Mercury Management

White Paper 2012

Minimizing Occupational Exposure
to Mercury in Hydrocarbon
Processing Plants

White Paper 2012

Minimizing Occupational Exposure to Mercury

Ron Radford, Roberto Lopez-Garcia

Mercury and mercury compounds are found in all geologic hydrocarbons including
coal, natural gas, gas condensates and crude oil. Mercury can accumulate in

hydrocarbon production, processing and transportation systems. Occupational

exposure to mercury and mercury compounds poses serious health risks to
maintenance and inspection personnel working on hydrocarbon processing

equipment potentially contaminated by process streams and products containing

mercury. Mercury exposure risks are often underestimated, underscoring the

need for companies engaged in hydrocarbon processing to develop a comprehen-

sive mercury management strategy that accurately quantifies risks and minimizes
worker exposure.

Introduction
The general perception of produced mercury in hydrocarbon processing systems

Contributing Factors
for Underestimating
Mercury Exposure Risks
Hg in vapor form is colorless
and odorless
Hg toxicity is gradual and
generally produces no
immediate impairment
that can be attributed to
a specific occupational
exposure event
Hg exposure monitoring is
not routine or performed at
all in some hydrocarbon processing work environments
Precise Hg concentrations
in process streams are
often unknown
Concentrations of speciated
Hg compounds in process
streams and products are
rarely known

has changed over the last decade as its effect on processes has become better
understood and the analytical methods for detecting and quantifying mercury in
various matrices and media have improved. Over the past eight years, PEIs
Mercury and Chemical Services Group have been engaged in occupational
mercury exposure studies in hydrocarbon processing facilities worldwide.

The main objective of these studies has been to determine worker exposure risks
during routine as well as non-routine maintenance and inspection activities associated with turnarounds, shutdowns and inspections. The appropriate approach for
assessing mercury exposure risk is based on four components:

1. The development of sampling and analysis plans that are based on each plants
process design and scheduled maintenance events.

2. The identification and development of plant and process specific Similar

Exposure Groups (SEG).

3. The use of a combination of exposure measurement techniques including

portable field monitoring instruments, and active and passive sorbent trap
sampling techniques.

4. The identification and use of appropriate analytical methods for the detection

and quantification of total mercury and specific mercury compounds (speciation).

Sampling campaigns are designed and focused on the measurement of mercury

vapor concentrations in worker breathing zones during specific maintenance
events including; pipe pigging, process filter replacement, process vessel
inspection and hot-work (cutting, welding and grinding).

This white paper presents an overview of mercury management program components and occupational exposure monitoring methods in hydrocarbon processing
plants, including the evaluation of an emerging passive dosimeter technology.

www. p e i - tx . c om

rradford@pei-tx.com

White Paper 2012

Minimizing Occupational Exposure to Mercury

Ron Radford, Roberto Lopez-Garcia

Mercury in Hydrocarbons
The development of plans to minimize occupational mercury exposure requires
an understanding of how mercury is distributed in hydrocarbon processing sys-

tems and how mercury reacts with process equipment surfaces. In hydrocarbon

liquids, dissolved mercury occurs in its elemental form (Hg0), as organic (dialkyl,
monoalkyl) mercury [Hg(CH3)2, Hg(C2H5)2, HgCH3Cl], and as inorganic (HgCl2)

forms. In addition, produced liquids and some process streams contain suspended mercury compounds, such as mercuric sulfide (HgS), which can be
a significant fraction of the measured total mercury concentration.

In natural gas, mercury exists almost exclusively in its elemental form at con-

centrations below saturation suggesting that no liquid mercury phase exists in

most reservoirs. However, there are a number of reservoirs which are known to

produce gas at saturation (with respect to elemental mercury). Organic mercury

compounds in produced gas, under normal operating conditions, will partition to

separated hydrocarbon liquids as the gas is cooled. Therefore, if organic mer-

cury is present in the reservoir, it would be most likely found in gas condensates.
Measuring dialkyl mercury compounds in hydrocarbon liquids is complicated due

to several aspects of mercury chemistry that make it difficult to detect and quantify.
Crude oil and gas condensate can contain several chemical forms of mercury,
which differ in their chemical and physical properties.

