The Chemical Oxidation of Polycyclic Aromatic Hydrocarbons

116 Pages·2012·3.63 MB·English

by  Nichole Antin

The Chemical Oxidation of Polycyclic Aromatic Hydrocarbons at a Former Manufactured
Gas Plant in Bay Shore, New York

A Final Report Presented
By
Kevin M. Taylor

in Partial Fulfillment of the
Requirements
for the Degree of
Master of Science
in
Geosciences with Concentration in Hydrogeology

Stony Brook University

May 2012
Copyright by
Kevin M. Taylor
2012
Stony Brook University
The Graduate School

Kevin M. Taylor

We, the final report committee for the above candidate for the
Master of Science in Geosciences with Concentration in Hydrogeology degree, hereby
recommend acceptance of this final report.

Associate Professor Bruce Brownawell
Marine and Atmospheric Sciences

Professor Martin Schoonen
Geosciences

Associate Professor Anne McElroy
Marine and Atmospheric Sciences

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Abstract of the Final Report
The Chemical Oxidation of Polycyclic Aromatic Hydrocarbons at a Former Manufactured
Gas Plant in Bay Shore, New York
by
Kevin M. Taylor
Master of Science in Geosciences with Concentration in Hydrogeology
Stony Brook University
2012

This paper examines the history of manufactured gas plants (MGPs) and their impacts on
the environment with a specific focus on coal tar and polycyclic aromatic hydrocarbons (PAHs).
Based on their low solubility, relatively low volatility, and ability to remain sorbed to soils
within an aquifer, PAHs persist for long periods of time well after gas production operations
have ceased, and remediation that relies upon transfer to aqueous or vapor phases typically takes
a long time. Several remedial techniques have been employed to address MGP contamination,
namely, excavation and disposal, pump and treat and chemical oxidation. Chemical oxidation of
contaminants of concern (COCs) can be conducted ex-situ or in-situ. In-situ chemical oxidation
(ISCO) is an attractive remedial option since it requires fewer disturbances and is potentially a
cost-effective solution for site remediation. As such, this paper will highlight three (3) chemical
oxidation treatment technologies (fenton’s reagent/catalyzed hydrogen peroxide, persulfate and
ozone). In addition, a case study of the in-situ ozonation of PAH impacted groundwater and
aquifer materials will be provided using site-specific data obtained from publically accessible
sources.
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Table of Contents
Chapter 1 - Introduction to Manufactured Gas Plants and the Bay Shore MGP .......................................... 1
Gas Processes and Waste Streams ............................................................................................................ 3
The Bay Shore MGP Site .......................................................................................................................... 4
Sanborn Historical Map Review ............................................................................................................... 6
1897 – Figure 2 ..................................................................................................................................... 7
1915 – Figure 3 ..................................................................................................................................... 7
1949 – Figure 4 and 5 ........................................................................................................................... 8
Hydrogeologic Setting ............................................................................................................................ 10
Chapter 2 – Major Contaminants at the Bay Shore MGP (BTEX, PAHs and DNAPL) ............................ 12
Coal Tar .................................................................................................................................................. 12
Contaminants of Concern at the Bay Shore MGP – Pre Ozonation ....................................................... 15
DNAPL – Pre-Ozone .......................................................................................................................... 17
Shallow Groundwater System –Pre–Ozone Q3 2009 ......................................................................... 17
Intermediate Groundwater System – Q3 2009 .................................................................................... 17
Deep Groundwater System – Q3 2009 ............................................................................................... 18
Calculations of PAH Migration in the area of the Bay Shore MGP ................................................... 21
Conclusions ............................................................................................................................................. 23
Chapter 3 – ISCO and ISCO Using Hydrogen Peroxide ............................................................................ 25
CHP Chemistry ....................................................................................................................................... 26
Activation of Hydrogen Peroxide and Chelating Agents .................................................................... 29
Soil Mineral Interactions ..................................................................................................................... 31
Chelating Agents to Reduce Soil Mineral Interactions ....................................................................... 32
Natural Organic Matter ........................................................................................................................... 33
CHP and Combined Remedial Techniques ............................................................................................. 34
Summary of CHP ISCO .......................................................................................................................... 35
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Chapter 4 – ISCO Using Persulfate ............................................................................................................ 37
Background ............................................................................................................................................. 37
Activation of Persulfate .......................................................................................................................... 37
