NEIC
EPA-330/1-81-002
CAPABILITIES OF STATE LABORATORIES IN THE FEDERAL/
STATE COOPERATIVE ENFORCEMENT GRANT PROGRAM
Prepared by:
PEPIR SUBCOMMITTEE ON ANALYTICAL/TESTING ACTIVITIES
March 1981
National Enforcement Investigations Center, Denver
Office of Enforcement
-------
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
EPA-330/1-81-002
CAPABILITIES OF STATE LABORATORIES IN THE FEDERAL/
STATE COOPERATIVE ENFORCEMENT GRANT PROGRAM
Prepared by:
PEPIR SUBCOMMITTEE ON ANALYTICAL/TESTING ACTIVITIES
March 1981
Subcommittee Members:
Robert Schneider
Dean Hill
James Minyard
Ronald Thomas
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
Denver, Colorado
-------
CONTENTS
EPA REGION I 1-1
GENERAL 1-1
OVERVIEW OF LABORATORY CAPABILITY 1-1
SPECIFIC STATE LABORATORY CAPABILITIES ' 1-2
REGION I - TABLE 1-11
EPA REGION II II-l
GENERAL II-l
OVERVIEW OF LABORATORY CAPABILITIES II-l
SPECIFIC STATE LABORATORY CAPABILITIES II-2
REGION II - TABLE 11-10
EPA REGION III III-l
GENERAL '. . III-l
OVERVIEW OF LABORATORY CAPABILITIES III-l
SPECIFIC STATE LABORATORY CAPABILITIES III-3
REGION III - TABLE 111-17
EPA REGION IV IV-1
GENERAL IV-1
OVERVIEW OF LABORATORY CAPABILITIES IV-1
SPECIFIC STATE LABORATORY CAPABILITIES IV-3
REGION IV - TABLE IV-24
EPA REGION V V-l
GENERAL V-l
OVERVIEW OF LABORATORY CAPABILITIES V-l
SPECIFIC STATE LABORATORY CAPABILITIES V-2
REGION V - TABLE V-15
EPA REGION VI VI-1
GENERAL VI-1
OVERVIEW OF LABORATORY CAPABILITIES VI-1
SPECIFIC STATE LABORATORY CAPABILITIES VI-2
REGION VI - TABLE VI-14
EPA REGION VII VII-1
GENERAL '. . VII-1
OVERVIEW OF LABORATORY CAPABILITIES VII-1
SPECIFIC STATE LABORATORY CAPABILITIES VII-2
REGION VII - TABLE VII-10
EPA REGION VIII VIII-1
GENERAL VIII-1
OVERVIEW OF LABORATORY CAPABILITIES VIII-1
SPECIFIC STATE LABORATORY CAPABILITIES VIII-2
REGION VIII - TABLE VIII-10
EPA REGION IX IX-1
GENERAL IX-1
OVERVIEW OF LABORATORY CAPABILITIES IX-1
SPECIFIC STATE LABORATORY CAPABILITIES IX-2
REGION IX - TABLE IX-9
EPA REGION X X-l
GENERAL X-l
OVERVIEW OF LABORATORY CAPABILITIES X-l
SPECIFIC STATE LABORATORY CAPABILITIES X-2
REGION X - TABLE X-6
APPENDIX
-------
INTRODUCTION
Pesticides Enforcement Program Internal Review (PEPIR) was initiated
by the U.S. Environmental Protection Agency's Deputy Assistant Administra-
tor for General Enforcement to review and evaluate EPA/State pesticide
enforcement operations. A PEPIR Committee was established under the di-
rection of the Pesticides and Toxic Substances Enforcement Division (PTSED).
The specific charge of this Committee was to determine if EPA headquarters'
policy and guidance, along with Regional and State implementation of pesti-
cide enforcement, are effective.
Committee members are from the Program Operations, Scientific Support,
and Policy and Guidance Branches of PTSED; Regional Pesticide Branches and
the National Enforcement Investigations Center. Activities of the Committee
have been assigned to six subcommittees, each chaired by a Committee member.
These are: Investigation and Sampling Activities (Mitchell Wrich); Analy-
tical and Testing Activities (Robert Schneider); Case Review and Enforce-
ment Actions (Bruce Granoff); Recordkeeping and Reporting Systems (Kenneth
Gutterman); Grants Administration (William Danson); and Planning, Guidance
and Servicing Activities (Jack Neylan).
This report was prepared by the Analytical and Testing Activities Sub-
committee to provide the PEPIR Committee with an evaluation of equipment
and personnel in State pesticide laboratories operated under grants adminis-
tered by EPA. The contents of this report are based upon information sub-
mitted to the Subcommittee in a questionnaire titled "Pesticide Laboratory
Profile " [Appendix]. In some cases, it will be necessary to confirm or
clarify information submitted by the State laboratories; therefore, this
report is subject to revision by the Subcommittee, PEPIR Committee, or the
Agency. Review from individual State pesticide laboratory officials will
be solicited before a final report is published.
-------
1-1
STATE PESTICIDE FORMULATIONS AND RESIDUES LABORATORIES
ANALYTICAL SCIENTIFIC CAPABILITIES
EPA REGION I
GENERAL
Currently, all six New England states have pesticide enforcement grant
agreements with EPA. Each state has been provided funding for pesticide
formulation and residue laboratory analytical services. Program evaluation
discussed below is based upon information contained in the PEPIR laboratory
questionnaire returned to EPA by each participating state, and correspon-
dence from EPA Region I Pesticide Branch.
OVERVIEW OF LABORATORY CAPABILITY
Vermont has had a limited laboratory capability because it is staffed
by one chemist with limited experience, and only recently acquired instru-
mentation as an HPLC, UV, and Digital Electronic Balance. Laboratory staff
and equipment in the other grant-aided States in Region I range from ade-
quate to excellent. Two chemists and a technician are employed in the pes-
ticide laboratories in New Hampshire and Rhode Island while Connecticut has
three chemists and a technician. With the exception of Vermont (chemist
has 1% years' experience), the senior chemists in the Region I State lab-
oratories have 14 to 16 years' experience.
Rhode Island and New Hampshire appear to have laboratories equipped
and staffed to do routine pesticide analyses. Both have limited capability
in confirmatory analysis. The Connecticut laboratory is well equipped with
modern instrumentation including GC/MS capability. They appear capable and
adequately staffed to analyze a wide variety of pesticide products.
Maine Department of Agriculture has an agreement for pesticide analy-
sis with the Maine Public Health Laboratory (MPHL). Limited information is
available because no profile (completed PEPIR questionnaire) was provided
-------
1-2
to EPA; however, it is known that the laboratory has two chemists with ex-
perience in GLC instrumentation and recently they submitted acceptable re-
sults in a Formulation Check Sample Study in which they participated.
Currently, the Massachusetts Department of Food and Agriculture (MDFA)
has a provisional agreement where Maine provides laboratory services for
pesticide analyses. A contract for these same services between MDFA and
the University of Massachusetts Medical School in Worcester is imminent and
is expected to be in effect by April 1981.
Consensus among the State laboratory staffs was the need for more
training, especially on instrumentation such as TLC or HPLC, to strengthen
their capability for confirming pesticide analyses.
SPECIFIC STATE LABORATORY CAPABILITIES
Attached to this detailed analysis is a comparative tabulation of ca-
pabilities in the Region I State pesticide laboratories operating under EPA
grants.
Vermont
The laboratory is operated by the Vermont Department of Agriculture at
Montpelier. Mr. Robert N. Mullen is the Laboratory Director while Rudolph
Polli is the Chief Agricultural Chemist responsible for all pesticide ana-
lytical work. Mr. Polli is a new employee with 1% years' experience in
pesticide analysis. He holds a BS degree and has done several years of
graduate study also.
Laboratory activities other than pesticide residue and formulation
analyses include meat analysis, serology, and routine milk products analy-
ses. Thus, the time allotted for pesticide analyses appears very limited
and apparently will remain so until the Vermont laboratory is adequately
staffed to perform routine pesticide work along with other'assigned tasks.
-------
1-3
The laboratory receives a variety of pesticide products for analysis
including insecticides, herbicides, fungicides, plant growth regulators,
rodenticides, home and garden mixtures, antimicrobials, repellents, and
various pressurized containers or devices. Because the program is in its
developmental stages, only 26 samples were analyzed last year (since
April 16, 1979).
Laboratory equipment is new (under 1 year old) but limited. On hand
are two balances (analytical and top-loading), a pH/millivolt meter, an in-
frared spectometer, UV spectrometer, HPLC, and a gas chromatograph. Ac-
cording to the PEPIR questionnaire information, the GC has not been in-
stalled in the laboratory but should be functioning in the near future. It
is equipped with ECO, NPD, and FID detectors and has a Sigma 10 data sta-
tion with basic and magnetic tape capacity. The Vermont laboratory plans
to purchase columns and packings for their GC instrument from the Perkin
Elmer Company.
Vermont reported excellent chain-of-custody procedures. Samples are
officially sealed and transported to the laboratory in plastic bags by in-
spectors. At the laboratory, the incoming samples are dated and inspected
for general condition and seals. Once samples are unsealed for analyses
they are either in the immediate possession of the analyst or are kept
\
under lock and key. Standard solutions, reference standards, records,
documents, work sheets, and notebooks are kept under lock and key when not
in use also. Sample storage areas are locked and posted off-limits to
non-authorized personnel.
Vermont plans to participate in the AAPCO check sample program for
pesticide formulations. Official AOAC or other standard methods of analy-
sis are available to confirm violative samples. Routinely, the analyst
performs true duplicate tests to determine results of potentially violative
samples. Whenever possible, violative samples are verified for more than
one subsample. No second analyst is available at the Vermont laboratory to
recheck potentially violative samples so the analyst often consults the EPA
Beltsville laboratory to confirm tests.
-------
1-4
EPA Beltsville is the principal source of possible standards used in
the Vermont laboratory for formulation and residue analysis. The labora-
tory recently acquired some technical and analytical standards but is in
need of additional standards to complete their supply.
To date, the laboratory relies upon AOAC and EPA published methods for
pesticide analysis. No in-house methods have been prepared by the analyst.
The Vermont laboratory plans, in the near future, to screen for cross-
contamination of pesticide formulations. They consider cross-contamination
as being violative. They also consider chemical deficiencies, overformula-
tions, and mislabeling to be violative.
Training that Vermont believes would be beneficial includes analytical
techniques for GLC, HPLC, AA, and general residue analyses.
In summary, the Vermont laboratory has a very limited pesticide capa-
bility. Their single chemist is inexperienced and the laboratory has only
recently acquired adequate instruments and supplies to perform meaningful
pesticide analyses.
Rhode Island
Rhode Island Department of Environmental Management (DEM), Division of
Agriculture, has a contract with Mississippi State Chemical Laboratories.
All formulation samples and most dilution samples are analyzed at the Mis-
sissippi laboratory. Residue samples collected by DEM are sent to the pes-
ticide laboratory of the Rhode Island Department of Health at 50 Orms
Street, Providence, Rhode Island 02904, telephone (401) 274-1011. Dr.
Raymond Lundgren is the Laboratory Director. A Supervisory Chemist, Dr.
Combs, is the Pesticide Formulation Supervisor and he shares with Mr. Ron
Check the duties of Residue Analysis Supervisor also.
The laboratory profile submitted by Rhode Island to EPA through the
PEPIR questionnaire provided only information about pesticide residue work;
-------
1-5
thus, the following discussion does not pertain to formulation work that is
done under contract with Mississippi State Chemical Laboratories.
Two chemists and a technician are responsible for the pesticide resi-
due work. The senior chemist (MS degree) has 16 years' experience while
his associate chemist (BS degree) has 8. The technician has 1 year's ex-
perience and holds a 2-year medical technology degree.
Routinely, a variety of pesticide residue samples are analyzed at the
laboratory including: water, plant and animal tissues, foods, feeds, and
oils from transformers or engines (for PCB's). Most samples are screened
for organohalogen, organophosphorus, herbicides, and carbamates.
The residue laboratory is equipped with analytical balances and three
gas chromatographs (MT 220 with a variety of specific and nonspecific de-
tectors). There is also a GC/MS available nearby. By the staff report it
is ineffective for analyzing the low levels of pesticide residue encoun-
tered routinely. No HPLC is available. The GC columns are packed at the
laboratory but coatings are purchased from Supelco. External standards are
characteristically used for residue work.
Chain-of-custody and document control procedures are poor. Residue
samples are received in sealed plastic bags. The samples are inspected for
condition and seal and are usually dated. If the analyst is notified of
potential litigation, unsealed samples are kept under lock and key when not
in the analyst's immediate possession; otherwise, unsealed samples are not
always kept in locked areas. Bulk analytical and technical standards are
not stored in a locked area nor are records and related documents.
The residue laboratory participates in two quality assurance programs,
EPA (Region I) and FDA. Routinely, the laboratory uses AOAC, EPA, or other
appropriate confirmatory methods to analyze or verify residues (derivitiza-
tion, TLC and two-column verification).
-------
1-6
Principal source for residue standards is EPA. Neat standards are
reassayed and, as needed, replaced annually. Dilute standards for instru-
mental analysis are prepared every 3 months.
Laboratory staff attend the annual EPA Region I and Northeast Pesti-
cide meeting. No one from the laboratory staff has attended the AOAC
meetings, and the laboratory personnel do not participate in AOAC colla-
borative studies.
The laboratory staff feel that they would benefit from training in
chain-of-custody procedures, verification methods (HPLC, AA, GLC, TLC) and
general formulation techniques of analysis.
In summary, the Rhode Island pesticide laboratory appears capable of
limited residue analysis, with the major limitation on confirmatory
techniques.
New Hampshire
The New Hampshire Water Supply and Pollution Control Commission has
recently been designated by the Governor as the lead agency for receiving
pesticide enforcement grants. The state laboratory building is ori Hazen
Drive in Concord, New Hampshire 03301. The laboratory director is Dr.
Donald F. Bent, telephone (603) 271-3446. A staff of two scientists and a
laboratory assistant perform the pesticide formulation and residue work.
Francis D. Houghton is the senior supervisory chemist in the group with a
BS degree and 14 years' experience, while the laboratory assistant is a
newly-hired employee with 3 years' college training in microbiology.
The laboratory reported it has the capability to analyze residues in
water, soil, and food as well as checking a variety of pesticide formula-
tion products including insecticides, herbicides, fungicides, plant growth
regulators, rodenticides, home and garden mixtures, and animal repellents.
New Hampshire did not analyze any formulations for their own state or for
EPA last year (apparently they were not in the EPA State Cooperative
Agreement last year).
-------
1-7
The New Hampshire laboratory is equipped with, or has immediate access
to, analytical and top-loading balances (two each), a pH/millivolt meter,
two AA's, two IR spectrometers, a UV/visible spectometer, and four GLC's
with a variety of detectors and good data systems (EC, FID, AFID, and
CDS-111).
New Hampshire is planning some changes to improve their chain-of-
custody procedures. Currently they practice the following inspection and
laboratory procedures for handling samples. Upon collection, samples are
sealed in plastic bags by inspectors. When received at the laboratory, the
samples are checked for condition and seal, and they are dated. Provisions
are being made to keep samples under lock and key when they are not in the
immediate possession of the analyst. Currently the only precaution used is
to lock the laboratory at night. Bulk analytical and technical reference
standards and sample documents are not kept under special lock and key
(other than locking the laboratory at night).
New Hampshire does not actively participate in the AAPCO check sample
program. The laboratory confirms all potentially violative formulation
samples by official AOAC, EPA or similar available methods. Analysis on
potentially violative formulations are not performed by the original ana-
lyst in duplicate nor does the analyst maintain a personal set of Commonly
used titrants.
Pesticide reference standards are obtained from EPA and purchased from
Nanogens, Inc., or Chem Service. Neither technical nor analytical refer-
ence standards are maintained by the laboratory. Neat and diluted stan-
dards are prepared as needed.
The laboratory personnel reportedly have extensive experience as ex-
pert witnesses with respect to testifying to their analytical findings or
discussing the general field of pesticides.
The New Hampshire laboratory staff feels that training of benefit to
them would include chain-of-custody procedures, reporting procedures, and
-------
1-8
various technical courses on GLS, cross-contaminant screening and analyses
of pesticide spreaders or wetting agents.
Briefly, it appears that the New Hampshire laboratory has a minimal
capability for residue and formulation analysis. They have inadequate con-
firmatory techniques which could possibly be resolved through acquiring
additional equipment (GC/MS), and obtaining the appropriate technical
trainings.
Connecticut
The Connecticut Agricultural Experimental Station analyzes pesticide
formulation and residue samples for the Department of Environmental Pro-
tection (grantee) at no charge. The laboratory is in New Haven, Connecti-
cut. Mr. J. Gordon Hanna is the Laboratory Director. His assistant
chemist, Martha Fuzesi, serves as the laboratory supervisor and holds an MS
degree with 15 years' experience in pesticide analytical work. Two other
chemists working in the pesticide laboratory have a MS and BS degree, re-
spectively, and the laboratory technician holds a BS degree also.
The Connecticut laboratory is involved with a variety of activities
besides pesticide formulation analysis. These include analysis of ferti-
lizers, feeds, food, residues, veterinary specimens, and various drugs.
Formulation analyses are extensive also and involve routine analyses of
insecticides, herbicides, fungicides, plant growth regulators, rodenti-
cides, snail baits, home and garden mixtures, antimicrobials, repellents,
and various pressurized cans. Last year the laboratory analyzed 148 pes-
ticide formulation samples for their own state and 115 for EPA.
The Connecticut laboratory is well equipped with modern instrumen-
tation including analytical and top-loading balances, pH/millivolt meters,
AA, IR spectrometer, UV/visible spectrometer, four GC's, two liquid chro-
matographs, and GLC/mass spectrometer. The gas chromatographs are typi-
cally multi-column with a dual FID and electron capture detector. Columns
are packed at the laboratory as well as purchased; column coatings are
-------
1-9
purchased. Connecticut uses external standard techniques for formulation
work. They have an HPLC with gradient capability and LC-55B (Perkin Elmer)
detector. Peak response on the HPLC chromatograph is usually calculated by
peak height.