Chemical and Physical Properties of Mercury in Crude Oil and Gas

Dissolved Elemental Mercury (HgO): Elemental mercury is soluble in crude oil and hydrocarbon liquids up to a few parts
per million (ppm).
Dissolved Organic Mercury: This category includes dialkylmercury (i.e., dimethylmercury, diethylmercury) and monomethylmercury halides (or other inorganic ions).
Inorganic (ionic) mercury salts (Hg2+X or Hg2+X2, where X is an inorganic ion): Mercury salts are soluble in oil and
gas condensate but preferentially partition to the water phase in primary separations. Ionic salts may also be physically
suspended in oil or may be absorbed to suspended particles.
Complexed mercury (HgK or HgK2): Where K is a ligand such as an organic acid, porphyrin or thiol.
Suspended mercury compounds: Mercury sulfide (HgS) and selenide (HgSe) are insoluble in water and oil but may be
present as suspended solid particles.
Table 1.

In hydrocarbon processing and petrochemical manufacturing, mercury in process

feeds can contaminate equipment and can partition into sludge and other waste

streams. Steel piping and pressure vessels that are used to transport and process
produced fluids interact chemically with the mercury species in the fluids they

www. p e i - tx . c om

rradford@pei-tx.com

White Paper 2012

Minimizing Occupational Exposure to Mercury

Ron Radford, Roberto Lopez-Garcia

contain. In fact, in locations where mercury is known to be present in produced

reservoir fluid, rigorous safety precautions are required to detect mercury vapor
that emanates from steel vessels and pipe when opened for maintenance or

inspections purposes. A mercury-contaminated steel pressure vessel will emit

mercury vapor long after it has been ventilated and cleaned to remove sludge

and surface hydrocarbons. Under these conditions there is significant potential

for workers to be exposed to mercury and its compounds during routine repair,
maintenance and inspection activities, and when handling process fluid and
waste materials.

Occupational Mercury Vapor Exposure Limits

Mercury and its compounds are highly reactive toxic agents that can damage the
central nervous system, endocrine system, kidneys and other organs. Mercury is
highly volatile making vapor inhalation the most common pathway for exposure.
Exposure over longer periods of time can result in brain damage and ultimately
death. Therefore, companies operating oil and gas production and processing

facilities should be aware of the concentrations of mercury in processed trans-

ported fluids and gases in order to quantify the magnitude of contamination and potential for worker exposure.

Health, regulatory and advisory limits have been established for exposure
to mercury vapor (Chart 1). Workplace standards are generally based

on preventing adverse health effects from exposure over a 40-hour work

week and are higher than health/toxicological exposure values. The

Occupational Safety and Health Administration (OSHA) has established

a legally enforceable ceiling limit for work place exposure of 100 g/

m3. Mercury concentrations cannot exceed this level at any time during

the work day. The National Institute for Occupational Safety and Health

(NIOSH) has established a recommended exposure limit (REL) for mer-

cury vapor of 50 g/m3 expressed as a time weighted average (TWA) for

a 10-hour work day. The American Conference of Governmental Industrial

Exposure Level
Chart 1.

Hygienists (ACGIH) recommends a threshold limit value (TLV) of 25 g/

m mercury vapor as a time weighted average exposure for a normal 8-hour

3

work day.

The OSHA PEL for alkyl mercury compounds is 10 g/m3 and should be used
if the presence of dialkyl mercury is suspected in gas condensates. Samples
should be analyzed for organic mercury compounds in process streams and

ambient air in closed space equipment atmospheres to quantify alkyl mercury

w w w. p ei - tx . c om rradford@pei-tx.com

White Paper 2012

Ron Radford, Roberto Lopez-Garcia

Minimizing Occupational Exposure to Mercury

concentrations. Dialkyl mercury compounds are many more times toxic than

elemental mercury. Temperature, pressure, and chemical changes throughout

hydrocarbon processing systems allow mercury to change from one chemical

form to another. Knowledge of the amount and type of mercury present is required
for the design of effective exposure assessment and management programs.

