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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 Naga Raju Maddela
Centre for Environmental Studies Facultad de Ciencias de la Salud y
Anna University Departamento de investigación
Chennai, Tamil Nadu, India Universidad Técnica de Manabí
Portoviejo, Manabí, Ecuador
Mallavarapu Megharaj
Global Centre for Environmental Kadiyala Venkateswarlu
Remediation Nellore, Andhra Pradesh, India
The University of Newcastle
Newcastle, NSW, Australia

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.
The publisher, the authors, and the editors are safe to assume that the advice and information in this book
are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the
editors give a warranty, express or implied, with respect to the material contained herein or for any errors
or omissions that may have been made. The publisher remains neutral with regard to jurisdictional claims
in published maps and institutional affiliations.

This Springer imprint is published by the registered company Springer Nature Switzerland AG
The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland
Preface

Hydrocarbons are made of the elements carbon and hydrogen and are the most
abundant organic compounds in the bio-geosphere. Hydrocarbons are formed bio-
synthetically 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 revo-
lution and the present modern life of humans. The term “total petroleum hydrocar-
bons (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 petro-
leum hydrocarbons (PHs). Environmental pollution by PHs, as a result of industri-
alization 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 indus-
trialization, but less than a tenth of potentially contaminated lands have only been
remediated due to the challenging nature of contamination, cost, technical imprac-
ticability, insufficient land legislation, and enforcement. As such, there is no avail-
ability 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 pro-
cedures for TPHs-contaminated sites.
This book, intended to cover all the above different aspects of TPHs contamina-
tion, is organized into nine chapters. Chapter 1 introduces the readers to the produc-
tion 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

v
vi Preface

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 biologi-
cal. Chapter 5 provides the ecological impacts of TPHs that include the nontarget
effects of TPHs toward terrestrial organisms (microbes, plants, invertebrates, verte-
brates) and aquatic organisms − marine vs freshwater (microbes, plants, inverte-
brates, 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 environ-
mental regulations across the world and the available ecological-/health-based regu-
latory 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, remedia-
tion 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 provid-
ing 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 col-
leagues in the Faculty of Health Science, Department of Investigation, for their help
in literature collection.

vii
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

ix
x 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 xi

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
xii Abbreviations

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 xiii

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
Contents

1 An Overview of Total Petroleum Hydrocarbons����������������������������������    1


1.1 Introduction��������������������������������������������������������������������������������������    1
1.2 Definitions����������������������������������������������������������������������������������������    3
1.2.1 Hydrocarbon ������������������������������������������������������������������������    3
1.2.2 Crude Oil������������������������������������������������������������������������������    3
1.2.3 Petroleum������������������������������������������������������������������������������    3
1.2.4 PHs����������������������������������������������������������������������������������������    4
1.2.5 TPHs ������������������������������������������������������������������������������������    5
1.3 Sources of TPHs�������������������������������������������������������������������������������    6
1.4 Carbon Ranges in TPHs��������������������������������������������������������������������    6
1.5 Components of TPHs������������������������������������������������������������������������    7
1.5.1 Gasolines������������������������������������������������������������������������������    7
1.5.2 Kerosene ������������������������������������������������������������������������������    8
1.5.3 Diesel Fuels��������������������������������������������������������������������������    8
1.5.4 Jet Fuels��������������������������������������������������������������������������������   12
1.5.5 Stoddard Solvent������������������������������������������������������������������   13
1.5.6 Mineral-Based Motor Oils����������������������������������������������������   14
1.5.7 Fuel Oils No. 5 and 6������������������������������������������������������������   14
1.5.8 BTEX������������������������������������������������������������������������������������   15
1.5.9 PAHs ������������������������������������������������������������������������������������   16
1.6 Chemicals Included in TPHs������������������������������������������������������������   17
1.7 Summary ������������������������������������������������������������������������������������������   23
References��������������������������������������������������������������������������������������������������   23
2 Methodologies for Analysis and Identification of Total Petroleum
Hydrocarbons ������������������������������������������������������������������������������������������   29
2.1 Introduction��������������������������������������������������������������������������������������   29
2.2 Methods for PHs Analysis����������������������������������������������������������������   30
2.2.1 Collection and Preservation of Environmental
Samples ��������������������������������������������������������������������������������   31
2.2.2 Sample Extraction����������������������������������������������������������������   31

xv
xvi Contents

2.2.3 Concentration of the Extract ������������������������������������������������   35


2.2.4 Clean-Up of the Extract��������������������������������������������������������   36
2.2.5 Detection and Quantification of PHs������������������������������������   37
2.3 Resolving the Unresolved Complex Mixture in
TPHs-­Impacted Media����������������������������������������������������������������������   45
2.4 TPHs Levels in Environmental Samples������������������������������������������   46
2.5 Summary ������������������������������������������������������������������������������������������   50
References��������������������������������������������������������������������������������������������������   50
3 Fate of Total Petroleum Hydrocarbons in the Environment����������������   57
3.1 Introduction��������������������������������������������������������������������������������������   57
3.2 Fate of TPHs in Air ��������������������������������������������������������������������������   60
3.3 Fate of TPHs in Land-Spillage����������������������������������������������������������   62
3.4 Fate of TPHs in Aquatic Systems ����������������������������������������������������   65
3.4.1 Marine Environment ������������������������������������������������������������   65
3.4.2 Freshwater System����������������������������������������������������������������   70
3.4.3 Sediments������������������������������������������������������������������������������   72
3.4.4 Ice������������������������������������������������������������������������������������������   73
3.5 Summary ������������������������������������������������������������������������������������������   73
References��������������������������������������������������������������������������������������������������   74
4 Bioavailability of Total Petroleum Hydrocarbons��������������������������������   79
4.1 Introduction��������������������������������������������������������������������������������������   79
4.2 Definitions of Bioavailability������������������������������������������������������������   80
4.3 Importance of Bioavailability in Bioremediation ����������������������������   82
4.4 Surfactants to Enhance TPHs Bioavailability ����������������������������������   83
4.5 Assessing Bioavailability of TPHs����������������������������������������������������   83
4.5.1 Chemical Assays ������������������������������������������������������������������   84
4.5.2 Biological Assays������������������������������������������������������������������   87
4.6 Summary ������������������������������������������������������������������������������������������   91
References��������������������������������������������������������������������������������������������������   91
5 Ecological Impacts of Total Petroleum Hydrocarbons ������������������������   95
5.1 Introduction��������������������������������������������������������������������������������������   96
5.2 Terrestrial Organisms������������������������������������������������������������������������   98
5.2.1 Microorganisms and Their Activities������������������������������������   99
5.2.2 Plants������������������������������������������������������������������������������������ 102
5.2.3 Invertebrates�������������������������������������������������������������������������� 106
5.2.4 Vertebrates���������������������������������������������������������������������������� 110
5.3 Aquatic Organisms���������������������������������������������������������������������������� 116
5.3.1 Microorganisms�������������������������������������������������������������������� 116
5.3.2 Plants������������������������������������������������������������������������������������ 120
5.3.3 Invertebrates�������������������������������������������������������������������������� 122
5.3.4 Vertebrates���������������������������������������������������������������������������� 124
5.4 Summary ������������������������������������������������������������������������������������������ 130
References�������������������������������������������������������������������������������������������������� 131
Contents xvii

