FUNDAMENTALS OF CONTAMINATED SITE TREATMENT TECHNOLOGIES

A Lecture Series Presented at The China University of Mining and Technology (CUMT) Xuzhou, Peoples Republic of China by Professor Hilary I. Inyang
Honorary Professor, China University of Mining and Technology (CUMT) Xuzhou, Jiangsu, China Duke Energy Distinguished and Professor of Environmental Engineering and Science University of North Carolina, Charlotte, NC USA Pro-term Chancellor, African Continental, University (ACUS) Initiative, Abuja, Nigeria (h.inyang26@gmail.com) September, 2010

Examples of option categories and specific options (option categories have greater performance uncertainties and specific options).

A surface pond polluted by crude oil and brine behind Prof. H. I. Inyang, outside the City of Nizhnevartovsk, Russia

One of the several ponds polluted by oil leakages and drainage in the Samotlor Oil Field in the Khanty-Mansisk Region of Western Siberia, Russia

illustration of the spatial distribution of biogeochemical zones that may occur at a site contaminated with petroleum hydrocarbons. (NAVAL FACILITIES
ENGINEERING SERVICE CENTER Users Guide UG-2035-ENV, 1999)

CRITERIA FOR WASTE CLASSIFICATION AS BEING HAZARDOUS

Corrosivity Ignitability Reactibility

Toxicity CORROSIVITY
pH < 2 or > 12.5 Corrodes steel at the rate of 6035 mm/year

IGNITABILITY
Substance is a liquid with a flash point < 60o C Non-liquid that can cause fire and burns vigorously when ignited Compressed gas Oxidizer

Reactivity
Unstable substances Reacts with water Can generate toxic gases in combination with water When mixed with other substances it can explode Substance is a cyanide or sulfide-bearing (these generate toxic gases) Substance can explode when decomposing

Toxicity
Substance is poisonous Substance is carcinogenic Substance is listed as being EP-Toxic (or TCLP- toxic) as listed

RISK AND RELIABILITY ASSESSMENT FRAMEWORK FOR WASTE STORAGE SYSTEMS

The exposure Assessment Basic Equation:

(C )( IR )( EF )( ED ) IN ( BW )( AT )
IN = the intake defined as the amount of a specific chemical in a contaminated medium taken (mg/kg of body weight per day). C = the average chemical concentration contacted over the exposure period (mg/L for liquid and gases, and mg/mg for solids); IR = the intake rate defined as the amount of the contaminated medium contacted per unit of time or event (mg/day or L/day) EF = the upper-bound value of the exposure frequency (day/year) ED = the upper-bound value of the exposure duration (years) BW = the average body weight over the exposure period (kg) AT = the average time defined as the time period over which exposure is averaged (exposure duration for noncarcinogens and 70 years for carcinogens)

Control of Risks through Design, Siting and Management Options

EXPOSURE PARAMETER

APPROACH

MEASURE Siting controls Scavenging bans Reduction in work frequency Process automation Siting controls Scavenging bans Reduction in work frequency Process automation Reduction in stored waste quantity Occupational health and safety controls Effective waste coverage Effective leachate barrier system Exclusive distances for water wells

EF: exposure frequency

Minimization

ED: exposure duration

Minimization

C: Contaminant exposure concentration

Minimization

SUMMARY OF DEFAULT EXPOSURE FACTORS USED BY THE US EPA SUPERFUND PROGRAM FOR ESTIMATING THE REASONABLE MAXIMUM EXPOSURE (RME)

U.S. EPA - RISK ASSESSMENT GUIDANCE FOR SUPERFUND VOLUME I: HUMAN HEALTH EVALUATION MANUAL http://www.hanford.gov/dqo/project/level5/hhems.pdf

SOIL AND GROUNDWATER ACTION LEVELS AND RISK GOALS AT EXAMPLE SUPERFUND METALCONTAMINATED SITES (USEPA, 1995)

SOIL AND GROUNDWATER ACTION LEVELS AND RISK GOALS AT EXAMPLE SUPERFUND METALCONTAMINATED SITES (USEPA, 1995) (CONTD)

CLEANUP LEVELS FOR HYDROCARBON-CONTAMINATED SOIL MASSACHUSETTS (STOKMAN/SOGOKA, 98)

