**48^TH^ MEETING OF THE PETROLEUM ENVIRONMENTL RESEARCH FORUM GENERAL
MEETING - MARCH 1999**

**CHEVRON/LAWRENCE BERKELEY NATIONAL LABORATORY**

###### BERKELEY, CA -- MEETING SUMMARY

**Welcome**

Dr. Pier Odonne, Deputy Director of the Lawrence Berkeley National Lab,
kicked off the general meeting by providing the group with an overview
of the laboratory program. The lab employs approximately 4000 people
engaged in multi-disciplinary research. The lab emphasizes a
multi-disciplinary approach for their research program to pool the
expertise and capabilities of the lab to solve the nation's problems.

The lab has a strong Life Sciences Program (approximately 30% of their
total program) which originated from their early work on nuclear medical
treatment applications. The lab does not perform any weapons research,
which permits them to have an "open campus" environment with UCBerkeley.
Many of the university professors have dual appointments with the lab
and vice versa.

## **Atmospheric Program Overview -- Dr. Nancy Brown**

The Atmospheric Chemistry program is a relatively new program at the lab
and was formed to integrate many of the air programs. The vision of the
program is:

-   Build a program that takes advantage of current research expertise

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-   advanced instrumentation, high performance computing, modeling
    uncertainty and indoor environment

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-   Participate significantly in important air quality field studies

-   Develop a framework for assessing air quality modeling uncertainty

-   Participate in building the next generation, science-based air
    quality model

The Atmospheric Program maintains the following areas of expertise:

-   Emissions

-   Advanced Instrumentation

-   Modeling

-   Model uncertainty

-   Aerosols

-   Carbon Cycling

Dr. Brown provided the group with an overview of many projects, which
could not be discussed during the meeting, but are summarized in the
meeting summary.

Impact of Reformulated Gasoline on California Motor Vehicle Emissions -
Robert Harley

Unfortunately Rob was ill and could not join us.

#### Measurements of Oil Tank Emissions - Donald Lucas

Don provided the group with an overview of his work in studying VOC
emissions from heavy oil storage tanks. The project was initiated
several years ago when the regulatory community was debating the need
for air pollution control equipment on heavy oil storage tanks. As the
regulatory agencies looked to tighten the controls for VOC's in response
to more stringent ozone standards, it was apparent there existed
technical gaps in the current VOC measuring protocols for heavy oil
tanks that made it difficult for effective regulations to be developed.
A joint project team, consisting of regulatory agencies, LBNL and
industry, was chartered to develop new, scientifically valid procedures
for estimating emissions from heavy crudes. The project is in the third
year of development and has accomplished:

-   Developed the science which led to a low cost test method that
    predicts tank vapor phase composition -- working on developing an
    emission correlation

-   Data will be integrated into CARB and EPA regulations

-   Better understanding of tank emissions looking at the need for vapor
    recovery

Future plans for the project include:

-   Additional tank measurements to validate model estimates

-   Develop a scientifically-sound protocol acceptable to regulatory
    community and industry

#### Real-Time Particle Monitor - Susanne Hering

Susanne provided the group with a perspective on the state-of-the-art in
measuring atmospheric particles. The science has evolved from a simple
gravimetric method developed in the fifties to an advanced method
utilizing a Teflon filter that collects particles to the 2.5 mm size.
Air regulations today still retain a mass measurement approach, but do
not deal with real time issues nor identify chemical composition and
particle speciation data.

They have developed a new approach for an automated, high-resolution
time measurement of Particulate Matter ~2.5~ for Nitrate, Sulfate and
Carbon. The instrument collects real time PM data in 10 minute
increments and provides speciation data for sulfate and nitrate. The
methodology for carbon is still "work in progress". The instrument for
collecting the sample is very flexible (allows for calibration with
known standards, calculates collection efficiency, etc.).

In the future, field work will take place in the San Jacquin Valley to
determine the concentration of outdoor particles found inside homes in
the valley. They plan to work closely with LBNL to determine a detailed
indoor-outdoor relationship for particles, which will be integrated into
a comprehensive LBNL model for predicting indoor particle concentrations
originating from outdoor sources.

Sensitivity Analysis as a Tool for Explaining California Weekend
Effect - Laurent Vuilleumier

In California, higher concentrations of ozone are observed during the
weekends than during weekdays despite lower emissions and concentrations
of NOx, VOC and CO. This phenomena is most likely due to the California
lifestyle (increase in vehicle traffic during the weekends). In
designing strategies to attain the national ambient air quality standard
for ozone, it is very important to have a detailed understanding of the
weekend effect. Therefore, a predictive model was developed to predict
the effect with sensitivity analyses performed to obtain a more detailed
understanding of the uncertainties associated with the model.