6 Impact of Total Petroleum Hydrocarbons on Human Health ������������ 139


6.1 Introduction�������������������������������������������������������������������������������������� 139
6.2 TPHs Sources for Human Exposure ������������������������������������������������ 142
6.3 Routes of TPHs Entry ���������������������������������������������������������������������� 144
6.4 Effects of TPHs on Human Health��������������������������������������������������� 147
6.4.1 Effects on Mental Health������������������������������������������������������ 151
6.4.2 Effects on the Respiratory System���������������������������������������� 152
6.4.3 Effects on the Hematopoietic, Renal, and Digestive
Systems �������������������������������������������������������������������������������� 153
6.4.4 Carcinogenicity and Genotoxic Effects�������������������������������� 154
6.4.5 Teratogenic Effects �������������������������������������������������������������� 156
6.4.6 Immunotoxicity and Endocrine Toxicity������������������������������ 157
6.5 Health Risk Assessments������������������������������������������������������������������ 158
6.6 Summary ������������������������������������������������������������������������������������������ 161
References�������������������������������������������������������������������������������������������������� 162
7 Approaches for Remediation of Sites Contaminated
with Total Petroleum Hydrocarbons������������������������������������������������������ 167
7.1 Introduction�������������������������������������������������������������������������������������� 167
7.2 Risk-Based Clean-Up of TPHs-Contaminated Sites:
An Emerging Approach�������������������������������������������������������������������� 169
7.3 TPHs Risk Reduction������������������������������������������������������������������������ 169
7.3.1 Established Remediation Technologies�������������������������������� 170
7.3.2 Emerging Remediation Technologies ���������������������������������� 189
7.4 Summary ������������������������������������������������������������������������������������������ 196
References�������������������������������������������������������������������������������������������������� 196
8 Regulatory Guidelines for Total Petroleum Hydrocarbon
Contamination������������������������������������������������������������������������������������������ 207
8.1 Introduction�������������������������������������������������������������������������������������� 207
8.2 International Guidelines for TPHs Contamination �������������������������� 208
8.2.1 Canada���������������������������������������������������������������������������������� 208
8.2.2 New Zealand ������������������������������������������������������������������������ 212
8.2.3 Netherlands �������������������������������������������������������������������������� 214
8.2.4 United Kingdom������������������������������������������������������������������� 215
8.2.5 USA�������������������������������������������������������������������������������������� 217
8.2.6 Australia�������������������������������������������������������������������������������� 218
8.2.7 Asia �������������������������������������������������������������������������������������� 221
8.3 Suggestions for Improved Regulatory Regimes ������������������������������ 222
8.4 Summary ������������������������������������������������������������������������������������������ 223
References���������������������������������������������������������������������������������������������������������� 223
9 Case Studies on Remediation of Sites Contaminated with Total
Petroleum Hydrocarbons������������������������������������������������������������������������ 225
9.1 Introduction�������������������������������������������������������������������������������������� 225
9.2 Bioremediation of Oil Spill Site in Gujarat Oil Field in
Western India������������������������������������������������������������������������������������ 228
xviii Contents

9.3 Land Treatment Using a Bulldozer Equipped


with a Cultivator�������������������������������������������������������������������������������� 231
9.4 Passive Aeration in Biopiles Using Trackhoe Equipped
with a Mixing Head Unit������������������������������������������������������������������ 232
9.5 Land Treatment at the Brown Wood Preserving Superfund
Site in Live Oak, Florida, USA�������������������������������������������������������� 233
9.6 Bioventing Treatment at Eielson Air Force Base, Alaska,
USA�������������������������������������������������������������������������������������������������� 234
9.7 Slurry-Phase Bioremediation at the French Limited
Superfund Site, Crosby, Texas, USA������������������������������������������������ 236
9.8 Remediation of a JP-4 Fuel Spill at Hill AFB, Utah, USA�������������� 238
9.9 Bioventing Treatment of Underground Storage Tanks
at Lowry AFB, Denver, Colorado, USA ������������������������������������������ 240
9.10 Land Treatment at the Scott Lumber Company Superfund
Site, Alton, Missouri, USA �������������������������������������������������������������� 240
9.11 Density-Driven Groundwater Sparging at Amcor Precast,
Ogden, Utah, USA���������������������������������������������������������������������������� 241
9.12 Pump and Treat of Contaminated Groundwater at Langley
AFB, Virginia, USA�������������������������������������������������������������������������� 244
9.13 Dynamic Underground Stripping at Lawrence Livermore
National Laboratory Gasoline Spill Site, California, USA�������������� 245
9.14 Soil Vapor Extraction at North Fire Training Area Luke
AFB, Arizona, USA�������������������������������������������������������������������������� 246
9.15 Thermal Desorption at the McKin Company Superfund Site,
Gray, Maine, USA���������������������������������������������������������������������������� 247
9.16 In Situ Chemical Oxidation of Methyl Tertiary Butyl Ether������������ 247
9.17 Surfactant-Enhanced Ex Situ Oxidation of Diesel
Nonaqueous Phase Liquid in Georgia, USA������������������������������������ 248
9.18 Remediation of Former Filling Station Site in Glasgow, UK ���������� 249
9.19 Remediation of a Mega-site in China ���������������������������������������������� 249
9.20 Bioremediation of Petroleum Hydrocarbons in Bogota,
Colombia������������������������������������������������������������������������������������������ 250
9.21 In Situ Treatment of Toluene in Groundwater in
Helsingborg, Sweden������������������������������������������������������������������������ 251
9.22 In Situ Remediation of PHs at a Rail Depot, Bristol, UK���������������� 252
9.23 Ex Situ Chemical Oxidation of Soils at a Fuel Storage
Depot, Sweden���������������������������������������������������������������������������������� 252
9.24 Horizontal Well Injection Application at an Active Gas
Station Site in Colorado, USA���������������������������������������������������������� 253
9.25 Summary ������������������������������������������������������������������������������������������ 253
References�������������������������������������������������������������������������������������������������� 254

