Environment Risk Analysis (Schlumberger)

Soil Investigation and Risk Assessment for the spilled HCl in SLB storage Tawilla-, Hathramout', September 2005.
1
CONTENTS
ACKNOWLEDGEMENTS ...................................................................................................................................3
1. INTRODUCTION .........................................................................................................................................4
1.1 BACKGROUND ..........................................................................................................................................4
1.2 OBJECTIVES .............................................................................................................................................4
1.3 SCOPE OF WORK ......................................................................................................................................4
2. LEGAL AND ADMINISTRATIVE FRAME WORK ..................................................................................5
2. 1 CONCERNED AUTHORITY .......................................................................................................................5
2. 2 LAW AND ENVIRONMENTAL RISK ANALYSIS GUIDELINE ....................................................................5
3. SITE INVESTIGATION .............................................................................................................................8
3. 1 LOCATION AND TOPOGRAPHY ...............................................................................................................8
3. 2 GEOLOGY AND LITHOLOGY ...................................................................................................................8
3. 3 SURFACE WATER .....................................................................................................................................8
3. 4 BIODIVERSITY ENVIRONMENT ...............................................................................................................9
4. SAMPLING AND SITE REMEDIATION.................................................................................................10
4.1 SAMPLING METHOD AND PATTERN ......................................................................................................10
4.2 ACID CLEAN UP IN TAWILLA - RECOVERY PLAN ..................................................................13
4.3 SELECTING A LABORATORY AND ANALYTICAL METHODS .................................................................15
5. LABORATORY ANALYSIS AND DATA INTERPRETATION...............................................................16
5. 1 LABORATORY ANALYSIS ......................................................................................................................16
5.1.1 Soil Homogenization and Grinding ............................................................................................16
5.1.2 Equilibrium Geochemistry (pH) ..................................................................................................16
5.1.3 Major and Minor ions ..................................................................................................................16
5.1.4 Acidity analysis.............................................................................................................................16
5.1.5 Electrical Conductivity (E.C).......................................................................................................16
5.1.6 Cl content......................................................................................................................................16
5. 2 DATA REPORT ........................................................................................................................................16
5.2.1 Samples Notes ...............................................................................................................................17
5.2.2 Analysis Observation....................................................................................................................19
6. THE RISK ASSESSMENT.........................................................................................................................20
6.3.1 Impact on Human Health ...........................................................................................................21
6.3.2 Environmental risk Impact ..........................................................................................................21
6.3.3 Soil Quality ...................................................................................................................................21
6.3.4 Biodiversity ...................................................................................................................................22
6.3.5 Summary of potential risk............................................................................................................24
7. RECOMMENDATION AND CONCLUSION...........................................................................................25
ABBREVIATIONS...............................................................................................................................................26
APPENDIX 1 SOME GLOSSARY ......................................................................................................................27
APPENDIX 2 HCL SAFETY DATA SHEET ...................................................................................................29
REFERENCE .......................................................................................................................................................33
Soil Investigation and Risk Assessment for the spilled HCl in SLB storage Tawilla-, Hathramout', September 2005. 2
Acknowledgements
We wish to extend our appreciated for the support and hospitality of their
excellencies Mr. Ellen, Mr .Alex nciess Mr Ellen and Mr Alex and Eng. Sabri from
Canidian Nexen petroleum company .We would like to acknowledge the coarporation
assistance and hospitality of Eng. Murad, Eng.Khaled Al-Ahdal, Eng Mohammed Al-
jabri from Schlumberger and other staff at Schlumberger by providing information and
granting access to the company's sites .Thanks also to the environmental consultants,
local authority staff and who provided comments and help us during the investigation and
analysis period.
1. Introduction
1.1 Background
This report presents an Environmental Risk Assessment of the spilled hydrochloric
acid (HCl) in the storage area of SLB . Spillage of ( HCl) had been occurred in 22 Aug
2005 as a result of overturned of two drums 55 gal to the soil in the storage area. A
farmer near the area recognized it. SLB and Nexen had taken all necessary remediation
and emergency procedures to treat this problem as shown in chapter (4)
1.2 Objectives
The objectives of the report to analysis contaminated and uncontaminated soil

samples to determine the environmental or health risks posed by the spilled hydrochloric
acid (HCl ) in the soil, determine if hazardous substances in the soil pose a hazard to an
ecosystem and assess the applicability of a particular remediation option if needed. For
soil remediation depend on the type of remediation either excavation or in-situ treatment
by adding neutralizing agent like Soda ash .
1.3 Scope of work

Implement Environmental Investigation &Risk analysis study for the spilled (HCl)
acid in TAWILLA in 22nd Aug 2005 consist of the following
• Making survey for the site, storage, and the contaminated area.
• Taking samples the soil samples will be from the same points that the Government
committee & Nexen assigned them during the visit from 4th till 6th Sep 2005.
• Analysis of whole samples in approval laboratories according to the required

