As an analytical chemistry professor with
extensive background and contribution to the field of environmental,
clinical and forensic sciences, I will be pleased to accept
prospective students into my research group, where one may
tackle one of the challenging questions listed below:
I. Development and application of analytical methods
for environmental essays.
After the definition of a specific (micro-) ecosystem of
interest, the identification and quantification of its chemistry,
particularly its anthropogenic substances are quite essential.
This in many instances is the pre-requisite toward better
understanding, monitoring and characterizing such ecosystem.
Efforts will be made to adhere to EPA prescribed methods,
namely EPA 500 and 600 series. Specifically, volatile, semi-volatile
and chlorinated organic substances in a matrix of interest
will be separated, identified and quantified.
There are, however, occasions where the analysis of a sample
of interest may not be routine in nature; for example, extracts
from living organisms. In such cases, one must devise a careful
method by which the sample constituents could be identified.
Even though biosensors are not yet employed as the standard
EPA prescribed methods, one could nonetheless, envisage the
promising potential for their application as state-of-the
art tools for real-time monitoring of environmentally important
substances and metabolites. There are also other promising
applications in fields like Forensics and QA/QC monitoring.
A biosensor is defined as a molecular recognition component
coupled with a transducer.
The bio-molecular component may include :
- Cellular component
The transducer component may include:
(An optical fiber connected to a spectroscope)
(For measuring heat exchanges associated with a (bio-) chemical
(Microbalances to measure mass (ex-) changes associated
with a selective reactions)
(To measure electron exchanges associated with a redox reaction)
Generally speaking, the specificity of a biological element
when coupled with the molecular selectivity of a membrane
will provide a highly sensitive optimum condition where sample
pre-treatment or separation is not necessary. Our previous
track record in the exciting field of biosensors will enable
us to continue devising new sensors for novel applications.
One could mention ease of operation, sensitivity, selectivity,
stability, real-time capability, and cost effectiveness of
biosensors as some of those advantages over classical methods.
III. Persistence, Bioaccumulation and Toxicity
By David N.
Rahni and John Morelli
According to Chemical Abstract Service, published by the
American Chemical Society (ACS), there are currently over
17 million registered substances. That compares to over a
million words in the entire English Language! This vast library
of chemicals includes both naturally occurring and synthetically
manufactured materials (1). The number of chemicals, produced
in the US
since the mid 70's, is over 70,000. Of these, 15,000 were
manufactured in quantities with potential environmental impact
(2). This resulted in 306 million tons of hazardous waste
and 3.2 billion pounds of toxic chemicals (3,4). In light
of such vast number of potential chemicals with future anthropogenic
toxic output, a systematic method of ranking chemicals on
their environmental impact and health risk is essential. The
U.S. Environmental Protection Agency (EPA) is currently reviewing
a software package to assist such a ranking.
Chemical Manufacturers Association has prioritized this challenge
in a report entitled How Persistence, Toxicity, and Bioaccumulation
(PTB) are Defined and Used in Chemical ranking System (CMA
Report on PTB, March 24, 1995).
The EPA is committed to making pollution prevention the guiding
principle of the Agency’s environmental efforts. The
1984 Amendments to the Resource Conservation and Recovery
Act and the 1990 Pollution Prevention Act set in policy the
preference for source reduction over waste management. The
EPA administrator, Carol M. Browner, reaffirmed this commitment
with the release of the "Waste Minimization National
Plan" on November 18, 1994, which outlined the EPA’s
major goals, objectives, and action items to pave the way
toward national reductions in the generation of hazardous
waste. Of importance here, is the goal to reduce, as a nation,
the presence of the most persistent, bioaccumulative, and
toxic constituents by 25 percent by the year 2000 and by 50
percent by the year 2005. While the EPA does not expect that
each and every generator reduce PTB substances in hazardous
waste to this degree, it is, nevertheless, likely that at
some future juncture the pressure to reduce will be inevitable.
This pressure will most likely take the form of international,
national, and local legislation, monitoring, and compliance.
An example of the complexity of issues and challenges facing
the global business community was the extensive deliberation
on limiting Green House gases at the Conference on Global
Warming in Kyoto,
Japan in December 1997.