Index������������������������������������������������������������������������������������������������������������������ 257
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 biologi-
cal activities and worked as a Faculty in Microbiology for 15 years, teaching under-
graduate 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
xx About the Authors

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 sci-
entist (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 contami-
nants such as firefighting foams. Also, he and his colleagues have developed and
field implemented novel bioremediation technologies for petroleum hydrocarbon-­
contaminated 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
About the Authors xxi

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 trans-
portation, heating, and industry leads to the release of these petroleum products into
the environment through long-term leakage, accidental spills, or operational fail-
ures. 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 gaso-
line 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 infor-
mation 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 bal-
ance 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 oil-­
producing countries, viz., the USA, Saudi Arabia, Russia, Canada, China, Iran, Iraq,

© Springer Nature Switzerland AG 2020 1


S. Kuppusamy et al., Total Petroleum Hydrocarbons,
https://doi.org/10.1007/978-3-030-24035-6_1
2 1 An Overview of Total Petroleum Hydrocarbons

20
Oil production (×106 barrels day‒1)

16 15.6

12.2
12 11.2

4.9 4.8 4.7 4.5


3.7
4 3.3
2.8

0
USA Saudi Russia Canada China Iran Iraq UAE Brazil Kuwait
Arabia

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 uncer-
tainty of 200,000 metric tons per year (Kumari et al. 2013). Release of hydrocar-
bons 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 possibil-
ity of controlling the rehabilitation process, there is a great need to measure cor-
rectly 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 informa-
tion 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.
1.2 Definitions 3

100
Oil spills
Tanker spills
78.8
80
Average number of spills

60

45.4
40 35.8

24.5
20 18.1
9.4 7.7 6.4
3.2 1.9
0
1970-79 1980-89 1990-99 2000-09 2010-18

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 car-
bon (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 hydro-


carbon 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
4 1 An Overview of Total Petroleum Hydrocarbons

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 tem-
peratures 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 heavi-
est fractions with the highest distillation temperatures. The temperature of distilla-
tion 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 char-
acteristics. 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 petro-
leum 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 ben-
zene 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.
1.2 Definitions 5

Alkanes
> Contain single bonds between C atoms
Examples: Hexane, Heptane, Octane

Cycloalkanes
l
> Contain C atoms in cyclic structures
Aliphatics
Examples: Methylcyclopentane
Ethylcyclohexane
y y

Alkenes
> Contain one or more double bonds between
Petroleum atoms; Examples: Ethene, Propene
hydrocarbons
Monoaromatics
Monoaromati
t cs
> Contain one benzene ring as part of their
structure; Example: BTEX
Aromatics
Polyaromatics
Polyaroma
l t cs
ti
> Contain two or more fused benzene rings
Example: PAHs
P

Fig. 1.3 Types of PHs

1.2.5 TPHs

The term “TPHs” is associated with environmental sampling, and the analytical
results define TPHs as the gross quantity of measurable petroleum-based hydrocar-
bons (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 analyti-
cal 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-molecular-­
weight 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).
6 1 An Overview of Total Petroleum Hydrocarbons

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 includ-
ing refineries, sites where they are used as feedstocks (e.g., the manufacture of plas-
tics), 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 hydrocar-
bons, 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 anthropo-
genic 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, rail-
way yards). Places of transferring and handling of crude oils (for instance, tanker
terminals and oil refineries) are also potential sites of contamination. Shale oil retort-
ing plants provide another source of TPHs contamination in the soil as do coal gas-
works 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 pro-
cesses, and refuse burning (Freedman 1995; Zhou et al. 2014; Ţigănuș et al. 2016;
Turki 2016). TPHs occurring in the atmosphere may come from combustion (vehi-
cles, aeroplanes, cooking, and heating appliances), industry (leaking of USTs from
gas stations, manufactured gas plant sites, and refineries), household goods (clean-
ing 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
1.5 Components of TPHs 7

(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 car-
bon 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 naph-
tha, hydrocrackate), olefins (catalytic naphtha, steam-cracked naphtha), and aro-
matics (catalytic reformate), all providing blending components for automotive
gasoline production (Hsu and Robinson 2007). The typical composition of automo-
tive 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 aro-
matics. 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% aro-
matics. 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 enhanc-
ers (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-1,2-­
propanediamine) (Waynick 2001), ignition controllers (e.g., tri-o-cresylphosphate)
8 1 An Overview of Total Petroleum Hydrocarbons