analysis that will be assigned by the Government committee and SLB.
• Identify and analysis of potential human health and environmental risks for the
spilled HCl acid on the site.
• The study will cover the following risk
Human health
Soil Quality.
Biodiversity
2. Legal and administrative frame work
2. 1 Concerned authority
Several ministries and government bodies are directly or indirectly responsible
involved in the proper operation and management of environmental impact that
result from petroleum exploration and production process including
- Ministry of Oil and mineral resources (MoMR)
- Ministry of water and Environment (MoWE)
- Ministry of public health (MoPH)
- Petroleum Production and Exploration Authority (PEPA)
- Environmental Protection Authority (EPA).
2. 2 Law and Environmental Risk Analysis Guideline
Law 26 of 1995 is by far the most comprehensive environmental legislation to date.
It defines (in article 5 ) the scope and responsibilities of Environmental Protection
Authority ( EPA ), calls (in articles 6 - 14 ) for the protection of water and soil and the
establishment of Protected Areas, provides legal framework for control and use of
pesticides ( articles 15 - 21 ), provides legal framework for the control of pollution and
the conservation of natural resources and the protection of wildlife and marine organism
specially those endangered and threatened of extinction (articles22-29), same articles also
prohibit hunting of specified types of wild birds and animals ( article 28) as well as the
destruction of their natural habitats, authorize EPA and relevant agencies to prepare and
enforce environmental standards, criteria's and specifications( articles 30 - 34 ), spells out
the necessity of environmental impact assessments as a pre-requisite for development
projects licensees (articles 35-43), provides legal framework for handling hazardous
wastes and materials (articles 44 - 55 ) establishes environmental monitoring networks (
article 58-61 ) , and forbids the discharge of ships pollution into the sea water ( articles 62
- 64 ). Articles 75-86 cover the protection of air, water and land from all sources of
pollution. Articles 75-86 deal with violation and penalties. The law defines the
organisation of environmental protection, environmental information system and
participating in the management and protection of the environment ,as well as the
reasonable authority .International Standards and guidelines are relied upon . The Site
Investigation and Analysis of Soils in the contaminated land management guidelines
(clmg) series produced by the ministry for the environment in new zealand was used as a
guideline in this report.The guideline highlights four areas of an investigation
The principles of site investigation -Soil sampling -Laboratory analysis-The basics of
data interpretation.
Table (1)Some Extracted items from the law (26)
Chapter
No. Title Key Points
No.
Definitions Terms such as environmental effect,
1 waste, dangerous waste,
environmental damage are relevant
Aims and General Objectives to protect the
Basis environment, prevent and combat
2 pollution, maintain natural
1. General
resources. Economic plans must
Regulations
include EIA.
EPC, currently Responsibilities of EPC (EPA)
(EPA) determined including making
3 national policy, supervision of
projects through concerned
authorities
Protection of Water Protection of surface and ground
and soil and water. Land Use Planning must take
2. Protection of Establishment of into account environmental
Water and Soil 1 Protected Areas elements. Limit damage to soil.
and Use of Agricultural lands are protected
Eradicative against commercial and Industrial
Substances development.
Use of Eradicative Control and use of pesticides and
2
Substances harmful chemicals
Chapter
No. Title Key Points
No.
Prevention of dumping, collection,
discharging or burying environmental
Control of activities
pollution.
1 harmful to
Designation of areas, green places and
environment
preserved areas to be clear of pollution.
Protection of natural resources etc.
Aim to protect the environment,
Environment
specially surface and ground water, air
Specifications,
2 sea and noise
standards and
EPA shall decide specification
Magnitude
standards and parameter limits
All projects and establishments which
Permits for projects are source of pollution or may harm the
and evaluation of environment must be given a permit.
3
3. Activities Environmental Submission of EIA for existing
harmful to effects projects, establishments and activities
Environment within a period of six months
List of dangerous and toxic substances,
Circulation of their control, prohibition.
4 dangerous materials Prohibition of public, private party to
and waste import, store or dispose of dangerous,
toxic or radio active substances
Environmental Economic plans must take into account
Protection and environmental factors.
5
Economical Projects must not be approved if they
Development damage the environment
EPA or other authorities may supervise
and operate construction of
Environmental
6 environmental monitoring networks.
monitoring
EPA may impose monitoring on
projects and keep registers of the result
3. Site Investigation
3. 1 Location and Topography
The site located in Almasillah _Hathramout governorate at altitude more than 900
m above mean sea level .Map (1) show the location of the site . the site located in
predominantly rural and there are not population residing predominant in the area near
the storage area. The closest receptors to the site are the residential unit at the village
faraway about 3 kilometre, one house at the left side of the storage from the north west
(100m) ,another one at the right side (500 m) , and one inside the storage belongs to the
owner of the storage land .
3. 2 Geology and Lithology
The out cropping rocks of the area are predominately from Quaternary and Jurassic
era which mainly of carbonate rocks (Limestone) and thin non continuous layers of
clayey soil ,silt, and gravel overlay limestone. The soil characterized as Coarse-grained
soil From gravel to silt( Sandy-stiff) . The silty clay loam has low infiltration rate and is
prone to surface crusting. The chemical characteristic of the soil in the site indicate that it
is alkaline (moderate to high) and generally poor in organic matter content and nitrogen
.While concentration of heavy metals are within acceptable range. Table ( 4 )present the
chemical analysis of soil sample that were collected from the site .
3. 3 Surface water
No perennial surface water bodies exist ,and such the water supply system in the
region are based entirely on available ground water resources and rain .The direction of
water flow is west-southwest and the depth of the nearest aquifer.The average rainfall in
the area reaches 300mm/year (based on data from 1985-1991)although rainfall is known
to vary considerably between the year and the wet season is in March –May
predominantly .Ambient temperature in the area assumed to have the similar
meteorological to that in Hathramout range between (20 C˚ - 45 C˚)
3. 4 Biodiversity Environment
The site appears to be located within an area identified as site of low biodiversity
in dry to dry-mesic and wilderness (desert habitats) .The area hosts endemic or near
endemic species of plant and animals The principal trees are palm tree ,grass , herbage
and thistle. The stature of trees is short and spacing of trees is sparsely In general Eastern
Desert characterised with those Plant Species; Panicum turgidum; Desmostachya
bipinnata, Suaeda aegyptiaca, Salsola imbricata and Tamarix aphylla; Aerva javanica and
Rhazia stricta; Acacia tortilis, Chrysopogon plumulosus and Aerva javanica.; Pennisetum
sp.,Panicum turgidum and a dwarf shrub species; Acacia tortilis, Panicum turgidum and
Salsola imbricate .Animals like Camels, Goats, Sheep and Arabian gazelle Striped Hyena
(Hyaena hyaena), Arabian Wolf (Canis lupus arabs), Jackal (Canis aureus
Representative bird species as Philby’s and Arabian Partridges, Arabian Woodpecker,
Yemen Thrush, Arabian Wheatear, Arabian Golden Sparrow, Arabian Waxbill r, Arabian
Olive-rumped and Yemen Serins, Yemen Linnet, and Golden-winged Grosbeak.
4. Sampling and Site Remediation
4.1 Sampling Method and Pattern
The sample locations were pointed by using randomly spaced to cover the
suspected contaminated area and uncontaminated area (judgemental sampling) through
Global Position System GPS device. The total number of samples was 16 samples. Nexen
and SLB persons took four of them . The other samples were determined their location by
the committee from government authority based on site inspection and discussions with
the engineers. Samples are located around the edge of the site, along the contaminate
area, under the spilled drums ,and at uncontaminated points as background samples (S1&
C*3)that are not affected by the contaminant sources on the sit.The method of collecting
samples was hand auger sampling. The samples are collected from the surface and from
depth 20cm to 30 cm .Samples Location and pattern is shown in the map (1&2)
Figure (1) show the sample pattern taken by Nexen
Figure (2) indicate the samples pattern in 5 Sep
4.2 ACID CLEAN UP IN TAWILLA - RECOVERY PLAN
All the following procedures have been done and finished since 6 Sep 2005 .The
following procedure was written after the site meeting between Schulumberger and
Nexen companies .They took place after the site had been secured .
Phase 1 – Mobilization
Mobilize the following equipment from Schlumberger Masila Base