The Environmental Protection Agency (EPA) sets a reference concentration (RfC)

of 0.3 g/m3 for inhalation exposure to mercury. The reference concentration is a

screening tool used to help risk assessors determine where to focus their investigations into hazardous exposures. Similarly, the Agency for Toxic Substances

and Disease Registry (ASTDR) has set a minimal risk level (MRL) for inhalation
exposure at 0.2 g/m3.

Mercury Management Program Components

Mercury accumulates in hydrocarbon processing system components such as

heat exchangers, separators and filters, slug catchers, and other process towers
and vessels. Mercury reacts with and chemically modifies steel surfaces such

that hydrocarbon and surface layers as well as substrate layers (mercury pen-

etrates steel surfaces several millimeters) will emit mercury vapor when equipment is opened for inspection and maintenance.

Hydrocarbon processing companies can minimize potential worker exposures by

the implementation of a mercury management strategy. Some key components
of a comprehensive mercury management strategy include the following:
1. Risk Assessment

2. Worker Health and Safety Protocol

3. Exposure Monitoring Plan
4. Data Quality Objectives
5. Medical Surveillance

6. Mercury Awareness Training

1. Risk Assessment
Risks associated with producing, transporting and processing petroleum and

natural gas containing mercury fall into several categories. Of primary importance
is the risk to workers who handle fluids or repair and maintain equipment. As-

sessing health risks to workers includes the acquisition of analytical information

required to make the correct judgments.

www. p e i - tx . c om

rradford@pei-tx.com

White Paper 2012

Ron Radford, Roberto Lopez-Garcia

Minimizing Occupational Exposure to Mercury

There are clear economic risks associated with mercury in process feeds such as:
Compromise of product quality.

Potential interaction with process equipment.

Detrimental impact on the environment.

Human and economic risks generally are related to the concentration of mercury in

process hydrocarbons. They are determined according to the total mercury concentration obtained using analytical procedures and suitable quality assurance measures.

Threshold Values for Specifying Levels of Risk

LOW RISK

MEDIUM RISK

HIGH RISK

Less than 10 ppb liquid

(<5 g/Sm3 gas)

Between 10 and 100 ppb liquid

(5-50 g/Sm3 gas)

Greater than 100 ppb liquid

(>50 g/Sm3 gas)

Table 2.

2. Worker Health and Safety Protocol

Avoiding exposure to mercury, in most maintenance and inspection activities, can

be accomplished if some steps are taken to identify the situations in which exposure
is possible. This is commonly achieved by employing the right equipment for worker
protection from inhalation and/or dermal absorption. Policies designed to ensure

the health and safety of workers should be based on a rigorous chemical analysis

of the process streams and ambient air monitoring in work areas. With this information, exposure to mercury can be avoided using conventional personal protective
equipment (PPE) and engineering controls.

< 25 g/m3

PPE Decision Tree

25 - 50 g/m3

> 50-100 g/m3

50 - 100 g/m3

Chart 2.

www. p e i - tx . c om rradford@pei-tx.com

White Paper 2012

Minimizing Occupational Exposure to Mercury

Ron Radford, Roberto Lopez-Garcia

3. Exposure Monitoring Plan

Oil and gas processing equipment and appurtenances contaminated with mercury

require stringent safety precautions and exposure monitoring procedures to mitigate

risks to personnel during inspection and maintenance activities.

(Note: One square meter of steel holding 1 gram of elemental mercury can contaminate around
40,000 cubic meters of air to a level that exceeds the TLV of 25 g/m3.)

Preventative Exposure Controls

Controls to reduce or prevent exposure can be accomplished through the following:
Engineering: Eliminate or reduce the risk of exposure through the use or
substitution of engineered machinery or equipment.

Administrative: Reducing the risk of exposure through employee training,

housekeeping and rotation of personnel.

Personal Protective Equipment: Used when the implementation of engineering

and administrative controls do not eliminate the risk of exposure.