(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 corro-
sion 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 flam-
mable 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 cook-
ing 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 Physico-chemical properties of selected TPHs constituents
Spent BTEX
mineral-
based Fuel oils
Stoddard motor No. 5
S. No. Property Gasolines Kerosene Diesel fuels Jet fuels solvents oils and 6 Benzene Ethylbenzene Toluene Xylenes
1 Molecular 100–105 170 200 180 135–145 NA NA 78 106 92 106
weight
2 Color Colorless Colorless Colorless to Colorless to Colorless Yellow Brown to Colorless to Colorless Colorless Colorless
to pale to brown brown pale brown brown to black light yellow
brown or black
pink
3 Physical state Liquid Liquid Liquid Liquid Liquid Liquid Liquid Liquid Liquid Liquid Liquid
4 Melting point NA –46 18 −40–72 −34 NA 6 −95 −95 −25–13
(°C)
5 Boiling point 39–204 175–325 282–338 45–300 154–202 360 >260 80 136 111 137–140
(°C)
6 Density 0.7–0.8 0.8–0.9 0.8–1 0.7–0.8 0.8 NA 0.9–1 0.9 0.9 0.9 0.9
(g cm−3)
7 Odor threshold 0.03 0.08 1 NA NA 5 0.03–3 0.02–0.2 0.005–0.05
(mg L−1)
(continued)
Table 1.1 (continued)
Spent BTEX
mineral-
based Fuel oils
Stoddard motor No. 5
S. No. Property Gasolines Kerosene Diesel fuels Jet fuels solvents oils and 6 Benzene Ethylbenzene Toluene Xylenes
8 Solubility
(a) Water Insoluble Soluble 5 38–57 Insoluble Insoluble Insoluble 2 140–208 526 106–178
(mg L−1 at
20 °C)
(b) Organic Soluble in Soluble in NA Soluble in Soluble in NA NA Soluble in Soluble in Soluble in Soluble in
solvents ethanol, other benzene and ethanol, alcohol, alcohol and alcohol, alcohol,
ether, petroleum cyclohexane benzene, chloroform, ether chloroform, ether, and
chloroform, solvents ether, carbon carbon other
and chloroform, disulfide, disulfide, organic
benzene carbon carbon glacial solvents
tetrachloride tetrachloride, acetic acid,
and carbon glacial acetic diethyl
disulfide acid, diethyl ether and
ether, and acetone
acetone
9 Partition
coefficients
(a) Log Kow 2–5 3–7 3–7 3–5 3–7 NA NA 2 3–4 3 3
(b) Log Koc 2–5 3–7 3–6 NA 3–7 NA NA 2 2–3 2–3 2
10 Vapor pressure 465–773 2–26 2–26 91–2480 4–5 NA 0.2 75 1–10 29 6–9
(mmHg)
11 Henry’s law 5 × 10−4 6–7 × 10−5 6–7.4 × 10−5 1–10 × 10−4 4–7.4 × 10−4 NA NA 5.5 × 10−3 7–8 × 10−3 7 × 10−3 5–7 × 10−3
constant at
20 °C
(atm m3 Mol−1)
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In dogs there are the same general symptoms with vomiting. The
vomited material is usually remasticated and swallowed. The
swelling in the pharynx can be felt from without, or seen through the
open mouth. The tonsils are usually enlarged. Pressure on the
pharynx or gullet produces instant regurgitation.
Treatment consists in the removal of the tumor when possible.
Malignant growths and multiple tumors are not favorable for
treatment. Actinomycosis can be treated throughout by iodides, or
these may supplement the surgical measures. In the short-faced
animals an ecraseur, or a wire-snare passed through a tube may be
employed. (See pharyngeal polypi).
ESOPHAGITIS. INFLAMMATION OF THE
GULLET.

Causes: Alimentary and therapeutic; parasitic and accidental traumatisms;


mechanical irritants; acrids; caustics; parasites—gongylonema, coccidia,
spiroptera. Extension inflammations. Lesions: hyperæmia; epithelial degeneration
and desquamation; erosion; petechiæ; suppuration; fibroid contraction;
sacculation; polypi. Symptoms: dysphagia, difficult deglutition; eructation; cough;
upward wave motion in jugular furrow; colicy pains; probang arrested; fever.
Treatment: liquid or semi-liquid food; for caustics, antidotes; cold water; ice;
antiseptics; derivatives; open abscess; potassium iodide.

