Total petroleum hydrocarbons environmental fate toxicity and remediation saranya kuppusamy

Total Petroleum Hydrocarbons

Environmental Fate Toxicity and Remediation Saranya Kuppusamy

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Saranya Kuppusamy  Naga Raju Maddela  Mallavarapu Megharaj  Kadiyala Venkateswarlu

Total Petroleum Hydrocarbons

Environmental Fate, Toxicity, and Remediation

Total Petroleum Hydrocarbons

Saranya Kuppusamy • Naga Raju Maddela Mallavarapu Megharaj • Kadiyala Venkateswarlu

Total Petroleum Hydrocarbons

Environmental Fate, Toxicity, and Remediation

Saranya Kuppusamy

Centre for Environmental Studies

Anna University

Chennai, Tamil Nadu, India

Mallavarapu Megharaj

Global Centre for Environmental Remediation

The University of Newcastle Newcastle, NSW, Australia

Naga Raju Maddela Facultad de Ciencias de la Salud y Departamento de investigación Universidad Técnica de Manabí Portoviejo, Manabí, Ecuador

Kadiyala Venkateswarlu Nellore, Andhra Pradesh, India

ISBN 978-3-030-24034-9 ISBN 978-3-030-24035-6 (eBook) https://doi.org/10.1007/978-3-030-24035-6

© Springer Nature Switzerland AG 2020

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed.

The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use.

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Preface

Hydrocarbons are made of the elements carbon and hydrogen and are the most abundant organic compounds in the bio-geosphere. Hydrocarbons are formed biosynthetically through living organisms or through the transformation of biogenic organic matter in the geosphere. The exploitation of hydrocarbon-based fossil fuels as energy resources has played an important role in the evolution of industrial revolution and the present modern life of humans. The term “total petroleum hydrocarbons (TPHs)” is used for any mixture of several hundreds of hydrocarbons that are found in crude oil. Thus, TPHs represent the sum of volatile and extractable petroleum hydrocarbons (PHs). Environmental pollution by PHs, as a result of industrialization and anthropogenic activities, is one of the major growing concerns in the world today due to its potential harms to both terrestrial and aquatic ecosystems. In fact, there are more than five million potentially contaminated lands worldwide which represent, in general, a lost economic opportunity and threat to the health and well-being of humans and the environment. Also, petroleum-contaminated sites constitute almost one-third of the total contaminated sites around the world. The land contamination was recognized as early as the 1960s due to the legacy of industrialization, but less than a tenth of potentially contaminated lands have only been remediated due to the challenging nature of contamination, cost, technical impracticability, insufficient land legislation, and enforcement. As such, there is no availability of a single source that provides a complete information on the different aspects of TPHs such as sources and range of products, methods of analysis, fate and bioavailability, ecological implications including their impacts on human health, various potential bioremediation approaches, and regulatory assessment procedures for TPHs-contaminated sites.

This book, intended to cover all the above different aspects of TPHs contamination, is organized into nine chapters. Chapter 1 introduces the readers to the production of TPHs, their environmental release, extent of contamination, and environmental concerns of TPHs contamination. It also provides an overview of TPHs with description about the different range of TPHs products and their physico-chemical properties. Chapter 2 describes the chemical analytical methods used to detect and measure different types of TPHs from varied environmental matrices. Chapter 3

focuses on the fate of TPHs in different environments of air, terrestrial, and aquatic (marine vs freshwater vs sediments). Chapter 4 describes the bioavailability of TPHs and the methods used to measure the bioavailability, i.e., chemical vs biological. Chapter 5 provides the ecological impacts of TPHs that include the nontarget effects of TPHs toward terrestrial organisms (microbes, plants, invertebrates, vertebrates) and aquatic organisms marine vs freshwater (microbes, plants, invertebrates, vertebrates). Chapter 6 describes the potential impacts of TPHs on human health with emphasis on the routes of exposure (dermal vs inhalation) and their potential toxicity and carcinogenicity. Chapter 7 deals with the approaches for remediation of TPHs-contaminated sites which includes the risk-based, traditional, and modern emerging remediation technologies. Chapter 8 focuses on the environmental regulations across the world and the available ecological-/health-based regulatory guidelines adopted by different countries. Finally, Chapter 9 describes several available case studies on successful remediation of sites contaminated with TPHs all over the world because of historical oil spills. Thus, this state-of-the-art book is the first compilation of all the critical information and updated knowledge required for understanding the TPHs fate, behavior, and their remediation in contaminated environments. We believe that this comprehensive book will be a good source of reference for graduate students, researchers, technicians of oil industries, remediation practitioners of contaminated sites, as well as policy-makers who are interested in working on the sites contaminated with TPHs.