Connecticut has an excellent chain-of-custody for samples (from in-
spector through the laboratory). Samples are sealed in plastic bags upon
collection by inspectors and kept in bags at the laboratory. All samples
incoming to the laboratory are dated, and checked for condition and seal.
The samples are kept under lock and key when not in use. Unsealed samples
are officially resealed by the analyst upon completion of analyses. Bulk
analytical and technical reference standards are stored under lock and key
also.
Connecticut confirms all potentially violative formulation samples by
official AOAC or other standard methods. Analysis on potentially violative
formulations are performed by the original analyst in true duplication, and
verified on more than one subsample. Analysis is not checked by a second
analyst. Each analyst maintains a personal set of commonly used titrants
and ^standardization of titrants or determination of reagent blanks are
performed as part of the verification procedure for potentially violative
samples.
Pesticide reference standards are obtained from EPA or the manufac-
turer. Both technical and analytical reference standards are maintained by
the laboratory.
Methodology for formulations are primarily those prepared by EPA-NEIC
and in-house.
Connecticut considers chemical deficiencies to be the major criterion
for citing a sample as potentially violative. The defective sample cri-
terion for the laboratory with respect to formulation analysis is:
-------
1-10
Allowable Deviation
Guarantee (%) Below Guarantee
less than 1.0 15% of Guarantee
1.0 - 19.99 0.1 plus 5% of Guarantee
20.00 - 49.99 0.5 plus 3% of Guarantee
50.00 - 100.00 1.0 plus 2% of Guarantee
The laboratory staff feel that training in HPLC and TLC analytical
techniques would be beneficial to them. They also feel the need for more
training in the residue field as well as the need to communicate with other
chemists in the pesticide field.
In summary, the Connecticut laboratory appears well staffed, equipped,
and capable of meeting current pesticide work loads.
-------
REGION I
i-n
Vermont
Rhode Island
New Hampshire
Connecticut
Chemist/Other Scientists Formulations Residues Formulations Residues Formulations Residues Formulations Residues
STAFF
Chemists/Other Scientists
Ph 0
M.S
B.S.
B.A.
Total
Techn i cian/Support
Clerical Support
Administrative
Total - all Staff
Analytical Balances
Top Loading Balances
pH Meter
Atomic Absorption Specs.
Infrared Spectrometers
UV/Vis Spectrometers
Electrodeposition
Gas Chromatographs
Liquid Chromatographs
GC/Mass Spec.
Other
Internal Standards
External Standards
Column pkg. capabil.(GLC)
In-lab
Purchased
Sealed Samples
Plastic Bag Enclosure
Inspector
Laboratory
Receipt Inspec. of sample
Security of samples
Storage
Check Sample programs
EPA
AAPCO
Southern Assn FFPCO
USDA/FSQS
Analysis Verification
Formulations
Residues
Standard Sources
Beltsville EPA
EPA/RTP
Manufacturer
Commercial
Methods
AOAC
FDA-PAH
EPA Formulation Methods
NEIC
ZWEIG
In-house
Methods Development
Samples per year
EQUIPMENT
1-a
1-a
1-a
1-a
1-a
1-a
1-a
Yes
Yes
Yes
Yes
Yes
Yes
Excellent
Excellent
1-b
METHODOLOGY
3-b
1-e
Yes
Packed
Yes
CHAIN-OF-CUSTODY SAMPLES
Yes
Yes
Yes
Poor
Good
QUALITY ASSURANCE
Good
Yes
Yes
S=26
Good
Yes
Yes
Yes
2-a
2-d
1-d
2-d
2-d
1-d
2-d
Yes
Yes
Yes
Yes
Yes
Yes
Poor
Poor
Poor
Yes
Yes
Yes
1-c
1-d
1-d
1-d
1-d
1-d
1-a 3-d
1-a 1-d
1-d
Yes
Yes
Packed
Yes
Yes
Yes
Yes
Yes
Excellent
Excellent
5=11
S=0
Good
Yes
Yes
Yes
Yes
Yes
In-house-AOAC
S=148, EPA=115
Equipment Use Code.
a = Formulations Lab, dedicated
d = Available in Lab elsewhere
b = Residue Lab. dedicated
e = Available outside Lah
c - Formulations/Residues Shared
-------
II-l
STATE PESTICIDE FORMULATION AND RESIDUES LABORATORIES
ANALYTICAL SCIENTIFIC CAPABILITIES U™'UKltb
EPA - REGION II
GENERAL
Currently, New Jersey, New York, and Puerto Rico have cooperative pes-
ticide laboratory grant agreements with EPA. Responses to the PEPIR lab-
oratory profile questionnaire were received from all three grantees and
laboratory capabilities for each are evaluated below.
OVERVIEW OF LABORATORY CAPABILITIES
The New Jersey, New York, and Puerto Rico laboratories appear to have
good capabilities for analyzing pesticide formulation products. New York
also has the capability to perform routine residue analyses. The other two
laboratories have the potential to perform residue work if given additional
instrumentation and appropriate training.
The largest staff of chemists (5) is at the Puerto Rico laboratory-
next is the New York facility with two chemists and three technicians- New
Jersey has one chemist and one technician. Senior people on each analytical
team have 3 to 18 years' experience.
The Puerto Rico laboratory has the largest inventory of laboratory
equipment. It is equipped with balances, PH meters, AA, Ir and UV/visible
spectrophotometers, gas chromatographs, and a liquid chromatograph. Lab-
oratory equipment at the New Jersey facility includes essential items for
formulation work such as balances, IR and UV/visible spectrophotometer, and
gas chromatographs. New York has two GLC's with a variety of detectors a
UV spectrophotometer, and other necessary equipment for pesticide formula-
tion and residue analytical work.
-------
II-2
SPECIFIC STATE LABORATORY CAPABILITIES
Attached to this detailed analysis is a comparative tabulation of ca-
pabilities in the Region II State pesticide laboratories operating under
EPA grants.
New Jersey
The New Jersey Department of Environmental Protection, Office of Pes-
ticide Control operates a pesticide formulation analytical laboratory at
380 Scotch Road, West Trenton, New Jersey 08628. The laboratory Director,
Peace Paubionsky, also serves as the principal chemist. The Director or
Principal Chemist has an MA degree with 9 years' experience in pesticide
formulation work. Louis D. Mattia, a Senior Laboratory Technician, assists
with the laboratory work. He has an AAS degree and about 5 years' ex-
perience.
Routinely, pesticide formulation products analyzed by the New Jersey
laboratory include: fungicides, plant growth regulators, rodenticides,
antimicrobials, insect repellents, and pressurized containers. Last year
the laboratory analyzed 50 formulation samples for EPA.
The New Jersey laboratory is equipped with an analytical balance and
dialogram scale, IR spectrometer, UV/visible spectrometer, and two gas
chromatographs with a variety of detectors. All of this equipment is dedi-
cated to pesticide formulation work. The laboratory does not do column
coating or packing; both columns and packings are purchased from Supelco in
Bellefonte, Pennsylvania. New Jersey uses external standard for their for-
mulation work.
New Jersey maintains a good chain-of-custody control on formulation
samples. Upon collection, the samples are normally labeled and sealed in
plastic bags by the inspector. At the laboratory the samples are checked
for condition and seal and dated as to receipt. Then they are stored until
analysis in a locked area with limited key access. Unsealed samples are
-------
II-3
not under lock and key when they are not in the analyst's immediate posses-
sion. Neither reference standards nor documents (work sheets, notebooks,
sample records) are kept locked when not in use.
The laboratory participates in Check Sample Programs of EPA and AAPCO.
Pesticide formulation analysis for potentially violative samples are con-
firmed using official AOAC, CIPAC, EPA, or AWPA methods. The original an-
alyst performs true duplication tests on all potentially violative formu-
lation samples. Routinely, these are verified by more than one subsample
but there is no second analyst available to recheck every potentially vio-
lative sample analysis. The analyst maintains a personal set of commonly
used titrants and ^standardization of titrants is performed as a verifi-
cation technique.
The principal source of pesticide standards is the EPA laboratory in
Beltsville, Maryland. Both analytical and technical reference standards
are maintained by the New Jersey formulation laboratory. Bimonthly or when
erratic results occur, dilute standards are replaced or reassayed. Method-
ology routinely used for formulation analysis is from EPA manuals (Belts-
ville and NEIC) and AOAC (12th edition).
Currently, the laboratory personnel do not participate in AOAQ collab-
orative studies; however, a representative from the laboratory occasionally
attends the annual AOAC meetings. The staff also participates in regional
ACS meetings at which pesticide formulation methodology is discussed.
New Jersey believes methodology is needed for benomyl, arsenicals,
carbendazim, and baygon in oil.
Pesticide formulations are not routinely screened for cross-contam-
ination. In the near future, the New Jersey laboratory hopes to set up TLC
as a general method for screening of formulation samples. The laboratory
staff have received training (from EPA) and have on-hand the supplies for
thin-layer chromatography.
-------
II-4
New Jersey considers chemical deficiency and cross-contamination to be
major criteria for citing a formulation sample as potentially violative.
The staff has been using AAPCO criteria for the laboratory defective sample
criteria with respect to formulation analysis.
Training that the laboratory believes would be beneficial includes:
basic chemistry (as for redox reactions), verification methods and analy-
tical techniques (HPLC and microbiology).
New York
The New York Department of Environmental Conservation operates a pes-
ticide formulation and residue analytical laboratory at the Hale Creek
Field Station, 7235 Steel Avenue Extension in Gloversville, New York.
Samuel Jackling is the Laboratory Director. Mr. Jackling's phone number is
(518) 773-7318. Stephanie Hoff serves as the senior analytical chemist and
supervisor in both the residue and formulation sections. She holds a BS
degree in chemistry and has 3 year's experience in pesticide work. Ms.
Hoff is assisted by a chemist (BS degree) and a technician in the formula-
tion laboratory and by two other technicians in the residue laboratory.
These four assistants each have approximately 1 year's experience in pes-
ticide analytical work. The laboratory analyzed 460 formulation samples in
the cooperative federal/state program for EPA from October 1979 to Septem-
ber 1980.
Routinely, the formulation laboratory analyzes insecticides, herbi-
cides, fungicides, plant-growth regulators, rodenticides, anti-fouling
paints, baits, home and garden mixtures, antimicrobials, repellents, and
pressurized containers. Residue samples routinely encountered are drinking
water, surface water, animal tissues, fish and marine organisms, soil, sed-
iment, vegetation, and various types of household swabs (curtains, toys,
rugs, and dishes that may have been accidently sprayed with pesticides).
The residue laboratory is equipped to do organohalogen and organophosphorus
screening, specific herbicides, carbomates, and element-specific screening
for copper, cadmium, mercury, and other metals.
-------
II-5
The laboratory Is adequately equipped to perform routine pesticide
analytical work. Both the formulation and residue sections have analytical
balances and they share a top-loading balance. The formulations laboratory
has a pH meter, an infrared spectrophotometer, UV/visible spectrometer,
electrodeposition, and liquid chromatograph. The formulation laboratory
also shares with the residue laboratory the use of two gas chromatographs
and an atomic absorption spectrometer. The gas chromatographs are equipped
with EC/FID/FPD, N-P detectors on one unit and an EC detector on the other.
No GC/MS equipment is available.
Typically, GLC columns are packed at the laboratory; columns and/or
packings are purchased from Supelco or Analabs. Internal standard method-
ology is used for GLC analysis in the formulation laboratory and external
standard methods for residue work. The HPLC unit in the formulation lab-
oratory is equipped with variable wavelength, model U6K loop injector, and
UV-fluorometer detector. Peak response is usually measured by integration
using external standards.
The New York laboratory reported an excellent chain-of-custody pro-
cedure. Sealed samples are received at the laboratory from inspectors.
The samples are checked for date and condition before being stored in
locked areas. Unsealed samples are always kept under lock and key(when not
in the immediate possession of the analyst. Standard solutions as well as
bulk analytical and technical reference standards are also kept under lock
when not in use. All samples are officially resealed by the analyst upon
completion of the analyses.
The New York formulation laboratory participates in the EPA Check
Sample Program. The residue section did not report any participation in
Check Sample Programs.
Formulations and residues are analyzed and confirmed by AOAC, CIPAC,
EPA or AWPA methods. Potentially violative formulations are analyzed as
true duplicates and verified from more than one subsample if available.
A second analyst checks the work for each potentially violative sample,
preparing new dilute sample solutions, re-standardizing titrants, and
-------
II-6
checking reagent blanks but each analyst does not maintain an independent
set of titrants. Pesticide residue results are confirmed by analysis on a
different GLC column and different (more specific FPD, N-P) detector where
appropriate or by TLC specific methods.
Formulation and residue reference standards are obtained from the EPA
laboratories in Beltsville or RTP. Both technical and analytical reference
standards are maintained by the formulation and residue laboratories. Neat
standards are replaced every 6 months to 1 year, or upon discovery of a
problem. Dilute standards are prepared for every instrumental analysis.
Methods used for formulation work include those from AOAC, EPA, and the
Zweig series. In addition to these forementioned sources, the residue
section also uses FDA/PAM I and II. The laboratory has prepared a compi-
lation of in-house formulation and residue methods.
There is no reported participation in AOAC Collaborative Studies by
the New York group. Both residue and formulation analysts attend the
annual Fall AOAC meetings every year but do not attend other regional or
national meetings where methodology is discussed.
Specific methods are needed in formulation analyses for dormant oil
and Monuron-TCA, and in residue work for ammonium sulfamate, urea,s, and
phenylureas. The laboratory used the NEIC Quality Control Document for
formulation assurance and the EPA Analytical Quality Control Document for
residues.
Pesticide formulations are routinely screened for cross-contamination.
Antimicrobials, rodenticides, and inorganics (e.g., copper sulfate, etc.)
are not screened. Thin layer chromatography and gas chromatography are the
usual method for screening cross-contamination in organophosphates and
chlorinated hydrocarbons. The New York laboratory considers chemical de-
ficiencies, overformulation and cross-contamination as grounds causing for-
mulation samples to be potentially violative.
-------
II-7
nor the re
due
*-•*•
HPLC- GLC-
ana,ysts suggested no "1
Puerto Rico
Under
=--.:——=-'—--=
contaiwrs. Last 1° ', rePe"entS' a"d ^°"S f^
, samP,es ft, toTcol Ty analyzed 40°pesticide f-
i-uerto Rico and an addittowi 10 samples for the EPA.
-------
II-8
The laboratory is equipped with three analytical and two top-loading
balances, two pH/millivolt meters, and an AA, two IR spectrophotometers,
two UV/visible spectrophotometers, an electrodeposition, two gas chromato-
graphs with a variety of detectors and data acquisition accessories, and a
liquid chromatograph with a H-P UV-variable detector.
Gas chromatograph columns and packings are purchased from commercial
sources. The pesticide formulation analytical laboratory uses internal
standards for routine sample analysis.
The Puerto Rico laboratory reports an excellent chain-of-custody for
its formulation samples. Inspectors seal formulation samples in plastic
bags for transport to the laboratory. The plastic bag procedure is used
through the laboratory handling of the sample also. Upon receipt, the lab-
oratory staff date and check the incoming samples for condition and seal.
Until analysis begins, the samples are locked in an area with limited key
access. All standards (solutions, references) and documentation are locked
when not in use also. When unsealed samples are not in the immediate pos-
session of the analyst, the samples are kept under lock and key. After
analysis is complete, the analyst officially reseals the sample.
For verification and check analysis of pesticide formulation, the
chemists follow official AOAC, EPA, or equivalent methods. When a standard
formulation methodology is not available, the analyst seeks help from his
associate chemists; some samples are sent to NEIC also. All potentially
violative formulation samples are analyzed by the original analyst in true
duplicate, verified for more than one subsample, and checked by a second
analyst. Although each analyst does not individually maintain a set of
commonly used titrants, in cases of deficiency, the second chemist who re-
checks the analysis prepares fresh solutions. Verification also involves
restandardization of titrants or determination of reagent blanks.
Pesticide reference standards are obtained from either or both EPA and
manufacturers. The laboratory maintains analytical reference standards
only. Neat standards are replaced or reassigned annually, while diluted
standards are prepared for each instrumental analysis performed.
-------
II-9
Routine methods used by the Puerto Rico laboratory are from EPA man-
uals, AOAC, and various manufacturers. The laboratory has not compiled
in-house methods.
Laboratory staff believe that method improvements are needed for work
in both formulations and residues. For formulations, they believe methods
are needed for monuron TCA, metaldehyde, and isopropylamine salt of glypho-
sate (Round up). For residue, chlorophenoxy herbicide and triazine herbi-
cide methods are needed.
The Puerto Rico laboratory is in the process of starting cross-
contamination tests for screening pesticide formulations. This testing
program will not include tests on disinfectants, rodenticides, sprays, re-
pellents, or antimicrobials, but will include others listed earlier in this
discussion. General methods for these proposed screening tests are bromine
fluorescein detection for organophosphates and silver nitrate detection for
chlorinated hydrocarbons.
The formulation laboratory considers chemical deficiencies and over-
formulations to be major criteria for potentially violative samples.
As discussed, the major work done by the Puerto Rico laboratory is in
pesticide formulations. The residue work done by the laboratory is not
performed in a separate area. Both formulation and residue sample prepara-
tion and cleanup are done in the same laboratory space. Glassware storage
is separate, but the same instruments are used for both types of testing.
Laboratory chemists feel that training of benefit to them includes
formulation analytical techniques in TLC and GLC screening tests, and gen-
eral residue sample preparation.
-------
11-10
REGION II
Chemist/Other Scientists
Chemists/Other Scientists
Ph. 0
M.S
B.S.
B.A.
Total
Technician/Support
Clerical Support
Administrative
Total - all Staff
Analytical Balances
Top Loading Balances
pH Meter
Atomic Absorption Specs.
Infrared Spectrometers
UV/Vis. Spectrometers
Electrodeposition
Gas Chromatographs
Liquid Chromatographs
GC/Mass Spec.