The model took into account both vehicle and stationary source
emissions. Vehicle emissions were examined in detail -- focusing in on
the variability in the types of emissions generated. The initial results
of the model showed:

-   Simulations conducted using weekend conditions resulted in ozone
    concentrations about 20% higher than simulations with weekday
    conditions

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-   Ozone sensitivities to emission fluxes are typical of a VOC-limited
    system

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-   Sensitivity analysis shows the differences in peak ozone
    concentrations between weekdays and weekends are of correct sign and
    order of magnitude.

-   Sensitivity analysis shows that the decrease in NOx emissions on
    weekends is the main cause for the ozone concentration increase.

Uncertainty analysis can be a powerful tool to help better understand
the limitations of a model and test the basis of model assumptions. In
this case, sensitivity analysis inaccuracies were used to identify
changes and needed improvements in the fundamental model mechanism.

Free Radical Observations and Chemical Kinetics in the Atmosphere - Ron
Cohen

Dr. Cohen's project is aimed at the following research areas:

1.  What controls ozone and particles in the surface layer

-   mechanisms of NOx and HOx photochemistry

-   field observations that isolate individual components of models

-   comprehensive observations

2\. How does regional photochemistry interact with global ozone, OH,
aerosol and climate

-   export of NOx and organic nitrites to the global atmosphere

-   global ozone increases set the stage for regional chemistry

3.  Observing and Measuring Atmospheric Change

-   develop tools for observing trends in NOx on a global scale

As part of the program, they are developing the next generation of
instruments capable of measuring NOx in the urban setting (10-100 ppb)
and in the remote atmosphere (1-100 ppt). Presently, they are developing
a tool, using laser-induced fluoresence technology, which looks
promising. The instrument is now capable of collecting data with a
sensitivity of 10 ppt/10 sec averaging. Future work will look at
decreasing the sensitivity to 1 ppt.

Carbonaceous Aerosols: Distributions, Concentrations and Properties -
Tica Novakov

Dr. Novakov provided the group with an overview of his work on
carbonaceous aerosols. Sources of aerosols can be found from:

-   direct emissions form incomplete combustion

-   Gas to particle conversion of reactive anthropogenic and biogenic
    hcs

-   carbonate from mineral dust

Learnings

-   Using the most sophisticated analytical techniques, we can only
    identify 10% of the organic compounds.

-   Significant differences in aerosol concentrations depending on
    geography (East Coast vs. West Coast) and the season of the year.

Work to be done

-   how to sample and analyze for aerosols

-   molecular identified organic compounds

-   Advance in-situ methods are being developed but filter and impactor
    sampling will be used for a while

-   How representative are surface-based measurements of column
    properties

-   Optical properties of organic carbon and black carbon vs. chemical
    composition

-   Effects of relative humidity on scattering and absorption of pure
    and mixed aerosols

-   formation processes of organic aerosol components

-   water solubility of the organic component and relationship to CCN
    activity

-   Organic concentrations and sources in marine atmospheres

#### Organic Aerosols: Distribution and Properties - Allen Goldstein

Knowledge of the fundamental processes which regulate trace gas exchange
between the biosphere and the atmosphere is critical to the
understanding of aerosol formation. The goal of Dr. Goldstein's work is:
Regional photochemistry focusing on impacts of biogenic and
anthrogogenic VOC emissions for ozone and particulate matter formation

He has been studying the effect of methylbutenol on atmospheric
photochemistry. Presently, methylbutenol accounts for approx. 20+% of
the total reactivity of the hydrocarbon photochemistry downwind from the
Sacramento area. The project also determined the current models did not
take into account humidity and the effect of temperature.

Polarized Light Scattering Measurements for Sizing Diesel Particles -
Arlon Hunt

The goals of Dr. Hunt's project are to develop accurate real time
measurements of PM from diesel engines and to improve current
measurement methods. The objectives of his project are:

-   Develop a method to characterize diesel exhaust soot from polarized
    light scattering

-   Develop a real-time light scattering instrument to measure diesel
    particle size

-   Study the effect of particulate characteristics of

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-   Running conditions (engine)

-   Fuel composition

-   Post-combustion factors (humidity, dilution, etc.)

# Approach

-   Measure diesel exhaust streams in-situ

-   Model soot scattering as spheres and agglomerates

-   Determine size distribution and optical properties of soot by
    comparing experimental data with modeled scattering (refractive
    index and absorption)

Particulate data is being collected from several different diesel
engines as a function of engine load. This data has been used to
validate the analytical instrument (Scatterometer). The instrument is
now being developed for future commercial use.