Beyond the legislative and regulatory pressure, there are
market driven factors to induce voluntary compliance with
adopted standards. An example of recent voluntary compliance
with adopted standards is the recent worldwide success and
acceptance of ISO 9000 series that deal with quality assurance,
and quality control systems management since 1987. Correspondingly,
a new series of environmentally related standards for industry
are the ISO 14,000 series. In October of 1996, the International
Standard Organization released a set of international standards
for environmental management called ISO 14000. These standards
are deemed to revolutionize the way both corporations and
government approach environmental issues and natural resources
consummations (e.g., energy and raw materials). Furthermore,
such standards will provide a common language for environmental
and natural resource management, thereby establishing a framework
for third party regulation of environmental management systems,
and helping industry satisfy the demands of consumers and
regulatory agencies for corporate environmental accountability.
ISO 14000 series can only be applied in a truly integrated
multi-disciplinary team approach comprised of scientists,
engineers, plant managers, legal, regulatory safety and accounting
staff to name a few.
EPA outlines the objectives of the Waste Minimization National
Plan (5) as follows:
To reduce, as a nation, the presence of the most persistent,
bioaccumulative, and toxic constituents by 25% by the year
2000 and by 50% by the year 2005.
To avoid transferring these constituents across environmental
To ensure that these constituents are reduced at their source
whenever possible, or, when not possible, that they are re-cycled
in an environmentally sound manner
Such targets are national in nature, in that each corporation
would define its own baseline, and demonstrate improving trends
to contribute toward national targets on a voluntary basis
at this time. The EPA guidelines set objectives as follows:
Develop a framework for setting national priorities; develop
a flexible screening tool for identifying priorities at individual
facilities; identify constituents of concern.
EPA currently offers a beta-test version of a software package
which will prioritize chemicals according to their persistence,
bioaccumulation, toxicity, and quantity. We will evaluate
this package for those classes of chemicals that are of the
highest priority by the Grantor for specific purpose (6).
The chemical stability of PCBs is paralleled by their environmental
stability and potential for environmental transport and it
is evident from analytical surveys that PCBs are the most
ubiquitous chemical pollutant in the global ecosystem (7).
Several reports suggest that the toxicity of PCBs is structure
dependent (8). A global model to track the distribution of
PTBs (9) using chlorophenolic compounds were chosen to illustrate
the transport of PTBs . The model is applicable to any other
similar substituents. It is generally accepted that there
are three basic components of a hazard assessment of organic
compounds discharged into aquatic environment persistence
to both abiotic and biotic degradation; partition from the
aquatic phase into the sediment phase and into biota, and
toxicity to biota (10).
The currently practiced regulation is that a newly manufactured
substance can be marketed and released without any initial
approval. In the United States, for instance, if the EPA can
not determine an industrial chemical’s suitability for
the market within 90 days of submission, that chemical is
automatically approved under the Toxic Substance Control Act.
There is no minimum data requirement. Given the half a million
dollars expense, at a minimum, and the two to five years required
to test a single chemical for long-term effects, such testing
is inevitably limited (10). We however, predict that with
rapid advances in computer modeling, more versatile testing
methodology, and the public pressure, that such exhaustive
testing may be required soon as a pre-requisite toward approval.
This does not even take into consideration the synergistic
effect of chemicals on human health and ecological status.
For instance, John MacLachlan of Tulane-Xavier Center for
Biomedical Research and his colleagues recently showed that
two weakly estrogenic chemicals, when used in combination,
were up to 1,600 times more potent than when each was used
alone. And pesticides such as malathion and other organophosphates,
when administered simultaneously are up to 50 times more toxic.
In light of the rather large number of chemicals used in society
today, it is almost impossible to test all of the combinations
to which we are routinely exposed. To test the 1,000 new chemicals
released each year just in the possible combination of three,
would require more than 166 million tests, each for a two
year study, to assess the long-term effects such as cancer
and endocrine disruption. Yet, in the US only 500 tests are
undertaken each year, thereby leaving more than166 million
tests left for the following year! Automated Combinatorial
techniques may revolutionize this lag time (11)
A model for screening, ranking and scoring chemicals by potential
human and environmental impacts have been reported (12). Among
all substances, perhaps, PCBs, Dioxins, and organophaosphates
are the most extensively studied ones in terms of toxicokinetics,
and PTBs (13, 14)
Currently, bioaccumulation is screened as a measure of the
lipophilicity of a compound.