Other
Internal Standards
External Standards
Column pkg. capabil. (GLC)
In-lab
Purchased
Sealed Samples
Plastic Bag Enclosure
Inspector
Laboratory
Receipt Inspec. of sample
Security of samples
Storage
New York
New Jersey
Formulations Residues Formulations Residues
1
1
1-a
1-a
1-a
1-a
1-a
1-a
Yes
Yes
Yes
Yes
Yes
Yes
STAFF
1
2
EQUIPMENT
1-b
1-d
1-d
1-c 1-d
METHODOLOGY
Yes
CHAIN-OF-CUSTODY
Yes
Yes
Yes
Yes
Excellent Excellent
Excellent Excellent
1
1
1
2
1-a
1-a
1-a
2-a
Dialogram scale
Yes
Yes
SAMPLES
Yes
Yes
Yes
Yes
Good
Good
Puerto Rico
Formulations Residues
5
5
5
1-a
2-a
1-a
1-a
2-a
1-a
Yes
Yes
Yes
Yes
Yes
Yes
Excellent
Excellent
3-b
2-b
1-b
1-b
1-b
QUALITY ASSURANCE
Check Sample programs
EPA
AAPCO
Southern Assn FFPCO
USDA/FSQS
Analysis Verification
Formulations
Residues
Standard Sources
Beltsville EPA
EPA/RTP
Manufacturer
Commercial
Methods
AOAC
FOA-PAM
EPA Formulation Methods
NEIC
ZWEIG
In-house
Methods Development
Samples per year
Yes
No
Good
Yes
Yes
Yes
Yes
Yes
Yes
EPA = 460
Good
Yes
Yes
Yes
Yes
Yes
Yes
Good
Yes
Yes
Yes
PPPC
Good
Yes
Yes
Yes Yes
Yes
Yes
Yes Yes
Yes
EPA=50
S=400, EPA=10
Equipment Use Code.
a = Formulations Lab, dedicated
d = Available in Lab elsewhere
b = Residue Lab. dedicated
e = Available outside Lab.
Formulations/Residues Shared
-------
III-l
STATE PESTICIDE FORMULATIONS AND RESIDUES LABORATORIES
ANALYTICAL SCIENTIFIC CAPABILITIES
EPA REGION III
GENERAL
Region III states having current cooperative enforcement grant agree-
ments, including laboratory analytical services with EPA, are: Delaware,
Maryland, Virginia, and West Virginia. Laboratory questionnaire responses
from all participating states in Region III were received and are evaluated
below.
OVERVIEW OF LABORATORY CAPABILITIES
The four states responding in this region have widely-differing levels
of capabilities and experience in analysis of pesticides and pesticide res-
idues. Virginia has the largest programs in both areas, with an experi-
enced (18-plus years) staff of six people in formulations and 17 in resi-
dues; large and well-equipped laboratories; good control on samples, meth-
ods, and participation of staff in Check Sample Programs; professional de-
i
velopment activities in scientific and regulatory related associations.
Maryland also has a good program, with five in formulations and one staff
member in residue activities. Chemists in the Maryland Department of
Agriculture laboratories are experienced and well-trained, but with lesser
number of years' experience, on the average, than Virginia. West Virginia
has a smaller program, but it appears to be quite solid, with three formu-
lation chemists, two residue chemists, and adequate equipment for good reg-
ulatory programs in pesticides and their residues. West Virginia has re-
cently lost a long-term, experienced, pesticide chemist, and is rebuilding
their program laboratory staff. Delaware has the smallest program with one
chemist and one laboratory technician in the formulation section and one
chemist in the residue section. Adequate equipment is available for the
residue and formulation analytical program undertaken in Delaware.
-------
III-2
All states have most personnel at the BS or BA level of training, with
occasional MS and PhD level scientists at director or assistant director
levels. Average number of year's experience ranged from less than 1 year
(formulation) and 7 years' (residues) for Delaware, 5.5 years' (residues)
for Virginia, 4.7 years' (formulation and residues) for Maryland, to 2.4
years' for West Virginia.
Available equipment is similar in all four state laboratories; staff
and sample loads differ appreciably. Sample loads range from 41/year to
1,700 for the four state formulation laboratories. Laboratory equipment
available generally includes two or more balances, pH meters, and atomic
absorption spectrometers. Each laboratory is equipped with one or more
infrared and UV/visible spectrophotometers, from two to eleven gas chroma-
tographs (GC), and one to three high-pressure liquid chromatographs (HPLC).
Two of the four laboratories either own or have access to a GC/Mass spec-
trometer. Most of the equipment is less than 10 years old. Wide selec-
tions of detector systems for GLC and HPLC equipment are available, the
most common being flame ionization and thermal conductivity detectors for
formulation equipment, and electron capture, Hall, and flame photometric
detectors commonly available on many of the residue GLC's.
All four respondents are using AOAC and EPA methodology supplemented
by methods from literature sources and those developed in-house. All
states participate in either or both the AAPCO and EPA (NEIC) pesticide
formulations check sample programs. Virginia and West Virginia participate
in the Southern Association of Food and Drug Officials' pesticide residue
Check Sample Program. All states have adequate methodology, good control
of sample security and integrity (in the EPA programs, at a minimum) and
good verification of analyte identity and analytical standards from
EPA-Beltsville or Research Triangle Park groups, or from basic producers of
the pesticides.
All four respondents are interested in improved methodology development,
participating in AOAC and other related activities. All are interested in
-------
III-3
continued staff training courses. Topics of interest are verification pro-
cedures, microbiological techniques, wet-chemistry techniques, GLC, HPLC,
AA, new TLC and GLC techniques, GC/MS training, cross contamination, disin-
fectants, and pressurized-container sampling techniques.
SPECIFIC STATE LABORATORY CAPABILITIES
Attached to this detailed analysis are comparative tabulations of the
Region III responding laboratory capabilities.
Delaware
The responsible Director, laboratory and agency, in this state pes-
ticide program is Dr. Harry W. Otto, Technical Services Section, Department
of Natural Resources and Environmental Control, 150 East Water Street,
Dover, Delaware 19901. Dr. Otto's telephone number is (302) 736-4771.
Mr. Charles M. J'Anthony serves as the Formulation and Residue Laboratory
Supervisor. Each laboratory has one chemist with either a BS or BA degree.
The chemist in the residue laboratory has 7 year's experience while the
formulation laboratory chemist has about 2 years of experience. The lab-
oratory technician associated with the formulation laboratory has a BS in
chemistry and has about 1 year of experience.
The Delaware laboratory operates in a state laboratory that also is
involved with analyzing crop residues, investigating pesticide use and mis-
applications. Pesticide products routinely analyzed include insecticides,
herbicides, fungicides, plant-growth regulators, home and garden mixtures,
antimicrobials, insect repellents, and pressurized containers. Residue
samples encountered are water, animal tissues, fish and marine organisms,
soil, and vegetation. The residue laboratory is equipped to do organohalo-
gen and organophosphorus screens, specific herbicide residue determina-
tions, and element-specific screening for compounds containing nitrogen,
phosphorus, and sulfur. Delaware analyzed 41 pesticide formulation samples
for their own state program last year.
-------
III-4
The Delaware laboratory is well equipped with analytical and topload-
ing balances, pH meter, infrared and UV/visible spectrophotometers, four
gas chromatographs with a variety of detectors and data acquisition acces-
sories, liquid chromatograph and GLC/mass spectrometer. Gas chromato-
graphic columns are packed but not coated in the laboratory. Columns are
also purchased from a commercial supplier. The HPLC unit is equipped with
UV-vis detector and has gradient capability and variable wavelength. The
unit has an oven-type column temperature control and Rheodyne injection
system. Peak response on HPLC chromatograms are usually calculated by peak
height. External standard technique is usually used for formulation sample
analysis while both internal and external standard techniques are used for
residue work.
Delaware has a good chain-of-custody control of samples from the in-
spection steps through the laboratory. Samples for formulation analysis
are sealed upon collection by inspectors, enclosed in plastic bags and kept
in bags at the laboratory. Residue samples are not sealed or bagged in
plastic. Incoming samples are dated, inspected for condition and seal, and
kept under lock and key when they are not in the analyst's immediate pos-
session. However, bulk analytical and technical reference standards, stan-
dard solutions and sample records are not stored in locked areas when not
in use.
Delaware participates actively in Check Sample Analysis Programs. For
pesticide formulation work they participate in the AAPCO Check Sample Pro-
gram. For residue work they participate in EPA Drinking Water Program,
CORE, Water Pollution Control, and Check Sample Programs. Delaware con-
firms all potentially violative formulation samples by official AOAC,
CIPAC, EPA or AWPA methods if available. Otherwise they use the Beltsville
EPA-CBIB Laboratory to check such samples. Analysis of potentially vio-
lative formulations are performed by the original analyst in true dupli-
cate, verified on more than one subsample, if available, and by a second
analyst. Analysts do not use an independently maintained set of titrants.
New dilute standard solutions are used by the second analyst, however, and
titrants are restandardized and blanks used to check reagents. Pesticide
-------
III-5
residue results are typically confirmed by an alternate method and second
gas chromatograph column. Plans are to use GC/MS for confirmation in the
near future.
Pesticide reference standards are obtained from the Beltsville EPA
Laboratory; both technical and analytical reference standards are main-
tained. Dilute standards are prepared weekly for formulation analysis and
yearly for residue work. Methodology for formulations and residues are
primarily AOAC and/or EPA published methods. In-house methods have also
been compiled.
Analysts do not participate in AOAC collaborative studies and report-
edly never attend AOAC or similar national meetings at which pesticide for-
mulation or residue methodology is discussed.
Delaware believes methodology is needed for some carbamates and qua-
ternary ammonium products. They also feel a need for a better residue
method in analyzing pentachlorophenol.
Pesticide formulations are not routinely screened for cross-
contamination of carbamates and quaternary ammonium chlorides. The
screening method for organophosphates and chlorinated hydrocarbon^ is by
TLC. The laboratory currently has experience and supplies for thin-layer
chromatography also.
Delaware considers chemical deficiency, overformulation, and cross-
contamination as major criteria for citing a sample as potentially viola-
tive. Personnel in the laboratory (formulation and residue) have had no
experience in testifying in court or enforcement actions. Delaware rou-
tinely analyzes use-dilution pesticide samples. The residue and formula-
tion laboratories share some instrumentation but all sample preparation and
storage are separated.
Training needs recommended by analysts include screening techniques,
HPLC analysis, residue techniques, and GC/MS procedures.
-------
III-6
On balance, the Delaware laboratory is well equipped and properly
staffed for the program funded; expansion of the perogram would require
more staff. Participation in regional or national meetings at which meth-
odology is discussed would be beneficial in accommodating some of the
training needs expressed by the analysts.
Maryland
The responsible Director, laboratory and agency, in this state pesti-
cide program is Mr. David Clarke, State Chemist, Division of Inspection and
Regulation, Maryland Department of Agriculture, University of Maryland,
0231 Chemistry Building, College Park, Maryland 20742. State Chemist
Clark's telephone number is (301) 454-2722. Mr. Paul D. Jung is the Pesti-
cide Formulation Laboratory Supervisor. The Residue Analysis Laboratory
Supervisor is Mr. Spencer K. Carrigan. Both of these gentlemen have BS
degrees in chemistry, with many years of experience. Mr. Jung's formula-
tion section has three chemists with BS degrees and one laboratory assis-
tant with a high school education. Maryland has a single chemist with a BS
degree and 12 year's experience in the pesticide residue section.
The Maryland laboratory operates in a state laboratory that also ana-
lyzes fertilizers, feed, lime, sludge, soil conditioners, soil residues,
meats, and does toxicology work connected with agricultural products.
Pesticide formulation products of all types, including insecticides, herbi-
cides, fungicides, plant growth regulators, rodenticides, slug and snail
baits, home and garden mixtures, insect and animal repellents, pressurized
containers, and antimicrobials are all encountered routinely. Residue sam-
ples encountered are animal tissues, fish and marine organisms, soil, sedi-
ment, vegetation, foods, animal feeds, and the like. They are equipped to
do organohalogen and organophosphorus screening, specific herbicide residue
determinations, rodenticides and strychnine, and element-specific screening
for compounds containing nitrogen, phosphorus, and sulfur. Maryland ana-
lyzed 1,700 pesticide formulation samples for their own state program last
year. They apparently were not in the EPA State Cooperative Agreement last
year.
-------
III-7
The Maryland laboratory is well equipped with analytical and top-
loading balances, two high-quality absorption spectrometers (available in
other sections of the laboratory), two dedicated research-grade infrared
spectrometers, one research UV/visible spectrophotometer, and electrodepo-
sition equipment. They have relatively new Hewlett-Packard gas chromato-
graphs, two in the residue laboratory and one in the formulations labora-
tory. Two liquid chromatographs are available, one dedicated to residue
work, the other available elsewhere in the laboratory. Maryland has access
to a Hewlett-Packard 5985 GLC/mass spectrometer, probably in another sec-
tion of the University of Maryland. The gas chromatographs are typically
multi-column, dual-flame ionization detectors, with sulfur/phosphorus de-
tectors on one, a dual FID and electron capture plus nitrogen/phosphorus
detector on the other. Several are equipped with auto-sampling units and
several are equipped with localized microprocessors or data acquisition and
manipulation. Columns are packed and coated at the laboratory, as well as
purchased. Maryland uses external standard techniques for both pesticide
formulation and residue work. They have a Spectrophysics 8,000 HPLC unit,
with a variable wavelength Schoeffel detector and fluorescence detection
capabilities. Additionally, they have a Perkin-Elmer HPLC available in the
laboratory. Peak response on HPLC chromatograms are usually calculated by
integration rather than peak height, using an internal microprocessor.
Maryland maintains good chain-of-custody control of samples from the
inspection steps through the laboratory. Samples are sealed upon collec-
tion by inspectors, enclosed in plastic bags and kept in bags at the lab-
oratory on both formulations and residues. Incoming samples are controlled
as to date of receipt, condition of sample, and condition of seal, and kept
under lock and key when not in use. Unsealed samples are not under lock
and key when they are not in the analysts' immediate possession, however.
Sample storage is locked with limited key access, but bulk analytical and
technical reference standards and sample records and documentation are not
kept under special lock and key, other than general locking of the labora-
tory. Residue samples are not normally locked in a freezer until analysis.
-------
III-8
Maryland participates actively in the EPA and AAPCO formulation Check
Sample Programs. It does not participate in any pesticide residue program.
Maryland confirms all potentially violative formulation samples by official
AOAC, CIPAC, EPA, or AWPA methods if available. Otherwise, they use the
Beltsville EPA-CBIB Laboratory to check such samples. Analysis on poten-
tially violative formulations are performed by the original analyst in true
duplicate, verified on more-than one subsample if available, and by a
second analyst. They do not use an independently, maintained set of ti-
trants for each chemist. New dilute standard solutions are used by the
second analyst, however, and titrants are restandarized and blanks done on
reagents. Pesticide residue results are typically confirmed by TLC or two
GLC columns or instruments.
Pesticide reference standards are obtained from the Beltsville EPA
Laboratory; both technical and analytical reference standards are main-
tained. Dilute standards are prepared daily for formulations and residues
analyses. Methodology for formulations are primarily AOAC and EPA methods,
whereas the FDA-PAM I and II and Zweig references are used in the residue
work. In-house formulation and residue methods have been compiled.
AOAC activities of the laboratory are at the Associate Referee and
Collaborator level. Chemists attend AOAC meetings each year from both for-
mulation and residue groups. Other courses and professional development
seminars are attended regularly by Maryland chemists, including EPA train-
ing courses and the Associations of American Pesticide Control Officials
and Plant Food Control Official's Seminars.
Maryland believes methodology is needed for some carbamates and for-
mulations containing 1% or less active ingredient in oil solutions. They
feel a need for methods for carbamates, herbicides, and rodenticides in the
residue section.
Pesticide formulations are not routinely screened for cross-contamina-
tion in Maryland. If they are, they screen organophosphates using acetone
extraction on a GLC equipped with phosphorus/sulfur detector. Chlorinated
hydrocarbons are screened by TLC. Experience and supplies are available
for TLC screening.
-------
III-9
Maryland considers chemical deficiency as the major criterion for
citing a sample as potentially violative. Personnel in both formulation
and residue groups have had some experience testifying in court, and local
or immediate capability is available for efficacy and toxicology testing of
pesticide formulations. Maryland routinely analyzes use-dilution pesticide
samples. The formulation and pesticide residue analyses areas, glassware,
instrumentation, sample preparation, and sample cleanup are kept strictly
separated.
On balance, it is evident that the Maryland Laboratory is a high-
quality analytical unit which could stand a little strengthening in per-
sonnel in residue activities. It is quite competent and able to handle a
relatively large formulation load.
Virginia
The Virginia program is located in the Virginia Department of General
Services, Division of Consolidated Laboratory Services, One N. Fourteenth
Street, Richmond, Virginia 23219, telephone (804) 786-3766. Paul B.
Ferrara, PhD, is Laboratory Director. Mr. Leo M. Cox is the Pesticide
Formulations Supervisor and Mr. Frank D. Griffith, Jr., the Residue
Analysis Supervisor. Mr. Leo Cox also serves as Assistant Director in the
Laboratory as well as head of the pesticide formulations group.
