Wastewater Characteristics from Marcellus Shale … Characteristics from Marcellus Shale Gas...

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Wastewater Characteristics from Marcellus

Shale Gas Development in Pennsylvania

Managing the Risks of Shale Gas Development

Resources for the Future

Washington, DC

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RFF project focuses on environmental risks

from shale gas development Purpose of this work

• Statistically analyze characteristics of flowback,

produced water, and drilling fluid waste sent to

wastewater treatment facilities in PA, 2008-2011.

• If recycling, treatment, and disposal options involve

exposure to the environment/human health, knowledge

of wastewater constituents helps quantify risks.

• Results may be useful in: • Evaluating current and future wastewater treatment

technologies, infrastructure capacity, and siting.

• Understanding potential impacts of treated wastewater on rivers

and streams.

• Setting effluent standards

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from shale gas development Comparison with Other Analyses

• Marcellus Shale Water Characterization funded by

Marcellus Shale Coalition and ASWCMC Consortia. • Consistent sampling from 19 locations, analysis performed by a

single lab, flowback samples at 0, 1, 5, 14, 90 days.

• GE also has a database (data from various shales).

• Data in our analysis are publicly available, focus on

waste sent to treatment facilities (rather than recycling,

deep injection), include drilling fluid waste and other

categories.

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from shale gas development Data Source: Form 26R, submitted

to PADEP by “residual waste” generators

• Generator information

• Waste description (pH range, physical

state, appearance)

• Chemical analysis attachments

• Process description, schematic diagrams

• Management of residual waste – location

information for processing/disposal

facilities, information about beneficial use

• Certification

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from shale gas development When is a Form 26R required?

• A company that generates > 2200

pounds of residual waste from a

“generating location” in a single

month during the calendar year

must file a Form26R by March 1 of

the following year.

• Non-hazardous industrial waste

• Individual chemical analysis

required for each waste type (DEP

waste codes)

2540-PM-BWM0404 Rev. 8/2010 Codes

RESIDUAL WASTE CODES (RWC)

GENERIC MANUFACTURING WASTES (Continued) 413 Asphalt (Bituminous), Asphalt Shingles 414 Ceramic Waste 415 Linoleum Wastes 416 Thermal Insulation Wastes (Cellulose, Glass,

Wool) 417 Wiring, Conduit, Electrical Insulation 418 Sawdust, Wood Shavings/Turnings 419 Empty Containers (Metallic, Non-Metallic Drums,

Pails) 420 Process Wastewaters (Non-Haz) (Do Not Report

Sanitary Sewage Or Uncontaminated Non-Contact Cooling Water)

421 Contaminated Non-Contact Cooling Waters 422 Oil/Water Emulsions, Oily Wastewaters 423 Landfill Leachate 424 Treated Wood, Railroad Ties 430 Food Waste (Excluding Wastewater Treatment

Sludge) 440 Resins 450 Polymers (Other Than 407, 409) 460 Vinyl (Sheet, Upholstery) 470 Spent Filters (Air/Gas) 471 Spent Filters (Aqueous) 472 Spent Filters (Non-Haz Fuel, Oil, Solvent) 473 Paint Filters, Other Cloth/Paper Filters,

Supersacs 474 Grease 480 Refractory (Furnace, Boiler) (Other Than 103) 481 Carbon/Graphite Residue/Scrap 482 Baghouse Dust (Other Than 105, 106) 483 Blasting Abrasive/Residue (Other Than 109) 484 Gypsum Plaster Molds, Drywall 499 Other Generic Waste

SPECIAL HANDLING WASTES 501 Asbestos Containing Waste (insulation, brake

lining, etc.) 502 PCB containing waste 503 Oil Containing Waste (absorbant, rags) 504 Paints (Liquid) 505 Spent Catalysts 506 Contaminated Soil/Debris/Spill Residue (Non-

petroleum) (Dredge Material, Water Intake Debris and Sediment, Coal Mill Rejects)

507 Waste Petroleum Material Contaminated Soil/Debris

508 Virgin Petroleum Fuel Contaminated Soil/Debris 509 Waste Oil That Is Not Hazardous Waste Oil

(automotive, machining, cutting, etc.) 510 Waste Tires

INDUSTRIAL EQUIPMENT, MAINTENANCE WASTE/SCRAP 701 Pumps, Piping, Vessels, Instruments, Storage