Lipophilicity is the tendency of a substance to be attracted
primarily by a non-polar, usually
organic solvents, in contrast to hydrophilic substances, which
are attracted by polar solvents such as water. As a measurement
unit of lipophilicity, most often the partition coefficient
between water and n-octanol is taken and designated as Pow
or Kow (or Ko/w). The relationship between
the steady state bioconcentration factor (BCFs)
and Kow has been found many times to follow a logarithmic
regression of the form:
Log BCFs=aX log Kow+ b
Work by Bronson et al. in 1994 outline two step strategy
for assessing the ecotoxicological aspects of complex wastewater
from a chemical-pharmaceutical plant. All substances were
classified on the basis of environmental effects using acute
toxicity, biodegradation, and bioaccumulation criteria. The
first step is to utilize a chemical-oriented strategy. This
strategy utilizes data on discharged amounts of material from
the plant and ecotoxicological data for each compound. Discharge
amounts can be estimated using mass balance calculations or
through actual analytical measurements of water phase effluents.
In this phase, ecotoxicological data for each compound is
available. For water phase effluents with less defined chemical
characterization or ecotoxicological data, an extensive characterization
program, including chemical analyses, acute toxicity testing,
and ecotoxicological parameterization, is required to assess
environmental risk. Bronson et al. showed that while toxicity
and bioaccumulating organic compounds were very low, and easily
degraded by activated sludge, the presence of individual chemicals
with high toxicity at low concentrations had measurable unfavorable
effects. The end result is that standard bulk chemical (AOX,
EOX, DOC, TOC, etc.) and biological testing alone cannot accurately
predict bioaccumulation, toxicity, and persistence of plant
effluents. A screening of water effluents for bioactivity/toxicity
with these bulk tests followed by a characterization program
using mainly available ecotoxicological data for chemicals
discharged to wastewater when available or a limited set of
ecotoxicological test when such data is absent is necessary.
The foundation of the persistence, toxicity, bioaccumulation
data is analytical measurements. Myriad methods for determining
specific levels of compounds in a variety of media including
soil, animal and plant tissues must be applied. Much of this
might be presented in the literature; therefore, a thorough
literature search will be conducted to identify such methods.
For materials and matrices that are not represented in the
literature model methodology would be developed or proposed.
For one system of Grantor’s choice this methodology
would be demonstrated.
a. Persistence & Bioaccumulation Issues
b. Analytical Chemistry and Method Improvements
c. Review of current data on specific manufactured Chemicals
Biology Causation Section
A review on Human data, Animal Data, and Ecosystem Data
On those specific class of up to four chemicals specified
by the grantor, and with emphases on aquatic and microbial
ecology will be prepared.
EPA in concert with other Federal and State Agencies have
enacted a series of Legislation
On National Waste Minimization Strategies, with Persistence,
Bioaccumulation and Toxicity as their main objects.
Certain steps to standardize chemical sale internationally
have already been taken. Prior Informed Consent (PIC) Treaty,
a proposed Convention that would require exporting countries
and corporations to provide information on whether the chemical
that they are exporting is restricted or banned nationally,
is expected to be considered by early 1998(11).
Pace University’s LL.M. Environmental Law program is
consistently recognized by external peers such as US News
&World Report as being among the top three in the
One of the Principal Investigator of this proposal, David
N. Rahni has taught in this program, he is currently serving
students from this program, and he has a close on-going collaborative
relationship with several colleagues from the Environmental
Law School Dean, Richard Ottinger, a past eight times US
Congressman who was instrumental in drafting and legislating
most of the Federal laws on the environment in the 60’s
and the 70’s has been a close colleague. Dive Sie, the
Guru of environmentalism is a Professor-in-Residence at the
Law School as well. One of our Law colleagues was representing
Texaco in the Valdez, Alaska oil accident.
Professor Nicholas Robinson is an internationally renowned
Environmental Law expert who is currently leading many activities
in the former Soviet Union and East European Countries. Such
efforts will ultimately lead to environmental legislation
and regulation in these countries.
We will draw upon such intellectual resources, in particular
that of Professor Robinson to research, investigate, and prepare
an annual report on EPA National Waste Minimization Act, its
trends, and its pertinent regulations and requirements. Particular
emphasis will be placed on those up to four specific classes
of compounds of interest to the Grantor.