The Virginia Laboratory has a large, well-equipped, and experienced
group. Five BS or BA chemists (one part-time) and one Laboratory Tech-
nician comprise the formulations group. Average experience in pesticide
formulations for this group is 5.6 years, with two of the chemists having
16 and 13 years, respectively, two with approximately 2 years, and one with
6 months' experience. These same individuals have up to 20 years addi-
tional experience as chemists to other parts of the laboratory. The pes-
ticide residue section under Mr. Griffith has one MS and eight BS chemists,
four chemical assistants ranging from high school to 3.5 years of college,
and four laboratory technicians ranging from high school to 3 years of
college training. Average experience of the BS and MS level chemists is
-------
111-10
8.8 years, ranging from 18 to less than 1 year. The Laboratory analyzed
1,227 formulation samples for the state and 303 for EPA from July 1, 1978
to June 30, 1979, plus approximately 5,000 residue samples, primarily for
state programs. The formulations laboratory routinely analyzes insecti-
cides, herbicides, fungicides, plant growth regulators, rodenticides, anti-
fouling paints, home and garden mixtures, insect and animal repellents,
pressurized containers, and all types of antimicrobials. Their residue
sample matrices include drinking waters, discharges from plants, lake and
river waters, animal, fish and marine tissues, soil, vegetation, feeds,
foods of all types, including fresh fruit, dairy products, poultry and veg-
etable oils, and the like. They are equipped to do organohalogen and or-
ganophosphorus screening, herbicides, and have N, P, and S element specific
screening capabilities. They perform microcoulimetric screens for halogen
and sulfur compounds, and have GC/MS capability in the residue group.
The formulation laboratory is well equipped with balances and a poten-
timetric tritrator. Two research-grade atomic absorption units are avail-
able elsewhere. They have one infrared spectrometer and access to a UV/
visible spectrometer. The residue laboratory has similar access to these
instruments. The formulation laboratory has three dedicated gas chromato-
graphs and three HPLC's. The residue group has six dedicated GC's and one
dedicated HPLC, plus a Hewlett-Packard 5985 GC/mass spectrometer .now on
board. Chromatographs in the formulation laboratory typically have FID
detectors. One unit has a nitrogen/phosphorus detector and FID dual-column
capability. No auto-sampling equipment is available on GC's in the formu-
lation group, but one of the Chromatographs is connected to a central com-
puter unit. In the residue group, all of the gas Chromatographs either
have a disk integrator or microprocessor data acquisition units, and many
are equipped with auto-samplers. Columns are routinely packed in the lab-
oratory, but coatings are purchased rather than being coated in the lab-
oratory. Internal standards are characteristically used for pesticide for-
mulation work, external for residue work. Several of the HPLC units are
equipped with variable wavelength detectors, plus refractive index and
fixed UV wavelength detectors.
-------
III-ll
Chain-of-custody of samples is good in the laboratory. Sealed samples
are delivered for both formulation and residues from the inspectors. Plas-
tic bags are utilized for enclosing EPA samples by the inspectors and re-
tained throughout the residue and formulation laboratories. Incoming sam-
ples are noted for both groups as to date of receipt, condition of sample,
and condition of seal. Unsealed samples are kept under lock and key in
both formulation and residue groups, and when the samples are not in the
analysts' immediate possession; samples are not resealed upon completion of
analyses, however. The sample storage area is typically not locked with
limited key access in the formulations or residues groups, except for EPA
program samples or others involving potential litigation. Bulk analytical
and technical standards are not stored under lock and key in either group,
nor are records, documentation and the like. Residue samples are locked in
the freezer until analysis.
The formulations group participates in both the EPA and AAPCO Check
Sample Programs. The residue group participates in the Southern Associa-
tion of Food and Drug Officials' Check Sample Program, and the EPA Clean
Drinking Water Program Check Sample series. Formulations and residue are
typically analyzed and confirmed by AOAC, CIPAC, EPA, or AWPA methods.
Other methodology is obtained from current literature, including JAOAC, J^
Ag. and Food Chem.. and consultation with USDA, FDA, or EPA as necessary.
Manufacturer's methods of analyses are also used in both formulations and
residues. Potentially violative formulation samples are analyzed in true
duplicate, routinely verified, if possible, with more than one subsample,
and a check analysis performed by a second analyst when possible. New di-
lute solutions are routinely made by the second analyst and reagents re-
standardized. These reagents are not kept as personal sets, but are com-
monly used among the groups. Confirmation on residues always uses two de-
terminative steps with a different polarity column or two or more gas
chromatographs.
Principal sources of information reference standards are the pesticide
manufacturers and the EPA group, presumably at Beltsville; other sources are
the National Bureau of Standards. Both technical and analytical reference
-------
111-12
standards are maintained in the formulation laboratory. Neat standards are
reassayed and replaced as needed, dilute standards being prepared for every
analysis for instrumental work. Dilute standards in the residue group are
replaced as needed. Principal reference sources for standards for pesti-
cide residue work are the EPA group at Research Triangle Park, as well as
the principal manufacturer.
Methods employed for formulation work include those published by AOAC,
EPA, and manufacturers. Virginia has compiled a number of in-house methods
for both formulation and residue analyses.
AOAC participation by the formulation group is only as a collaborator.
No present Associate or General Referees for AOAC are in the Virginia group,
although they have served in such positions in the past. Formulation and
residue chemists attend pesticide sessions every year at the AOAC fall and
spring meetings. Other meetings attended are the American Chemical Soci-
ety/Division of Pesticide Chemistry, Florida Pesticide Conference, and the
Association of Feed, Fertilizer, and Pesticide Control Officials.
The formulation group feels that methods needing development are
Basagran, Diphacinone, DDVP, Metasystox-R, Fosamine Ammonium, Strychnine,
and Tetramethrin with Resmethrin. There is presently a formulation quality
assurance document on board in Virginia.
Pesticide formulations are routinely screened for cross-contamination,
with less than 13. being found cross-contaminated. The pesticide formula-
tion section has HPLC experience and supplies, and routinely screen for
organophosphates and chlorinated hydrocarbons.
Virginia considers chemical deficiencies, over-formulations, cross-
contaminations, net weight deficiencies, poor blending, and breakdown of
emulsions in emulsion concentrates or dilutions as potentially violative
samples. Laboratory formulation personnel have no experience as court wit-
nesses on violative samples, but some of the residue chemists have such
experience.
-------
111-13
Neither efficacy nor toxicology screening capabilities are available.
The laboratory occasionally analyzes use-dilution pesticide samples, and
keeps the pesticide residue and formulation analysis work completely sepa-
rated in two areas.
Virginia feels that training in formulation in use-dilution analyses
would be useful, and training on HPLC, new TCL and GLC techniques, and
GC/MS techniques in residue work is appropriate.
West Virginia
The West Virginia Department of Agriculture, Laboratory Services Di-
vision, Charleston, West Virginia 25305, telephone (304) 348-2582, is the
agency involved in state-EPA pesticide enforcement activities. The lab-
oratory Director is Mr. Terry W. Hall, the Pesticide Formulation Supervisor
is Mrs. Ruth E. Wargacki, and the Residue Analysis Supervisor is Dr. James
A. Smith.
The formulation section is comprised of three BS or BA Chemists, with
an average of 1.2 years' experience. This group has recently lost a long-
term employee with many years of experience in pesticide formulation analy-
sis. The residue section is headed by Assistant Laboratory Director J. A.
Smith, PhD, with 7 years' experience, 1.5 of it in residues. The labora-
tory analyzes both formulations and pesticide residues, with some analyti-
cal toxicology in trace metals and mycotoxins being performed in the resi-
due group. Other sections of the laboratory cover feeds, fertilizers, and
the like.
Pesticide formulation products routinely encountered are insecticides,
herbicides, fungicides, plant growth regulators, rodenticides, slug and
snail baits, home and garden mixtures, antimicrobials, insect repellents,
and pressurized containers. Residue samples are analyzed in drinking, lake
and river waters, animal tissues, soil, vegetation, and feeds and foods,
including fruits and vegetables. Analyses in the residue group include
organohalogen and organophosphate screens, herbicides, and screens for ni-
trogen and phosphorus-containing compounds.
-------
111-14
Last year West Virginia analyzed 385 samples for the state, 51 for
EPA, and 127 samples for the state of Pennsylvania, for a total of 569
samples.
The Laboratory appears to be well-equipped for both formulation and
residue activities, with balances and pH meters, one atomic absorption unit
being available elsewhere in the Laboratory. One infrared spectrometer is
available, although it is fairly old, and a UV/visible spectrometer is also
available. Three GC's are dedicated to the residue group, and two GC's are
dedicated in the formulations analysis. One dedicated HPLC is in each of
the two groups. The residue section gas chromatographs are equipped with
flame photometric and nitrogen-phosphorus detectors, Hall, and EC detec-
tors. The formulation units contain flame photometric, electron capture,
flame ionization, and thermal conductivity detectors. No data acquisition
accessories are available, nor are autosamplers. Columns are routinely
packed at the Laboratory. Packings are not coated in the Laboratory, but
purchased. Pesticide formulations are routinely analyzed by internal stan-
dard, residues by external standard methodology.
HPLC's are available with solvent-gradient programming capability, UV
detectors at several wavelengths, and variable temperatures for column
ovens. Peak response is normally measured by peak height in the residue
section and by integrated area in the formulation group.
West Virginia samples are normally officially sealed by the Inspector
on collection for both formulations and residues and are kept in plastic
bags from the Inspector through the Laboratory. Incoming samples are noted
as to date of receipt, condition of sample, and condition of seal. Un-
sealed samples are not kept under lock and key when not in the analyst's
immediate possession. They are resealed upon completion of analysis, and
the sample storage area is locked with limited key access. Bulk analytical
and technical standards are not stored under lock and key, nor are records
and worksheets. Residue samples are stored in a freezer until analysis,
but not locked.
-------
111-15
The formulation laboratory participates in both the EPA and AAPCO
Check Sample Programs, and the residue laboratory in the Southern Food and
Drug Officials' Association residue program. Official AOAC, CIPAC, EPA or
AWPA methods are used to confirm all potentially violative formulation sam-
ples. If methods are not available, the laboratory frequently consults
with other laboratories nearby. Analyses on potentially violative formu-
lations are routinely done as true duplicates, verified on more than one
subsample if available, but not by a second analyst. Each analyst does
maintain his/her set of titrants, which are routinely restandardized for
potentially violative sample analyses. Residue results are confirmed on
two GC columns with specific but different GC detectors, as well as by
HPLC, TLC, and "P-values". Principle sources of pesticide standards are
the EPA CBIB Beltsville Laboratory and basic manufacturers. Both technical
and reference analytical standards are maintained in the formulation group,
and these samples are replaced or reassayed every 18 months. Dilute stan-
dards are re-prepared for instrumental analysis about every 2 months.
Principle sources of pesticide standards used in residue analysis are
basic procedures, EPA at Beltsville, and the EPA group at Research Triangle
Park. These standards are replaced or reassayed every 18 months, or more
often as needed. Methods routinely used for pesticide formulation and res-
idue analyses are AOAC and the FDA-PAM I and II Manuals for residue work,
EPA's formulation and residue methods, and USDA formulation methods. The
laboratory has compiled a manual of in-house residue methods and is pres-
ently doing the same for formulations.
Personnel participate as AOAC Associate Referees in the residue group,
and as collaborators in both formulation and residue groups. Staff from
both groups attend AOAC meetings every year. Other regional and national
meetings attended are the Association of Southern Feed, Fertilizer, and
Pesticide Control Officials, the Florida Pesticide Residue Conference, and
the Pittsburgh Conference on Analytical Instrumentation.
West Virginia feels that improved formulation methods should be de-
veloped for time-release baits and pressurized cans, and on carbamates,
-------
111-16
Roundup, and PCP residue methods. There is no present day-to-day quality
assurance document in use in West Virginia in either formulation or residue
groups.
Pesticide formulations are routinely screened for cross-contamination,
but very few are found contaminated. Disinfectants are screened. Organo-
phosphates and chlorinated hydrocarbons are two major screening categories,
done by CG and TLC. The residue section has both experience and supplies
for this work.
West Virginia considers chemical deficiencies, overformulations, and
cross-contamination as rendering a formulation potentially violative. For-
mulation chemists have had no experience, but residue chemists have had
some experience in court testimony on violative samples. Local and imme-
diate capability does not exist for either efficacy or toxicology testing
of pesticide formulations.
West Virginia routinely analyzes use-dilution pesticides; all formu-
lation and residue work is segregated into two different laboratory
locations.
West Virginia feels that GLC and TLC training courses would be useful
for both formulation and residue groups, as well as training on cross-
contamination, pressurized containers, and disinfectant analyses.
The state laboratory, though presently small and having few chemists
with long experience in pesticide formulations, seems quite capable of
having a good quality-regulatory program. They need more equipment and
another chemist with pesticide formulations and residue experience.
-------
REGION III
111-17
Chemist/Other Scientists
Chemists/Other Scientists
Ph. D
M.S
B.S.
B.A
Total
Technician/Support
Clerical Support
Administrative
Total - all Staff
Analytical Balances
Top Loading Balances
pH Meter
Atomic Absorption Specs.
Infrared Spectrometers
UV/Vis. Spectrometers
Electrodeposition
Gas Chromatographs
Liquid Chromatographs
GC/Mass Spec.
Other
Internal Standards
External Standards
Column pkg. capabil. (GLC)
In-lab
Purchased
Delaware
Maryland
Virginia
West Virginia
Formulations Residues Formulations Residues Formulations Residues Formulations
1
1
1
2
1-c
1-a
1-a
1-d
1-c
1-d
1-a 1-c
1-c
Yes
Packed
Yes
1
1
1
1-d
2-b
Yes
Yes
Yes
STAFF
4
4
1
5
EQUIPMENT
2- a
1-a
2-d
2-a
1-a
1-a
1-a
1-d
1-e
METHOOOLOGY
Pack, coat
Yes
1
1
1
1-b
2-b
1-b
2-b
1-b
5
5
1
6
1-a
2-a
1-a
1-a
3- a
3-a
Yes
Pack, coat Packed
Yes
Yes
1
8
9
8
17
*
1-c 1-d
4-b
1-b
2-d
1-d
8-b
1-b
Yes
Packed
Yes
3
3
3
1-a
1-a
1-d
1-a
1-a
2-a
1-a
Yes
Packed
Yes
Residues
1
1
2
2
1-b
3-b
1-b
Yes
Packed
Yes
CHAIN-OF- CUSTODY SAMPLES
Sealed Samples
Plastic Bag Enclosure
Inspector
Laboratory
Receipt Inspec. of sample
Security of samples
Storage
Check Sample programs
EPA
AAPCO
Southern Assn FFPCO
USDA/FSQS
Analysis Verification
Formulations
Residues
Standard ources
Beltsville EPA
EPA/RTP
Manufacturer
Commercial
Methods
AOAC
FDA-PAM
EPA Formulation Methods
NEIC
ZWEIG
In-house
Methods Development
Samples per year
Yes
Yes
Yes
Yes
Good
Good
Yes
Excellent
Yes
Good
Good
Yes
Yes
Yes
Yes
Yes
Good
Good
QUALITY ASSURANCE
Yes
Yes
Excellent
2-Column CG TLC,
Yes
Yes
Yes
Yes
In-house
S=41
Yes
Yes
Yes
Yes
Yes
Yes
Yes
In- house- AOAC
S-1700
Yes
Yes
Yes
Good
Good
Yes
Yes
Yes
Yes
Fair
Good
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Fair
Excellent
Yes
Excellent
2 instrum
Yes
Yes
Yes
Yes
In-house
.
Yes
Yes
Yes
Yes
Yes
Excellent Multi.
columns detec.
Yes
Yes
USDA
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Fair
Good
Yes
Yes
Excellent
2-colmn
Yes
Yes
Yes
Good
GC, HPLC,
TLC, P-valves
Yes
Yes
Yes
Yes
USDA
Yes
In-hOUse-AOAC No In-house-AOAC
S-1227
, EPA- 303
Yes
Yes
Yes
Yes
Yes
Yes
Yes
In-house
AOAC
S- 385, EPA-57. 0-127
Equipment Use Co«ie: a = For-ulations Lab, dedicated
d = Available in Lab elsewhere
b = Residue Lab. dedicated
e = Available outside Lab.
c = Formulations/Residues Shared
-------
IV-1
STATE PESTICIDE FORMULATIONS AND RESIDUES LABORATORIES
ANALYTICAL SCIENTIFIC CAPABILITIES
EPA REGION IV
GENERAL
Region IV states having current cooperative enforcement grant agree-
ments with EPA, including laboratory analytical services, are: Florida,
Kentucky, Mississippi, North Carolina, and Tennessee. Laboratory question-
naire responses from all of these were received and are evaluated below.
States not having an agreement, or having no present laboratory capabili-
ties are Alabama, Georgia, and South Carolina. All of these states are be-
lieved to have moderate-to-good laboratory capabilities.
OVERVIEW OF LABORATORY CAPABILITIES
The five responding states in Region IV have widely-differing levels
of capabilities and experience in analysis of pesticides and pesticide res-
idues. Florida has the largest program in both areas, as might be ex-
pected, as a consequence of their subtropical climate and heavy emphasis on
i
vegetable and fruit crops. Their formulation laboratory has an experienced
staff of eight, with a similarly-experienced group of 16 in the chemical
residue laboratory. Florida has large, well-equipped laboratories, and
good-to-excellent quality control on samples, methods, and participation of
staff on Check Sample Programs and professional development activities in
scientific and regulatory related associations. Mississippi and North
Carolina have excellent programs as well, with Mississippi having four
highly-experienced scientists in formulations and six in residues, and
North Carolina with six full-time chemists and one part-time (3-month)
employee available for formulations, four of whom are also involved in
residue analysis. Both laboratories are well-equipped and have good
quality control on samples and methods, and participate actively in pro-
fessional development activities. Tennessee has a relatively new program,
with one chemist with "less than 2 years' experience and a newly-hired
-------
IV-2
technician in formulations, and one chemist with 5 years' experience in
residues, operating under an experienced laboratory director. Kentucky has
one individual in each of the two areas, each with 3 years' experience.
The laboratory director in Kentucky is the chief chemist in the residue
section. All five states appear to have viable programs, though Tennessee's
and Kentucky's are relatively new and need augmentation in personnel and
equipment.
The five states have most of their personnel at BS or BA levels of
training, with occasional MS and PhD scientists, sometimes at director or
assistant-director levels. Average number of years of experience ranged
from 7.4 years (formulations) and 6.3 years (residues) for Florida; 3.0
years for both fields for Kentucky; 13.1 years (formulations) and 3.6 years
(residues) for Mississippi; 6.5 years for both fields for North Carolina;
and 0.8 years for formulations, and 5.0 years for residues for Tennessee.