Chennai, Tamil Nadu, India

Saranya Kuppusamy Portoviejo, Ecuador Naga Raju Maddela Newcastle, NSW, Australia Mallavarapu Megharaj Nellore, Andhra Pradesh, India Kadiyala Venkateswarlu

Acknowledgments

Dr. Saranya Kuppusamy gratefully acknowledges the Science and Engineering Research Board of the Department of Science and Technology for the award of DST-SERB Ramanujan Fellowship (Sanction Order No. SB/S2/RJN-182/2017) and the Centre for Environmental Studies, Anna University, Chennai, India, for providing facilities during this fellowship period.

Dr. Naga Raju Maddela greatly acknowledges the Universidad Téchnica de Manabi, Portoviejo, Ecuador, for the facilities and encouragement and his colleagues in the Faculty of Health Science, Department of Investigation, for their help in literature collection.

Abbreviations

AAL Arizona Action Levels

ACGIH American Conference of Governmental Industrial Hygienists

ADD Average Daily Dose

AFB Air Force Base

AIS Alveolar Interstitial Syndrome

API American Petroleum Institute

ASTM American Society for Testing and Materials

ASTM American Society of Testing and Materials

BAAQMD Bay Area Air Quality Management District

BaP Benzo(a)Pyrene

BER Bioelectrochemical Remediation

BES Bioelectrochemical System

BOD Burden of Disease

BTEX Benzene, Toluene, Ethylbenzene, and Xylenes

CCEH Center for Children’s Environmental Health

CCME Canadian Council of Ministers of the Environment

CERCLA Comprehensive Environmental Response, Compensation and Liability Act

CEV Critical Exposure Values

CHD Coronary Heart Disease

CNS Central Nervous System

CoNPs Cobalt Nanoparticles

CPT Cone Penetrometer Technology

CYPs Cytochrome P450 Monooxygenases

DOI Department of Interior

DRO Diesel Range Organics

DUS Dynamic Underground Striping

DWH Deepwater Horizon

EA Environment Agency

ECIA Electrochemical Immunoassay

EFR Enhanced Fluid Recovery

Abbreviations

EK Electrokinetic

ELISA Enzyme-Linked Immunosorbent Assay

EPA Environmental Protection Agency

EPHs Extractable Petroleum Hydrocarbons

ESLs Ecological Screening Levels

EU European Union

F Fractions

FHCs Fuel Hydrocarbons

FID Flame Ionization Detector

FLTG French Limited Task Group

FPAC Fine Particle Associated Carbon

GAC Granular Activated Carbon

GC-MS/FID Gas Chromatography-Mass Spectrometry/Flame Ionization Detector

GE Genetic Engineering

GMOs Genetically Modified Microorganisms

GRO Gasoline Range Organics

GSA Gasoline Spill Area

HC Hazardous Concentration

HEPA High-Efficiency Particulate Air

HEWAF High-Energy WAF

HI Hazard Index

HIP Health Information Products

HMW High-Molecular-Weight

HPCD Hydroxypropyl-β-Cyclodextrin

HPLC High-Performance Liquid Chromatography

HQ Hazard Quotient

HRH High-Range Hydrocarbons

HSLs Health Screening Levels

HTTD High-Temperature Thermal Desorption

IARC International Agency for Research on Cancer

IC Internal Combustion

IR Infrared Spectroscopy

IRIS Integrated Risk Information System

IUR Inhalation Unit Risks

IVOCs Intermediate-Volatile Organic Compounds

KOC Kuwait Oil Company

LC Lethal Concentration

LLNL Lawrence Livermore National Laboratory

LMW Low-Molecular-Weight

LOEC Lowest Observed Effect Concentration

LRH Low-Range Hydrocarbons

LTA Land Treatment Area

LTTD Low-Temperature Thermal Desorption

LTU Land Treatment Unit

M Modules

Abbreviations

MBC Microbial Biomass Carbon

MCL Maximum Contaminant Level

MEK Methyl Ethyl Ketone

MFCs Microbial Fuel Cells

MGP Manufactured Gas Plants