Site Controls
Performance of some work tasks may require definition of three clearly established
work zones: an Exclusion Zone (EZ), a Contamination Reduction Zone (CRZ), and
a Clean Zone (CZ). Work zones are established based on the extent of anticipated
contamination and projected work activities. Field measurements combined with
climatic conditions may, in part, determine the control zone distances.

Exclusion Zone (EZ): The EZ includes any area(s) of potential contamination. All

personnel entering the EZ must wear the appropriate PPE for the tasks they are

to perform in that area and meet training, and medical surveillance requirements.

Contamination Reduction Zone (CRZ): The CRZ is the area where hazardous sub-

stances are removed from site personnel and their protective equipment. Access
to the contamination reduction zone from the clean zone is allowed only through
established control points.

Clean Zone (CZ): The CZ is a non-contaminated area where support services,

non-hazardous materials storage and administrative activities generally occur.

The CZ should be equipped with potable water, first aid kits, safety equipment,

and supplies of clean PPE. In some cases the CZ is also equipped with hand/face
washing facilities.

w w w. p ei - tx . c om

rradford@pei-tx.com

White Paper 2012

Ron Radford, Roberto Lopez-Garcia

Minimizing Occupational Exposure to Mercury

Personal Exposure Sampling and Analysis

The personal exposure sampling and analysis methodology includes the development of Similar Exposure Groups (SEGs). Prior to completing final design of an

exposure monitoring plan interviews should be conducted with plant operations/

engineering personnel to identify plant specific exposure profiles. A key goal

is to identify exposure profiles that are specific to similar types of plants and/
or processes.

Real-Time Monitoring
Ambient air monitoring is conducted to assess airborne concentrations of mercury.

Real-time baseline ambient air monitoring is performed just prior to work conditions
during which the potential for mercury vapor exposure may occur to assist in determining exposure risk and appropriate PPE selection. Real-time monitoring should
also continue throughout work tasks during which the potential for mercury vapor

exposure exists. There are a variety of field mercury vapor analyzers available on

the market today, each of which has some limitations associated with interference
gases and conditions common in hydrocarbon processing. Understanding these

limitations is critical when developing occupational exposure monitoring plans. The

research and development team at PEI has expanded previous industry research
and performed detailed comparative studies using cold vapor atomic florescence

spectrometry (CVAFS) and available atomic adsorption (AA) field-portable mercury

vapor analyzers. Data from those comparative studies will be presented in a separate white paper.

Portable mercury vapor analyzers used extensively by PEI proven to be accurate, reliable and robust.
MERCURY TRACKER 3000 IP

THE OHIO LUMEX RA-915 LIGHT

Mercury Vapor Analyzer (detection limit = 0.1 g/m3)

Mercury Vapor Analyzer (detection limit = .02 g/m3).

Mercury
Vapor
Analyzer
Example 1.

Control zones and work areas should be regularly monitored with a portable

Mercury Vapor Analyzer (MVA) for accurate detection and measurement of toxic
mercury vapor in the air. Frequency of testing is based on multiple conditions,

such as, work tasks, process changes, weather conditions, or voluntary testing.

w w w. p ei - tx . c om

rradford@pei-tx.com

White Paper 2012

Ron Radford, Roberto Lopez-Garcia

Minimizing Occupational Exposure to Mercury

Passive Personnel Sampling

Passive personal exposure samples are collected from exposure assessment

program participants identified and selected from specific SEGs. Passive personal
exposure samples consist of a solid sorbent sample media with an engineered
diffusive membrane that allows for a specific air diffusion rate to occur during

the sampling period. The sampling takes place as the work activities start and
throughout the duration of activities.

Two types of passive samplers (SKC and Radiello) have been tested for use during recent Occupational Exposure
Monitoring Studies.
SKC PASSIVE DOSIMETER

RADIELLO DIFFUSIVE SAMPLER

Passive Sampler for Inorganic

Mercury (520 Series) which has
been validated by the OSHA ID-140
Mercury Vapor in Work Place Atmospheres method. The sampling media
consists of Anasorb C300.