• Forklift• 50 bbl Batch Mixer and hoses• Empty Acid Trailer• Empty Pallets• Soda
Ash Neutralizing Agent• Safety shower• Eyewash Station• Spill Kit• PPE for handling
Acid• Air Compressor• Wilden transfer pump and hoses• Drum Banding Machine•
Empty Acid Storage Containers• 2 x Flat Bed Trailers.
Phase 2 – Removal of Drums

• Prior to this phase of the operation, a pre-task safety meeting will be held with all
personnel involved. All team members involved will be suited up with full acid PPE.
• The first priority will be to determine the status of the overturned drums. The preferable
option would be to upright the drums and transfer the product to an empty drum.
• The new drums will be re-palletized, banded and relocated to a holding area to be
determined prior to transport.
• The forklift will then be utilized to commence the moving of the pallets. The condition
of the pallet and drums will be assessed prior to moving.
• If possible, pallets in good condition will be removed first. An assessment will be

performed on each pallet to determine suitability for transport. If acceptable; they will be
moved to the holding area. If not, then the drums will be re-palletized and banded.
• Pallets of drums, which have been stored in the holding area, will have all previous
identifying marks removed, with the exception of the transportation hazard identifier,
which is presently on all drums.
• Official Schlumberger H033 Identifier label will be attached on each individual drum.
• Each pallet will be tied down and secured.
• If there is any doubt about the stability of the drums and an imminent danger of spillage,
the option of transferring the acid to the batch mixer for immediate neutralization will be
paramount.
• If neutralization occurs the spent product will be transferred to the acid trailer after a pH
test of the fluid has been completed.
• Permission and approval required for disposal of neutralized fluids at Nexen liquid
waste pit.
Phase 3 – Transportation of Drums

• Complete inventory of recoverable acid to be logged prior to departure from site.
• Loading Note Manifest will be issued to verify correct amount being transported and
including destination.
• A designated Supervisor will be assigned to this activity.
• Loadmaster will be appointed during the loading operation.
• A qualified forklift driver will be the only person who can load the drums.
• The trucks and flat bed trailers assigned to this operation will be subject to vehicle
inspection from Schlumberger and Nexen.
• The truck drivers will hold a valid Yemeni driving license and have completed
defensive driving training program.
• All rigging and tie down equipment will be inspected prior to loading the pallets.
• Pre Trip safety meeting will be conducted with the drivers and convoy leader prior to
departure from the site.
• Once two flat beds are loaded, they will travel in convoy with a canter escort back to
Masila base.
• One copy of Loading Note to be kept at receiving location.
• These convoy’s will continue until all product has been removed from the site.
• If there is a non conformance event, the job will be suspended and a documented
meeting will take place to rectify the non compliance.
• After area has been cleared, environmental specialist’s report and action items will be
implemented.
• Remedial action to be determined based on results of the study.
4.3 Selecting a laboratory and Analytical methods