Project Accomplishments to date include:

-   characterized diesel exhaust particulates (size morphology, optical
    properties

-   Background for Scatterometer Development -- collaboration with Oak
    Ridge

-   Designed built and tested scatterometer to measure particle size in
    real time

#### Analysis of Real-World Emissions from In-Use Vehicles - Tom Wenzel

Dr. Wenzel provided the group with an overview of his project which
focuses on studying emissions from vehicles presently in use throughout
the country rather than new vehicle emissions because:

-   new car emission standards are 90-95 percent less than emissions
    from pre-control cars

-   vehicle miles traveled has doubled over the same time period, so
    overall emissions have been reduced by much less..

-   and "unregulated" sources of emissions now dominate overall
    emissions

####### Sources of Data on Vehicle Emissions 

####### EPA/CARB 

+-----------------------+-----------------------+-----------------------+
| **Test Method**       | **Pros**              | **Cons**              |
+-----------------------+-----------------------+-----------------------+
| -   EPA/CARB testing  | Consistent and        | Small samples,        |
|                       | detailed emissions    | recruitment problems  |
| -   certification     | measurements          |                       |
|                       |                       |                       |
| -   in --use          |                       |                       |
|     compliance        |                       |                       |
|                       |                       |                       |
| -   surveillance      |                       |                       |
+-----------------------+-----------------------+-----------------------+
| State IM Data         | Large representative  | Emissions not         |
|                       | samples of vehicles   | directly with FTP     |
| -   idle              | driven under real     | results               |
|                       | world conditions      |                       |
| -   remote sensing    |                       |                       |
|                       |                       |                       |
| -   loaded mode       |                       |                       |
+-----------------------+-----------------------+-----------------------+
| OBD                   | Large samples         | No emission data      |
+-----------------------+-----------------------+-----------------------+
|                       |                       |                       |
+-----------------------+-----------------------+-----------------------+

The current project focused on the IM 240 test method which measures
mass, different test durations and varying start conditions. Data is
being collected on state IM programs, with emphasis on the IM 240 data
(Arizona, Colorado and Wisconsin.).

Analyze Seasonal effects -- (ambient temperature, fuel composition) on
in-use emissions

-   In oxyfuel states, CO and HC are lower in the winter months

-   Winter CO and HC emissions in Colorado comparable to those in
    Arizona, even though Colorado has much lower temperatures

-   In reformulated gasoline states, CO and HC emissions are lower
    overall, with less seasonal variation

-   NOx trends similar in all three states studied (Arizona, Colorado
    and Wisconsin)

-   NOx is noticeably higher in warmer Arizona than colder Colorado or
    Wisconsin.

Evaluate Effectiveness of Enhanced IM Programs

-   Initial CO emissions reductions from Arizona IM program are
    comparable to those predicted by MOBILE5

-   Remote sensing data show initial emission reductions comparable to
    IM program

-   IM programs repairs are not durable. 40% of vehicles that fail
    initial test but pass final test (most of which are repaired) fail
    their initial test 2 years later

-   Large numbers of vehicles are escaping the program: 30% of vehicles
    that fail initial IM test never receive a passing IM test

-   Remote sensing data indicate that 30% of these "no final pass"
    vehicles are still being driven

# Future Analysis Include:

-   why do vehicles repeatedly fail IM

-   IM evaluations over multiple years in multiple states

-   Are new technology Tier 1 vehicles more durable than older vehicles?

-   Are average emissions by vehicle model consistent across different
    IM programs

### Center for Environmental Biotechnology, Dr. Jennie Hunter-Cevera

The Center for Environmental Biotechnology (CEB) at Lawrence Berkeley
National Laboratory was established in November, 1994. It coordinates
and facilitates interdisciplinary, multi-divisional and
multi-institutional research projects in the area of environmental
biotechnology. Both basic and applied research projects are being
carried out under three focus areas:

-   Biogeochemical Transformations

-   Environmental Diagnostics

-   Environmental Health Risk Assessment Based on Bioavailability

The Center is a joint collaboration with UC Berkeley and has
approximately 40 people working in the group. The Center encourages
project teams to extend their research by getting out to the field to
better understand how they can develop real-world solutions to
environmental problems.

The Center has taken a lead role in developing the advanced biological
program for the overall carbon management program. More to come.