Alkaline Activation ............................................................................................................................. 38
Transition Metals and Chelating Agents Activation ........................................................................... 38
Soil Minerals and Natural Organic Matter .............................................................................................. 40
Persulfate Effectiveness .......................................................................................................................... 41
Summary of Persulfate ISCO .................................................................................................................. 41
Chapter 5 – ISCO Using Ozone .................................................................................................................. 43
Background ............................................................................................................................................. 43
Ozone Radicals ................................................................................................................................... 46
Ozone Demand........................................................................................................................................ 47
Natural Organic Matter and Soil Minerals .......................................................................................... 47
Ozone Effectiveness on PAH Sorbed Soils ............................................................................................ 47
Ozone in Aqueous Environments ........................................................................................................... 48
Summary of Ozone ISCO ....................................................................................................................... 50
Chapter 6 – Bay Shore MGP ISCO Using Ozone ...................................................................................... 51
Background ............................................................................................................................................. 51
Ozone ISCO Case Study ......................................................................................................................... 51
Ozone Design .......................................................................................................................................... 53
Well Locations ........................................................................................................................................ 55
Up-Gradient Wells – Pre-Ozonation and Future Contributions to the Ozone ........................................ 57
Treated Down-gradient Wells - Q4 2009 ................................................................................................ 62
OMMW-26 ......................................................................................................................................... 63
OZMW-26S 5’ – 15’ ....................................................................................................................... 63
OZMW-26I 20’ – 30’ ...................................................................................................................... 66
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OZMW-26I2 35’ – 45’ .................................................................................................................... 68
OZMW-26D .................................................................................................................................... 70
OZMW-23 ........................................................................................................................................... 72
OZMW-23S 5’ – 15’ ....................................................................................................................... 72
OZMW-23I 20’ – 30' ...................................................................................................................... 75
OZMW23I2 35’ – 45’ ..................................................................................................................... 77
OZMW-23D 55’ – 65’ .................................................................................................................... 79
OZMW24 ............................................................................................................................................ 81
OZMW24S 5’ – 15’ ........................................................................................................................ 81
OZMW24I 20’ – 30’ ....................................................................................................................... 82
OZMW24I2 35’ – 45’ ..................................................................................................................... 85
OZMW24D 55’ – 65’ ..................................................................................................................... 88
Conclusions of the Ozone System .......................................................................................................... 89
Implications of Ozone and Further Research .......................................................................................... 96
References ............................................................................................................................................... 98
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List of Figures
Figure 1 - Map of Operable Units at the Bay Shore MGP - Modified from Dvirka and Bartillucci 2003 ... 6
Figure 2 - A map of OU-1 in 1897 – Modified from Sanborn 1897 ............................................................. 7
Figure 3 - A map of north side of OU-1 in 1915 – Modified from Sanborn 1915 ........................................ 8
Figure 4 - Northern End of OU-1 in 1949 bound by Clinton Avenue and 5th Avenue – Modified from
Sanborn 1947 ................................................................................................................................................ 9
Figure 5 - A map of the southern end of OU-1 in 1947 – Modified from Sanborn 1947 ............................. 9
Figure 6 - Structure of PAHs encountered at MGPs – Modified from Pariaba et al. 2011......................... 13
Figure 7 - Fate and Transport Model of Plume from Cross Section View – Modified from Dvirka and