The government committee determined the choice of analytical method and discussing
analysis requirements with the laboratory specialists in Sana'a University and in ACP to
ensure the detection limits for the tests requested will be appropriate for the purposes of
the soil risk analysis. To determine if a site poses significant potential environmental and
social risks that could be occurred from the spilled hydrochloric acid (HCl), and whether
or not a site requires further evaluation or remediation. Consideration had taken to the
dissociation of hydrochloric acid to hydrogen ion and chlorine), when exposed to soil;
hydrochloric acid will neutralize carbonate-based soil components. The samples were
sent to two different laboratories for analysis. One laboratories (Sana'a University Lab) ,
and the other laboratory is (ACP Lab) . Because they have a documented test method
procedure , have suitable equipment, and have staff with the knowledge, experience and
There are differences in the analysis methods between the two lab ,for example
University lab analyzed for chlorine by conductivity analysis and ACP laboratory
analyzed for chlorine ion as chloride salt by X-ray (Seem for pH).
5.Laboratory Analysis and Data Interpretation
5.1 Laboratory Analysis
5.1.1 Soil Homogenization and Grinding

It will be used to for some samples for XRF, Conductivity and Cl content analysis. This
will done through screening and homogenizing prior feeding into X-ray device...By using
of grizzly and grinding to separate out large rocks continuously ,then oversized will
discarded and the remaining solids will homogenizes to very fine particles prior making
the analysis. Because the fine grains have the highest specific surface area and the
inorganic contaminant preferentially bind to clay, silt, and organic soil particles. Treated
samples that result from this method will be used to make other analyses.
5.1.2 Equilibrium Geochemistry (pH)

The purpose is to determine the alkalinity of the soil and compare it with pH of
uncontaminated samples. Hydrochloric acid will neutralize carbonate-based components
in the soil but significant amounts of HCl could remain, it will acidify the soil.
5.1.3 Major and Minor ions

The purpose to determine the percentage of chlorine and compare it with uncontaminated
samples, since concentration of chlorine or hydrogen chloride (which would dissolve in
moist soil or water) would be far more hazardous. It will by done with X ray instrument
for four samples, it can reduce number of analytical samples; can obtain large data sets to
make a clear comparison.
5.1.4 Acidity analysis

To determine the acidity of the soil samples
5.1.5 Electrical Conductivity (E.C)

HCl will neutralize to an extent while transporting through the soil forming hydrogen ion
and chloride ion which could by determined by this analysis.
5.1.6 Cl content
To determine the Cl content as chloride ion, dissolved salt in all samples for comparison,
and estimate the quantity and size of contamination.
5.2 Data Report

5.2.1 Samples Notes
• Samples (S1*,C2*, C3*) was collected by Sabaik and G.C from two different points
in the same horizon, and (CI1,CI2,CI3) was collected from 3 different points and three
other samples for the same points from depth ( 20 to 50 cm) at 5 Sep 2005 . However,
Samples (C1, C2, U1, U2) was collected by SLB and Nexen persons each one from
one point at 26 Aug 2005.
• The samples were dried samples ,and the depth of contaminated samples is Max 30
cm. within the storage area (hardness of the rocks)
• Cl¯ analysis also repeated for sample S1 because it was taken from uncontaminated
area ( in distance from contaminated area 114 m SW )
• The use of judgmental sampling, so the confidence intervals can not be reported ( not
accurate).
• The samples were collected in two different ways and date.
• Lack of homogenization of samples on the site.
Table (2,3) the analysis results of soil samples No (C1, C*2, CI2, CI3, U2) from ACP
Sample
C1 CI2 C2 CI3(30cm) U2
NO
SiO2% 15.59 15.20 16.94 17.59 22.40
Al2O3% 3.32 3.23 3.30 3.55 4.62
Fe2O3% 3.39 2.22 2.29 2.72 2.94
CaO% 34.81 39.00 37.43 37.26 33.21
MgO% 2.17 1.76 2.12 2.59 2.76
SO3% 0.23 0.11 0.04 0.08 0.04
K2O% 0.58 0.57 0.59 0.63 0.75
CL% 6.07^ 0.21 0.00 0.98 0.00
Sample
C1 C2 C*2(50cm) CI320cm CI2(50cm) C*2(50cm) U2
No
PH 8.5 8.5 8.5 8.5 8.5 8.5 8.5
Table No. (4 ) indicate the results of Samples No.(S1,CI3s,U1,CI130,CI1,C*3,C*2) from

Sana'a University
Cl¯ content
Sample No. Acidity x10¯4 PH value E.C.µS
g/kg
ٍS1 7.678 2.28 6.88 136
CI3(s) 55.21 5.76 6.9 295
U1 28.155 2.28 7.41 213
CI1(30)cm 10.238 2.28 7.35 118
CI1(s) 13.529 2.28 6.57 114
C*3(50cm) 0.7313 2.28 7.76 25
C*2 2.1939 2.28 7.90 81
*: samples taken on 5 sep2005

S: Surface sample
^ : Out limit value
5.2.2 Analysis Observation
1) High concentration of chlorine is occurred on samples No (C1 & CI3s) which are
located on the spilled region as shown from the samples pattern. CI3 have the
maximum concentration in Cl¯ content .(It was taken from 3 different points across
the contaminated area).
2) The concentration of Cl¯ in the samples (U1,S1) is also high despite of its location
was not in the contaminated area .
3) The analysis results table (5) indicate the relationships between Cl¯ content and
acidity ,Cl¯ content increased significantly with increasing acidity (lowering pH)
However, in sample (U1 ) the reverse was occurred that can arise from the selective
nature of the sampling process , and the added soda ash in the process of remediation .
4) The concentration of Cl¯ decrease rapidly in samples far away from the high
concentration samples (C1,CI3) location .as shown in analysis results of samples
(CI1&CI2 &C2&C*2)
5) C*2 sample not contaminated (15 m N from the storage area).
6) There is no effect or alternation in mineral composition of the soil .It was recognized
from comparison of analysis results of contaminated and uncontaminated samples.
7) Concentrations of chlorine in the area represented by the samples are clearly below
the accepted human contact criteria (900mg/cu m) value except 3 surface samples
inside the storage area.
8) pH values indicated small alteration on the alkalinity of the soil had been occurred .
6. The Risk Assessment
It based on the hazardous nature of the substance, and the likely exposure of humans or
the environment to that substance by using available toxicological or environmental
impact studies to determine maximum permissible levels. It also assesses the risk to
humans and the various ecosystem components (receptors) separately.
6.1 Risk acceptance criteria and Specification of HCl (contaminant)