MnNPs Manganese Nanoparticles

MOS Marine Oil Snow

MPC Maximum Permissible Concentration

MPPS Multiprocess Phytoremediation System

MRH Midrange Hydrocarbons

MS Mass Spectrometry

MtBE Methyl Tertiary Butyl Ether

NAPL Nonaqueous Phase Liquid

NCP National Contingency Plan

NCQA National Committee for Quality Assurance

NEPC National Environment Protection Council

NEPMs National Environment Protection Measures

NLM National Library of Medicine

NOAA National Oceanic and Atmospheric Administration

NOEC No Observed Effect Concentration

NPL National Priorities List

O&M Operations and Maintenance

OECD Organization for Economic Cooperation and Development

ONGC Oil and Natural Gas Corporation

OPA Oil Particulate Aggregates

ORO Oil Range Organics

OSPM Oil Soil Particulate Matter

OWP Oil Weathering Processes

PAHs Polycyclic Aromatic Hydrocarbons

PBMC Peripheral Blood Mononuclear Cells

PCA Principal Component Analysis

PED Polyethylene Device

PGPR Plant Growth-Promoting Rhizobia

PH Petroleum Hydrocarbon

PHC CWS Canada-Wide Standards for Petroleum Hydrocarbons

PHs Petroleum Hydrocarbons

PIC Petrochemical Industrial Complexes

PM Particulate Matter

PNEC Predicted No-Effect Concentration

PRGs Preliminary Remediation Goals

PRPs Potentially Responsible Parties

PVA Polyvinyl Alcohol

PYR Pyrene

RACER Remedial Action Cost Engineering and Requirements

RBCA Risk-Based Corrective Action

RBCLs Risk-Based Clean-Up Levels

RBR Risk-based Remediation

RCLs Recommended Clean-Up Levels

RCRA Resource Conservation and Recovery Act

ReTec Remediation Technologies, Inc.

RfC Inhalation Reference Concentrations

RfDo Oral Reference Doses

RME Reasonable Maximum Exposure

ROD Record of Decision

ROS Reactive Oxygen Species

ROS-LIF Rapid Optical Screening Tool Laser-Induced Fluorescence

RSLs Regional Screening Levels

RVIM The National Institute for Public Health and the Environment

S/S Stabilization/Solidification

SDWA Safe Drinking Water Act

SEPA State Environmental Policy Act

SIM Selected Ion Monitoring

SMCs Splenic Melano-macrophage Centers

SMRT Single-Molecule Real Time

SOA Secondary Organic Aerosols

SPM Suspended Particulate Materials

SPMD Semipermeable Membrane Device

SPME Solid-Phase Microextraction

SQGE Soil Quality Guidelines for Environmental Health Protection

SRC Serious Risk Concentration

SRCs Serious Risk Concentrations

SSD Species Sensitivity Distribution

SVE Soil Vapor Extraction

SVOCs Semi-volatile Organic Carbons

SW Soil Washing

TCE Trichloroethylene

TCICs Total Carcinogenic Indicator Chemicals

TCLP Toxicity Characteristic Leaching Procedure

TD Thermal Desorption

TDI Tolerable Daily Intake

TERI The Energy and Resources Institute

TLC Thin-Layer Chromatography

TOC Total Organic Carbon

TOFMS Time-of-Flight Mass Spectrometry

TPHs Total Petroleum Hydrocarbons

TRPHs Total Recoverable Petroleum Hydrocarbons

UCMs Unresolved Complex Mixtures

UFPs Ultrafine Particles

US EPA United States Environmental Protection Agency

USAF United States Air Force Abbreviations

Abbreviations

USTs Underground Storage Tanks

UT Ultrasound Technology

UVIF Ultraviolet-Induced Fluorescence

VOCs Volatile Organic Compounds

VPHs Volatile Petroleum Hydrocarbons

WAFs Water Accommodated Fractions

WHP Wellness and Health Promotion

1 An Overview of Total Petroleum Hydrocarbons

1.1 Introduction

1.2 Definitions

3 1.2.1 Hydrocarbon

1.2.2 Crude Oil

1.2.3 Petroleum

3 1.2.4 PHs

1.2.5 TPHs

5 1.3 Sources of TPHs.