#### Molecular Environmental Science (MES) at the ALS - Glenn Waychunas

The Advanced Light Source (ALS) produces the world\'s brightest light in
the ultraviolet and soft x-ray regions of the spectrum. The national
user facility is the first low-energy third-generation synchrotron
source in the world. The ultrabright light of the ALS provides
unprecedented opportunities for research in science and technology not
possible anywhere else. For the study of Microbial Environmental
Science, the ALS provides researchers with capabilities not available in
the lab:

1.  High flux rates allow study of very dilute systems, low
    dimensionality systems and transport systems

2.  Tunability allows spectroscopy over wide range (IR to hard x-rays)

3.  Brightness allows microimaging and microspectroscopy techniques for
    studying small regions or even more dilute systems

4.  Time structure allows for kinetic studies

######## Characterization, Risk and Remediation Using an Innovative Biopile

**Design at a Polish Petroleum Waste Lagoon - Terry Hazen**

Dr. Terry Hazen is the CEB lead for the bioremediation field program in
working with the Polish Institute for Ecology to develop a remediation
cleanup strategy for old refinery lagoon treatment systems. The goals of
the program are:

-   Demonstrate cost effective remediation of a refinery lagoon

-   reduce the risk associated with both the soil and lagoon water

-   remediate to a level which will support green grass

The lagoons date back to the early operations of the refinery (early
1900's). A complete site characterization was completed to provided site
data. Treatability tests were done to determine the optimum nutrient and
soil conditions to facilitate cleanup. A risk assessment was performed
to identify parameters of concern. A treatment program was developed
which included different types of aeration to increase microbial
activity (bioventing application).

For additional information, please contact Dr. Hazen directly.

######## Electrochemical Acceleration of Bioprocesses for Remediation and

**Production - John Kerr**

Electrochemical bio-catalysis can be used to enhance cell growth
resulting in increased toxics reduction. The objectives of the program
are:

-   Demonstrate that electrochemical methods of energy delivery to
    chemical and biological systems are clean, selective, energy
    efficient and bio-compatible

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-   Make the connection between electrode surfaces and biological
    systems by the design of appropriate electron carriers

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-   Demonstrate delivery of nutrients to systems by electrochemical
    control of electrolytes

Management of the electrolyte systems is critical to success of the
process. If not controlled properly, the contamination can actually get
worse, rather than better. The process has been used successfully on a
TNT site cleanup with ideal

conditions. They are currently working to validate the study and develop
the process by:

-   Monitoring biological activity

-   Estimate impact on diversity

LBNL is working jointly with GO Kinetics to develop the electrokinetic
treatment process and have secured several patents in the area.

#### PAH Biotransformations - William T. Stringfellow

Dr. Stringfellow is studying the biotransformation of PAH compounds,
specifically in the following areas:

1.  MTBE biodegradation

2.  Biogeochemistry of mixed wastes

3.  Partial transformations of petroleum hydrocarbons

-   crude oil upgrading

-   monitoring intrinsic remediation

Monitoring intrinsic remediation -- Taking the concepts of intrinsic
remediation for BTX compounds and applying to PAHs. Technical
difficulties of this approach are: slow rate process precludes the
normal monitoring parameters of CO2, nutrients, etc.

Business Impact - Proving PAH turnover and reductions could save
millions of dollars on property transfers (petroleum industry
applications).

Experimental Hypothesis

-   During periods of active PAH degradation, there will be a standing
    pool of labile (intermediate products) PAH degradation products in
    contaminated soils

-   Measurement of labile intermediates in soils can be used to indicate
    active metabolic turnover of PAH

Preliminary work in the lab is developing methods for measuring fatty
acids and known PAH metabolites. Early work is looking at metabolites
from lab experiments on known compounds and samples from Chevron PERF
project experiments.

Proposed research efforts include:

-   Finish first round of methods development

-   Apply methods to contaminated soils undergoing active remediation

-   Signature compounds for metabolite analysis

-   Apply methods to developing intrinsic remediation protocols

Dr. Stringfellow requested guidance from the PERF members on program
direction, objectives, etc. and support for future funding for the
planned research.

Treatment of Agricultural Drainage for Selenium and Nitrate Removal
Using an Algal-Bacterial Pond System - Nigel Quinn

The Grassland Bypass project area are working together to manage the
amount of selenium discharged from agricultural drainage. The goal of
the project is to develop a cost-effective treatment technology
(\$150/acre-ft) which is easy to operate. The objectives of the project
are to:

-   Determine unit process configuration that maximizes selenium and
    nitrate load reduction

-   Determine carbon source and feed rates to optimize bacterial growth
    and viability

-   Determine maximum seasonal drainage influent loading without
    breakthrough

-   Install real-time sensors and develop operating guidelines for plant
    operation

The site involves a two-pond process system having a 40-day residence
time and requires CO2 and phosphate to stimulate algae growth. The North
system uses feed grade molasses as carbon source. The molasses as a
carbon source was critical for maximum treatment removal as the system
was carbon limited. Dentrification and Selenium removal in the reduction
pond observed 93% nitrate removal and 80% Se removal.