Product Parameter/Constituent Notification Level1 Cleanup Level2 A/B/C Gasoline Benzene 10/60g/g 10-200g/g Toluene 90/500g/g 90-2500g/g Ethylbenzene 80/500g/g 80-2500g/g Total Xylenes 500/500g/g 500-2500g/g MTBE 0.3/200g/g 0.3-200g/g Naphthalene 4/1000g/g 4-1000g/g C5-C8 Aliphatic Hydrocarbons 100/500g/g 100-500g/g C9-C12 Aliphatic Hydrocarbons 1000/2500g/g 1000-5000g/g C9-C10 Aromatic Hydrocarbons 100/500g/g 100-500g/g Diesel/ Naphthalene 4/1000g/g 4-1000g/g #2 Fuel 2-Methylnapthalene 4/1000g/g 4-1000g/g Phenanthrene 100/100g/g 100g/g Acenaphthene 20/2500g/g 20-4000g/g C9-C18 Aliphatic Hydrocarbons 1000/2500g/g 1000-5000g/g C19-C36 Aliphatic Hydrocarbons 2500/5000g/g 2500-5000g/g C11-C22 Aromatic Hydrocarbons 200/2000g/g 200-500g/g
NS=Not Specified in regulation, MT 1 Two notification thresholds have been established for "high" and "low" exposure potential areas. 2 Nine generic cleanup standards have been established depending upon exposure potential/accessibility of soil, and use/classification of underlying groundwater. Alternative cleanup levels are permissible based upon a site-specific risk characterization. See Massachusetts regulations 310 CMR 40.000 and associated support/policy documents for complete details and requirements

RATINGS OF THE RELATIVE EASE OF CLEANING UP OF CONTAMINATED GROUNDWATER (MACDONALD AND KAVANAUGH, 1994)

Mobile, Dissolve Mobile, Hydrogeology (degrade/volatilize) Dissolve Fractured Heterogeneous, multiple layers Heterogeneous, single layer Homogeneous, multiple layers 3 2 2 1 3 2 2 1-2

Strongly Sorbed, Strongly Dissolve Sorbed, DNAPL LNAPL (degrades/volatilizes Dissolve 3 3 4 4 3 3 2 3 3 2-3 4 4 3 3 3 2-3

1 is easiest and 4 is most difficult DNAPL = Dense Nonaqueous-phase liquid LNAPL = Light Nonaqueous-phase liquid

Change of waste hazardous characteristics fits within the following general hazard reduction techniques

1. Changes in chemical function of the contamination to reduce mobility 2. Changes in chemical form to reduce toxicity 3. Changes in form to reduce volume 4. Changes in characteristics of the contaminant transport media
5. Removal of waste from the site

GENERAL TYPES OF WASTE TREATMENT APPROACHES Chemical Treatment Processes These processes are mainly intended to accomplish one or more of the following functions. pH adjustment Oxidation Reduction Pre-treatment

BASIC APPROACHES TO MITIGATING HAZARDOUS CHARACTERISTICS

Waste hazard Corrosive waste

Basic Response action pH adjustment

Ignitive waste
Reactive waste Toxic waste

Oxidation or reduction
Oxidation or reduction Oxidation, reduction, lysis for organics

Soil Technologies
Bioremediation (ex situ) Bioremediation (in situ) Contained recovery of Oily wastes (CROWTM) Cyanide oxidation De-chlorination Hot air injection In situ flushing Physical separation Plasma high temperature metals recovery Soil vapor extraction Soil washing Solvent extraction Thermal desorption Vitrification

Groundwater Technologies
Air sparging Bioremediation (in situ) Dual-phase extraction In-situ oxidation In-situ well aeration Passive treatment walls

TREATMENT TECHNOLOGY SELECTION APPROACHES

Factors considered:
1. Chemical Factors Effectiveness of technology relative to the chemistry and concentrations of contaminants, affected by: a) Reaction conditions b) Concentration variations c) Composition variations Physical Factors Effectiveness of the technology with respect to media of concern. Other Factors Physical restraint at the site Health and safety Sensitivity of the site * All the factors relate to the costs associated with the implementation of a particular site treatment technology

2. 3.