1. Chemical &Engineering News, October 5, 1997.
2. U.S. Congress. 1995. Screening and testing chemicals in
commerce. OTA-BP-ENV-166. Background Paper. Office of Technology
Assessment, Washington, DC.
3. 1991 Biennial Report Data, US EPA
4. 1992 Toxic Release Inventory; Public Data Release,"
US EPA, EPA 745-R-94-001, April 1994.
5. The Waste Minimization National Plan, EPA, November 16,
Password: Your Internet address
7. S. Safe, L. Safe, M. Mullin Polychlorinated Biphenyls:
Congener-Specific Analysis of a Commercial Mixture and a Human
Milk Extract. J. Agr. Food Chem. 1985, 33, 24-29.
8. Poland and Knutson, et al 1977-85)
9. F. Wania and D. Mackay, Tracking the Distribution of Persistent
Organic Pollutants Env. Sci and Tech., Vol 30, No. 9, 390A-396A,1996
10. Neilson, A.S. Allard, P-A. Hyanning, M. Reberger Env.
Sci. Technol. Vol. 28, No. 6, 278A-287A,1994
11. J. D. Mitchell, Nowhere to hide: The global spread of
high-risk synthetic chemicals, World Watch Institute (1997)
12. M.B. Swanson, G.A. Davis, L.E.Kincaid, Environmental
Toxicology and Chemistry, Vol. 16, No. 2, pp. 372-383, 1997
13. M. Van den Berg, J. de Jongh, H. Poiger, J. R. Olson
Critical Reviews in Toxicology, 24(1):1-74 (1994)
14. V. McFarland, J.U. Clarke, A. B. Gibson Changing Concept
and Improved Methods for Evaluating the importance of PCBs
and Dredged sediments contaminants, Report D-86-5, US Dept.
Army, US Corp of Engineer, 1986
In response to above Plan, the Chemical Manufacturers Association
(CMA) is in the process of developing a comprehensive strategy
of programs and tools that define a risk based approach for
the quntitation of persistence, toxicity and bioaccumulation
of chemicals manufactured. The current accepted method of
extraction followed by spectroscopic method is inadequate
at best. We plan to understand the current methodology. We
then plan to devise chromatographic based mass spectrometric
methods to assess PTB. Such methods when fully developed must
replace the current insensitive methods.
This is an interdisciplinary approach to manufacturing, where
environmental and natural resource conservation objectives
will be met while economic development considerations are
still satisfied. Even though based on scientific and technological
breakthroughs of the 21st century, it involves environmental
accounting and reporting, environmental law, regulation, monitoring
and compliance, environmental policy, etc.
V. Sustainable Development, Intergenerational
Equity and Internationalization as a vehicle for moving the
VI. Other Scholarly Activities
- Synthesis and Conformation of Chiral Seven- and Eight-Membered
Germanium, Phosphorous Heterocyclics;
- Nano-Engineering and Electrodeposition of Compositionally
- Process Analytical Chemistry and Manufacturing Engineering.
- Environmental and clinical forensics
|Mathieu Orfila (1787-1853),
the Founder of Modern Forensic Toxicology
Paul L. Kirk (1902-1970), the American Founder of Forensic
PROPOSED PLAN OF ACTIVITIES
By David N. Rahni
The science of analytical chemistry has undergone
through tremendous growth within the past decade.
However, advanced instrumentation and detection technologies
have not been fully integrated into the forensic science.
In particular, portable detection technologies applicable
to environmental forensics, will be a major focus
in the next decade.
COLLECTION OF EVIDENCE
- Sampling and its stabilization
- Sample reconstitution
- Statistical and Probability tools
- Calibration (Instrument, methodology)
- Method development, validation, and verification
- Parallel, independent analysis and correlation
(e.g., RFLP, STR)
- Computation, calculation, biometrics, chemometric,
statistically and probabilistically based error
analysis, and data interpolation
- Exploration, Recognition, and Promotion of the
Latest Methodologies and Technologies
- Standardization (e.g., ISO 9000 and 14,000 series,
- Accreditation (Am. Soc. Crime Lab. Dir./Lab.
- Appropriate pedagogical approach to training professionals
with and, or without science backgrounds
- Lab and field methods inauguration
- State and local lab assistance implementation
- 23+ International lab installations
- DNA typing
- Collection of evidence
- On site field assessment
- Modes of training: on-site, off-site, CD-ROM,
Distance learning technology (e.g., Internet as
a medium,) synchronous and, or asynchronous video
interactive technology, simulations, tutorials.
