquire data in SIM Acquisition ModeAcquire data in SIM Acquisition Mode

EPA Method 8261AEPA Method 8261A

• Sample is placed in a distillation chamberSample is placed in a distillation chamber

• The chamber is placed under vacuumThe chamber is placed under vacuum

• The vapor is passed through a chilled coil The vapor is passed through a chilled coil at 5 at 5 ooC to condense the water C to condense the water

• The uncondensed distillate is The uncondensed distillate is cryogenically trapped at -196 cryogenically trapped at -196 ooC (liquid C (liquid nitrogen temp)nitrogen temp)

• Analytes transferred to GC/MS Analytes transferred to GC/MS

EPA Method 8260B EPA Method 8260B AdvantagesAdvantages

• Most labs familiar with P&T techniqueMost labs familiar with P&T technique

• Minimal sample prepMinimal sample prep

• Automation possibleAutomation possible

• Can achieve reporting limits 2-5 ppb Can achieve reporting limits 2-5 ppb

EPA Method 8260B EPA Method 8260B DisadvantagesDisadvantages

• 1,4-Dioxane has poor purging 1,4-Dioxane has poor purging efficiency, can be compensated for efficiency, can be compensated for by heated purge and isotope dilutionby heated purge and isotope dilution

• If Method not managed correctly can If Method not managed correctly can encounter problems with carry over encounter problems with carry over or poor reproducibilityor poor reproducibility

Method 8270C AdvantagesMethod 8270C Advantages

• Most labs familiar with techniqueMost labs familiar with technique

• Can achieve reporting limits 1-3 ppbCan achieve reporting limits 1-3 ppb

• Modified to use isotope dilution Modified to use isotope dilution

Method 8270C Method 8270C DisadvantagesDisadvantages

• Possible losses during extraction Possible losses during extraction procedureprocedure

• Possible losses during collection and Possible losses during collection and transport (samples collected with transport (samples collected with headspace)headspace)

• Labor intensive for some labsLabor intensive for some labs

EPA Method 8261 EPA Method 8261 AdvantagesAdvantages

• Easily achieve 1-2 ppb reporting limitEasily achieve 1-2 ppb reporting limit

• Potential for sub-ppb reporting limits Potential for sub-ppb reporting limits with SIMwith SIM

• Minimal sample prepMinimal sample prep

• Isotope dilution is standard Isotope dilution is standard procedureprocedure

Method 8261A Method 8261A DisadvantagesDisadvantages

• New TechniqueNew Technique

• Not common for most labsNot common for most labs

• Only 1 Instrument ManufacturerOnly 1 Instrument Manufacturer

• Requires liquid nitrogenRequires liquid nitrogen

• Cost of equipment and operationCost of equipment and operation

Misc. InfoMisc. Info

• Ref: "1,4-Dioxane - Environmental Ref: "1,4-Dioxane - Environmental and Measurement issues" - Timothy and Measurement issues" - Timothy W. Fitzpatrick & Kerry Tate, State of W. Fitzpatrick & Kerry Tate, State of Florida Department of Environmental Florida Department of Environmental Protection“Protection“

1,2-Dibromoethane1,2-Dibromoethane

• Available MethodsAvailable Methods– Purge & Trap GC/MS (SIM Acquisition)Purge & Trap GC/MS (SIM Acquisition)– Micro-Extraction GC/ECDMicro-Extraction GC/ECD

Purge & Trap GC/MSPurge & Trap GC/MS

• Method 8260Method 8260– 5 or 25 mL purge volume5 or 25 mL purge volume– SIM acquisition allows for lower SIM acquisition allows for lower

reporting limitreporting limit

GC/ECDGC/ECD

• Methods 8011 or 504Methods 8011 or 504– Micro extraction with hexaneMicro extraction with hexane– Direct injection on GC/ECDDirect injection on GC/ECD– Dual column confirmationDual column confirmation– ECD selective for halogenated ECD selective for halogenated

compoundscompounds

1,4 Dioxane – Background Sampling Requirements, Treatment Technologies and Initial Results

Frederick J. McGarry, P.E., DEE, Assistant Director, WMD

O

O

CH2

CH2

H2C

H2C

1,4 Dioxane

Background, Sampling Requirements, Treatment and Initial Results

Sept. 12, 2008

1,4 Dioxane

What is it? Why are we concerned about it? What are the sampling requirements? How can it be treated?