Radiello Diffusive Sampler (Code 120

Diffusive Body) and was used with
FSTM media provided by Frontier
Global Sciences (FGS) is analyzed
by the same method employed for
the Anasorb media. The Radiello
Diffusive Sampler has potential
attractive passive sampling dynamics
although it is not a validated
approach at this time and is
considered experimental only.

Occupational Exposure
Monitoring Samples
Example 2.

During the comparative testing of the SKC and Radiello, FGS, the National Envi-

ronmental Laboratory Accreditation Program (NELAP), and ISO 17025 accredited

laboratory, provided analytical services. The analytical method used for passive
dosimeters during the comparative study consisted of FGS-SOP-136: Analysis

of Hg in Air via Capture on Sorbent Trap based on the principles of US EPA 1631
Revision E. The comparative results of the Radiello, and SKC to the standard

OSHA ID-140 method (active pump) indicate that the Radiello samplers collect
mercury at a higher rate than the SKC samplers.
Passive dosimeter have two notable limitations:

1. Particulate bound mercury compounds cannot be collected with the device.

2. The dosimeter is sample rate depends on air velocity and should not be used

in areas where the air velocity is greater than 229 m/min (750 ft./min). A sampling

pump (active sampling method) and collection media are required for this for
particulate collection and during those times when air velocity exceeds the
recommended limit.

www. p e i - tx . c om

rradford@pei-tx.com

White Paper 2012

10

Minimizing Occupational Exposure to Mercury

Ron Radford, Roberto Lopez-Garcia

Active Personnel Sampling

Mine Safety Appliances (MSA) Escort LC Pumps (low-flow active sample pumps)

Active Personnel Sampling

calibrated to 0.2 to 0.4 liters per minute are used for active sampling events.

Low Flow Sample Pump,

Sample Tubing
and FGS Sample
Calibration
of the sampling
pump isTrap
a critical aspect of insuring the quality of the

LOW-FLOW SAMPLE PUMP

sample collection process. A sampling assembly is connected to a calibrated

pump using flexible tubing. If a prefilter is used, it should be connected to the

sampling tube with a minimum amount of Tygon or Teflon tubing. The pumps
can be placed on employees and also staged around the perimeter of control
zones (Table 3).
SAMPLE TUBING
FGS SAMPLE TRAP

A total air volume in the range of 3 to 100 L is typically employed to collect mercury
onto the sorbent media cartridge. The analytical procedure used for the analysis of

all three types of personal exposure samples (Illustration 1) during the comparative
study is the FGS Standard Operating Procedure FGS 069.4.1 Determination of

Total Mercury in Various Matrices by Cold Vapor Atomic Fluorescence Spectrometry (Modified EPA Method 1631E).

Personal Sampling
Example 3.

Illustration 1.

w w w. p ei - tx . c om

rradford@pei-tx.com

White Paper 2012

11

Ron Radford, Roberto Lopez-Garcia

Minimizing Occupational Exposure to Mercury

4. Data Quality Objectives

QA/QC Samples
and Performance
Criteria

Performance
Criteria

PERSONAL EXPOSURE SAMPLES

Passive SKC

Passive Radiello

Active

AMBIENT AIR SAMPLES

Passive SKC

Passive Radiello

Sampling Method

OSHA ID - 140

OSHA ID - 140

Analytical Method

FGS-136: FGS-SOP-136: Analysis

of Hg in Air via Capture on Sorbent
Traps (based on the principles
of US EPA 1631).