Causes. This usually arises from injury to the mucous membrane


and in the milder forms remains confined to this structure. In the
more severe, it extends to the muscular coat and even to the
periœsophagean tissues. The causes may be divided into alimentary
and therapeutic irritants; parasitic or accidental traumatisms; and
extension of inflammation from the pharynx or other adjacent part.
Among irritants taken as food, may be named hot mashes, bolted
by a hungry and gluttonous horse, and temporarily arrested in the
gullet by reason of the resulting irritation of the mucous membrane.
In other cases, coarse fibrous fodder is bolted without previous
mastication, and scratches and abrades the œsophagean mucosa
leading to transient or progressive inflammation. In other instances
diseases of the teeth, jaws, temporo-maxillary joint, or salivary
glands prevent the necessary trituration of the food, and it is
swallowed in a rough, fibrous, or even a dry condition. Again the
impaction of a solid body (turnip, apple, potatoe, egg) or of a
quantity of finely divided grain or fodder so as to obstruct the lumen
of the gullet, is an occasional cause. The density of the epithelium
reduces these dangers to the minimum, yet a too rough morsel, or an
undue detention of the less irritating material will determine
hyperæmia and even inflammation and infective invasion. Acrid and
irritant vegetables in the food are less injurious when thoroughly
insalivated, as their contact with the œsophagean walls is then very
slight and transient.
Irritant and caustic chemical agents given for therapeutic
purposes, attack the mouth, pharynx and stomach, more severely
than the gullet through which they are passed with great rapidity. In
some cases, however, the agent will adhere by reason of its powdery,
gummy or balsamic character and will then act as a direct irritant.
Solutions of caustic alkalies (weak lye) given to correct acid gastric
indigestion in the horse, and ammonia to remedy tympany in cattle,
when insufficiently diluted, will dangerously attack the œsophagean
mucosa.
Parasitic irritation is not so common here as in other parts of the
intestinal canal where the contents are longer delayed and are passed
with less friction, yet certain parasites are found in this region and
may even produce considerable irritation. The gongylonema of the
thoracic œsophagean mucosa of ruminants and swine are apparently
harmless. The psorospermia of the œsophagean muscles of the same
animals are alleged to cause œdema of the glottis, asphyxia and
epilepsy. The spiroptera microstoma of the horse has in one instance
known to us caused extensive denudation of the muscular coat
within a foot of the cardiac end of the gullet. Finally we have found
bots hooked on to the œsophagean mucosa close to the cardia,
causing much irritation and spasm. The spiroptera sanguinolenta is
often present in chambers hollowed in the œsophagean mucosa of
the dog.
Traumatic causes appear in the form of contusions and bruises
from without, but much more frequently from foreign bodies, and
probangs operating from within. The use of a whip or of a rope
without a cup-shaped end for the relief of a choked animal. Short of
the occurrence of laceration this often produces contusion and
abrasion which results in local inflammation. Even the too forcible
dislodgment of a solid body by a probang of approved pattern, may
bruise and scratch the gullet when the seat of violent spasm. Pins,
needles, wire, thorns and other sharp bodies are liable to do serious
damage during their passage in an ordinary bolus and when they
transfix the mucosa violent infective inflammation may ensue.
Extension inflammations from the throat, and from phlegmous,
abscesses, tumors, etc., in the jugular furrow need only be mentioned
in this connection, as the primary disease will be clearly in evidence.
Lesions. These are usually circumscribed when due to a traumatic
injury and extended when caused by caustics or irritants. The
affected section is swollen, and surrounded by some serous effusion.
When the muscular coat is involved it is often paler than normal, and
microscopically shows extensive granular and fatty degeneration.
The mucosa usually sloughs off its epithelial layer, sometimes over
an extensive area (thoracic portion, Renault; whole gullet, Bertheol),
and the exposed raw surface is of a deep red or violet. When the
epithelium is not shed, it is infiltrated, swollen and friable breaking
down under the slightest manipulation. Petechiæ and slight blood
extravasations are abundant, and diffuse suppuration is not
uncommon. In traumatic injuries necrosed areas are found in the
muscular and mucous coats. Strictures, dilatations, and polypoid
growths are liable to follow as sequelæ.
Symptoms. These usually manifest themselves from two to four
days after the operation of the cause. There is much difficulty in
deglutition, the effort to swallow either solids or liquids causing
acute suffering, with extension of the head on the neck and strained
contraction of the facial muscles. If the liquid succeeds in passing the
pharynx, it is arrested at the seat of inflammation and regurgitated
through the nose and mouth, or in solipeds through the nose only.
This takes the appearance of emesis even if nothing actually comes
from the stomach. The animal shakes the head violently, breathes
hurriedly, and has fits of paroxysmal coughing. A wave extending
from below upward along the jugular furrow and followed by nasal
discharge is a marked symptom, as the violence of the inflammation
increases. Uneasy movements of the limbs, pawing and lying down
and rising, indicate the existence of colic, and this is aggravated by
the administration of anodynes or antispasmodics by the mouth. In
cattle, rumination is arrested, froth accumulates around the lips, the
rumen becomes tympanitic, and colicy movements appear.
Oftentimes a swelling extends upward in the jugular furrow, and
even in its absence, pressure with the fingers along the furrow will
often detect an area of tenderness with or without local swelling.
Fever with more or less elevation of temperature, is a general
symptom. There may be wheezing breathing or loud stertor. The
passage of a probang is arrested by the swelling or spasm at the
diseased part and when withdrawn may be covered with pus or fœtid
debris. In the horse a small probang may be passed through the
nose.
Treatment. In a slight congestion at the seat of a recent
obstruction and which tends to renewed obstruction, little more is
necessary than to restrict the feed for a few days to soft mashes so
that irritation of the sensitive surface, spasm and the arrest of the
morsel may be obviated. Plenty of pure water or of well boiled
linseed or other gruel should be allowed.
In cases in which the obstruction is still present in the gullet, its
removal by probang or looped wire is the first consideration, to be
followed by the measures mentioned above.
In case of the swallowing of a caustic agent, no time should be lost
in giving an antidote. For the mineral or caustic organic acids, lime
water, magnesia, or other bland basic agent is demanded. For caustic
alkalies or basic agents, bland acids, such as vinegar, citric acid, or
even a mineral acid very largely diluted will be in order. In both these
cases and in that of caustic salts, albuminous and mucilaginous
agents, eggs, linseed tea, slippery elm, gums, and well boiled gruels
are indicated. To these may be added small doses of laudanum when
the irritation is great. Iced drinking water, iced milk, or iced gruels
are often soothing to the suffering animal, and cold compresses,
snow or ice applied along the jugular furrow is often valuable. To
counteract the septic developments on the affected mucous
membrane, chlorate of potash, boric acid, salol, naphthalin,
naphthol, pyoktannin, or even weak solutions of phenic acid or
creolin may be used. In the slighter forms of inflammation or when
the acute form threatens to persist, an active counter-irritant of
mustard or cantharides may be applied along the jugular furrow.
In case of abscess, as manifested by fluctuation following a hard,
indurated, painful swelling, a free incision should be followed by
frequent injections of antiseptic lotions or by the packing of the
cavity with such bland antiseptics as salol, boric acid, or iodoform on
cotton.
As inflammation subsides, potassium iodide may be given, both as
an antiseptic and a resolvent, to counteract the tendency to fibroid
contraction and stricture of the gullet.
SPASM OF THE ŒSOPHAGUS.
ŒSOPHAGISMUS.

Causes: nervous disorders or lesions, pharyngeal, œsophagean, or gastric


disease, œsophagean parasites, choking, tumors, ulcers, cold drinks. Symptoms:
extended drooping head, working jaws, frothing, pawing, attempts at swallowing,
alkaline regurgitation, cries, rigid gullet, tenderness. May be paroxysmal with
intervening dullness. Treatment: by sound; by removal of obstruction; by
antispasmodics. Embrocations. Tonics.