ASSESSMENT OF THE FEASIBILITY OF A TECHNOLOGY

A) Bench scale treatability studies For demonstrated technologies, Duration: 2 - 6 weeks Cost: $10,000 - $50,000
For innovative technologies, Duration: 4 16 weeks Cost: $25,000 - $200,000

ASSESSMENT OF THE FEASIBILITY OF A TECHNOLOGY

B) Plot scale treatability studies

For demonstrated technologies with available testing units Duration: 3 12 months Costs: $100,000 - $ 1milion These studies are conducted if, 1) The level of certainty of success of technology is low 2) Consequence of failure of technology is high

SUPERFUND REMEDIAL ACTIONS: TREATMENT TRAINS WITH INNOVATIVE TREATMENT TECHNOLOGY

SUPERFUND REMEDIAL ACTIONS: TREATMENT TRAINS WITH INNOVATIVE TREATMENT TECHNOLOGY (Contd)

Treatment Technologies for Site Cleanup: Annual Status Report (Eleventh Edition), EPA-542-R-03-009, February 2004

Schematic illustration of the arrangement of injection extraction, treatment and disposal network for reactants used in enhancement of pump-and-treat systems

(EPA, 1996, Pump-and-Treat Ground-Water Remediation A Guide for Decision Makers and Practitioners) http://www.epa.gov/ORD/WebPubs/pumptreat/pumpdoc.pdf

Pulsed pumping removal of residual contaminants from saturated media

(EPA, 1996, Pump-and-Treat Ground-Water Remediation A Guide for Decision Makers and Practitioners)

Schematic illustration of solubility and diffusion limitations to pump-and-treat Systems: (a) Contaminants are mobilized; (b) sorption of contaminant onto mineral surface
USEPA - Introduction to Pump-and-Treat Remediation http://www.epa.gov/ORD/WebPubs/pumptreat/pumpdoc.pdf

ALKYLBENZENE SULFONATE

Hydrophobic Moiety

Hydrophobic Moiety

An illustration of the configuration of a type of surfactant (USEPA, 1992)

AGGREGATION OF SURFACTANT MOLECULES INTO A MICELLE (USEPA, 1992)

Model of an Air Sparging System

Treatment Technologies for Site Cleanup: Annual Status Report (Ninth Edition), EPA-542-R99-001, Number 9, April 1999

VAPOR PRESSURE OF COMMON PETROLEUM CONSTITUENTS (USEPA, 1995)

THE MOST PREVALENT NATURAL ATTENUATION MECHANISM (USEPA, 1995)

SCHEMATIC OF CROSSHOLE SEISMIC TOMOGRAPHY IMAGING SYSTEM (US DOE, 1994A)

Model of Phytoremediation

(Federal Remediation Technologies Roundtable - http://www.frtr.gov)

Model of Phytoremediation

Illustration of nickel uptake through the process of phytoremediation

(Federal Remediation Technologies Roundtable - http://www.frtr.gov)

Model of Phytoremediation

Illustration of nickel uptake through the process of phytoremediation

(Federal Remediation Technologies Roundtable - http://www.frtr.gov)

Model of Phytoremediation

Illustration of nickel uptake through the process of phytoremediation

(Federal Remediation Technologies Roundtable - http://www.frtr.gov)

Model of Phytoremediation

Illustration of nickel uptake through the process of phytoremediation

(Federal Remediation Technologies Roundtable - http://www.frtr.gov)

Model of Phytoremediation

Treatment Technologies for Site Cleanup: Annual Status Report (Ninth Edition), EPA-542-R99-001, Number 9, April 1999

EXAMPLES OF HYPERACCUMULATORS OF METALS (USEPA, 1996B)

Metal Plant Species Thlaspi calaminare Zn Viola species Cu 1 1 3.8 Europe Zaire New Caledonia Southern Europe and Turkey % of Metal in Dry Weight of Leaves <3 Native Location Germany

Aeolanthus biformifolius
Phyllanthus serpentinus Alyssum bertoloni and 50 other species of alyssum

Ni

>3 25 (in latex)