Equipment, staff, and sample loads generally paralleled each other in
these states. Formulation sample loads ranged from 7,030 for Florida to
150 for Kentucky, with an average of 2,190/yr (405 samples/man-yr) for the
five-state formulation laboratories. Excluding Florida, which has year-
round agriculture and thus year-round sample load on pesticide formulation
and residues, average production is 286 samples/man-yr. This latter figure
is somewhat depressed because of the low-sample loads in Kentucky and Ten-
nessee, whose programs are just beginning.
Equipment available in each laboratory include two or more balances,
pH meters, and atomic absorption spectrometers. Each laboratory is
equipped with one to two infrared spectrometers and UV/visible spectrom-
eters, from two to 34 gas chromatographs (GC), and from one to three
high-pressure liquid chromatographs (HPLC). Two of the laboratories,
Florida and Mississippi, either own or have access to a GC/mass spectrom-
eter (GC/MS). Most of the equipment is less than 10 years old. Wide se-
lections of detector systems for GLC and HPLC equipment are available, the
most common being flame ionization and thermal conductivity detectors for
formulation equipment. Electron capture, flame photometric, and other de-
tectors are commonly available on the residue GLCs.
-------
IV-3
All respondents are using AOAC and EPA methodology, supplemented by
methods from literature sources and those developed in-house. Florida does
not necessarily use AOAC methods on all potentially violative samples, if
available, but the other four states do. All states participate in the
AAPCO and EPA (NEIC) pesticide formulation Check Sample Programs. Florida,
Kentucky, and Mississippi all participate in the Southern Association of
Food and Drug Officials' Residue Check Sample Program. All states have
good control of sample security and integrity (in the EPA program, at a
minimum) and good verification of analyte identity and analytical results
in their quality-control programs. Florida and North Carolina obtain for-
mulation reference analytical standards from EPA/Beltsville. Kentucky,
Mississippi, North Carolina, and Tennessee also obtain samples for both
formulation and residues from EPA at Research Triangle Park, North Caro-
lina. They also obtain samples from basic producers of the pesticides.
All respondents are interested in improved methodology development and
participate in AOAC and other related activities. All are interested in
continued staff training courses. Topics of interest are chain-of-sample-
custody; reporting; GC/mass spectrometer use for confirmation of cross-
contamination and confirmation problem residues; paint analysis, microbio-
logical analyses; TLC screening for cross-contamination; atomic absorption;
gas liquid chromatography; HPLC; phenol disinfectants; pressurized(contain-
er sampling; and similar techniques.
SPECIFIC STATE LABORATORY CAPABILITIES
Attached to this detailed analysis are comparative tabulations of the
State Laboratory capabilities in Region IV.
Florida
The responsible director, laboratory and agency, in this state pesti-
cide program is Dr. Charles H. Van Middelem, State Chemist, Florida Depart-
ment of Agriculture and Consumer Services, Division of Chemistry, Mayo
Building, Tallahassee, Florida 32301. Dr. Van Middelem1s phone number is
-------
IV-4
(904) 488-0295. Mr. Marshall Gentry is the pesticide formulation labora-
tory supervisor, phone (904) 488-9375. Mr. Doyle C. Golden is the chemical
residue laboratory supervisor, phone (904) 488-9670. Both of these gentle-
men have BS degrees or equivalent in chemistry with 20 years of experience
for Mr. Gentry and 27 years for Mr. Golden. Mr. Gentry's formulation sec-
tion has four BS chemists besides himself (one is paid under the EPA grant)
and three high school graduates as technologists or technicians. Mr.
Golden1s pesticide residue laboratory has one PhD, two MS chemists, six BS
chemists (one is paid under EPA grant), two BS biologists, and three high
school graduates. The latter five individuals are working as technologists
or technicians and have considerable laboratory experience. All of the
pesticide formulations laboratory personnel are located at Tallahassee,
whereas the chemical laboratory residue has seven laboratory positions at
Tallahassee, two at Sanford, and four at Fort Lauderdale branch laboratories.
The main pesticide formulation and chemical residue laboratories in
Florida are located in the Laboratory Complex at Tallahassee, in the Divi-
sion of Chemistry, which includes four additional bureaus which analyze fer-
tilizers, feed, food, and seed. The Division of Chemistry, in addition,
has three sections: Methods Development Laboratory, Commodity Testing Lab-
oratory, and Laboratory Services. Four field inspectors work under Mr.
Golden in the Chemical Residue Bureau; other inspectors work out of Tal-
lahassee under the direction of the Division of Inspection.
Pesticide formulations of all types, including insecticides, herbi-
cides, fungicides, plant-growth regulators, rodenticides, anti-fouling
paints, slug and snail baits, home and garden mixture, all types of anti-
microbials, insect and animal repellents, and pressurized containers are
analyzed by Florida. The residue samples encountered are found in animal
tissue, fish and marine organisms, soil and sediment, vegetation, foods of
all types, and animal feeds. They are equipped to do organohalogen and
organophosphorus screening, screening for herbicides, miscellaneous com-
pounds, heavy metals such as arsenic, mercury, lead, cadmium, and zinc, and
have GC/MS capability. Florida analyzed 7,030 samples of pesticide formu-
lations for their own state program last year prior to joining the EPA
State Cooperative Agreement. They analyzed approximately 5,500 pesticide
residue samples as well.
-------
IV-5
Florida is extremely well equipped, with analytical and top-loading
balances in their formulation and residue groups, pH meters in both, and an
atomic absorption spectrometer in the residue group. The formulations lab-
oratory has an infrared spectrophotometer with data manipulator and four
gas chromatographs. The residue laboratory has a total of approximately 30
gas chromatographs of various makes including Varian, Perkin-Elmer, Hewlett-
Packard, Tracer, and homemade units adapted from Varian-Aerograph equipment.
The formulations laboratory has two HPLCs and the residue laboratory has
three. The residue laboratory, or bureau, has a GC/MS and shares it with
the formulations laboratory. Formulation gas chromatographs are typically
multi-column, dual flame, or FPD/NPD detectors with electron capture and
thermal conductivity detectors also available. All are interfaced with a
Perkin-Elmer Sigma-10 system for data acquisition and manipulation. Auto-
samplers are available in the formulations laboratory and chemical residue
laboratories. Data acquisition equipment is available on some of the resi-
due section units, with detectors being FPD, ED, TI, and NPD.
The laboratory coats and packs gas chromatographic columns. The formu-
lations laboratory typically uses external standard techniques in GLC, as
does the residue laboratory. The formulations laboratory has an HPLC with
a variable wavelength UV detector and an autosampler. In the chemical res-
idue laboratory, packings are not coated but are packed. Columns and pack-
ings are purchased from suppliers having them available at lowest cost.
Peak response measurements on the HPLC systems are typically by integration
rather than peak height; both bureaus use external standard techniques for
quantification by HPLC.
Florida maintains good chain-of-custody control of samples from the
inspectors through the laboratories on EPA samples, where maximun security
and chain-of-custody procedures are followed scrupulously. This is not ne-
cessarily true with state samples. Formulation samples are officially
sealed by inspectors, enclosed in plastic bags and kept in bags at the
laboratory (both formulations and residues) for EPA samples. Incoming
samples are controlled as to date of receipt, condition of sample, and
condition of seal; EPA samples are locked away when not in the analysts'
-------
IV-6
immediate possession. Unsealed EPA program samples are not kept locked
when not in use, but are resealed by the analysts upon completion of an-
alysis. Sample record, documentation, worksheets, and notebooks are not
under lock in the residue laboratory, but are in the formulations labora-
tory for EPA samples. All residue samples are stored in a locked freezer
or cooler until analysis. Standard solutions, bulk analytical, and tech-
nical reference standards are not in locked storage in either laboratory,
except for general locking of laboratory doors.
Florida participates in both the EPA and AAPCO Check Sample Program in
their formulations group and in the Southern Association of Food and Drug
Officials and USDA-FSQS Check Sample Programs for Pesticide Residues. In
the formulations group, not all potentially violative formulations are
checked by official AOAC, CIPAC, EPA, or AWPA methods, although they are
rechecked by a second independent analytical method. Residue samples are
not always confirmed by official methods either. Both formulation and res-
idue laboratories prepare standard and sample solutions in true duplicate
on recheck analysis and verify samples on more than one subsample if
available. Potentially violative samples are not typically rechecked by a
second analyst in either laboratory. New dilute standards solutions are
not made up by a second analyst, but each analyst maintains his set of
reagents, which are restandardized on recheck samples. The residue labora-
tory uses a second GC column, TLC, and GC/MS for confirmation of sample
identity.
Pesticide reference standards for formulation analyses are obtained
from EPA/Beltsville or RTP, or basic manufacturers. Both technical and
analytical reference standards are maintained in the formulation labora-
tory. Standards are replaced or reassayed every 2 years, or more often,
according to the shelf-life of the reference standard.
In the chemical residue laboratory, principal sources of pesticide
standards are FDA, EPA, or the manufacturer. Neat standards are replaced
or reassayed yearly. Dilute standards are not prepared for every analysis,
but as needed, at least quarterly.
-------
IV-7
Methods used in the formulation laboratory are in-house, AOAC, and
manufacturers, whereas the residue unit uses FDA-PAM I and II, AOAC, and
manufacturers' methods. In-house formulation and residue methods have been
compiled.
AOAC activities of the formulation laboratory are at the General Ref-
eree, Associate Referee, and Collaborator levels in formulations; AOAC col-
laborative work is done in the residue laboratory whenever deemed fruitful
and necessary. Chemists from the Florida laboratories attend AOAC meetings
every year, alternating pesticides and formulation groups each year. Lab-
oratory scientists attend a number of other professional development meet-
ings, including the Southern Association of Feed, Fertilizer, and Pesticide
Control Officials, the Florida Pesticide Residue Conference, and the Amer-
ican Association of Feed, Fertilizer, and Pesticide Control Officials.
Florida believes that residue methods are needed for carbamates and
triazines, but did not suggest any needed methods for formulation analyses.
There is a quality-assurance document in use in the residue section,
but not in the formulation group. Florida does not routinely screen for
cross-contamination in formulations, although about 80% of the formulations
are indirectly screened through routine analysis using GC, HPLC,-or IR.
EPA samples are screened by GLC and TLC.
Florida considers chemical deficiencies, over-formulations, cross-
contaminations, and net-weight deficiencies as criteria for stating a
sample is potentially violative. Personnel in both groups have had some
experience in court testimony; no available capability exists for efficacy
or toxicology testing. The formulations laboratory seldom analyzes tank
use-dilution samples. No cross-utilization of laboratory areas occurs, in
either preparation, cleanup, instrumentation, or glassware, between the two
groups.
On balance, it is evident that the Florida laboratory is extremely
competent in both fields and handles a heavy sample load quite efficiently.
-------
IV-8
The laboratory reportedly uses in-house methods rather than AOAC methods
because the Florida chemists feel that AOAC methods: (1) have not been
developed for residue analysis of newer pesticides, and (2) are often
out-of-date for use with modern analytical instrumentation.
Kentucky
The Kentucky Laboratory is located in the Kentucky Department of Agri-
culture, State/Federal Meat Laboratory, 613 Teton Trail, Frankfort, Ken-
tucky 40601, telephone (502) 564-3530. Mr. Ernest Collins is Laboratory
Director. Mr. Scott Bryan serves as Chief Chemist in charge of the Pesti-
cide Section and Assistant to the Director. Mr. James Smith is a principal
chemist in the Section.
Mr. Bryan and Mr. Smith are the only chemists in the Kentucky pesti-
cide program. Both have BS degrees in chemistry; each has 5 years' ex-
perience in the pesticide field. The laboratory analyzed 200 samples in
the cooperative federal/state program for EPA last year, none in a routine
state regulatory program.
The formulation laboratory analyzes use-dilution, fertilizer-pesticide
mixes and crop residues, routinely analyzing insecticides, herbicides, fun-
gicides, plant growth regulators, rodenticides, anti-fouling paints, slug
and snail baits, home and garden mixtures, all types of antimicrobials,
insecticide and animal repellents, pressurized containers, and devices.
Residue samples routinely encountered are drinking waters, discharge
waters, lake and river waters, animal tissues, fish and marine organisms,
soil and sediment, vegetation, foods, and feeds. They are equipped to do
organohalogen and organophosphorus screening, specific herbicides, and do
element-specific screening for phosphorus and sulfur.
Much of the equipment is cross-shared between the formulation and the
residue groups. Both groups have analytical balances, and they share top-
loading balances. The formulations laboratory has a pH meter and an infra-
red spectrophotometer, and one Hewlett-Packard liquid chromatograph. The
two groups share an atomic absorption spectrometer, two UV-visible
-------
IV-9
spectrophotometers, and two Hewlett-Packard gas chromatographs. The three
gas chromatographs (HP 5830) are equipped with EC/FID detectors on one
unit, EP/FPD detectors on the other. All are equipped with microprocessor/
integrator units, but none have an autosampler. No GC/MS equipment is
available.
Column packings for GLC work are not typically coated in the labora-
tory, but are packed there. Columns are purchased from Supelco. External
standard methodology is used for analysis by GLC in the residue labora-
tories, while the formulation laboratory uses internal standard methods.
The HPLC unit in the formulation laboratory is equipped with a variable
wavelength, semi-automatic injection system, UV detector and a micropro-
cessor. Peak response is typically measured by integration using external
standards for both formulations and residues.
Chain-of-custody of samples is good in the laboratory. Sealed samples
are delivered for both formulations and residues from the inspectors.
Plastic bags are used for samples from the inspectors and in the laboratory.
Incoming samples are noted by both groups as to date of receipt, condition
of sample, and condition of seal. Unsealed samples are kept under lock and
key and when not in immediate possession of the analyst, as are samples and
standard solutions. All samples are officially resealed by the analyst
upon analysis completion. Sample storage area, bulk, analytical and tech-
nical reference standards, and all records and documentations are kept
under lock and key when not in specific use, with limited key access.
Residue samples are stored in a locked freezer until analysis.
The Kentucky formulations laboratory participates in both EPA and
AAPCO Check Sample Programs. The pesticide residue section participates in
the USDA/FSQS Organohalogen Residue Check Program from Beltsville, but not
in any EPA Check Sample Program.
Formulations and residues are analyzed and confirmed by AOAC, CIPAC,
EPA, or AWPA methods on potentially violative samples. Samples are reana-
lyzed with different samples and standards if standard methodology is not
-------
IV-10
available or appropriate. Potentially violative formulations are analyzed
as true duplicates, and verified from more than one subsample if available.
A second analyst checks the work for each potentially violative sample,
preparing new dilute sample solutions, restandardizing titrants, and check-
ing reagent blanks, but does not maintain an independent set of titrants.
Pesticide residue results are confirmed using two TLC systems and secondary
GLC systems.
Formulation reference standards are obtained from EPA/RTP, Beltsville,
and Denver as well as from Chem Services. Some technical standards are
maintained in the formulation laboratory, but usually only 90% or better
analytical standards are kept. Neat organochlorine standards are replaced
yearly, organophosphorus standards, every 6 months. Dilute samples and
standards are prepared monthly for pesticide residues. Methods employed
for formulation work include those from AOAC, JAOAC, and EPA manuals.
Residues are analyzed by AOAC methods, FDA/PAM I and II, the RTP Manual and
the Zweig series. The laboratory has prepared a compilation of in-house
formulation and residues methods.
There is no participation as yet in AOAC Collaborative Studies by the
Kentucky group. Both formulation and residue analysts attend the annual
fall or spring AOAC meetings occasionally, but do not attend other-regional
or national meetings where methodology is discussed.
Specific methods are needed in formulation analyses for use-dilution
herbicides and rodenticides. There is a laboratory quality-assurance docu-
ment in use by the Kentucky laboratory for both formulation and residue
units.
Pesticide formulations are routinely screened for cross-contamination,
with less than 1% being found contaminated. Disinfectants are not screened.
Thin layer chromatography is the usual method for screening cross-
contamination in organophosphates and chlorinated hydrocarbons. TLC capa-
bility, experience and supplies, are thus available. Kentucky views chem-
ical deficiencies, over-formulations, and cross-contaminations as causing
formulation samples to be potentially violative. Defect!ve.sample criteria
-------
IV-11
for the laboratory with respect to formulation analysis are those issued by
NEIC. The formulations chemist has not had experience in court testimony,
but the residue chemist has. Labels or copies are routinely prepared and
submitted with each formulation sample. There is no local or immediate
capability for efficacy or toxicology testing in the Kentucky group, and
the laboratory routinely analyzes use-dilution pesticide samples.
Pesticide residue and formulation analyses are kept separated during
the sample preparation and cleanup, but instrumentation is shared between
the two groups. Glassware storage and cleaning is performed in the same
general area.
Kentucky believes that additional general training in HPLC, AA, GLC,
and microbiological analysis would be helpful in the formulations group.
The residue group would be interested in having training of HPLC and GLC
techniques.
On balance, this group appears to be competent and well-enough
equipped to perform a small sample load. Another chemist in each of the
two groups, or one who could be cross-shared between the two, would be
helpful. The group apparently is relatively new in the pesticide formu-
lation and residue regulatory program activities. More participation in
AOAC and other methods validation/development meetings and training pro-
grams would be helpful.
Mississippi
The Mississippi State Chemical Laboratory (MSCL), P. 0. Box CR,
Mississippi State, Mississippi 39762, telephone (601) 325-3324, is the
agency laboratory involved in State/EPA pesticide enforcement activities.
The laboratory subcontracts analytical and technical support for the pesti-
cide formulation and residue programs from the pesticide lead state agency,
the Division of Plant Industry, Mississippi Department of Agriculture and
Commerce (DPI/MDAC), P. 0. Box 5207, Mississippi State, Mississippi 39762.
Dr. James P. Minyard, Jr., State Chemist, is Director of MSCL which is a
-------
IV-12
separate state agency from the DPI/MDAC, headed by the State Entomologist
and Director, Mr. Jack D. Coley. Mr. Coley's phone number is (601) 325-3390.