Characteristics of 1,4-Dioxane

Solubility – Infinite solubility in water Low Koc therefore low affinity for activated

carbon Low vapor pressure Most mobile contaminant @ solvent release

sites Footprint may be many times greater than

TCA plume (up to 6X greater)

Characteristics (cont.) Occurs more in water than in soil Stays more in water than going to air Volatilization is slow Resistant to biological degradation Will not hydrolyze Attenuation?

Dilution Dispersion Volatilization

Uses for 1,4-Dioxane

Stabilizer for chlorinated solvents (TCA) added 2-8% by volume

Paint strippers Dyes De-greasers Varnishes Impurity in antifreeze and deicing fluids Deodorants, shampoos, & cosmetics

23 ppm in Clairol Herbal Essence shampoo 12 ppm in Hello Kitty Bubble Bath

Health Effects of 1,4 Dioxane

Group B2 carcinogen:

“. . . reasonably anticipated to be a human carcinogen”

Cancer of gall bladder, lungs, skin, and liver in laboratory mice.

Drinking Water Standards for 1,4-Dioxane

EPA IRIS: 1x10-6 cancer risk – 3 ppb EPA Regions 3 & 6 screening level – 6.1 ppb State cleanup guidelines – 3 to 85 ppb World Health Organization – 50 ppb (10-5 cancer

risk) NH AGQS – 3 ppb NJ – 3 ppb Conn, Vt – 20 ppb Maine – 32 ppb (10-5 cancer risk) Mass – GW-1 of 3 ppb

Presence of 1,4 Dioxane

Superfund Sites: Keefe (Epping) – Max. conc. of 842 ppb

In Mar. 2004 present in 28 of 35 wells Ottati & Goss (Kingston) – Max. conc. 260 ppb

Presence of 1,4 Dioxane (cont.)

Likely present in wastewater discharges (0.25 mg/person/day = 1 ppb)

Landfill leachate – Colebrook - 98 ppb; in 21 of 34 wells Newmarket - 610 ppb; in 22 of 29 wells Newport - 240 ppb; in 6 of 9 wells Hopkinton - 14 ppb; in 3 of 8 wells

Groundwater in Tokyo – 0.05 to 113 ppb, avg. 2.23 ppb

Tama River in Japan 0.06 to 5 ppb (likely due to flow from WWTF)

1,4-Dioxane At Haz. Waste Sites

1,1,1-TCA AGQS – 200 ppb 2-8% 1,4-dioxane in TCA Dioxane could be controlling contaminant at

TCA site (3 ppb vs. 200 ppb) TCA breaks down to 1,1-DCA or 1,1-DCE DCA could be primary contaminant w/o TCA

& dioxane be present & controlling

Dioxane Sampling Requirements

New haz. waste sites after Jan. 30, 2008 Sites receiving new GWMP in 2008 GWMPs where public/ private wells sampled GWMPs or sampling programs where dioxane

is an identified analyte Haz waste sites w/ TCA, DCA, or DCE present Haz waste sites, salvage yards, landfills after

Jan.1, 2009 Waiver of sampling w/ 2 rounds ND

Remediation for 1,4-Dioxane

SVE for removal from soil but . . . Biodegradation in presence of THF GAC generally inappropriate Air stripping poor due to low Henry’s Law

coef. but does work (47% and 28% removal Colebrook, 65% removal Hadco)

AOP appears best process Ozone/peroxide Peroxide and UV light

Remediation for 1,4-Dioxane (cont.)

Air sparging is ineffective Zero-valent iron walls don’t work ISCO has worked

H2O2 plus ozone Fenton’s reagent Permanganate Persulfate Ozone alone

Phytoremediation effective

1,4 Dioxane Summary

Highly mobile, recalcitrant compound Present at many haz. waste sites Likely present at active & inactive landfills Low AGQS May be controlling contaminant at some sites Can be treated in-situ by ISCO and ex-situ by

AOP Additional sampling results beginning 2009

will help define extent of this contaminant