Tanks 702 Scrap From Maintenance And Product

Turnaround 703 Batteries (Non-Haz) 704 Grinding Wheels, Sanding Disks, Polishing

Belts, Welding Rods, Broken Tools 710 Plant Trash 799 Other Maintenance Waste NON-COAL MINING, OIL AND GAS, AND OTHER WELL DRILLING WASTES 801 Drilling Fluids, Residuals (other than those

under 802-810; includes drill cuttings from monitoring well and drinking water well construction)

802 Brine (natural salt water separated at oil and gas wells)

803 Drilling Fluid Waste (oil and gas drilling mud, other drilling fluids other than fracing fluid and spent lubricant)

804 Fracing Fluid Waste (oil and gas drilling fracturing fluid, flow-back fracturing fluid, flow-back fracturing sand)

807 Basic Sediment (oil and gas production storage impurities, sediment from produced oil at storage tank battery)

808 Servicing Fluid (oil and gas production well maintenance/work over fluids, oil/water-based mud and foam)

809 Spent Lubricant Waste (spent oil and gas drilling lubricants, spent plug drilling lubricants)

810 Drill Cuttings (oil and gas drill cuttings)

MISCELLANEOUS 901 Auto Shredder Fluff 902 Non-Hazardous Residue From Treatment Of

Hazardous Waste (other than 203) 999 Other DO NOT REPORT SANITARY SEWAGE OR UNCONTAMINATED NON-CONTACT COOLING WATERS. DO NOT REPORT OFFICE, LUNCHROOM, RESTROOM WASTES

DO NOT REPORT CONSTRUCTION/DEMOLITION DEBRIS

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from shale gas development Form 26R Required Analytes for

Marcellus Shale or Other Gas Wells

Acidity Chemical Oxygen

Demand Magnesium Silver

Alkalinity (Total as CaCO3) Chlorides Manganese Sodium

Aluminum Chromium MBAS (Surfactants) Specific Conductance

Ammonia Nitrogen Cobalt Mercury Strontium

Arsenic Copper Molybdenum Sulfates

Barium Ethylene Glycol Nickel Thorium

Benzene Gross Alpha Nitrite-Nitrate Nitrogen Toluene

Beryllium Gross Beta Oil & Grease Total Dissolved Solids

Biochemical Oxygen

Demand

Hardness (Total as

CaCO3) pH Total Kjeldahl Nitrogen

Boron Iron – Dissolved Phenolics (Total) Total Suspended Solids

Bromide Iron – Total Radium 226 Uranium

Cadmium Lead Radium 228 Zinc

Calcium Lithium Selenium

Additional constituents that are expected or known to be present in the wastewater.

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from shale gas development Data Collection

N: number of laboratory reports in our database

N = 85

N = 11

N = 74

N = 8

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from shale gas development Dataset Summary

Variable Count

laboratory report 178

company 22

well 104

well with location info. 95

wastewater treatment facilities 37

wastewater treatment facilities with location info. 21

Sample year Freq.

2009 75

2010 77

2011 18

NA 8

Total 178

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from shale gas development Categories of Chemicals

• Lab samples are tested for a total of 432 different

analytes that we are able to identify in the data, in

the following categories:

• General chemicals

• Organics

• Pesticides

• Metals

• Radioactive Materials

• Only 198 of these analytes are actually measured

in one or more samples (many NAs, NDs, BDLs).

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from shale gas development Comparison of General Chemicals

in Brine and Fracking Fluid Waste

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from shale gas development Comparison of Metals in

Brine and Fracking Fluid Waste

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from shale gas development Comparison of Organics

in Brine and Fracking Fluid Waste

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from shale gas development Comparison of Naturally Occurring Radioactive

Materials in Brine and Fracking Fluid Waste

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from shale gas development Waste Shipments: Cl- Concentrations

at Wells and Treatment Facilities

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from shale gas development Preliminary Conclusions

• High chemical concentrations are observed pre-

treatment, emphasizing need for effective treatment.

• When barium is detected (92% of samples), median concentration is

> 40 times Pennsylvania’s wastewater effluent standard and > 200

times the SDWA maximum contaminant level for barium.

• Concentrations of chloride, TDS, bromide, radium-228 and strontium

in pretreatment wastewater are also far higher than either

wastewater effluent standards or drinking water standards.

• Wastewater composition is highly variable over the

course of the shale gas extraction process -- a

challenge for effective treatment and management.

• Form26 filed once/year/waste type/generating location – constituent

concentrations could vary even within this temporal/spatial window.

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from shale gas development Preliminary Conclusions, cont.