(Appendix 2 )
♦ Toxicological Information Inhalation rat LC50: 3124 ppm/1H; oral rabbit LD50: 900
mg/kg (Hydrochloric acid concentrated); investigated as a tumorigen, mutagen,
reproductive effecter.
♦ Ecological Information
Environmental Fate: When released into the soil, this material is not expected to
biodegrade.
♦ Disposal Considerations
Whatever cannot be saved for recovery or recycling should be handled as hazardous
waste and sent to waste facility. Dispose of container and unused contents by rinse,
crush, and ship to sanitary landfill .
6.2 The exposure Area
The Exposure Area is correspond to the lower part of the storage site (300m from the
storage entrance ) and 80 m distance in NW direction (exposure route) and 30 m
distance to the WS direction from the edge of this portion of the site and 0-30 cm depth .
Based on the pattern of contamination ( location and soil analysis ). As indicated on the
figure (3).
6.3 Risk Impact
6.3.1 Impact on Human Health

In general, hydrochloric acid is not considered a carcinogenic substance to humans. A
major HCl effect is local irritation. After digestion or skin contact with HCl occurs, the
mucous membranes of the nose, throat, and esophagus become corroded. HCl present in
the lungs may cause pulmonary edema. HCl ingestion causes glottis edema. HCl
inhalation causes coughing, inflammation, pain, and edema of the upper respiratory tract.
HCl exposure normally will not affect those vital organs furthest from the point of
contact on the body. Eye contact with HCl may induce vision reduction or blindness. HCl
concentrations, 35 ppm or greater, can cause throat irritation after short-term exposure.
Hydrochloric acid is very corrosive, and, if contacted with the skin, irritation and burns
may occur. In our case , as a result of recovery plan ( isolated hazard area, kept
unnecessary and unprotected personnel from entering , neutralized with alkaline material
soda ash,), there was no human contact occurred with the acid, . There are no residents
in the contaminated area ( the nearest houses are far away from the site 2 km except the
guard house and two other houses on the both sides of the storage area which aren't
inhabited ) So there are no effects on human health
6.3.2 Environmental risk Impact

The toxicity and mode of action of the spilled hydrochloric acid (55 gal) and of its
breakdown products or any contaminants, and their persistence and areas of concentration
are not harmful to the surrounding environment. Because anhydrous hydrogen chloride
readily evaporates when exposed to soil .. However, hydrogen chloride will infiltrate
through soil if exposed. (Moisture present in the soil influences the rate at which the HCl
moves through the soil). While moving, the HCl will dissolve carbonate-based particles
(limestone rocks - see X-ray analysis ) found in the soil ,so HCl will neutralize to an
extent while transporting through the soil .
6.3.3 Soil Quality
The amount of HCl remaining will depend on the amount of soil and the amount of
moisture in the soil. Upon transport through the soil, hydrochloric acid will dissolve the
soil materials (those with carbonate bases) lead to change in pH with the effect of
acidifying the soil this is clear from pH values of the surface samples (CI1,C1,and CI3
).A neutralization reaction produces calcium chloride and water. The spilled a cid was
caused increasing in the insoluble calcium –chloride and electric conductivity of the soil
as shown in the samples (C1,CI3, U1and CI1s) . However, the amount of the spilled acid
comparison to the amount of the soil is very small, so all those effects without any
potential impact. However the location of significant grazing fields and adjacent to area
that used for animal grazing and agricultural production ,it is recommended to remove
the contaminated area as shown in the fig (3 )(30m N * 20m W from CI1) or make site
validation samples to confirm absence of any risk from the spilled acid.
6.3.4 Biodiversity
Hydrochloric acid fumes are yielded when the acid exposure to water or moisture of any
kind upon hydrolysis .Or may be evaporated upon sunrise This was clarified from the
amount of salts formed is within the normal range in most samples analysis .The impact
on organic matter is not marked or detectable. The review of the analytical data from
these samples indicated that a relatively very small area (600 sq m) of the site was
contaminated with high concentrations of chlorine that may cause direct impact in the
habitats and associated fauna in this area. Because the contaminated area has been
neutralized with soda ash and the mineralogical of the soil (carbonate bases rocks –Lime)
,the biodiversity at the site is expected to be enhanced and return to its original
characteristic quickly.
Table (5) Soil pH and associated impacts (Batjes, 1995, London, 1991.Mengel and Kirby, 1982
pH Soil
Impact interpretation
Value classification
Possible Aluminum toxicity and excess availability of
Cobalt, Cupper, Iron, Manganese, and Zinc
Deficient in Calcium, Potassium, Nitrogen, Magnesium,
Phosphorous, and Sulfur
Boron deficiency below pH of 5
Strongly Molybdenum becomes more available with decreasing pH
5.5≥
acidic Bacterial and actinomycete activity is reduced along with a
predominance of Fungi
Mineralization of Organic matter and nitrification are
restricted
Below a pH of 3 , functioning of cell membranes is impaired
,resulting in leakage of elements
Preferred pH range for most crops ,lower end of range may
be too acidic for some
Moderately
pH between range of 6.0 and 7.0 hampers phosphorous
acidic
-5.5 fixation
,Slightly
7.3 Neutral pH favors the fixation of molecular Nitrogen by free
acidic ,and
living soil microorganisms and by symbiotic organisms
neutral soils
Above a pH value of 7.0 the availability of Iron ,Manganese,
Zinc, Cobalt, and Cupper declines
Above a pH of 7.0 there is an increase in the availability of
Iron , Manganese , Zinc, Cobalt , and Cupper
Slightly
Increased risk of ammonia volatilization
- 7.3 alkaline and
First increasing availability of Phosphorus and Boron ,but
8.5 Moderately
deficiencies may occur at higher pH values
alkaline soils
Insoluble Calcium –phosphates may be formed at higher pH
Electric conductivity is generally high at higher pH values
Calcium and magnesium are liable to become unavailable to
most crops
Often high Sodium levels lead to toxicity and structural
Strongly to
damage
8.5≤ very strongly
Toxicity of bicarbonates and other anions
alkaline soils
Possible Boron toxicity common in saline and or sodic soils
Availability of most micronutrients and of Iron, Manganese,
Zinc, Copper, and Cobalt is reduced except for Molybdenum
6.4 Summary of potential risk
Table (6) Summary of Potential impact
Impact Potential Magnitude