Causes. This has been noticed as a concomitant of certain diseases


of the nervous centres, such as rabies, tetanus, or epilepsy, and those
of the pharynx or stomach. Cadeac has seen it in connection with
stricture, and the present writer has observed it as a result of larvæ of
œstri hooked on to the mucosa above the cardia. It is an important
factor in most cases of choking, and may depend on tumors, ulcers,
or even cold beverages. Animals with a specially nervous
organization are particularly subject to it and it may thus be an
hereditary family trait. It has been especially noticed in solipeds and
calves.
Symptoms. A feeding animal suddenly ceases to eat, extends the
head on the neck, drops the nose toward the ground, moves the jaws
constantly, froths at the mouth or lets the saliva drivel to the ground,
moves the fore feet uneasily pushing the litter under the belly, makes
efforts at deglutition during which, waves may be seen to descend
along the jugular furrow, followed by regurgitation and discharge of
the liquid as by emesis. The act is often followed by a slight cry.
Manipulations of the left jugular furrow detects the gullet as a firm,
rigid cord, unless when liquids are passing as above, and
auscultation reveals a rattling or gurgling noise as if in jerks.
Pressure on the gullet is often very painful, increasing the spasm and
rigidity, and causing the animal to cry out. Wheezing breathing may
attend the discharge of saliva through the nose, and violent
paroxysms of coughing may be caused by the entrance of this liquid
into the larynx.
In the majority of cases no food is swallowed and nothing but
saliva is disgorged, which together with the absence of an acid odor
distinguishes this from true vomiting. In an exceptional case of the
author’s, occurring in a colt, the animal continued to masticate and
swallow green food which gradually filled the whole length of the
gullet, practically paralyzing it. In ordinary cases a small sound can
usually be passed into the stomach. In cases of obstruction, however,
by a solid morsel, or by an accumulation of soft solids, the probang
will enable one to detect the condition. The acute symptoms may
occur in paroxysms of a few minutes in length, between which, the
animal remains dull and disspirited until the new attack supervenes.
Recovery is at times as sudden as the onset, though there remains,
for a length of time, liability to a relapse. Cadeac has seen a
succession of such attacks which extended over a year and a half.
Treatment. In many cases the passage of a probang or sound, will,
by the mere distension of the gullet, overcome the local spasm,
though it may be necessary to repeat the operation several times. In
case the sound causes much pain the end of the instrument may be
well smeared with solid extract of belladonna, and after passing this
as far as the obstruction a short time may be allowed, before its
passage is again attempted. In case obstruction by soft solids has
taken place, the passage of the wire loop will serve to break up the
mass and even to draw it up toward the mouth.
The administration of antispasmodics is the next indication.
Chloroform or ether by inhalation or in solution in water, chloral
hydrate as an enema, morphia or atropia hypodermically may be
used according to convenience. Bromide of potassium and other
antispasmodics given by the mouth, too often fail to pass the
obstruction and thus prove useless, except in the intervals of the
spasms.
Fomentations of the lower border of the neck with warm water,
and frictions over the region of the gullet with camphorated spirit,
essential oils, ammonia, or in calves with oil of turpentine, often
contribute to relieve the spasm.
Finally after the severity of the attack has passed, a course of bitter
tonics and above all of nux vomica will fortify the system against a
relapse.
PARALYSIS OF THE ŒSOPHAGUS.

Causes: nervous lesions and disorders; arytenectomy; over distension; stricture;


parasites. Symptoms: dysphagia; regurgitation; cough; dyspnœa; hard packed
gullet. Inhalation pneumonia. Lesions. Treatment: remove cause; liquid food;
dilatation; nerve sedatives and stimulants; electricity; counter-irritants.