• Produced water has very different composition than

flowback, typically having higher chloride, TDS and

radium-228 concentrations. Obviously more difficult to

recycle, requiring different technology/higher costs.

• Many constituents may be effectively removed by

chemical waste treatment facilities currently treating this

waste (e.g., metals); others may not (e.g., salts).

• Further research on potential risks from wastewater

treatment and release to rivers and streams is

warranted.

Thank you!

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from shale gas development Life Cycle of Water

Surface

water

fracing

fluid

additives

Groundwater

Hydraulic

fracturing Pound/

tank

Onsite

treatment

Offsite

WWTF

Surface

discharge

Other high

value reuse

landfill

Drilling fluid

additives

Drilling Pound/

tank

Onsite

treatment

Flowback

water

Produced

water

Deep well

injection

Pound/

tank

Sampling location

Clean water

Chemicals

Wastewater

Recycling

Mixing tank

Chemicals

Chemicals

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from shale gas development Fracing Fluid Waste (Flowback) and

Brine (Produced Water)

Fracing Fluid Waste (Flowback) Brine (Produced Water)

Complete

fracking Connect wellhead

to gas pipe to

start production

The length of

flowback can be

from 2 weeks to

one month or

longer. It varies

by developer.

Some reports don’t distinguish them using above method, but call

them all flowback and distinguish them by days after fracing

completion. For example, completion day 0, 1, 3, 5, 14, 30 and 90.

We use 30 days as a cut off to assign waste type and code for

these reports.

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from shale gas development Compare Form 26R and MSC Results

F26R_802

MSC Study F26R_804 Produced

Parameter Influent 5-Day Flowback 14-Day Flowback Flowback Water

pH 7.2 6.6 6.2 6.9 5.8

Alkalinity 52.5 138 85.2 1819.7 2521.9

TDS 334 67300 120000 60156.5 182948.6

TSS 9.6 99 209 387.5 205.7

TOC 3.8 62.8 38.7 79.8 1928.5

BOD 149 2.8 2.8 595.4 855.6

Oil & Grease 31 < 5 7.4 NA NA

Sodium 67.8 18000 16383 35887.7

Calcium 32.9 4950 4982 15003.6

Magnesium 6.7 559 491.6 1412.4

Iron 1.2 39 41.9 106.5

Barium 0.4 686 1025.8 84328.8

Chloride 42.3 41850 40462.5 99711.8

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from shale gas development Compare Concentrations to Standards/Criteria

Primary environmental public health concerns:

Parameter NOB

Median

(mg/L)

Standard

(mg/L) Note

Barium 159 651 2 EPA MCL

Barium 159 651 10

PA wastewater effluent standards

monthly average

Strontium 156 1275 4

EPA recommended limit for finished

municipal drinking water

Strontium 156 1275 10

PA wastewater effluent standards

monthly average

Benzene 44 0.05 0.005 EPA MCL

Ecological and secondary drinking water concerns:

Chlorides 154 53250 250

EPA SMCL, PA wastewater effluent

standards

Magnesium 152 581 0.05 EPA SMCL

TDS 156 87150 500

EPA SMCL, PA wastewater effluent

standards

Sulfate 78 86 250 EPA SMCL

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from shale gas development Previous Data Sampling and Analysis of

Flowback Water

Marcellus Shale Water Characterization • Funded by MSC and ASWCMC Consortia

• Sampling from 19 locations

• Includes general chemistry and detailed analysis of constituents of interests

• Lists of constituents of interest provided by the PADEP

• Over 250 determinations performed on samples

• Samples taken at 0, 1, 5, 14 and 90 days following the frac job at each

location

• Sampling at Day 0: raw water without additives; raw water with chemical

additives before sand addition

• Uniformity of sampling and analysis:

• Standardized Plans

• Sampling performed by URS

• Analyses performed by one lab (Test America)

GE also maintains a database, including data from various

shales.

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from shale gas development Wastewater Streams Considered

Code Description

801

Drilling Fluids, Residuals (Other than those under

802-810; includes drill cuttings from monitoring Well

and drinking water well construction)

802 Brine (natural salt water separated at oil and gas

wells)

803

Drilling Fluid Waste (oil and gas drilling mud, other

drilling fluids other than fracing fluid and spent

lubricant)

804

Fracing Fluid Waste (oil and gas drilling fracturing

fluid, flow-back fracturing fluid, flow-back fracturing

sand)

Wastewater Characteristics from Marcellus Shale … Characteristics from Marcellus Shale Gas...

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