6 1.4 Carbon Ranges in TPHs

1.5 Components of TPHs

Gasolines

2.3 Resolving the Unresolved Complex Mixture in TPHs-Impacted Media

2.4 TPHs Levels in Environmental Samples

6.1 Introduction .

6.2 TPHs Sources for Human Exposure

6.3 Routes of TPHs Entry

6.4 Effects of TPHs on Human Health.

6.4.1 Effects on Mental Health

6.4.2 Effects on the Respiratory System

6.4.3 Effects on the Hematopoietic, Renal, and Digestive Systems

6.4.5

9.3 Land Treatment Using a Bulldozer Equipped with a Cultivator

9.4 Passive Aeration in Biopiles Using Trackhoe Equipped with a Mixing Head Unit

9.5 Land Treatment at the Brown Wood Preserving Superfund Site in Live Oak, Florida, USA

9.6 Bioventing Treatment at Eielson Air Force Base, Alaska, USA

9.7 Slurry-Phase Bioremediation at the French Limited Superfund Site, Crosby, Texas, USA

9.8 Remediation of a JP-4 Fuel Spill at Hill AFB, Utah, USA

9.9 Bioventing Treatment of Underground Storage Tanks at Lowry AFB, Denver, Colorado, USA

9.10 Land Treatment at the Scott Lumber Company Superfund Site, Alton, Missouri, USA

9.11 Density-Driven Groundwater Sparging at Amcor Precast, Ogden, Utah, USA

9.12 Pump and Treat of Contaminated Groundwater at Langley AFB, Virginia, USA

9.13 Dynamic Underground Stripping at Lawrence Livermore National Laboratory Gasoline Spill Site, California, USA

9.14 Soil Vapor Extraction at North Fire Training Area Luke AFB, Arizona, USA

9.15 Thermal Desorption at the McKin Company Superfund Site, Gray, Maine, USA

9.16 In Situ Chemical Oxidation of Methyl Tertiary Butyl Ether

9.17 Surfactant-Enhanced Ex Situ Oxidation of Diesel Nonaqueous Phase Liquid in Georgia, USA

9.18 Remediation of Former Filling Station Site in Glasgow, UK

9.19 Remediation of a Mega-site in China

9.20 Bioremediation of Petroleum Hydrocarbons in Bogota, Colombia

9.21 In Situ Treatment of Toluene in Groundwater in Helsingborg, Sweden

9.22 In Situ Remediation of PHs at a Rail Depot, Bristol, UK

9.23 Ex Situ Chemical Oxidation of Soils at a Fuel Storage Depot, Sweden

9.24 Horizontal Well Injection Application at an Active Gas Station Site in Colorado, USA

9.25 Summary

About the Authors

Saranya Kuppusamy obtained her MSc in Agricultural Microbiology (2009–2011) from Tamil Nadu Agricultural University, Coimbatore, India. She joined the University of South Australia, Mawson Lakes, Australia, in 2012 for her doctoral research with the prestigious International Postgraduate Research Scholarship together with the top-up fellowship from the Centre for Contamination Assessment and Remediation of the Environment and obtained her PhD in Environmental Remediation and Public Health in 2015. Her research findings on “A new microbial formulation to clean-up contaminated sites” have been highlighted in Research Edge Newsletter of the University of South Australia in 2015. Later, she joined the Gyeongsang National University, Jinju, South Korea, in November 2015 and worked as a Research Professor until June 2018. She received “Excellent Thesis Presentation Award” offered by the Korean Society of Environmental Agriculture (KSEA) in the International Symposium and Annual Meeting of the KSEA held at Muju, Republic of Korea, in 2016. She has been availing the DST-SERB Ramanujan Fellowship (Scientist D) (2018–2023) awarded by the Government of India at the Centre for Environmental Studies, Anna University, Chennai, India. She has been actively involved in different areas of Agriculture and Environment (Soil Chemistry, Fertility and Management, Environmental Biotechnology, Biochar, Soil and Water Remediation, Waste Management, Crop Quality Improvement) and published 46 journal articles (over 900 citations, h-index of 17, and i10-index of 23), 2 book chapters, and a book, Agricultural and Industrial Microbiology.

Naga Raju Maddela received his MSc (1996–1998) and PhD (2012) in Microbiology from Sri Krishnadevaraya University, Anantapuramu, India. During his doctoral program in the area of Environmental Microbiology, he investigated the effects of industrial effluents/insecticides on soil microorganisms and their biological activities and worked as a Faculty in Microbiology for 15 years, teaching undergraduate and postgraduate students. He received “Prometeo Investigator Fellowship” (2013–2015) from Secretaría de Educación Superior, Ciencia, Tecnología e Innovación (SENESCYT), Ecuador, and “Postdoctoral Fellowship” (2016–2018) from Sun Yat-sen University, China. He also received external funding from “China

xix

Postdoctoral Science Foundation” in 2017, worked in the area of Environmental Biotechnology, participated in 19 national/international conferences, and presented research data in China, Cuba, Ecuador, and Singapore. Currently, he is working as a Professor at the Facultad de Ciencias de la Salud, Universidad Técnica de Manabí, Portoviejo, Ecuador. He has 37 research papers to his credit besides coauthoring 2 books, one published by SpringerBriefs and the other by Springer.

Mallavarapu Megharaj joined the Global Centre for Environmental Remediation (GCER), University of Newcastle, as Professor of Environmental Biotechnology in May 2015. Prior to joining the University of Newcastle, he worked as Professor of Environmental Biotechnology (University of South Australia), senior/research scientist (CSIRO Land & Water), and postdoctoral fellow (Otago University, New Zealand; GBF-National Research Centre for Biotechnology, Germany; University of Liverpool, UK). Also, for the past 14 years, he has been leading the “Remediation Technologies Program” within the Cooperative Research Centre for Contamination Assessment and Remediation of the Environment (CRC CARE). He is an Internationally Recognized Expert in the areas of Microbial Degradation of Pollutants and Environmental Toxicology/Remediation. Most of his research involved multidisciplinary teams for which he provided the leadership role. He and his colleagues have field implemented and monitored natural attenuation as an effective remedial option for petroleum hydrocarbon-contaminated sites in addition to providing new scientific knowledge on fate and behavior of emerging contaminants such as firefighting foams. Also, he and his colleagues have developed and field implemented novel bioremediation technologies for petroleum hydrocarboncontaminated soils. He currently serves as a Member of Editorial Board for Environmental Geochemistry and Health and Ecotoxicology and Environmental Safety. He is an Author/Coauthor of 390 refereed journal papers, 18 invited book chapters, and 5 patents and Coeditor of 4 books. He supervised 37 PhD students and has an h-index of 62, i10-index of 279, and total citations over 14,500.