Causes. This has been noticed in a number of cases in solipeds,


and attributed to central nervous lesions, cerebral concussion
(Straub), encephalitis (Hering, Bornhauser), paralysis of the fore
extremities (Meier), pharyngeal paralysis (Puschmann). Möller has
seen it several times consequent on arytenectomy, while Dieckerhoff
and Graf have seen it occur without any clearly defined cause. In a
case referred to above, the present writer found it connected with the
attachment of larvæ of œstri in the lower end of the gullet. Stricture
and impaction may be a further cause.
Symptoms and lesions. There is more or less interference with
deglutition, culminating in complete inability to swallow, and the
rejection of morsels of masticated food by the nose. Cough may also
occur from the descent of food toward the lungs, with more or less
dyspnœa and oppression of the breathing. Manipulation along the
left jugular furrow, detects the œsophagus as a prominent hard,
rope-like mass which fills up the groove unduly. When death occurs
rapidly the gullet is found gorged with masticated food throughout
its entire length. In certain instances gangrenous pneumonia is
found, the result of the penetration of food into the bronchia. In
other cases there are lesions of the medulla oblongata, or of the
vagus or glossopharyngeal nerves or their œsophagean branches.
Death usually results from obstruction, inanition, or, in case the
paralysis is partial, from pneumonia or exhaustion.
Treatment. First remove or correct the existing cause of the
disease. Impaction may be broken up by the use of the wire loop, or
pincer probang; parasites may be expelled by passing a cupped
probang; the impactions following arytenectomy can be obviated by
feeding gruels, milk and other liquid foods only, and from a bucket
set on the ground; stricture may be dilated by the use of graduated
sounds; and nervous diseases may be dealt with according to their
specific nature in each several case. When any definite cause of this
kind has been overcome the persistent use of strychnia, subcutem, or
by the mouth, may be effectual in overcoming the paresis of the
gullet. Hypodermic injections are best made along the left jugular
groove, and frictions, stimulating embrocations, and galvanic
currents may be employed with excellent effect.
ŒSOPHAGEAN TUMORS.
Forms of neoplasm in gullet of horse, ox, sheep, pig, dog. Symptoms: dysphagia;
eructation; vomiting; bloating; cough; dyspnœa; stertor; fœtor; palpitation.
Treatment.
These have been often noticed in the lower animals. In the horse
have been noticed melanoma (Olivier, Röll, Kopp, Besnard,
Pouleau), fibroma (Dandrieu, Dieckerhoff), Carcinoma (Chouard,
Lorenz, Cadeac, Laurent), epithelioma (Blanc, Lorenz), Leiomyoma
(Lucet, Lothes), cystoma (Caillau, Legrand), mucous cysts (Lucet).
In cattle papilloma is especially common, having been noted by
Johne, Mons, Fessler, Schütz, Lusckar, Gratia, Beck, Cadeac and Kitt.
Tubercles, and fibroid masses with cystic purulent centres are
not uncommon. Actinomycosis is also frequent, sometimes hard
and warty and at others soft and vascular.
In the Sheep, Dandrieu found between the muscular and mucous
coats a hard tumor as large as a hen’s egg, the removal of which put a
stop to a persistent choking. In both cattle and sheep, swellings
from coccidiosis are common; in cattle and swine from
gongylonema, and in sheep from filaria (Harms) or spiroptera
(Zurn).
In pigs, fibroma is met with in the walls of the gullet (Raveski)
and in dogs fibroma, papilloma, and the tumors of spiroptera.
Symptoms. The coccidia and spiroptera usually cause few
symptoms or none, but neoplasms usually develop symptoms of
obstruction, dysphagia, eructation, vomiting, and all the indications
of choking according to their seat. These do not come on suddenly
and recover as in simple choking, but even though there may be
periodic obstructions, spasms and paroxysms, there is a slow,
progressive advance as the neoplasms increase. Stertorous or
mucous breathing, cough, dyspnœa and fœtid exhalations are
common, the symptoms may be aggravated when the head is bent,
and the tumor may even be felt on palpation of the throat or left
jugular furrow. In ruminants tympany occurs after feeding.
Treatment is surgical and consists in the removal of the tumors by
incision and ecraseur or otherwise. Thoracic œsophagean tumors are
usually inoperable.
IMPACTION OF THE CROP. INGLUVIAL
INDIGESTION.
Gallinaceæ and Palmipeds. Causes; Overfeeding after privation; fermentation;
lack of water; green food in geese and chickens; food containing paralyzing
element. Symptoms; dull; motionless; erect plumes; drooping wings and head;
gapes; ejects liquid from bill; firm cervical swelling. Treatment; manipulation;
incision; surgical precautions. Convalescent feeding.
The cervical dilatation of the œsophagus known as the crop is well
developed in all granivorous birds, (Gallinaceæ, etc.;) and like the
macerating cavities of the ox (first two stomachs) is subject to
overdistension and paralysis. In the palmipeds (ducks, geese) there is
no distinct crop but in its place the cervical portion of the gullet has a
fusiform dilatation, and under given conditions this may be also the
seat of impaction.
Causes. The impaction may result from overfeeding when the bird
has been starved, or when it suddenly gains access to food of a
specially appetizing kind and to which it has been unaccustomed.
The crop like every other hollow viscus is rendered paretic by
overdistension. Then the food undergoes fermentation still further
distending the cavity, affecting the brain by reflex action, and
paralyzing the vagus and its peripheral branches in the lungs, heart,
stomach, liver, intestines, etc. When the food is dry as in the case of
beans, peas, bran, farinas, it may be a simple firm impaction which
the muscular walls of the crop are unable to break up or move
onward. When green food is taken there is often superadded the
additional evil of active fermentation from the great number and
activity of the bacterial ferments contained in it and the soft aqueous
fermentescible nature of the food (See tympany in ruminants).
Dupont states that young geese led out to fresh spring grass may lose
two-thirds of their number in a few hours from such overloading and
that some species of Carex and cynodon dactylon are particularly
injurious. Chickens also gorge the crop with clover, etc. In all such
cases, plants that contain a paralyzing principle like lolium
temulentum, ripening lolium perenne, chick vetch, etc., are to be
specially dreaded. (See Trichosoma Contortum).
Symptoms. There are first dullness and sluggish movements,
followed by indisposition to move, the bird standing in one place
with ruffled feathers and drooping wings, and at intervals, projecting
the head forward with open beak and in some cases a little liquid is
rejected. If the bird is now caught and examined the crop is found to
be firmly distended, and more or less compressible or indentable
according to the nature of the food impacted. In most cases and
especially if the food has been green or aqueous, there is a certain
resiliency from the presence of gas outside the solid impacted mass.
Treatment. This must be in the line of seconding the physiological
efforts of regurgitation which is a normal and common act in birds.
The duck which has gulped a mouse half-way down the cervical part
of the œsophagus will readily disgorge it when he finds it impossible
to pass it further. The carnivorous birds often reject by vomiting the
indigestible debris such as feathers and bones, after all the more
soluble parts have been disposed of in the stomach. The pigeon even
feeds its young by disgorging into their open bills, the semi-digested
food and milk from its crop. Following these indications we must
break up the contents of the crop by manipulation and force them in
small masses upward into the bill and downward to the
proventriculus. The rejection by the bill may be further stimulated by
introducing the finger into the fauces to rouse the reflex active
emesis. Usually the crop can be quickly and satisfactorily emptied in
this way.
When this proves impossible there remains the operation of direct
incision through the walls of the crop and the evacuation of its
contents. This can be done by a pocket knife or even a pair of
scissors. The crop is punctured in its lower part and the incision is
continued upward as far as may be necessary to allow the escape of
the contents. Usually half an inch will suffice. Then the crop is
squeezed so as to press the contents through this opening and it is
emptied by a process of enucleation. If the contents are fibrous it
may be necessary to employ forceps to dislodge the material. The
empty crop may be washed out with tepid water, any food attached
to the raw edges of the wound must be removed and the skin stitched
accurately together. The wound rarely fails to heal by first intention.
To avoid stretching it, the food for a day or two should be restricted
to milk, gruels, or a little soft mash.
Lerein notices jaundice as a sequel of impacted crop, and
recommends treatment by sulphate of soda in the water.
TYMPANITIC INDIGESTION IN THE
RUMEN. BLOATING.
Definition. Susceptible Genera. Causes; gastric paresis, overloading, cold, fear,
exhaustion, poisons, fermentescible food,—new grain, leguminosæ, frosted
vegetables, ruminitis, foreign bodies in rumen, microbian ferments. Symptoms,