- LEGAL: Expert witness training at the interface
of science and law; Educating judges, prosecutors,
attorneys, jurors, and the public at-large.
RESEARCH AND DEVELOPMENT (applied)
- Pro-active and pre-emptive detection and deterrence
- Portable instrumentation technologies for Environmental
- MSDNA (4,000-20,000m/z)
- Field detection Sensor technology, and new instrumentation
- Cell separation, DNA processing and hybridization,
based on dielectric variations on a chip.
- Chip-based degenerate oligonucleotide primed
polymerase chair reaction (DOP-PCR) for 250 bp.
- Standardization of Forensic Science Assays, analyses,
- DNA typing library databank (e.g., CODIS, DRUGFIRE)
- Thermal cycler DNA preparation and other methods
(e.g., PCR amplification, HPLC-Fluorescence, HPLC-Electrospray-MS/MS
used for drugs in hair)
- Combinatorial chemistry and analytical automation
(100,000 assays per day soon)
- High Performance Iso-electric Focusing Capillary
Electrophoresis, & capillary electro-chromatography
- Mass Spectrometry (e.g. MALDI-TOF-MS, or Electrospray-MS)
- Refining and streamlining DNA profiling
- Imaging and Surface Characterization Technology
(SEM, STM, TEM, X-ray Fluorescence, Optical and
Fluorescence Microscopy, SFM)
- Capillary Electrophoresis with laser induced
fluorescence down to attomole, i.e. single cell
- Identification and adoption of the latest instrumentation
for forensic science applications.
- The April 29 signature by the US on Chemical
Weapon Convention, will lead to tremendous need
in development of chemical and biological arms detection
and assessment technologies.
- Environmental Forensics.
- Prepared to serve as a liaison on public issues
at the pleasure of the Lab. & Training (TBD)
- Communication with other government agencies
(NSF, NIH, DOD, DOE, ATF, NIST, DEA, Armed Forces,
etc) to define and prioritize Forensic Science R&D
through grants and other incentives to academia,
government labs, and corporate world.
- Communication with corporate world in promoting
the development and offering of instrumentation
and methodology to the field of forensic science,
an integral support component of crime prevention
and law enforcement.
- Attaining the plateau of learning curve in context
in a reasonable time frame
- Utilizing human relations principle with mutual
respect, interpersonal skills, communicative skills,
multi-tasking abilities, meeting deadlines, responsibility
and accountability concept, professional integrity
to further enhance the fulfillment of the Mission.
- Recognizing the best talents and potentials in
colleagues and peers, and then support them best
in realizing the team’s goals.
- Utilizing one’s interdisciplinary academic,
teaching, and research track records in a wide array
of natural, physical, and engineering fields.
- Build further on one’s administrative and
service leadership track records.
- Promoting of, and providing leadership to Professional
Societies of Forensic Chemistry and Science.
- Contributing on Public Relations, image, standardization,
certifications, and continuing education.
- Articulating and facilitating extramural R&D
and technology transfer as applied to forensic science.
- Contributing toward accreditation, and methods
and protocol standardization.
- Contributing toward physical plant construction,
renovation, and procurement and maintenance of analytical
- Providing leadership in further enhancing Symposia
proceedings in forensic science, particularly environmental
- Contributing scholarly manuscripts, reviews and
communications internally and when appropriately
authorized to professional journals and the scientific
Restriction Fragment Length Polymerization
Technical Working Group for DNA Analysis Methods
The basic analytical procedure involves the following
- Digestion of extracted DNA with restriction enzyme
- Amplification of DNA
- Electrophoretic separation of the resulting bands
with agarose slab gel.
- Southern blot immobilization of separate fragments
onto nylon mesh.
- Hybridization with radiolabeled specific sequences
of DNA (probes).
- Autoradiographic visualization of labeled DNA
fragments hybridized to their specific complements
- Determination of relative position of calibration,
i.e., sizing ladder.
- Sample bands on the autoradiogram.
- Calculation of the apparent molecular weights
as expressed as number of base pairs (bp).
Source: JAMES L. MUDD et al Anal Chem. 1997, 69,
1882-1892, and references therein.