Kadiyala Venkateswarlu was a Professor of Microbiology, Sri Krishnadevaraya University, Anantapuramu, India, until 2011. He taught General Microbiology, Microbial Genetics, Molecular Biology, and Genetic Engineering to MSc students and served as Dean, Faculty of Life Sciences, and Professor-in-Charge of Biotechnology Department. His research area of interest has been Environmental Biotechnology, particularly concerned with Microbial Degradation of Pollutants and Environmental Toxicology/Remediation. He authored more than 150 research publications (over 3900 citations, h-index of 30, and i10-index of 80), largely in the area of Environmental pollutants–soil microflora interactions, and bioremediation in leading scientific journals of international repute, guided 12 students for the award of PhD degree and 8 for MPhil degree, and earned a US patent. He was awarded the Commonwealth Academic Staff Fellowship of the British Council to work in the University of Dundee, Dundee, Scotland, in 1989 and availed twice the Visiting Senior Research Associateship awarded by the National Research Council, USA, in 1995–1997 and 2001–2003 and the Endeavour Executive Award at the

University of South Australia, Adelaide, in 2010–2011. Furthermore, he received Andhra Pradesh State Universities Meritorious Teacher Award (India) in 2005 and was elected Fellow of the National Academy of Agricultural Sciences and Association of Microbiological Sciences, India, both in 2008. He also served as an Editor of the Indian Journal of Microbiology, edited two textbooks of Microbiology for BSc students, and coauthored a book, Insecticides – Soil Microbiota Interactions, published by Springer.

Chapter 1 An Overview of Total Petroleum Hydrocarbons

Abstract Total petroleum hydrocarbons (TPHs) are one of the common contaminants in the environment. They include a broad family of several hundred hydrocarbon compounds that originally come from crude oil which is used to make petroleum products. The widespread use of crude oil and other petroleum products for transportation, heating, and industry leads to the release of these petroleum products into the environment through long-term leakage, accidental spills, or operational failures. Since there are so many different chemicals in crude oil and other petroleum products, it is not practical to measure each one separately. However, it is useful to measure the amount of TPHs at a contaminated site. The TPHs include both volatile and extractable petroleum hydrocarbons (VPHs and EPHs) encompassing the gasoline range organics (>C6–C10), diesel range organics (>C11–C28), and oil range organics (C29–C35). Gasoline, kerosene, diesel fuels, jet fuels, Stoddard solvent, mineral-based motor oils, fuel oils No. 5 and 6, hexane, benzene, toluene, xylenes, and polycyclic aromatic hydrocarbons are the important chemicals that constitute TPHs. These chemicals have carbon ranges between ≥C5 and ≤C35. Detailed information about each of these chemicals included in TPHs is presented in this chapter.

Keywords Crude oil · Diesel · Petroleum hydrocarbons · PAHs · Sources of TPHs

1.1 Introduction

The development of human civilization led to severe disruption of the natural balance and the occurrence of different types of pollution. Among the chemicals that are relevant as environmental contaminants, petroleum hydrocarbons (PHs) used extensively in different spheres are of particular significance (Megharaj et al. 2000). In fact, in order to meet the current heavy oil demand, the average global crude oil production in 2019, as per the US Energy Information Administration database, is 80.62 million barrels day 1. Of this, nearly 68% comes from the top ten oilproducing countries, viz., the USA, Saudi Arabia, Russia, Canada, China, Iran, Iraq,

© Springer Nature Switzerland AG 2020

S. Kuppusamy et al., Total Petroleum Hydrocarbons, https://doi.org/10.1007/978-3-030-24035-6_1

1

Fig. 1.1 Top ten oil-producing countries in the world. (Based on data from Amanda 2018)

UAE, Brazil, and Kuwait, in that order (Fig.  1.1). The amount of natural crude oil seepage was estimated to be 600,000 metric tons per year with a range of uncertainty of 200,000 metric tons per year (Kumari et al. 2013). Release of hydrocarbons into the environment whether accidentally or due to human activities is the main cause of soil, water, and air pollution (Bardi et al. 2000). Thus, the processing of crude oil and the widespread use of different PHs for transportation, heating, industry, etc. result in the release of hydrocarbons into the environment through operational failures, long-term leakage, or accidental spills (Fig. 1.2).

The PHs are well known to be neurotoxic to humans and animals (Ritchie et al. 2001; Webb et al. 2018). For both the diagnosis of suspected areas and the possibility of controlling the rehabilitation process, there is a great need to measure correctly the amounts of total petroleum hydrocarbons (TPHs) in the environment. For this, much more detailed understanding of TPHs is required in the first instance. Hence, this chapter is dedicated to present an overview of TPHs as to (i) how are the terms hydrocarbons, crude oil, petroleum, PHs, and TPHs are defined, (ii) how TPHs enter the environment, (iii) what are the carbon ranges included in TPHs, and (iv) what are the common TPH components? More importantly, detailed information on all the TPHs constituents like jet fuels, diesel fuels, mineral oils, benzene, toluene, ethylene, xylene, polycyclic aromatic hydrocarbons (PAHs), as well as other petroleum products and gasoline components is included in this chapter in order to enhance readers’ basic knowledge on TPHs.