Ongoing research is focused on improving system performance and
cost-effectiveness of Se removal.

######## Engineering Metabolism and Biofilms for Bioremediation and

**Environmentally-Friendly Synthesis - Jay Keasling**

Dr. Keasling's work focuses on metabolic engineering which is the
redirection of enzymatically-catalyzed reactions for the production of a
new compound or the degradation of a compound. It can involve the
genetic modification of a single organism or the engineering of a
consortium of organisms. He is currently studying the application of
metabolic engineering for the following areas:

1.  Biodesulfurization of fossil fuels

-   Dibenzothiophene is typical of the organic sulfur compounds found in
    fossil fuels and is recalcitrant to hydrodesulfurization

-   FMN reductase may be a limiting factor in biodesulfurization removal
    rates

2\. Engineering Biofilms for Bioremediation

-   May be necessary if metabolism is too complex to manipulate
    genetically

-   May be more useful for biodegradation

-   Issues to consider (pattern formation, mass transport, microbial
    transformation)

######### Please visit his website for more information 

[www.cchem.berkeley.edu/\~jdkgrp](http://www.cchem.berkeley.edu/~jdkgrp)

**Assessing Petroleum Hydrocarbon Remediation by SR FTIR
Spectromicroscopy - Hoi-Ying Holman**

Dr. Holman provided the group with an overview of her work in developing
SR FTIR spectromicroscopy for assessing petroleum hydrocarbons for
remediation. SR FTIR Spectromicroscopy Techniques advances the
capabilities of the researcher by:

-   Enables monitoring and mapping of biological and chemical reactions
    as they occur in systems with environmentally relevant
    concentrations

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-   Non-destructive, in-situ, real-time microprobe

-   high signal intensity at a spatial resolution of 10 microns or finer

The technique can be used to develop a mapping of the intrinsic microbes
found on a sample of interest. The mapping data is very powerful in that
it can be used to generate a spectral image map for specific compounds
thought to be in the degradation pathway.

# The method is being developed to detect human exposure to aromatic hydrocarbons or dioxins. The current techniques for studying cell exposures to toxicants, RT-PCR, is very labor intensive and lengthy process. A study was conducted to determine if SR-FTIR could be used to replace the RT-PCT process. A study was conducted to determine the intracellular responses to dioxin or PAH's by following the biomarker: CYP1A1, which is a global biomarker for exposure. The results of the study were successful in developing a correlation between the new IR technique with the RT-PCR technique. 

Summary

1.  Synchrotron-based FTIR spectromicroscopy provides new and
    complementary scientific information from non-destructive, real-time
    monitoring of:

-   microbial and chemical reactions in environmental matrices

-   intracellular biological responses to low-dose exposures

2.  This information permits cost-effective and rapid:

-   evaluation of remediation processes as they occur

-   determination of acceptable risk-based cleanup levels

Further work remains on animal testing to validate the method.

Towards Human Health Hazard Assessment of PAHs - Regina Goth-Goldstein

Dr. Goth-Goldstein provided the group with an overview of her work on
human health of PAHs. Her work focuses on the problem of how to quantify
the human health risk of hydrocarbons in contaminated soil through human
ingestion. The concern is ingestion of contaminated soil by children
playing in the soil.

Project Goal -- to develop and validate methods for rapidly determining
the amount of systemically available hydrocarbons to provide relevant
information for the risk assessment process.

Factors Impacting the Ingestion Pathway:

-   Determination of Intestinal availability - Solubilization of
    soil-bound PAHs under simulated intestinal conditions. Results of
    the study indicate the following factors were important;

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-   Soil properties

-   Properties of PAHs

-   Concentration of contamination PAH

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-   Determination of Systemic Availability:

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-   Measuring intestinal transport of hydrocarbons in a cell culture
    system

-   In-vitro model for intestinal uptake into the bloodstream was used

-   Rate of permeation of PAHs across the intestinal cell layer is a
    function of PAH concentration

-   Significant metabolic transformation and detoxification of PAHs
    occurs presystemically in the intestinal cell layer

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-   Metabolic Transformation -- activation and detoxification

Biomarkers of Exposure to PAHs -- a global biomarker for presence of
PAHs is the induction of CYPIAI, an enzyme involved in the metabolism of
PAHs. An experimental assay was developed to detect PAH compounds and
dioxin. The experimental procedure is being developed to take a sample
of contaminated soils to ultimately arrive at an estimate of how much
available PAHs are available for ingestion.