4.1

Sebertia acuminata
Stackhousia tryonli

New Caledonia
Australia

Pb Co

Brassuca juncea
Haumaniastrum robertii

<3.5 1

India Zaire

EFFECTS OF ADDING EDTA TO Pb-CONTAMINATED SOILa WITH TOTAL SOIL Pb mg/kg ON Pb CONCENTRATION IN XYLEM SAP AND Pb ACCUMULATION IN SHOOTSb OF 21-DAY-OLD CORN GROWN IN CONTAMINATED SOIL (Huang et al; 1997)

EFFECTS OF ADDING EDTA TO Pb-CONTAMINATED SOILa WITH TOTAL SOIL Pb mg/kg ON Pb CONCENTRATION IN XYLEM SAP AND Pb ACCUMULATION IN SHOOTSb OF 21-DAY-OLD CORN GROWN IN CONTAMINATED SOIL (Huang et al; 1997)

RELATIVE EFFICIENCY OF FIVE SYNTHETIC CHELATESa IN ENHANCING Pb ACCUMULATION IN SHOOTS OF CORN AND PEA PLANTS GROWN IN PbCONTAMINATED SOIL WITH A TOTAL PB OF 2500 MG/KG (HUANG ET AL; 1997)

A SCHEMATIC ILLUSTRATION OF CONTAMINATED GROUNDWATER BIORECLAMATION (USEPA, 1986)

Illustration of the effects of Oxygen access on biodegradation of a contaminant plume (USEPA, 1995)

REFRACTORY INDICES OF SOME ORGANIC COMPOUNDS (data from Lyman et al; 1982)

REFRACTORY INDICES OF SOME ORGANIC COMPOUNDS (data from Lyman et al; 1982) (contd)

BOD5/COD RATIOS FOR VARIOUS ORGANIC COMPOUNDS (Lyman et al; 1982)

BOD5/COD RATIOS FOR VARIOUS ORGANIC COMPOUNDS (Lyman et al; 1982)

BOD5/COD RATIOS FOR VARIOUS ORGANIC COMPOUNDS (Lyman et al; 1982)

BOD5/COD RATIOS FOR VARIOUS ORGANIC COMPOUNDS (Lyman et al; 1982)

Principal mechanisms through which chlorinated hydrocarbons reduced by iron (Wilson, 1995)

Suggested pathways for the reduction of chloroethylenes by zero-valent iron (courtesy of undated USEPA information sheet)

Effects of zero-valent iron metal surface area concentration on pseudofirst-order reaction rate constant for nitrobenzene reduction (Agrawal and Tratnyek, 1996)

A SCHEMATIC ILLUSTRATION OF IN SITU VITRIFICATION PROCESS IN WHICH ELECTRODES ARE USED FOR HEAT APPLICATION

(Federal Remediation Technologies Roundtable - http://www.frtr.gov/)

An example of a silicate glass network structure (Mc Lelland and Strand, 1984)

TYPICAL RANGES OF OXIDE COMPOSITIONS IN SODA-LIME GLASS, BOROSILLICATE GLASS AND IN SITU VITRIFIED (ISV) GLASS (COMPILED BY USEPA, 1992)

APPROXIMATE RANGES OF SOLUBILITY OF ELEMENTS IN SILICATE GLASSES (Volf, 1984)

TCLP EXTRACT METAL CONCENTRATIONS IN LEACHATE FROM IDAHO NATIONAL ENGINEERING LABORATORY VITRIFIED SOILS (USEPA, 1994b)

ORGANICS DESTRUCTION AND REMOVAL EFFICIENCIES (DRE) RECORDED FOR CONTAMINATED MEDIA VITRIFICATION SYSTEMS (HWC, 1990)

COMPOSITION AND CHARACTERISTICS OF PRIMARY COMPOUNDS IN PORTLAND CEMENT

Schematic Diagram of One Electrode Configuration and Geometry Used in Field Implementation of Electrokinetic Remediation
(Federal Remediation Technologies Roundtable - http://www.frtr.gov/matrix2/section4/4_6.html )

ELECTROACOUSTICAL SOIL DECONTAMINATION PROCESS (USEPA, 1997)

Model of Phytoremediation

Illustration of nickel uptake through the process of phytoremediation

(Federal Remediation Technologies Roundtable - http://www.frtr.gov)