Fig. 1.2 Global oil spills in the last five decades. (Based on data from ITOPF 2018)

1.2 Definitions

1.2.1 Hydrocarbon

A “hydrocarbon” is any chemical compound that consists only of the elements carbon (C) and hydrogen (H). They all contain a C frame and have H atoms attached to the frame. Most hydrocarbons are combustible.

1.2.2 Crude Oil

Crude oil is a naturally occurring, unrefined petroleum product composed of hydrocarbon deposits and other organic materials. Crude oil, a type of fossil fuel, can be refined to produce usable products such as gasoline, diesel, and various other forms of petrochemicals. It is a nonrenewable resource, which means that it cannot be replaced naturally at the rate we consume it and is, therefore, a limited resource.

1.2.3 Petroleum

“Petroleum” can be defined as any hydrocarbon mixture of natural gas, condensate, or crude oil. Crude oil is the main source material for nearly all petroleum products. This material is distilled into a series of fractions to make different petroleum

products, each characterized by the temperature and pressure of distillation. Thus, the type of petroleum product is a direct result of the boiling point of the crude used in the product. For instance, lighter fractions of crude with lower distillation temperatures are used for diesel, jet fuels, and light heating oils. Heavy fuel oils are made up of the residue from the distillation process and are composed of the heaviest fractions with the highest distillation temperatures. The temperature of distillation also functionally defines the volatility of the fuel, with gasolines being highly volatile and residual fuels only slightly volatile (Blaisdell and Smallwood 1993). In addition to the process of distillation, the makeup of individual petroleum products is also dependent on refinery processes performed to give the product desired characteristics. For instance, gasolines are created by blending different products of distillation with various additives in order to create a product that meets engine performance criteria. The significance of the production process is that some petroleum products may have little resemblance to the initial distillate produced during the initial processing of crude.

1.2.4 PHs

“PHs” are compounds of petroleum that consist almost entirely of the elements of C and H. They are not distinct entities but rather represent a continuum over a broad range by the molecular weight of individual hydrocarbons. Gasoline, diesel fuel, and related products contain hundreds and sometimes thousands of different PHs. The PHs can be divided into four major structural groups (Fig. 1.3) as follows:

(a) Alkanes (or paraffins) – These hydrocarbons are saturated, which means that each carbon atom forms four single bonds with the H and other C atoms which make up each compound. These hydrocarbons are also aliphatic, which means that the carbon atoms are joined by straight or branched-chain arrangements. Examples of compounds in this group are hexane, heptane, octane, and decane.

(b) Cycloalkanes (or naphthalenes) – Hydrocarbons in this group are saturated hydrocarbons which are characterized by their ring-type structure. Methylcyclopentane and ethylcyclo-p-hexane are examples of hydrocarbons in this group.

(c) Alkenes (or olefins) – Hydrocarbons in this group are unsaturated, which means they contain at least two carbon atoms joined by more than one covalent bond and aliphatic. Ethene and propene are examples in this group.

(d) Arenes (or aromatics) – All compounds in this group contain at least one benzene ring. Benzene, toluene, ethylene, and xylene (BTEX) compounds fall into this group. Compounds in this group that contain three or more closed rings are termed polynuclear or polycyclic aromatic hydrocarbons (PAHs). Phenanthrene and pyrene are examples in this group.