Both state and EPA program activities in pesticides are jointly enforced by
the two groups, with sampling and field inspection work done by DPI/MDAC,
and laboratory support services by MSCL. The pesticide formulation super-
visor in the State Laboratory is Mr. Elwood Hodgins, Chief Chemist, phone
(601) 325-3250; the pesticide residue laboratory is directed by Mrs. Terri
Gray, Chief Chemist, same phone as Mr. Hodgins.
The formulations section is composed of three BS chemists and one lab-
oratory technician, with an average of 14 years of experience overall. The
residue section has two BS chemists, two PhD chemists, one BS laboratory
technician, one laboratory technician with 3 years of college, and one
part-time laboratory technician for glassware cleaning. The average ex-
perience is 4.9 years in residues. These two laboratory sections are part
of a larger laboratory with work in fertilizer, feeds, foods, microbiology,
and miscellaneous regulatory programs, as well as several major research
programs and service to industry and agriculture in the state.
Pesticide formulation products routinely encountered are insecticides,
herbicides, fungicides, plant growth regulators, rodenticides, slug and
snail baits, home and garden mixtures, all types of antimicrobials-, insect
repellents, and pressurized containers. Residue samples are analyzed in
drinking, discharge, and lake and river waters, animal and marine tissues,
soil, sediment, vegetation, foods, and feeds of all types. Transformer
oils are analyzed for PCBs, and a variety of other matrices are analyzed
for industrial and pesticidal chemicals.
The residue laboratory is equipped to do organohalogen, organophos-
phorus, and specific herbicide screens, and can do element-specific screens
for pesticides containing nitrogen, phosphorus, sulfur, and a large number
of heavy metals. They have GC/MS capabilities.
Last year Mississippi analyzed 1,430 formulation samples for the state
program, 297 more for EPA under state contract, 22 for EPA programs in the
-------
IV-13
State of New Hampshire, and three samples for EPA Region I in Boston. The
residue group analyzed 1,680 samples, 110 of which were for the State-EPA
Cooperative Program. A number of EPA Region IV official samples were also
analyzed among the 297 EPA samples done in the state. A total of 1,752
samples were analyzed in formulation regulation.
Mississippi is well equipped with a number of analytical and. top-
loading balances dedicated to both formulation and residue sections, pH
meters, a cross-shared atomic absorption spectrometer, two research grade
infrared spectrometers, two research grade UV-visible spectrophotometers,
and electrodeposition equipment. A GC/MS is cross-shared between the two
units. The formulation laboratory has three dual-column Hewlett-Packard
GLCs, whereas the residue unit has two dual-column GLCs. The two units
cross-share two HPLC units. The residue group has a gel permeation chroma-
tograph as well. GLC detectors available are EC, FPD, FID, and a Hall (NP)
detector. Columns are both coated and packed at the laboratory, as well as
purchased from Applied Science or other bidders. For routine sample analy-
sis, the formulation laboratory typically uses internal standard, the resi-
due laboratory external standard methodology.
HPLCs are equipped with variable wavelength and fixed wavelength ul-
traviolet detectors, refractive index, and fluorescence detectors.- Micro-
processors are available on all of the GLC units, and peak response is
normally integrated for formulations, measured by peak height on residue
analyses.
Chain-of-custody in the laboratory is good. Samples are sealed for
both formulations and residues by the inspector and are transmitted and
kept in plastic bags in both laboratories. Incoming samples are noted as
to date of receipt, condition of sample, and condition of seal. They are
officially resealed by the analyst upon completion of analysis and are kept
in a locked sample storage area with limited key access when received and
completed. Samples are not kept under lock and key when not in the ana-
lyst's immediate possession, nor are standard solutions, bulk analytical or
technical reference standards, sample records or documentation. Residue
samples are stored in an unlocked freezer until analysis.
-------
IV-14
The laboratory participates in the AAPCO and EPA Check Sample Programs
for formulations, and the residue group participates in the Southern Asso-
ciation of Food and Drug Officials' Check Sample Program.
All potentially violative formulation samples are checked by official
AOAC, CIPAC, EPA, or AWPA methods where available. Two or more methods are
routinely used to confirm findings on all potentially violative samples.
Analyses for these are performed in true duplicate, by a second chemist and
on a second subsample if available. New dilute standard solutions are used
by the second analyst who typically does not maintain an independent set of
titrants. Restandardization of tritrants and other verification procedures
for potentially violative samples are employed. Pesticide residue results
are confirmed on a second GC column of different polarity or with another
type of detector. GC/MS is often used for confirmation of residues.
Mississippi obtains most of its formulation and 'pesticide residue
standards from manufacturers, but also uses EPA-RTP as a source. Both
technical and analytical reference standards are maintained at the formu-
lation group, and neat standards are replaced or reassayed as needed.
Dilute standards are prepared for any instrumental analysis as often as
degradation indicates the need for replacement, typically every 6 months.
Neat standards are replaced or reassayed as needed, as determined by
checking against standards remade approximately every 3 months.
Methodology used in the residue group includes FDA/PAM I and II, as
well as AOAC, EAP, and Zweig sources. Formulations are usually analyzed by
AOAC methods where available, or EPA, Zweig, in-house, or those from other
state laboratories as available. The formulations laboratory has prepared
a compilation of in-house methods, but not the residue group.
Personnel in the laboratory participate in AOAC Collaborative Studies
at the General Referee, Associate Referee, and Collaborator level. Residue
laboratory chemists participate as Associate Referees and Collaborators.
Chemists from both groups attend AOAC fall and spring meetings every year;
the State Chemist is on the AOAC Board of Directors. Residue chemists
-------
IV-15
attend the Florida Pesticide Residue Conference each year, and formulation
chemists also participate each year in the Southern Association of Feed,
Fertilizer, and Pesticide Control Chemists Seminar.
The formulation group sees needs for new or improved methodology for
substituted urea herbicides, malathion, and guthion. The residue group
feels that methodology for general herbicide residue screens and general
methods for nitrogen-containing compounds would be helpful. There is pre-
sently no quality-assurance document in use by either group in Mississippi.
Pesticide formulations are routinely screened for cross-contamination,
with less than 1% being found contaminated. Samples not screened for
cross-contamination are those used on agricultural crops such as cotton or
soybeans. Screening is by TLC, HPCL, GLC, and Beilstein tests. Tests are
done for organophosphates, chlorinated hydrocarbons, and carbamates. TLC
methodology, experience, and supplies are available in the laboratory.
Mississippi considers chemical deficiencies, over-formulations, and
cross-contaminations as rendering samples potentially violative. Defective
sample criteria for the laboratory are those published by AAPCO in its
Official Publication. Laboratory personnel from both formulation and resi-
due sections have had some experience in court testimony. There is local
or immediate capability for efficacy and toxicology testing of pesticide
formulations on the Mississsippi State University campus. The laboratory
routinely analyzes use-dilution samples. Pesticide residue and formulation
analyses are performed in separate areas using separate equipment, with the
exception of HPLC and GC/MS equipment.
The laboratory believes that training would be of benefit in areas of
chain-of-custody, reporting, and GC/MS analytical techniques. Specific
product analysis training in the area of paint pesticide additives would
also be of value.
It is evident that the Mississippi Laboratory is competent in both
fields, having adequate personnel, equipment, and methodology. Mississippi
-------
IV-16
handles a moderately large sample load in both formulation and residue sec-
tions, and could handle more if EPA funds were available for staff and
equipment augmentation.
North Carolina
The responsible laboratory agency for this state is the North Carolina
Department of Agriculture, Constable Laboratory, 400 Reedy Creek Road,
Raleigh, North Carolina 27607. Mr. Robert T. league is the Laboratory
Director, telephone (919) 733-7366, with Mr. George R. Winstead, III the
supervisor for both the formulation and residue analysis sections. Mr.
Winstead has a BS degree in chemistry and 11 years' experience, and he is
assisted by five other BS chemists and one AB chemist, all except one
having 3h to 10 years' experience. Typically, the seventh chemist is an
inexperienced person from another laboratory assigned for a 3-month train-
ing period. Four of these chemists are involved in pesticide residue work
as well as performing the formulation analysis program. Residue exper-
ience is fairly limited compared to full-time residue analysis in other
laboratories.
The Constable Laboratory in North Carolina analyzes fertilizers,
feeds, foods, pesticide and drug residues, as well as the pesticide formu-
lation and residue samples from the Pesticide and Plant Protection Division
of the North Carolina Department of Agriculture (NCDA) and the Structural
Pests Division of NCDA. Pesticide formulation products routinely encoun-
tered include insecticides, herbicides, fungicides, plant growth regula-
tors, rodenticides, slug and snail baits, home and garden mixtures, all
types of antimicrobials, insecticide repellents, and pressurized contain-
ers. The residue samples encountered routinely involve soils, sediments
and cotton swabs of the use-dilution sprays on baseboards of homes and
outbuildings. The residue section is capable of doing organohalogen, or-
ganophosphorus, and herbicide screenings. North Carolina analyzed 1,500
formulation samples on their state program and 170 samples on the EPA pro-
gram last year.
-------
IV-17
North Carolina is well-equipped, with a number of analytical and top-
loading balances and several pH meters dedicated to the formulation group.
They have two high-quality atomic absorption units located elsewhere in the
laboratory, two reaearch quality infrared spectrophotometers, a research
grade UV/visible spectrophotometer, and electrodeposition equipment avail-
able in the formulations group. The laboratory has one gas chromatograph
cross-shared between residue and formulations, two dedicated to formula-
tions, and two other instruments available elsewhere in the laboratory.
One HPLC unit is cross-used between formulations and residues, and two
others are available elsewhere in the laboratory. North Carolina is work-
ing on an agreement to have analyses confirmed by an outside laboratory by
GC/MS on a contract basis because they do not have an instrument.
Gas chromatographs are typically dual-column units, equipped with FID
and EC detectors and several are equipped with data acquisition/integration
equipment. No autosamplers are attached to their gas chromatographs. The
laboratory does not coat packings, but does pack columns, purchasing ma-
terials from Applied Science and Supelco. The formulation group uses in-
ternal standard, the residue group external standard methodology for quan-
titative analysis.
The HPLC equipment available has a selective multiple wavelength UV
detector rather than a continuously variable one, except for one unit.
They also have a fluorescent detector and an autosampler attached to one of
the HPLCs. Peak response is normally measured by integration for HPLC
work, again using internal standard for formulations and external for resi-
due samples.
Chain-of-custody of samples is quite stringent for EPA samples, much
less so for state enforcement samples. Samples are officially sealed for
both formulations and residues by the inspector and transmitted and handled
through the laboratory in plastic bags. Samples are noted as to date of
receipt, condition of sample, and condition of seal for EPA program sam-
ples, but are not sealed for state programs. Unsealed EPA samples are kept
under lock and key wnen not in the analyst's immediate possession and are
-------
IV-18
resealed by the analyst upon completion of the work and stored in a locked
sample storage area with limited key access. Sample records and documenta-
tion are not kept under lock and key, nor are samples of standard solutions
or bulk analytical and technical reference standards. Residue samples are
stored in a freezer but not locked.
The North Carolina formulations section participates in the EPA and
AAPCO Check Sample Programs. The residue section does not participate in
any Check Sample Programs although the food laboratory, which also analyzes
pesticide residues in the Constable Laboratory, participates in a number of
them.
All potentially violative formulation and residue samples are con-
firmed by official AOAC, CIPAC, EPA, or ASPA methodology. If official or
standard formulation methods are not available or appropriate, North
Carolina calls EPA at Beltsville, checks with the basic producer, or their
methods-development group helps check the samples. If two different in-
house methods show violations and there is no reason to suspect methodology
problems, the violation is noted as substantiated if better methods are
unavailable.
Potentially violative formulation samples are not reanalyzed- in true
duplicate, but are verified on more than subsample if available, with a
second analyst doing the work for EPA samples. New dilute standard solu-
tions are used by the second analyst, but that analyst does not maintain an
independent set of titrants. Restandardization of titrants and determi-
nation of reagents blanks are conducted by the analyst. North Carolina
notes that they have insufficient amounts of standards to perform all an-
alyses on all potentially violative samples in true duplicate and then by
a second analyst. Pesticide residue results are confirmed by a combination
of two or more GCs with different detectors, such as electron capture of
flame photometric or nitrogen phosphorus detectors, by different columns on
such GCs, by HPLC, and by TLC.
-------
IV-19
North Carolina obtains their formulation and residue pesticide stan-
dards primarily from the producers, supplemented by EPA/RTP. Both refer-
ence and technical standards are maintained in the laboratory, and neat
standards are replaced as primary standards annually, and secondary stan-
dards are reanalyzed more frequently if degradation is suspected. Dilute
or secondary standards are reprepared for every instrumental analysis, and
primary standards as well for potentially violative samples. Neat .residue
standards are reassayed or replaced yearly and dilute standards replaced
whenever major deterioration is suspected or for potentially violative
samples.
The formulation group routinely uses methods from AOAC, EPA, in-house
and the basic producer. The residue section uses AOAC methods primarily.
The laboratory has compiled formulation in-house methods, but not for
residues.
Laboratory personnel participate in AOAC Collaborative Studies as Col-
laborators and Associate Referees on formulations, but do not participate
to any extent for residue methodology development. Chemists attend AOAC
meetings almost every year, as well as the Southern Association of Feed,
Fertilizer, and Pesticide Control Officials. There are no current quality-
assurance documents available for day-to-day operation in either the for-
mulation or residue group.
North Carolina routinely screens approximately 90% of the EPA samples
and 10% of the state samples for cross-contamination. Approximately 7% of
those screened are found contaminated. Samples not screened are disinfec-
tants, bleaches, and acids. General methods used for screening are AOAC
6.026 (12th Edition, Methods of Analysis, a thin-layer method for chlori-
nated hydrocarbons) and thin-layer methods for organophosphates. Carba-
mates and others are screened by GLC using flame-ionization detectors. The
formulations section currently has TLC capabilities, both experience and
supplies.
-------
IV-20
North Carolina considers chemical deficiencies, over-formulations, and
cross-contaminations as sufficient to render samples potentially violative.
They have had some experience in both formulation and residue sections in
court testimony; labels or copies of same are routinely prepared and sub-
mitted for each formulation sample. They have local or immediate capabil-
ity available for efficacy and toxicology testing of pesticide formulations
and routinely analyze use-dilution samples. Instrumentation is shared
between residue and formulation sections, but all other activities, in-
cluding sample preparation, cleanup, and glassware, are scrupulously
separated.
This state feels that a manual covering all of the topics considered
in the PEPIR questionnaire [Appendix] would be helpful. They also feel
that availability of specific methodology would be of benefit for specific
product analyses in phenolic disinfectants, paints, fertilizer-pesticide
combinations, and pressurized containers.
On balance, North Carolina's laboratory is well-equipped, staffed with
capable people, and conducts a good regulatory program with a moderately
large sample load. Their residue section capability for pesticide regula-
tory programs is less strong than other states' in Region IV, but they have
additional capability in their foods laboratory which may help supplement
their pesticide regulatory group.
Tennessee
The responsible agency in this state for the pesticide laboratory is
the Tennessee Department of Agriculture, Division of Plant Industries, Box
40627, Melrose Station, Nashville, Tennessee 37204, telephone (615) 741-1547.
Mr. Sylvester Davis is the pesticides formulation and residue analysis su-
pervisor for the laboratory. Mr. Davis has a MS degree and many years of
experience in pesticides. One BS chemist with 19 months' experience, and
one BS technician with 1 month experience assist Mr. Davis in the formula-
tion section, and one BS chemist with 5 years' experience works in the
residue section.
-------
IV-21
This laboratory performs residue or formulation assay work for other
agencies within the Tennessee Department of Agriculture in the feeds, fer-
tilizers, foods, and other sections. Pesticide formulation products rou-
tinely encountered include insecticides, herbicides, fungicides, plant
growth regulators, rodenticides, slug and snail baits, home and garden
mixtures, all types of antimicrobials, insect repellents, and pressurized
containers. Residue samples are analyzed in drinking, lake, and .river
waters; soil; sediment and vegetation. The residue section is equipped to
do organohalogen, organophosphorus, and herbicide screening. The formu-
lation section analyzed 50 samples in the state program and 450 in the
EPA-supported program last year.
Tennessee's laboratory is well equipped with much new equipment, most
of it being less than 6 years old. They have both analytical and top-
loading balances dedicated to both forumulation and residue sections, with
pH meters in both groups as well. They have no atomic absorption specto-
photometer. They have two research grade infrared spectrophotometers and
one UV/visible spectrophotometer, as well as electrodeposition equipment
available to the pesticide formulation group. They cross-utilize three
Varian gas chromatographs and one Perkin-Elmer Series 2 HPLC between the
residue and formulation groups. Available on the gas chromatographs are
alkali flame ionization, EC, flame photometric, and TC detectors.- They
have a data acquisition unit attached to one GC but no autosamplers.
Columns are neither coated nor packed at the laboratory, but are purchased
from Varian. For routine sample analyses they use external standards in
the formulation laboratory and both internal and external standards in the
residue group. Their HPLC is equipped with a variable wavelength UV de-
tector, but not with an autosampler. Response is normally measured by peak
height using internal standard technique for the residue group, external
standard technique for formulations.
Chain-of-custody of samples is good in Tennessee, with formulation and
residue samples both being officially sealed by the inspector upon collec-
tion. Plastic bags are used to enclose the sample by the inspector for
transmission to and in the laboratory. Incoming samples are noted as to
-------
IV-22
date of receipt, condition of sample, and condition of seal. Unsealed sam-
ples are kept under lock and key when not in the analysts' immediate pos-
session, as are samples and standard solutions. All samples are officially
resealed by the analyst upon completion of analysis. The sample storage
area is locked with limited key access. Analytical and technical reference
standards are stored under lock and key, as are sample records and documen-
tation. Residue samples are stored in an unlocked freezer until analysis.