Human Health and Safety 0
Soil Quality -
Terrestrial Biodiversity 0
Socio-economics +
Surface and Ground Water quality 0
(- ) Low potential negative impact ( 0) Neutral Impact (+) Low potential positive
impact
6. Recommendation and Conclusion
• Chlorine content decreased significantly away from hot spot (CI3 sample) location
in all directions, and significantly lower and rapidly decreased below surface (5-30
cm depth ) at the exposure area.
• There is no significant effect out side the storage area either on chlorine content or
on pH of the soil.
• There are no adverse effects on human health (no human contact and the site have
been securing since incident was seoccurred).
• There is no probability of environmental contamination from the spilled acid (55

Gallon) outside the exposure area .
• There are no major effects on the salt index and solubility of the soil.
• There are no adverse effects of the substance on biological and chemical

interactions in the ecosystem, including the physiological effects of HCl on soil
organisms, crops and livestock.
• The area shown in the sample pattern (approx 600sq m &30 cm in depth) may still
have concentrated contaminant, so it requires additional remediation (neutralization
) .Or to conduct additional site investigation and collecting more (2-3) samples to
confirm neutralization of contaminated soil .Since the site is locate adjacent to area
that used for animal grazing and agricultural activities.
• The amount of the spilled acid could not be expected to leach into groundwater.
• All potential effects resulting from the spilled HCl acid are either minor or zero ;
therefore, site validation is not required .
• In general, soils are much buffered and thus a little contamination is not a problem
with soils .
Abbreviations
Slb : Schlumberger company
CE: Soil Threshold Concentration – Environment
CH : Soil Threshold Concentration - Human Health
PPM : Parts per million (1 in 106)
NaOH : Sodium Hydroxide
HCl : Hydrochloric acid
ACP : Amran Cement Plant.
G.C: Government committee
Cl: chlorine
TDS : Total Dissolved Solids
BOD: Biochemical oxygen demand
Appendix 1
GLOSSARY
Acceptance criteria - Levels of contaminants, which are not considered to pose an
unacceptable risk to human health or to the environment.
Acute - An exposure or response, which operates over a short term.
Auger - A soil-sampling device manually or mechanically driven into the soil.
Background levels of substances or chemicals levels that are commonly found in the
local environment.
Bioaccumulation - general term for the process by which an organism stores a higher
concentration of a substance within its body than is found in its environment.
Bioavailability -The availability of a chemical in the surrounding environment for uptake
by organisms.
Biodegradation -Decomposition of substances into more elementary compounds by the
action of micro-organisms.
Biomagnifications - The serial accumulation of a chemical by organisms in the food
chain, with higher concentrations of the substance in each .succeeding trophic level.
Chronic -An exposure or response, which operates over a long term.
Clean-up -The removal, treatment or containment of soil contaminated with chemicals at
unacceptable concentrations.
Conservative- In risk assessment or management, an analysis or a course of action which
overestimates the risk to human health or the environment.
Contaminated -A condition or state which represents or potentially represents an
adverse health or environmental impact because of the presence of potentially hazardous
substances.
Environmental risk assessment -The process of estimating the potential impact of a
chemical or physical agent on a specified ecological system under a specific set of
conditions.
Exposure - Contact with a chemical, physical or biological agent.
Exposure assessment - The estimation (qualitative or quantitative) of the magnitude,
frequency, duration, route and extent of exposure to a chemical substance or contaminant.
Fate and transport -Chemical, physical and biological processes that modify the
concentration of a chemical through transformation (e.g. degradation), transfer between
environmental media (e.g. soil to groundwater) and transport (e.g. moving with
groundwater).
Hazard -The capacity to produce a particular type of adverse health or environmental
effect.
Hazard index -Sum of hazard quotients for exposure to more than one chemical
simultaneously.
Health risk assessment - The process of estimating the potential impact of a chemical or
physical agent on a specified human population under a specific set of conditions.
No observed adverse effect level (NOAEL) - An exposure level at which there are no
statistically or biologically significant increases in the frequency or severity of adverse
effects between the exposed population and its appropriate control.
Quality assurance - A system of activities which provides assurance that defined
Standards is met for the product or service concerned.
Quality control – The day-to-day operations which deliver the quality standards
Specified.
Receptor - An organism, plant, human or physical structure which may be exposed to a
chemical or other hazardous agent.
Remediation -The clean-up or mitigation of contamination
Risk - The probability of an adverse outcome in a person, a species, a group, or an
ecosystem that is exposed to a hazardous agent. Risk depends on both the level of toxicity
of the hazardous agent, and the level of exposure.
Risk assessment - The process of estimating the potential impact of a chemical or
physical agent on an ecosystem or specified human population under a specific set of
conditions.
Threshold -The dose or exposure below which a significant adverse effect is not
expected.
Uncertainty -Imperfect knowledge concerns the present or future state of the system
under consideration; a component of risk resulting from imperfect knowledge of the
degree of hazard or its spatial and temporal distribution.
Ground water – water occurring beneath the surface of the earth that fills available
openings in the rock or sediment such that they may be considered saturated.
Hazardous substance – any substance or mixture of substances or radioactive
substances, which, when released into the environment, presents an imminent and
substantial hazard to the public health or welfare, including but not limited to, fish,
shellfish or other wildlife.
Hydrocarbon – Any organic compound, gaseous, liquid, or solid, consisting primarily
of carbon and hydrogen.
Operator – Any person in control of, or having responsibility for, the daily operation of
a tank.