Aliphatics

Petroleum hydrocarbons

Alkanes

> Contain single bonds between C atoms

> bonds between atoms

Examples: Hexane, Heptane, Octane

Cycloalkanes

> Contain C atoms in cyclic structures

Examples: Methylcyclopentane

> atoms in cyclic structures yy

Ethylcyclohexane

Alkenes

> between

> Contain one or more double bonds between atoms; Examples: Ethene, Propene

Monoaromatics

one as of their

> Contain one benzene ring as part of their structure; Example: BTEX

Polyaromatics

> Contain two or more fused benzene rings

Example: PAHs

The term “TPHs” is associated with environmental sampling, and the analytical results define TPHs as the gross quantity of measurable petroleum-based hydrocarbons (Blaisdell and Smallwood 1993). It depends on the analysis of the medium in which hydrocarbons are found. The definition of TPHs thus depends on the analytical method used, because TPHs refer to the total concentration of PHs extracted and measured by a method. The TPHs can be simply stated as the total recoverable PHs and can also be defined as mixtures of hundreds of PHs that vary in structure (alkanes, alkenes, cycloalkanes, and aromatics) and size (6 to more than 35 carbon atoms in a molecule). These TPHs include the aliphatics (consisting of hexane, gasoline, kerosene, and mineral oils), aromatics (consisting of lower-molecularweight compounds like BTEX as well as higher-molecular-weight lubricants, greases, and PAHs that are recalcitrant to natural attenuation), and petroleum-based hydrocarbon molecules with different composition and axial orientations (McIntosh 2014). In short, TPHs is a term used to describe a broad family of several hundred chemical compounds (Todd et al. 1999) that originally come from crude oil that is used to make petroleum products. Generally, TPHs testing provides a means to quantify the magnitude (in relative terms) of petroleum contamination that remains in the environment, i.e., to determine if petroleum contamination (gasoline range, diesel range, oil range, or all the three) is present in the environment that could pose a direct contact risk (Vermont 2017).

Aromatics

Aromatics

Fig. 1.3 Types of PHs

1.3 Sources of TPHs

TPHs are common contaminants in soil, water, and air. Being components of crude oil and products derived from it, TPHs are consequently found in a variety of sites including refineries, sites where they are used as feedstocks (e.g., the manufacture of plastics), manufactured gas production sites, and sites where hydrocarbons are used as fuel or lubricants and retail service stations. They may also be present as a result of spills and leaks during transportation. Although most TPHs occur in the soil due to human activities that include accidents, managed spills, or as unintended by-products of industrial, commercial, or private actions, there are some natural sources of these materials. Included in this category are seeps from oil deposits and degradation of organic matter. Some of the higher plants are also capable of synthesizing hydrocarbons, may be in small amounts, and are unlikely to result in significant contamination (Pinedo et al. 2012, 2013). Inputs from natural sources are generally low compared to those from anthropogenic sources (Li et al. 2010). One of the most familiar anthropogenic sources of TPHs in the soil is through leakage from underground storage tanks (USTs) of former petrol stations. Other such sources include spillage of gasoline, diesel fuel, aviation, and other fuels from refueling and lubrication (for instance, railway yards). Places of transferring and handling of crude oils (for instance, tanker terminals and oil refineries) are also potential sites of contamination. Shale oil retorting plants provide another source of TPHs contamination in the soil as do coal gasworks sites, particularly those at which “benzole recovery” was practiced. Chemicals used at home or work or certain pesticides that contain TPH components as solvents could be the other potential sources (Sadler and Connell 2003).

The occurrence of TPHs in the sediment, marine environment, surface, and groundwater may come from natural seeps, atmospheric deposition/fallout, urban runoff and discharges, riverine discharges, sewage disposal, coastal refineries, other coastal effluents, accidents from tankers at sea, operational discharges from tankers, losses from non-tanker shipping, offshore production and transport losses, and pyrolysis/combustion of fossil fuel such as vehicles, power plants, industrial processes, and refuse burning (Freedman 1995; Zhou et al. 2014; Ţigănuș et al. 2016; Turki 2016). TPHs occurring in the atmosphere may come from combustion (vehicles, aeroplanes, cooking, and heating appliances), industry (leaking of USTs from gas stations, manufactured gas plant sites, and refineries), household goods (cleaning products), and/or natural sources (seeps, natural gas, and naturally occurring organic matter in soil like peat).

1.4 Carbon Ranges in TPHs

TPHs include all undifferentiated hydrocarbons for carbon range compounds (≥C5–≤C35) that are divided into three fractions such as:

(a) Low-range hydrocarbons (LRH) – for carbon range ≥C5–<C9

(b) Mid-range hydrocarbons (MRH) – for carbon range ≥C9–<C19

(c) High-range hydrocarbons (HRH) – for carbon range ≥C19–≤C35

The terms gasoline range organics (GRO) for carbon range >C6–C10, diesel range organics (DRO) for carbon range >C11–C28, and oil range organics (ORO) for carbon range >C28–C35 have been used to refer to TPHs (Williams et al. 2006). Typically, the sum of volatile PHs (VPHs) and extractable PHs (EPHs) refers to TPHs. VPHs include C6–C12 aliphatics, BTEX, methyl tertiary-butyl ether (MtBE), naphthalene, and C9–C10 aromatics. EPHs include C9–C35 aliphatics and C11–C22 aromatics (Brewer et al. 2013).

1.5 Components of TPHs

Common TPH constituents include jet fuels, diesel fuels, mineral oils, BTEX, and PAHs as well as other petroleum products and gasoline components as detailed below.