Tennessee's formulation group participates in both EPA and AAPCO Check
Sample Programs, but the residue group does not participate in any. Offi-
cial AOAC, CIPAC, EPA, or AWPA methods are used for confirming all poten-
tially violative formulation samples. If such are not available, the lab-
oratory uses company or in-house methods or outside consultation with other
laboratories. Analyses of potentially violative formulations are performed
in true duplication, with violative samples routinely verified on more than
one subsample. The check analysis is not performed by a second analyst,
but all recheck work is performed with new dilute standard solutions. Ana-
lysts maintain independent sets of titrants, and restandardization and re-
determination of blanks are always done. Pesticide residue results are
confirmed by changing GC parameters or columns. Principal sources of pes-
ticide standards are from EPA/RTP or from basic producers. Both technical
and analytical reference standards are kept in the formulation laboratory,
and these are replaced as needed, with dilute standards being prepared
periodically for instrumental analysis. The pesticide residue standards
are obtained from manufacturers and from EPA/RTP and replaced or reassayed
as needed. Dilute standards are prepared as needed.
Methods routinely used for pesticide formulations are those from AOAC,
the EPA (NEIC) Manual, and in-house. The residue group uses FDA/PAM I and
II as their primary source. Both residue and formulation laboratories have
compiled in-house methods.
The laboratory participates in AOAC work as a Collaborator in the for-
mulations group, but has no participation in the residue section. Chemists
attend AOAC meetings every year from both formulation and residue groups,
-------
IV-23
and chemists from the formulation group attend the Southern Association of
Feed, Fertilizer, and Pesticide Control Officials meeting. Tennessee be-
lieves that formulation methods needing to be developed are those for di-
thiocarbamates, pressurized containers, and chlorotriazines. There is cur-
rently a quality-assurance document in use in both formulation or residue
groups.
The laboratory does not routinely screen pesticide formulations be-
cause of shortage of personnel. As soon as this is corrected they intend
to start. They lack experience but have supplies for TLC.
Tennessee considers chemical deficiencies and cross-contamination as
rendering samples potentially violative. Personnel from both formulation
and residue groups have had some experience in court testimony as experts.
Local or immediate capability is available for toxicology but not for ef-
ficacy testing. The laboratory routinely analyzes use-dilution samples.
It does not perform analyses on residues and formulations in the same area
as sample preparation, cleanup, or glassware cleaning but does share in-
strumentation on GC and HPLC.
Tennessee believes that training would be of value in verification and
reporting procedures, on TLC screening for cross-contamination, atomic ab-
sorption analysis, and HPLC work on formulations. They would also welcome
training in residue analysis using GLC, HPLC, and AA. They mentioned a
desire for specific product analysis training in phenolic disinfectants and
pressurized containers.
Tennessee appears to have a young program. They now have adequate
capabilities for a small program, but could handle many more samples if the
staff and equipment were slightly augmented, and as staff gains experience.
-------
IV-24
REGION IV
Chemist/Other Scientists
Chemists/Other Scientists
Ph. D
M.S
B.S
B.A.
Total
Technician/Support
Clerical Support
Administrative
Total - all Staff
Analytical Balances
Top Loading Balances
pH Meter
Atomic Absorption Specs.
Infrared Spectrometers
UV/Vis. Spectrometers
Electrodeposi tion
Gas Chromatographs
Liquid Chromatographs
GC/Mass Spec
Other
Internal Standards
External Standards
Column pkg. capabi 1. (GLC)
In-lab
Purchased
Sealed Samples
Plastic Bag Enclosure
Inspector
Laboratory
Receipt Inspec. of sample
Security of samples
Storage
Check Sample programs
EPA
AAPCO
"Southern Assn FFPCO
USDA/FSQS
Analysis Verification
Formulations
Residues
Standard Sources
Beltsville EPA
EPA/RTP
Manufacturer
Commercial
Methods
AOAC
FDA- PAN
EPA Formulation Methods
NEIC
ZWEIG
In-house
Methods Development
Samples per year
Florida Kentucky Mississippi
Formul. Residues Formul. Residues Formul. Residues
STAFF
1 6
2
5811 32
5 11 1 1 34
33 12
8 14 1 1 46
EQUIPMENT
1-a 1-b 2-a 1-c 1-b 2-a 1-c
4-a 1-b 1-d 1-c 1-d 1-a 1-b
1-a 1-b l-a
1-b 1-c 1-c
1-a 1-a l-a 1-c
2-d 2-d 2-c l-a 1-c
1-a
4-a 30-a 3-c 3-a 2-b
2-a 3-a 1-a 2-c
1-c i-c
Gel Perm. Chrom.
METHODOLOGY
Yes
Yes Yes Yes Yes Yes
North Carolina Tennessee
Formul. Residues Formul. Residues
j
5 211
57 17
£ ± £
1
X
5 222
4-a 1-a 1-b
4-a 3-a 1-b
2-a 1-a 1-c
2-d
2-a 2-a
1-a l-a
1-a T -a
° J. a
2-a 1-c 2-d 3-c
1-c 2-d l-c
c
YeS Vac
i ca f 55
Yes Yes Yes
Coated, Packed Packed No No Coat, Pack Coat, Pack Packed No No
No Yes Yes Yes Yes Yes Yes Yes Yes Yes
CHAIN-OF-CUSTODY SAMPLES
Yes Yes Yes Yes Yes Yes
Yes Yes Yes Yes Yes Yes
Yes Yes Yes Yes Yes Yes
Yes Yes Yes Yes Yes Yes
Excellent Excellent Excellent Excellent Excellent Good
Excellent Excellent Excellent Excellent Excellent Good
QUALITY ASSURANCE
Yes Yes Yes
Yes Yes Yes
Yes Yes Yes
Ues Yes
Good Excellent Excellent
2nd column 2-TLC,Sec GLC 2nd GC.G-C
CG/MS.thin layer Chromat. Mass Spec.
Yes Yes
FDA Yes Yes Yes Yes
Yes Yes Yes Yes
Yes
Yes Yes Yes Yes Yes
Yes Yes Yes
Manuf. Yes Yes Yes
Yes Yes Yes Yes
Yes Yes Yes Yes
In-house-AOAC In-house In-house In-house In-house, AOAC AOAC
S-7,030 S-5500 EPA-150 S-1430, EPA-
-------
V-l
STATE PESTICIDE FORMULATIONS AND RESIDUES LABORATORIES
ANALYTICAL SCIENTIFIC CAPABILITIES
EPA REGION V
GENERAL
Five State Pesticide Laboratories in Region V currently have cooper-
ative enforcement grant agreements with EPA. They are Illinois, Michigan,
Wisconsin, Minnesota, and Indiana. Laboratory questionnaire responses were
received from all but Indiana, and information contained in the question-
naires is used in the evaluations that follow.
OVERVIEW OF LABORATORY CAPABILITIES
Michigan and Wisconsin appear to have similar capabilities and exper-
ience in analysis of pesticide formulation and residues. The program in
Minnesota is smaller but capable, and the Illinois program is being organ-
ized. All four of the laboratories that responded to the PEPIR question-
naire reported that they had modern equipment for pesticide work. Michigan
appeared to be the best-equipped laboratory but it was closely followed by
Wisconsin and Minnesota. Presently, Illinois has not dedicated equipment
to the pesticide function which is proposed.
Chemists in the four laboratories are well-trained and have either BS,
BA, or MS degrees. Technicians are high school graduates with extensive
and specific training (experience) in pesticide work. Excluding Illinois
(new program), the reporting laboratories have senior chemists with 7 to 11
years' experience in formulation work and 9 to 20 years in residue.
All responding laboratories practice AOAC and EPA methods supplemented
by methods from literature. These laboratories participate in either or
both EPA and AAPCO Check Sample Analysis Programs. Document control and
-------
V-2
sample security (to protect integrity) varied widely among the four labora-
tories. Illinois plans to adopt the custody procedures already in place
elsewhere in the laboratory. These reported procedures were excellent.
Wisconsin and Minnesota have good sample document control programs while
the Michigan program apparently needs some upgrading.
All respondents are interested in methods development and specific
training in a wide variety of subjects including screening and verification
procedures, as well as reporting techniques. Michigan and Wisconsin ex-
pressed high interest in HPLC training for both formulation and residue
chemists. Other training subjects of interest cited by at least one of the
four laboratories were atomic absorption, infrared analysis, and screening
tests for cross-contamination.
SPECIFIC STATE LABORATORY CAPABILITIES
Attached to this detailed analysis is a comparative tabulation of the
state laboratory capabilities in Region V.
Illinois
Illinois Department of Agriculture operates a formulation analytical
laboratory at 531 East Sangamon Avenue, Springfield, Illinois 62706.
Robert L. Schwarberg is the Bureau Chief. The Chief Chemist is Leonard
Jann. The pesticide formulation laboratory is a new program in Illinois
and the profile information herein is based upon proposed actions by the
state.
Initially, the formulation laboratory will be staffed by one chemist
who holds a BS degree and has 9 years' experience in analytical chemistry.
Laboratory functions, other than formulation work, already include feeds
and fertilizers guarantee analysis. The proposed work with pesticide
formulations will initially be limited to analysis of insecticides, herbi-
cides, fungicides, and rodenticides.
-------
V-3
The new laboratory function (formulation analysis) in Illinois has no
equipment dedicated to it but there is substantial equipment available for
formulation analytical work elsewhere in the laboratory. Included are two
analytical and a top-loading balance, two pH/millivolt meters, an atomic
absorption unit, two UV/visible spectrophotometers, a gas chromatograph
with FID detector, a liquid chromatograph and a polarograph. All the
equipment is modern and most is less than 5 years old. The laboratory also
has access to a polarograph at a nearby facility. The instrument is only a
year old.
The pesticide formulation laboratory plans to use external standards
for quantification by HPLC. The available instrument is a Varian 5010 HPLC
with Varian Varichrome detector. It has variable wavelength UV and manual
10 ul 100 p injection system. Peak height will normally be used to measure
peak response.
Chain-of-custody procedures are already in practice in the Illinois
laboratory. The pesticide formulations laboratory will merely adopt these
excellent practices. Briefly, the procedures include sealing in plastic
bags all pesticide formulation samples collected by inspectors. Upon ar-
rival at the laboratory the seal and condition of the sample is checked,
and the sample is dated appropriately. Sample storage is under Tock and
key, and when samples are not in use they are secured in a locked area with
limited key access. Reference and standard solutions as well as sample
documents are also stored in locked areas when not in use.
The Illinois laboratory proposes to participate in EPA and AAPCO Check
Sample Programs. Verification and check analysis for formulation samples
will follow methods outlined by AOAC, CIPAC, EPA, or AWPA.
Analysts will be expected to perform true duplicate tests on all po-
tentially violative formulation samples. Usually only one subsample will
be used to verify potentially violative samples and, because only one chem-
ist will be working in the laboratory, there will be no routine recheck (by
a second chemist) of potentially violative samples.
-------
V-4
Principal source for reference standards will be EPA (Beltsville) or
the manufacturer. The Illinois laboratory will maintain both technical and
analytical reference standards.
Routine analyses will follow methodology outlined by AOAC, EPA and
various manufacturers. To date, no in-house laboratory methods have been
prepared.
The laboratory currently participates annually in AOAC meetings. Per-
sonnel either now serve or plan to serve as Collaborators in AOAC studies.
The Illinois laboratory staff feel that training in reporting methods
and use of proper forms would be helpful. They also feel that training in
such analytical techniques as TLC and cross-contamination screening would
be beneficial to their new program.
The Illinois laboratory will need additional staff and equipment as-
signed to pesticide analysis as their program develops.
Michigan
The responsible agency in Michigan's state pesticide program is the
Michigan Department of Agriculture, Laboratory Division, at 1615 South
Harrison Road, Lansing, Michigan 48909. The Laboratory Director is
Donald A. Muenterer. The laboratory division is involved in both pesticide
formulation and residue analysis. Mr. Richard Valencourt is the Formula-
tion Laboratory Supervisor. He holds a BA degree and has 8 years' exper-
ience. The laboratory assistant has a BS degree and 1 year experience.
The Residue Laboratory is headed by Mr. Barry Griffin who holds a BS de-
gree and has 10 years' experience. Three laboratory scientists and two lab-
oratory assistants work with Mr. Griffin in the residue section. The senior
scientist in the laboratory holds an MS degree and has 12 years' experience.
The other two scientists each have BS degrees with 5 years' experience,
while the two laboratory assistants are high school graduates with 11 and
15 years' experience.
-------
V-5
In addition to pesticide formulation and residue analysis, the Michi-
gan laboratory is involved in analytical work with feeds, fertilizers,
food, meat, fruits, vegetables, dairy products, liquor, drugs, toxicolog-
ical specimens, seeds, environmental samples, serology, animal pathology,
milk, and microbiology. Routinely, the laboratory analyzed formulation
products such as insecticides, herbicides, rodenticides, plant growth reg-
ulators, home and garden mixtures, antimicrobials, insect repellents, and
various pressurized cans. The residue laboratory routinely encounters an
equally diverse series of sample types including water, animal tissues,
fish, soil, vegetation, feeds, and dairy products. These various samples
are screened for organohalogens and organophorous pesticides, as well as
for various herbicides.
Last year the Michigan laboratory analyzed 37 pesticide formulation
samples for their state program in addition to 67 EPA samples and 8 AAPCO
samples.
Laboratory equipment for the most part is shared by analysts doing
formulation and residue work (sample preparation, storage, and cleanup are
separated). Available equipment includes analytical and top-loading bal-
ances, three pH/millivolt meters, two atomic absorption units, an IR
spectrophotometer, six UV/visible spectrophotometers, electrodeposition,
six gas chromatographs, two liquid chromatographs, and two GLC/mass
spectrometers.
Gas chromatographs are equipped with a variety of detectors and data
acquisition accessories. Three have oven-programming capability and one
has an autosampler. The laboratory packs, but does not coat, gas chromato-
graphic columns. The columns and/or packings are purchased from ANSPEC.
Both formulation and residue workers use external standard techniques
in GLC. The formulations group has two HPLC available. Both have UV de-
tectors and sample loop injection systems. One has variable wavelength and
the other has wavelengths 254, 280, and 365 available. Peak response
measurements on these HPLC's are typically by peak height rather than by
-------
V-6
integration; both residue and formulation groups use external standard
techniques for quantification by HPLC.
Michigan needs to upgrade custody control practices for samples. Both
formulation and residue samples are sealed in labeled plastic bags by in-
spectors. When received at the laboratory the samples are dated and in-
spected for condition and seal. Formulation samples are stored in a locked
area with limited access while residue samples are placed in an unlocked
freezer until analysis. Typically, unsealed samples are not kept under
lock and key when not in the immediate possession of the analyst. Once
sample analyses are complete, the analyst is not required to officially
reseal the sample. Bulk analytical and technical reference standards are
stored under lock and key but standard solution and sample documentation
are not.
As part of the quality-assurance program, the Michigan laboratory par-
ticipates in State, FDA, EPA, and AAPCO check sample programs. Formulation
and residue analyses are verified through the use of official AOAC, CIPAC,
EPA or AWPA methods. In addition, the Michigan laboratory has used spiked
samples to check methods. Potentially violative formulation samples are
verified for more than one subsample and the originaal analyst performs
analyses in true duplicate with newly prepared standard and sample solu-
tions for each result. Check analysis is not typically performed by a
second analyst. Pesticide residue analyses are confirmed by TLC GLC-mass
spectrometric techniques.
Reference standards for formulation or residue work are obtained from
EPA at Research Triangle Park, North Carolina. The laboratory maintains
both technical and analytical reference standards. Neat standards are re-
assayed or replaced on the basis of analytical use (frequency) and sta-
bility. Dilute standards are prepared for instrumental analysis in residue
and formulation work every 6 months.
Routinely, pesticide formulation and residue analysis follow proce-
duies published in AOAC, Pesticide Analytical Manual I and II, scientific
-------
V-7
journals, and/or manufacturer methods. The laboratory has prepared a com-
pilation on in-house methods for both formulation and residue work.
Personnel from the formulation and residue sections at the Michigan
laboratory participate as Collaborators in AOAC studies. Annually, persons
from the laboratory attend AOAC meetings to discuss methodology and related
pesticide chemistry. Additionally, the laboratory personnel participate in
meetings of ASTM, Central States Association of Food and Drug Officials,
and the Pittsburg Conference.
Laboratory workers feel that formulation methods are needed for ana-
lyzing rodenticides such as Zm3P2, and residue methods are needed for her-
bicides and various industrial chemicals.
Michigan considers chemical deficiencies, overformulations, cross-
contamination, and net-weight deficiencies to be major criteria for poten-
tially violative formulation samples.
Personnel working in the formulation section have had appreciable ex-
perience in testifying as expert witnesses. Scientists in the residue sec-
tion have had some experience also with respect to defending their findings
in enforcement cases.
Laboratory staff feel that training in verification procedures would
be of benefit to them. Workers in the formulation section feel that train-
ing in HPLC, AA, and IR analytical techniques would improve their overall
capability while residue workers would like to have additional training in
HPLC techniques.
In summary, the Michigan laboratory has adequate equipment and exper-
ience to perform work in both formulation and residue analysis. As work-
loads increase additional staff may be needed to meet analytical demands,
especially in the formulation work.
-------
V-8
Wisconsin
The Bureau of Laboratory Services, Wisconsin Department of Agriculture,
Trade and Consumer Protection, is the agency involved with the Federal-State
Pesticide Enforcement Grant agreement. The laboratory is at 4702 Univer-
sity Avenue, Madison, Wisconsin 53705. Donald N. Willett is the Labora-
tory Director, and John P. Daubert serves as the Supervisor of the formula-
tion and residue section. Four chemists and a laboratory technician work
in pesticide analysis. A senior chemist is the formulation specialist. He
holds a BS degree and has 11 years' experience. Three chemists, two with
BS degrees and one with an MS degree, do residue analysis. They have ex-
perience ranging from 3 to 9 years. The laboratory technician has 6 years'
experience and works primarily in the residue section.