Over excavation – The total amount of contaminated native soil removed beyond that
needed to actually remove any or all of the UST system.
Owner – Any person who owns a tank used for the storage of dispensing of regulated
substances.
person – any individual, partnership, association, public or private corporation; trustee,
receiver, assignee, agent, municipality, or other governmental subdivision, public agency,
officer or governing or managing body of any municipality, governmental subdivision or
public agency, or any other legal entity except the department
Appendix 2
HCl Identification
HYDROCHLORIC ACID, 33 - 40%
Synonyms: Muriatic acid; hydrogen chloride, aqueous
Molecular Weight: 36.46
Chemical Formula: HCl
Physical and Chemical Properties
Appearance: Colorless, fuming liquid.
Odor: Pungent odor of hydrogen chloride.
Solubility: Infinite in water with slight evolution of heat.
Density: 1.18
pH: For HCL solutions: 0.1 (1.0 N), 1.1 (0.1 N), 2.02 (0.01 N)
% Volatiles by volume @ 21C (70F):100
Boiling Point:53C (127F)
Melting Point:-74C (-101F)
Vapor Density (Air=1):No information found.
Vapor Pressure (mm Hg):190 @ 25C (77F)
Evaporation Rate (BuAc=1):No information found.
Stability and Reactivity
Stability: Stable under ordinary conditions of use and storage. Containers may burst when
heated.
Hazards Identification
Emergency Overview :Poison , Corrosive. Liquid and mist cause serve burns to all body
tissue.
Inhalation may cause lung damage.
Health Rating: 3 - Severe (Poison)
Flammability Rating: 0 - None
Reactivity Rating: 2 - Moderate
Contact Rating: 3 - Severe (Corrosive)
Lab Protective Equip: goggles & shield; lab coat & apron; vent hood;proper gloves
Storage Colour Code: White (Corrosive)
Potential Health Effects
Inhalation: Corrosive! Inhalation of vapours can cause coughing, choking, inflammation
of the nose, throat, and upper respiratory tract, and in severe cases, pulmonary edema,
circulatory failure, and death.
Ingestion: Corrosive! Swallowing hydrochloric acid can cause immediate pain and burns
of the mouth, throat, oesophagus and gastrointestinal tract. May cause nausea, vomiting,
and diarrhea. Swallowing may be fatal.
Skin Contact can cause redness, pain, and severe skin burns. Concentrated solutions
cause deep ulcers and discolour skin.
Eye Contact Vapours are irritating and may cause damage to the eyes. Contact may cause
severe burns and permanent eye damage.
Chronic Exposure: Long-term exposure to concentrated vapours may cause erosion.
Aggravation of Pre-existing Conditions: Persons with pre-existing skin disorders or eye
disease may be more susceptible to the effects of this substance.
Accidental Release Measures
Ventilate area of leak or spill. Wear appropriate personal protective equipment. Isolate
hazard area. Keep unnecessary and unprotected personnel from entering. Contain and
recover liquid when possible. Neutralize with alkaline material (soda ash, lime), then
absorb with an inert material (e.g., vermiculite, dry sand, earth), and place in a chemical
waste Container. Do not use combustible materials, such as sawdust. Regulations
(CERCLA) require reporting spills and releases to soil, water and air in excess of
reportable quantities. Acid neutralizers are recommended for spills of this product such as
soda ash.
Handling and Storage
Store in a cool, dry, ventilated storage area with acid resistant floors and good drainage.
Keep out of direct sunlight and away from heat, water, and incompatible materials. Do
not wash out container and use it for other purposes. When diluting, the acid should
always be added slowly to water and in small amounts. Never use hot water and never
add water to the acid. Water added to acid can cause uncontrolled boiling and splashing.
When opening metal containers, use non-sparking tools because of the possibility of
hydrogen gas being present. Containers of this material may be hazardous when empty
since they retain product residues (vapours, liquid).
Exposure Controls/Personal Protection
Airborne Exposure Limits:-OSHA Permissible Exposure Limit (PEL):5 ppm Ceiling
ACGIH Threshold Limit Value (TLV):5 ppm Ceiling
Personal Respirators (NIOSH Approved) If the exposure limit is exceeded, a full face
piece respirator with an acid gas cartridge may be worn up to 50 times the exposure limit
or the maximum use concentration specified by the appropriate regulatory agency or
respirator supplier, whichever is lowest. For emergencies or instances where the exposure
levels are not known, use a full-face piece positive-pressure, air-supplied respirator.
WARNING: Air purifying respirators do not protect workers in oxygen-deficient
atmospheres.
Skin Protection: Rubber or neoprene gloves and additional protection including
impervious boots, apron, or coveralls, as needed in areas of unusual exposure to prevent
skin contact.
Eye Protection: Use chemical safety goggles and/or a full face shield where splashing is
possible. Maintain eyewash fountain and quick-drench facilities in work area.
Hazardous Decomposition Products: When heated to decomposition, emits toxic
hydrogen chloride fumes and will react with water or steam to produce heat and toxic and
corrosive fumes.
Hazardous Polymerization: Will not occur.
Incompatibilities:
A strong mineral acid, concentrated hydrochloric acid is incompatible with many
substances and highly reactive with strong bases, metals, metal oxides, hydroxides,
amines, carbonates and other alkaline materials. Incompatible with materials such as
cyanides, sulfides, sulfites, and formaldehyde.
Conditions to Avoid: Heat, direct sunlight.
Toxicological Information Inhalation rat LC50: 3124 ppm/1H; oral rabbit LD50: 900
mg/kg (Hydrochloric acid concentrated); investigated as a tumorigen, mutagen,
reproductive effecter.
Ecological Information
Environmental Fate: When released into the soil, this material is not expected to
biodegrade.
Disposal Considerations
Whatever cannot be saved for recovery or recycling should be handled as hazardous
waste and sent to waste facility. Dispose of container and unused contents by rinse,
crush, and ship to sanitary landfill .
References
RISK-BASED GUIDANCE FOR THE SOIL - HUMAN HEALTH PATHWAY
VOLUME 2. TECHNICAL SUPPORT DOCUMENT.
Site Investigation and Analysis of Soils (Contaminated Land Management Guidelines
No. 5 ). Published in February 2004 by the Ministry for the Environment PO Box 10-362, Wellington, New
Zealand
DRAFT GUIDELINES RISK BASED SITE CHARACTERIZATION AND
SAMPLING GUIDANCE Minnesota Pollution Control Agency 1996
Soil Investigation and Human Health Risk Assessment for the Rodney Street Community,
Port Colborne: March 2002