abdominal, general. Gases formed under different aliments—carbon dioxide,
marsh gas, hydrogen sulphide, nitrogen, oxygen. Lesions, rupture of rumen or
diaphragm, compression or rupture of liver or spleen, petechiæ, congestion of
lungs and right heart, of cutaneous and cerebral vessels. Prevention, avoid
indigestible and fermentescible aliments, correct adynamic conditions, tonics,
avoid injurious ferments, make alimentary transitions slowly. Treatment, exercise,
bath or douche of cold water, rubbing and kneading, rope round abdomen spirally,
gag in mouth, dragging on tongue, movement of a rope in fauces, probang,
stimulants, antiseptics, alkalies, ammonia, oil of turpentine, oil of peppermint,
alcohol, ether, pepper, ginger, soda, potash, lime, muriatic acid, carbolic acid,
creosote, creoline, sulphites, kerosene, chloride of lime, chlorine, tar, common salt,
hypochlorite of soda, magnesia, eserine, pilocarpin, barium chloride, colchicum,
lard, trochar, Epsom salts, rumenotomy. Treatment of diseased gullet, mediastinal
glands, stomach or intestines.
Definition. The condition is a combination of paresis of the rumen
and gaseous fermentation of its contents. The initial step may be the
paresis or in the more acute forms the fermentation.
Genera susceptible. While all ruminating animals are subject to
this disorder, it is much more frequent in cattle and sheep than in
goats.
Causes. It commences in paresis of the rumen in the weak,
debilitated, convalescent or starved animals which are suddenly put
on rich, and appetizing food. Hence it is common in animals that
break into a cornbin, a store of potatoes, a field of growing corn or
small grain, or that are turned out on green food in early spring.
Cadeac maintains that paresis of the rumen is the essential cause in
all cases, while the nature of the aliments ingested fills a secondary
and comparatively insignificant rôle. According to this view the
torpid stomach can neither relieve itself through regurgitation for
rumination, nor expel through the œsophagus the constantly
evolving gas which therefore distends the viscus to excess. In support
of this view may be adduced the occurrence of tympany through
fatigue, fear, cold, enlarged (tubercular) mediastinal glands pressing
on the gullet and vagus, obstruction of the œsophagus by a solid
body (choking), impaction of a morsel of solid food in the demicanal
of the calf as noticed by Schauber, and the cessation of the normal
vermicular movements of the rumen in connection with
inflammation of its coats, or extensive inflammation elsewhere or
finally of fever. Even in paralysis of the stomach by poisons like lead,
tympany may be a result. Cadeac attributes tympany following the
ingestion of green food wet with a shower, or drenched with dew, of
frosted potatoes or turnips, or of iced water, to the paralyzing action
of the cold on the rumen. This view is manifestly too extreme, as the
bloating occurs often after a warm summer shower, or after the
consumption of potatoes and other roots and tubers which have been
spoiled by frost but which are no longer at a low temperature when
consumed.
Tympany may also start from the ingestion of certain kinds of
food which are in a very fermentescible condition. Green food,
especially if the animal has been unaccustomed to it, is liable to act
in this way. Clover and especially the white and red varieties, lucern
(alfalfa), sainfoin, cowpea and other specially leafy plants, which
harbor an unusual number of microbian ferments, and which
contain in their substance a large amount of nitrogenous material
favorable to the nourishment of such ferments are particularly
dangerous in this respect. All of these are most dangerous when wet
with dew or when drying after a slight shower, partly no doubt at
times by reason of the chilling of the stomach, but mainly because
the ferments have been stimulated into activity by the presence of
abundance of moisture. Drenching and long continued rains are less
dangerous in this respect than the slight showers and heavy dews,
manifestly because the former wash off a large portion of the
microbes, which under a slight wetting multiply more abundantly.
Frosted articles act in a similar way, partly when still cold by the
chilling and paralyzing of the stomach, but cold or warm, by reason
of the special tendency of all frozen vegetables to undergo rapid
fermentation when thawed out. This is true of green food of all kinds
when covered by hoarfrost, of turnips, beets, potatoes, carrots,
apples, cabbage, etc., which have once been frozen, and of frosted
turnips and potato tops, though, in the case of the latter agent, a
narcotic principle is added.
In the case of Indian corn, the smaller cereal grains, and certain
leguminous plants (vetches, tares, peas, beans) which have the seed
fully formed but not yet quite hardened nor ripened, there is the
double action of a paralyzing constituent and an aliment that is
specially susceptible of fermentation.
Inflammation of the rumen, already quoted as a cause, may be
determined by hot as well as cold food, by irritant drugs and poisons,
and by narcotico-irritant and other acrid plants in fodder or pasture.
In the same way the inflammation caused by the introduction of
foreign bodies into the rumen, such as nails, tacks, needles, pins,
wires, knife blades, and masses of hair or wool may at times cause
tympany.
The two main causative factors, of paresis of the rumen on the one
side and of specially fermentescible food and a multiplicity of
microbian ferments on the other, must be recognized as more or less
operative in different cases, and in many instances their combined
action must be admitted. The tympany is the symptom and
culmination of a great variety of morbid causes and conditions, and
its prevention and treatment must correspondingly vary.
Symptoms. The whole left side of the abdomen being occupied by
the rumen, its distension leads to an uniform swelling of that side,
differing from that caused by simple excess of solid ingesta in being
more prominent high up between the last rib and the outer angle of
the ilium, and in giving out in this region a clear tympanitic or
drumlike resonance on percussion. It has also a tense resiliency, like
that of a distended bladder, easily pressed inward by the finger but
starting out to its rotundity the moment the pressure of the finger is
withdrawn. The distension caused by overloading with solids bulges
out lower down, is not resonant but dull or flat when percussed, and
yields like a mass of dough when pressed retaining the indentation of
the finger for some time. The swelling of tympany, when extreme,
rises above the level of the outer angle of the ilium and even of the
lumbar spines on the left side, and if no relief is obtained the right
side may undergo a similar distension.
Auscultation detects an active crepitation over the whole region of
the rumen, finer in some cases and coarser in others, according to
the activity of evolution and the size of the bubbles of gas. The
crepitation is especially coarse and loud in fermentation of green
food, and of spoiled potatoes or other tubers or roots.
In all acute or severe cases, there is anorexia, suspension of
rumination, and the normal movements of the compressed bowels
seem to be largely impaired, though the anus is protruded and a little
semi-liquid fæces or urine may be expelled at intervals. The
breathing is accelerated, short, and labored. The nostrils are dilated,
the nose extended, the face anxious, the eyes bloodshot and the back
arched. Froth may accumulate around the lips, or the mouth may be
held open with the tongue pendent. Sometimes a quantity of gas may
suddenly escape with a loud noise, but without securing permanent
relief. The heart beats are violent and accelerated, the pulse
increasingly small and finally imperceptible, and the visible mucous
membranes are congested and cyanotic. Pregnant females are very
liable to abort.
When the right flank as well as the left rises to the level of the
lumbar spines death is imminent, and this may take place as early as
fifteen or thirty minutes after the apparent onset of the attack. Death
may result from nervous shock, from suffocation, or from the
absorption of deleterious gases, or from all of these combined.
In the less acute cases the animal may live several hours before the
affection terminates in death or recovery. As a rule he stands as long
as he can and finally drops suddenly, the fall often leading to rupture
of the diaphragm or stomach, to protrusion of the rectum, or the
discharge of ingesta by the mouth and nose.
In still slighter cases relief comes through vomiting or more
commonly through frequent and abundant belching of gas, the
swelling of the flanks subsides, rumbling of the bowels may again be
heard, and usually there is a period of diarrhœa.
Gases present. When the rumen is punctured before or after death
so as to give exit to the gas in a fine stream it proves usually more or
less inflammable, the lighted jet burning with a bluish flame. The
usual inflammable ingredients are carbon monoxide, hydrogen
carbide (marsh gas) and hydrogen sulphide, yet the relative
proportion of the gases varies greatly with the nature of the food and
the amount of gas evolved, carbon dioxide being usually largely in
excess. The following table serves to illustrate the variability:

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