1.5.1 Gasolines

Gasolines, including automotive gasolines (petrol) and older jet fuels (avgas), are the refined petroleum products made up of a mixture of hydrocarbons and additives including blending agents and are consumed as a fuel in spark-ignition engines, primarily those which power automobiles or certain aeroplanes (Hsu and Robinson 2007). The hydrocarbons produced by modern refining techniques (distillation, cracking, reforming, alkylation, isomerization, and polymerization) fall into three general types: paraffins (butane, isopentane, alkylate, isomerate, straight-run naphtha, hydrocrackate), olefins (catalytic naphtha, steam-cracked naphtha), and aromatics (catalytic reformate), all providing blending components for automotive gasoline production (Hsu and Robinson 2007). The typical composition of automotive gasoline or motor gasoline hydrocarbons includes 4–8% alkanes, 2–5% alkenes, 25–40% isoalkanes, 3–7% cycloalkanes, l–4% cycloalkenes, and 20–50% total aromatics. The typical composition of avgas or aviation gasoline includes 50–60% paraffins and iso-paraffins, 20–30% naphthalenes, 10% aromatics, and no olefins. By comparison, automotive gasoline may contain up to 30% olefins and 50% aromatics. Aviation gasoline has an octane number suited to the engine, a freezing point of 60 °C, and a distillation range usually between 30 and 180 °C compared to 1 to 200 °C for automotive gasoline (Speight 2011a).

Additives and blending agents are added to the hydrocarbon mixture to improve the performance and stability of gasoline. These compounds include octane enhancers (e.g., MtBE, ethanol) (Wright and Betz 1992; Nadim et al. 2001), antioxidants (e.g., N,N′-dialkylphenylenediamines, triethylene tetramine) (Jordan 2007), metal deactivators (e.g., N,N′-disalicylidene-1,2-ethanediamine, N,N′-disalicylidene-1,2propanediamine) (Waynick 2001), ignition controllers (e.g., tri-o-cresylphosphate)

(Blackmore and Thomas 1977), icing inhibitors (e.g., isopropyl alcohol) (Little et al. 1969), detergents/dispersants (e.g., alkylamine phosphates, poly-isobutene amines, long-chain alkyl phenols/alcohols/amines) (Vataru et al. 1987), and corrosion inhibitors (e.g., carboxylic/phosphoric/sulfonic acids) (Da Silva et al. 2005; Yücesu et al. 2007). At the end of the production process, finished gasoline typically contains more than 150 chemicals, including <0.1 to >5% of BTEX, MtBE, and sometimes lead (Deeb and Alvarez-Cohen 2000; Barnes et al. 2004) although as many as 1000 compounds have been identified in some blends (ASTDR 2018). How the gasoline is made determines which chemicals are present in the gasoline mixture and how much of each chemical is present. The actual composition also varies with the source of crude petroleum (Brewer et al. 2013). In general, gasolines are generally dominated by a mixture of volatile, flammable liquid hydrocarbons that have 5–12 carbon atoms in their molecular structure, boil below 180 °C or at most below 200 °C, and have an octane number of 60 (Speight 2015). Information regarding the physico-chemical properties of gasoline is presented in Table 1.1

1.5.2 Kerosene

Kerosene, also known as fuel oil No. 1, paraffin oil, lamp oil, or coal oil, is a flammable hydrocarbon liquid commonly used as fuel (Speight 2011a). It is obtained from petroleum and is used for burning domestic heaters, lamps, or furnaces and also used as a fuel component for diesel and tractor engines, jet engines, and rockets and as a solvent for greases and insecticides. It is used as one of the common cooking fuels (Dioha et al. 2012). The chemical composition of kerosene depends on its source and is complex. It is usually made up of C10–C16 hydrocarbons including 55.2% paraffins, 40.9% naphthalenes, and 3.9% aromatic hydrocarbons. Compared to gasoline, kerosene is less volatile with a higher flash point (38 °C) and hence is relatively a safe fuel to store and handle. With a boiling point of 175–325 °C, it is one of the so-called middle distillates or medium-weight distillates of crude oil along with diesel fuels, Stoddard solvents, and jet fuels. Kerosene can be produced either as straight-run kerosene (separated physically from other crude oil fractions by distillation) or as cracked kerosene (by chemically decomposing or cracking heavier portions of the crude oil at elevated temperatures) (Speight 2011b). Properties of kerosene are presented in Table 1.1

1.5.3 Diesel Fuels

Diesel fuels, also called as diesel oil, fuel oil No. 2, or home heating oil, are obtained from the fractional distillation of crude oil and are primarily used in automobiles and railroad engines. They are in general a mixture of C10 through C19 hydrocarbons with boiling points in the range of 150–380 °C and are less volatile and heavier with

Table 1.1 (continued)

Soluble in alcohol, chloroform, carbon disulfide, glacial acetic acid, diethyl ether and acetone

Soluble in alcohol and ether

Soluble in alcohol, chloroform, carbon disulfide, carbon tetrachloride, glacial acetic acid, diethyl ether, and acetone

Soluble in ethanol, benzene, ether, chloroform, carbon tetrachloride and carbon disulfide

Soluble in benzene and cyclohexane

8 Solubility (a) Water (mg L 1 at 20 °C) Insoluble Soluble 5

Soluble in ethanol, ether, chloroform, and benzene Soluble in other petroleum solvents NA

(b) Organic solvents

Soluble in alcohol, ether, and other organic solvents 9