FGS-136:
FGS-SOP-136

Sample Preparation Method

OSHA ID - 140

Sample Media
Target Detection
Limit*

g/scm

Field Duplicates

Field Spikes

Breakthrough
Sections

Field Blanks

OSHA ID - 140

Active

FGS SOP
009.04

FSTM

Anasorb
C300

FSTM

FSTM

12.5

12.5

12.5

12.5

12.5

12.5

10%, 1 per
2 days
minimum

10%, 1
per 2
days
minimum

25

25

(% RD)

25

25

NA

(% recovery)

NA

NA

pling campaigns (including the collection

of a large number of critical field data

parameters) and the importance to the

employees involved in oil and gas pro-

25

NA

studies due to the extensive field sam-

health and safety of a large number of

10%
1/day minimum

Frequency

quiring extensive collection of raw and

for occupational exposure monitoring

FSTM

5%, 1 per 2
days minimum

critical component of any project re-

analytical data. This is especially true

Anasorb
C300

Frequency

Data quality objectives (DQOs) are a

25

cessing operations. To support this

effort a detailed Quality Assurance

Frequency

NA

100%

NA

100%

B Section
Mass %

NA

5% of A
Section
Hg Mass

NA

5% of A
Section
Hg Mass

Frequency

1/day

1/day

Performance
Criteria

blank mass value

blank mass value

Project Plan (QAPP) is developed

to inform, and guide the team so that

data of desired quality is produced,

and a clear protocol for the acceptance/

rejection of data is established.

Data Quality Objectives

Table 3

The QAPP should include a QA/QC (quality assurance/quality control) sample

collection protocol for the field data collection phase as well as for the laboratory
analysis phase. Field data QA/QC samples consists of duplicate samples, field

spikes with NIST (National Institute of Standards and Technology) traceable spike
standards, field blanks, and breakthrough sections.

5. Medical Surveilance
Biological monitoring is the measurement of chemical agents in the blood, urine, or

other body tissue of exposed individuals to determine how much of the chemical has
been absorbed into the body. Biological monitoring of mercury is necessary if someone is exposed to mercury, or thinks they might be exposed. It serves as a back-up

to environmental exposure measurements, since air measurements cannot take into

consideration skin exposure or the effectiveness of protective equipment and work

practices. Biological monitoring measures the amount of an agent actually present in

the body and is usually better than air monitoring as an estimate of risk for adverse
health effects.

www. p e i - tx . c om

rradford@pei-tx.com

White Paper 2012

Minimizing Occupational Exposure to Mercury

Ron Radford, Roberto Lopez-Garcia

Measurements are taken regularly (several times a year) for chronically exposed
workers. Individual results and also group results are evaluated. To effectively
interpret the results, baseline levels need to be established before exposure
begins for comparison purposes.

Site personnel and subcontract personnel who may be at risk to mercury expo-

sure should follow the appropriate medical monitoring requirements in accordance

with the United States Department of Labor standard 29 CFR 1910.120(f). Each

individual entering a contaminated area should successfully complete an annual

surveillance examination and/or an initial baseline examination.

6. Mercury Awareness Training

Training is important to ensure worker health and safety and that plant environments are not contaminated by mercury. Workers should be:

Trained to anticipate situations in which they could be exposed.

Provided appropriate PPE, trained in the use of PPE.
Taught to recognize symptoms of exposure.

Ron Radford

James Vic Vickery

Roberto Lopez-Garcia

Director of Chemical

Vice President, and

Chief Scientist

Cleaning Operations

Technical Director of Mercury

Mercury and Chemical

Portnoy Environmental, Inc.

and Chemical Services Group

Services Group

1414 W. Sam Houston Pkwy. N.

Portnoy Environmental, Inc.

Portnoy Environmental, Inc.

Suite 170

1414 W. Sam Houston Pkwy. N.

London, England

Houston, TX 77043 USA

Suite 170

44-7791904-977

713-503-6803

Houston, TX 77043 USA

www.pei-tx.com

www.pei-tx.com

281-536-0899

rgarcia@pei-tx.com

rradford@pei-tx.com

www.pei-tx.com
vvickery@pei-tx.com

Bob Brunette
Frontier Global Sciences, Inc.
11720 N. Creek Pkwy. N.
Suite 400
Bothell, WA 98011 USA
206-660-7307
www.frontiergeosciences.com/
Bobb@frontiergeosciences.com

www. p e i - tx . c om

Copyright 2012 Portnoy Environmental, Inc. All Rights Reserved. PEI-FGS 4/2012

Contacts

rradford@pei-tx.com