Bartilucci 2003 ............................................................................................................................................ 16
Figure 8 - ISO-BTEX Map for Shallow, Intermediate and Deep Groundwater -southern end of OU-1 and
northern end of OU-2 – Pre ozonation Q3 2009 – Modified from GEI Consultants Q3 2009 OM&M
report; concentration contours are provided in units of µg/L ..................................................................... 19
Figure 9 - ISO-PAH Map for Shallow, Intermediate and Deep Groundwater -southern end of OU-1 and
northern end of OU-2 – Pre ozonation Q3 2009 – Modified from GEI Consultants Q3 2009 OM&M
report; concentrations are also provided in µg/L. ....................................................................................... 20
Figure 10 - 0.5% H2O2 at pH 3 - Modified from Teel et al. 2007, ............................................................ 31
Figure 11 - 0.5% H2O2 at pH 7 - Modified from Teel et al. 2007, ............................................................ 32
Figure 12 - Ozone Site Map - Modified from GEI Consultants Quarterly 2009-2011 ............................... 57
Figure 13 - Log of average individual and total PAH concentrations measured in up-gradient wells
BBMW-22 and OZMW-25 ......................................................................................................................... 61
Figure 14 - Ozone Effect on OZMW-26S 5' – 15, (a) BTEX response, (b) PAH response, (c) Long term
DO, PAH and BTEX response modified from GEI quarterly .................................................................... 65
Figure 15 – Ozone Effect on OZMW-26I 20' – 30, (a) BTEX response, (b) PAH response, (c) Long term
DO, BTEX and PAH response modified from GEI quarterly .................................................................... 67
Figure 16 - Ozone Effect on OZMW-26I2 35’ – 45’, (a) BTEX response, (b) PAH response, (c) Long
term DO, BTEX and PAH response modified from GEI quarterly ............................................................ 69
Figure 17 - Ozone Effect on OZMW-26D 55’ – 65’, (a) BTEX response, (b) PAH response, (c) Long
term DO, BTEX and PAH response modified from GEI quarterly ............................................................ 71
Figure 18 - Ozone Effect on OZMW-23S 5’ – 15’, (a) BTEX response, (b) PAH response, (c) Long term
DO, BTEX and PAH response modified from GEI quarterly .................................................................... 74
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Figure 19 - Ozone Effect on OZMW-23I 20’ – 30’, (a) BTEX response, (b) PAH response, (c) Long term
DO, BTEX and PAH response modified from GEI quarterly .................................................................... 76
Figure 20 - Ozone Effect at OZMW-23I2 35' - 45', (a) BTEX response, (b) PAH response, (c) Long term
DO, BTEX and PAH response modified from GEI quarterly .................................................................... 78
Figure 21 - Ozone Effect at OZMW-23D 55' - 65', (a) BTEX response, (b) PAH response, (c) Long term
DO, BTEX and PAH response modified from GEI quarterly .................................................................... 80
Figure 22 - Ozone Effect at OZMW-24S 5'-15', (a) BTEX response, (b) PAH response, (c) Long term
DO, BTEX and PAH response modified from GEI quarterly .................................................................... 82
Figure 23 - Ozone Effect at OZMW-24I 20'-30', (a) BTEX response, (b) PAH response, (c) Long term
DO, BTEX and PAH response modified from GEI quarterly ................................................................... 84
Figure 24 - Ozone Effect at OZMW-24I2 35' - 45', (a) BTEX response, (b) PAH response, (c) Long term
DO, BTEX and PAH response modified from GEI quarterly .................................................................... 87
Figure 25 - Ozone Effects at OZMW-24D 55’ – 65’, (a) BTEX response, (b) PAH response, (c) Long
term DO, BTEX and PAH response modified from GEI quarterly ........................................................... 89
Figure 26 – Log of average (n=7) individual PAHs and total PAH concentrations measured in quarterly
samples over 2010 -2011 period) in up-gradient untreated OZMW-25in comparison to treated down-
gradient wells OZMW-26 and OZMW-23 – Not affecting the compositional data or log scale reductions
in PAH concentrations as a function of treatment, concentrations were multiplied by 7 for graphical
purposes to allow for separation between concentrations reported at the quantification limit (most often 1
µg/L which would correspond to log C = 0 without the correction) and those below that detection limit
(shown with log C = 0) ............................................................................................................................... 92
Figure 27 - Log of average (n=7) individual PAHs and total PAH concentrations measured in quarterly
samples over 2010 -2011 period) in up-gradient untreated OZMW-25in comparison to treated down-
gradient wells OZMW-26 and OZMW-23 – Not affecting the compositional data or log scale reductions
in PAH concentrations as a function of treatment, concentrations were multiplied by 7 for graphical
purposes to allow for separation between concentrations reported at the quantification limit (most often 1
µg/L which would correspond to log C = 0 without the correction) and those below that detection limit
(shown with log C = 0) ............................................................................................................................... 93
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List of Tables
Table 1 - PAH Retardation Calculations ..................................................................................................... 23
Table 2 - Reactive Species Known or Suspected of Contributing to CHP Reactions – Modified from
Siegrist 2011 ............................................................................................................................................... 27
Table 3 - Solubility of ozone at temperature ranges encountered within Long Island Aquifers in degrees
celsius and at 1 atmosphere– Modified from Seigrist 2011 ........................................................................ 44
Table 4 - Solubility and Aqueous Phase PAHs at BBMW-22D ................................................................. 60

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