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Soil Investigation and Risk Assessment for the spilled HCl in SLB storage Tawilla-, Hathramout', September 2005.

APPENDIX 1 SOME GLOSSARY ......................................................................................................................27

APPENDIX 2 HCL SAFETY DATA SHEET ...................................................................................................29

The objectives of the report to analysis contaminated and uncontaminated soil

1.3 Scope of work

• Analysis of whole samples in approval laboratories according to the required

• The study will cover the following risk

3. 1 Location and Topography

3. 2 Geology and Lithology

4.1 Sampling Method and Pattern

Mobilize the following equipment from Schlumberger Masila Base

Phase 2 – Removal of Drums

• If possible, pallets in good condition will be removed first. An assessment will be

• Each pallet will be tied down and secured.

Phase 3 – Transportation of Drums

• A designated Supervisor will be assigned to this activity.

• Loadmaster will be appointed during the loading operation.

• One copy of Loading Note to be kept at receiving location.

• Remedial action to be determined based on results of the study.

4.3 Selecting a laboratory and Analytical methods

5.1 Laboratory Analysis

5.1.1 Soil Homogenization and Grinding

5.1.2 Equilibrium Geochemistry (pH)

5.1.3 Major and Minor ions

5.1.4 Acidity analysis

5.1.5 Electrical Conductivity (E.C)

5.2 Data Report

• The samples were collected in two different ways and date.

• Lack of homogenization of samples on the site.

Al2O3% 3.32 3.23 3.30 3.55 4.62

Fe2O3% 3.39 2.22 2.29 2.72 2.94

CaO% 34.81 39.00 37.43 37.26 33.21

MgO% 2.17 1.76 2.12 2.59 2.76

SO3% 0.23 0.11 0.04 0.08 0.04

K2O% 0.58 0.57 0.59 0.63 0.75

CL% 6.07^ 0.21 0.00 0.98 0.00

PH 8.5 8.5 8.5 8.5 8.5 8.5 8.5

Table No. (4 ) indicate the results of Samples No.(S1,CI3s,U1,CI130,CI1,C*3,C*2) from

*: samples taken on 5 sep2005

5) C*2 sample not contaminated (15 m N from the storage area).

6.1 Risk acceptance criteria and Specification of HCl (contaminant)

6.3.1 Impact on Human Health

6.3.2 Environmental risk Impact

Impact Potential Magnitude

• There is no probability of environmental contamination from the spilled acid (55

• There are no adverse effects of the substance on biological and chemical

Slb : Schlumberger company

CE: Soil Threshold Concentration – Environment

CH : Soil Threshold Concentration - Human Health

PPM : Parts per million (1 in 106)

NaOH : Sodium Hydroxide

HCl : Hydrochloric acid

ACP : Amran Cement Plant.

G.C: Government committee

TDS : Total Dissolved Solids

BOD: Biochemical oxygen demand

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Table No. (4 ) indicate the results of Samples No.(S1,CI3s,U1,CI130,CI1,C3,C2) from