The laboratory is also involved in routine analysis of fertilizers
(pesticide mixtures), heavy metals, industrial chemicals, drugs, and con-
taminants in foods and crops. Routine pesticide formulation products ana-
lyzed include insecticides, herbicides, fungicides, plant growth regula-
tors, rodenticides, home and garden mixtures, antimicrobials, and pres-
surized containers. Last year the laboratory analyzed 54 formulation
samples for the state.
i
Routine residue samples encountered include water, animal tissues,
soil, sediment, food, and feeds. These are typically screened for organo-
halogens, organophosphates, and herbicides, as well as nitrogen and
phosphorus.
Laboratory instrumentation is shared by chemists during formulation
and residue work. However, all other activities, such as sample prepara-
tion, storage, and cleanup, are separated. The laboratory equipment in-
cludes an analytical balance, two top-loading balances, a pH/millivolt
meter, an AA, IR, and UV/visible spectrophotometers, six gas chromato-
graphs, two liquid chromatographs and a spectrofluorometer. The laboratory
has supplies (and experience) for thin-layer chromatography.
-------
V-9
Gas chromatographs have a variety of detectors, data acquisition ac-
cessories, and one is equipped with an autosampler. Typically, the labora-
tory packs GC columns but column packings are not coated at the laboratory.
Applied Sciences is the principal supplier for columns and packings. In-
ternal standard technique is used for GLC analysis in formulations while
external standard methodology is used for residue work. Both HPLC units
have UV and RI detectors. One has variable wavelength while the other has
a 254 available wavelength. Neither unit has column temperature control
nor gradient capability. Peak response is normally measured by integration
technique.
The Wisconsin laboratory has a good chain-of-custody for samples.
Upon collection, formulation and residue samples are officially sealed in
plastic bags by inspectors. The incoming samples are dated and examined by
laboratory staff for condition and seal. The laboratory reportedly has
limited access with security sufficient not to warrant individual lock and
key for sample storage, standard solutions, and documentation. Only bulk
analytical and technical reference standards are stored under separate lock
and key. When analysis is completed, the chemist officially reseals all
samples.
The formulation section participates in the AAPCO Check Sample Pro-
gram. Official AOAC or equilavent methods are used to confirm all poten-
tially violative formulation samples. The original analyst performs true
duplicate tests and routinely verifies potential violative samples on more
than one subsample. Analysis is rechecked by a second analyst. Also as
part of the verification procedure for formulations, titrants are restan-
dardized or reagent blanks are determined.
The residue section participates in FDA and EPA programs of quality
assurance. Pesticide residue results are confirmed by a second method (if
available) with different GLC columns and detectors; TLC and tests are
always repeated by a second analyst.
-------
V-10
Pesticide reference standards for formulation and residue work are
obtained from EPA in Research Triangle Park, North Carolina; FDA; and manu-
facturers. Analytical methods for all pesticide work usually follow pro-
cedures published by AOAC and EPA. The residue and formulation laborato-
ries have prepared a compilation of in-house methods also.
Persons involved in both formulation and residue analysis attend AOAC
meetings annually. They also participate as Collaborators in AOAC studies.
Laboratory staff actively participate in ACS, Pittsburg Conference, Central
States Association of FDA officials, and various industry and university
seminars on pesticide methodology.
Specific pesticide types for which methods are needed according to the
Wisconsin laboratory staff are: (1) pesticide-fertilizer mixtures (formu-
lation), and (2) carbofuron, methomyl, and orthene (residue).
Cross-contamination screening is done routinely for many pesticide
formulations but not for pesticide-fertilizer mixtures, rodenticides, or
disinfectants. Residue screening is done for organophosphates (GLC and
TLC), chlorinated hydrocarbons (GLC and TLC), carbomates, and others (TLC).
Wisconsin considers chemical deficiency, overformulation, eross-
contaminants, and net-weight deficiency to be the criteria for a poten-
tially violative formulation sample. With respect to formulation analysis,
the laboratory also has established segregation, separation, and label
violations as defective sample criteria.
The Wisconsin laboratory staff would like to have additional training
in liquid chromatography, infrared analysis, verification procedures, and
any new methodology which is available. Both the residue and formulation
staffs are interested in training in HPLC techniques. Furthermore, staff
involved with formulation analysis would be interested in learning more
about IR, AA, and cross-contaminant methods.
-------
V-ll
Wisconsin appears to have adequate staff and equipment to conduct re-
sidue and formulation work. Another chemist to assist with formulation
work and additional technicians would be helpful as workload increases.
Minnesota
The agency involved in the State/Federal Pesticide Enforcement Grant
agreement is the Minnesota Department of Agriculture. Its laboratory is at
510 State Office Building, St. Paul, Minnesota 55155. Richard Schifsky is
the Laboratory Director. The Pesticide Formulation Supervisor is Craig
Markell who holds a BA degree and has 7 years' experience. Mr. Markell
also shares analytical responsibilities with chemists in the residue sec-
tion. Three other chemists with BS degrees have been recently hired (less
than 1 years' experience each) to work under Mr. Markell in formulation
analyses. Reino Matson is the supervisory chemist in the residue group.
This senior chemist has a BS degree and 20 years' experience. Another
chemist with a BS degree and 3 years' experience works in the residue
laboratory also.
In addition to residue and formulation work, the laboratory is en-
gaged in analysis of fertilizers, feeds, crops, food bacteriology, dairy
products, and water. Routinely, the formulation laboratory analyzes in-
secticides, herbicides, fungicides, rodenticides, plant growth regulators,
baits, home and garden mixtures, antimicrobials, insect repel 1 ants, and
pressurized containers. Routine residue work includes analysis of water,
soil, sediment, tissue, food, and feed. These media are screened for or-
ganohalogens, organophosphates, herbicides, and such elements as nitrogen
and phosphorus.
The State/Federal grant agreement in Minnesota is new. In the past 6
months the laboratory has analyzed seven formulation samples for its state
program and 63 EPA samples.
Residue and formulation facilities are separated. Sample storage,
preparation, glassware, cleanup, and instrumentation are duplicated where
-------
V-12
needed to provide independent space and instrumentation for the two basic
types of pesticide work.
The two laboratories have analytical and top-loading balances and gas
chromatographs with a variety of detectors and data-acquisition accesso-
ries. The formulation laboratory has a pH/millivolt meter, IR spectrom-
eter, and liquid chromatograph. Both laboratories have immediate access to
a UV/visible spectrometer and another liquid chromatograph. An atomic ab-
sorption unit is also available at a nearby facility. GLC columns are both
coated and packed at the laboratory as well as purchased from commercial
suppliers. For routine sample analysis, the formulation laboratory uses
internal standard methodology, while the residue group uses external.
HPLC units are equipped with UV detectors. One has a gradient capa-
bility variable wavelength, column temperature control (LC-100 oven) and an
autosampler. The other HPLC has available wavelengths of 254, 280, 313,
340, 365, 405, 436, and 546. Analysts use either peak height or integra-
tion techniques to measure peak response. Both groups use external stan-
dard techniques for HPLC work. The pesticide formulation section currently
has experience and the supplies to perform thin-layer chromatography studies.
Chain-of-custody in the Minnesota laboratory is good. Inspectors of-
ficially seal residue or formulation samples for transport to the labora-
tory. Formulation samples are always retained in plastic bags (inspector
through laboratory). Incoming samples are dated and inspected at the lab-
oratory as to condition and seal. The samples are then stored in a locked
area with limited key access until time for analysis. Sample records are
also locked up when not in use. When unsealed samples are not in the im-
mediate possession of the analyst, they are kept under lock and key. At
the termination of analysis, all samples are officially resealed by ana-
lysts. Neither standard solutions nor reference standard are kept in
locked areas.
Minnesota participates in the EPA Check Sample Program for pesticide
formulations and the AFOO-Central States Program for residues.
-------
V-13
Potentially violative formulation samples are confirmed using methods
described in AOAC, CIPAC, EPA, and AWPA, as well as those recommended in
the NEIC Pesticide Product Laboratory Procedures Manual. Analyses are per-
formed in true duplicate by a second chemist and on a second subsample if
available. New dilute standard solutions are used by each analyst, but
typically no analysts maintain their own set of commonly-used titrants.
Restandardization of titrants and other verification procedures are used
for potentially violative formulation samples. Pesticide residue results
are confirmed by TLC, LC, and the use of a second column and different
detector.
Residue and formulation reference standards are obtained from EPA or
manufacturers. There is no regular program for replacing or reassaying
neat standards. Dilute standards are prepared for instrumental analysis
before every group of analyses on a given day.
Formulation section staff routinely use methods prescribed by AOAC,
Zweig, and manufacturers, while residue workers rely on FDA-PAM I and II,
Zweig and manufacturers for methodology. Neither laboratory has complied
in-house methods.
Staff from the Minnesota laboratory occasionally attend AOAC-meetings
and frequently are active participants in the Central States AFDO meetings.
Formulation chemists feel that methods are needed for screening, de-
tergents (cleaners) and metaldehyde. Residue chemists would like to see
better techniques developed for carbamates as well as phenoxy and acid
herbicides.
Both formulation and residue chemists are involved in cross-
contamination screening. In the formulation work, the chemists screen only
products containing insecticides, herbicides and fungicides. In the
residue work, the chemists use TLC methods to screen organophosphates and
chlorinated hydrocarbons.
-------
V-14
The formulation laboratory considers chemical deficiencies, overformu-
lations, cross-contamination and net-weight deficiencies as being poten-
tially violative.
Residue chemists feel that training is needed in procedures for
chain-of-custody, reporting, and verification. Formulation chemists would
like additional training in screening techniques.
The Minnesota laboratory appears adequately equipped and staffed to
perform a moderate sample load in residue and formulation analysis. Acqui-
sition of technicians to assist the chemists in both groups appears needed
as workload increases. More participation in AOAC and other methods and
validation meetings appears appropriate also.
-------
REGION V
V-15
Indiana Illinois
Chemist/Other Scientists Fornul.
Chemists/Other Scientists
Ph. 0
M.S.
B.S.
B A.
Total
Technician/Support
Clerical Support
Administrative
Total - all Staff
Analytical Balances
Top Loading Balances
pH Meter
Atomic Absorption Specs.
Infrared Spectrometers
UV/Vis. Spectrometers
Electrodeposition
Gas Chromatographs
Liquid Chromatographs
GC/Mass Spec.
Other
Internal Standards
External Standards
Column pkg. capabil .(GLC)
In-lab
Purchased
Michigan
Wisconsin
Residues horrnul. Residues Formul Residues Formul. Residues
STAFF
1
1
1
EQUIPMENT
2-d
1-d
2-d
1-d
2-d
1-d
1-d
1-e
Polargraph-d
METHODOLOGY
Yes
Yes
Packed
Yes
1
1 3
1
2 4
2
6
2-a 3-d 1-b
3-d 1-b
3-d
2-d
1-a
1-a 5-d
1-d
4-c 3-b
2-d
2-d
Yes Yes
Packed
Yes ' Yes
1
1
1
1-c
1-a
1-d
1-d
1-c
1-d
6-c
2-d
1
2
3
1
4
1-b
Minnesota
Formul. Residues
3
1
3 1
2-a 2-d
1-a
1-a
1-d
1-a
1-c
1-a 1-d
1-a 1-c
2
2*4
2
1-b
1-b
2-b
Spectrofluorometer-d
Packed
Yes
Yes
Yes
Coat. Packed
Yes
CHAIN-OF-CUSTODY SAMPLES
Sealed Samples
Plastic Bag Enclosure
Inspector
Laboratory
Receipt Inspec. of sample
Security of samples
Storage
Yes
Yes
Yes
Yes
Excellent
Excellent
Yes Yes
glass or plastic
Yes Yes
Fair Fair
Fair Fair
Yes
Yes
Yes
Good
Good
Yes
varies
Yes
Good
Good
Yes
Yes
Yes
Yes
Good
Good
Yes
No
No
Yes
Good
Good
QUALITY ASSURANCE
Check Sample programs
EPA
AAPCO
Southern Assn FFPCO
USDA/FSQS
Analysis Verification
Formulations
Residues
Standard Sources
Beltsville EPA
EPA/RTP
Manufacturer
Commercial
Methods
AOAC
FDA-PAM
EPA Formulation Methods
NEIC
ZWEIG
In-house
Methods Development
Samples per year
Yes
Yes
Yes
Yes Yes
Yes
FDA
Mich labs.
Good
Yes
Yes
Yes
Yes
AOAC
New Program
Good
TLC-Mass
Yes Yes
Yes
Yes Occasionally
Yes Yes
Yes Yes
In- house, AOAC
S=37,EPA=67,AAPCO=8
Good
spec
Yes
Yes
Yes
Yes
Yes
FDA
2nd,GC
Yes
Yes
Yes
Yes
In-house, AOAC
S=54
Yes
Central
Good
,TCL
Yes
Yes
Yes
Yes
states
TLC, LC
Yes
Yes
Yes
Yes
Central States
S=7,EPA-63
Equipment Use Code:
a = Formulations Lab, dedicated
d = Available in Lab elsewhere
b = Residue Lab dedicated
e = Available outside Lab.
c = Formulations/Residues Shared
-------
VI-1
STATE PESTICIDE FORMULATIONS AND RESIDUES LABORATORIES
ANALYTICAL SCIENTIFIC CAPABILITIES
EPA REGION VI
GENERAL
States operating pesticide laboratories in Region VI currently with
Federal-State Enforcement Grant Agreements are: Texas, Arkansas, New
Mexico, Oklahoma, and Louisiana. Laboratory questionnaire responses* were
received from all these states and evaluations are presented below.
OVERVIEW OF LABORATORY CAPABILITIES
Arkansas has the largest staff (five chemists) assigned to formulation
analysis. New Mexico, Oklahoma and Louisiana have similar-sized formula-
tion analytical groups (two to three persons) and the Texas program in for-
mulation analysis is new. Modern equipment is available for formulation
work in all these laboratories; however, the Louisiana laboratory is in
need of additional gas chromatographic equipment for use by its three
chemists.
/•
Senior chemists in all five laboratories appear well-trained having
either BS or MS degrees and 5 to 31 years' experience. Analysts from all
the laboratories use AOAC and EPA methods supplemented by techniques pub-
lished in professional or technical journals.
Four of the five laboratories have only limited participation in AOAC
activities involving discussions of methods development and verification.
Arkansas, the exception, attends annual AOAC meetings and actively partici-
pates in AOAC collaborative studies as a Collaborator.
* Texas submitted the PEPIR questionnaire while information for the other four
states was obtained from a similar questionnaire titled "Pesticide Produce
Laboratory Profile".
-------
VI-2
New Mexico has an excellent sample document control and chain-of-
custody procedure. Oklahoma custody procedures are also good while Texas,
Arkansas, and Louisiana appear to have either no formal procedure or in-
adequate custody practices.
The laboratories that responded to inquiries about training reported
needs in either or both procedural or analytical areas. Principal procedu-
ral areas for which the staffs felt training would be beneficial were
chain-of-custody and verification practices. General analytical techniques
in which training was reported needed included IR, AA, TLC, and HPLC proce-
dures. Need was also expressed for training in the techniques for deter-
mining cross-contamination in formulation samples.
SPECIFIC STATE LABORATORY CAPABILITIES
Attached to this detailed analysis is a comparative tabulation of the
state laboratory capabilities in Region VI.
Texas
Texas Department of Agriculture operates a pesticide analytical lab-
oratory in Brenham, Texas. The laboratory is currently performing both
pesticide residue and formulation analyses. The Laboratory Director is
William E. McCasland who holds an MS degree. Two chemists (one is
part-time) work in the residue laboratory. Both have BS degrees and the
senior chemist has 11 years' experience while his associate has 4 years.
Four chemists work in the formulation laboratory. Each has a BS degree and
the chemist-in-charge has 12 years' experience. Currently, no technicians
are assigned to the laboratory.
The laboratory is involved routinely in analyzing a variety of residue
camples including water, soil, sediments, tissues, foods, feeds, clothing
and household items. The laboratory is capable of performing residue
screening tests for organohalogen, organophosphorus, and various herbi-
cides. In addition to residue analysis, the Texas laboratory performs such
-------
VI-3
analytical functions as mi Ik-testing, protein analysis and antifreeze
testing.
New equipment has already been dedicated for future use in formulation
work while the residue laboratory equipment ranges in age from 4 to 10
years. Instrumentation and associated functions (sample storage, prepara-
tion, glassware, cleanup) are in separate areas for planned formulation and
existing residue work. Both the residue and formulation sections are
equipped with two analytical and a top-loading balance, a pH/millivolt
meter, UV/visible spectrophotometer, and two gas chromatographs with a va-
riety of detectors. The formulation section also has a new atomic absorp-
tion unit, IR spectrophotometer and liquid chromatograph.
Gas chromatographic columns are packed but not coated at the labora-
tory. Columns and/or packings are purchased from Supelco. The residue
V.
group uses external standard techniques for routine GLC sample analysis.
The HPLC which will be in use in future formulation work is equipped
with gradient capability, UV and photoconductivity detector and variable
wavelength. It has a rheodyne-variable volume injection system but no auto-
sampler or column temperature control. Peak response will normally be mea-
sured by peak height.
The Texas laboratory has good chain-of-custody procedures for formula-
tion samples. All samples are delivered to the laboratory by inspectors.
Samples always have an official seal and are placed in plastic bags as re-
quired or necessitated by type and size of sample. Samples are logged in
and stored in a locked room with limited key access. After analyses are
completed, chemists reseal samples and return them to the locked storeroom.
Residue samples are not routinely sealed but are delivered to the labora-
tory by the inspector. Standard solutions and standard references are not
under lock and key when not in use. Access to the laboratory itself is
limited.
-------
VI-4
Residue chemists at the laboratory participate in IPQAP and FDA
(Southern Regional) Check Sample Programs as part of the overall laboratory
quality assurance program. Residue results are confirmed on various col-
umns and/or by selective detectors.
Pesticide reference standards used in the residue work are obtained
from EPA, FDA, and manufacturers. Neat standards are replaced or reassayed
at least annually. Dilute standards are prepared for instrumental analysis
every 3 to 6 months.
Routinely, the methods used for residue analysis follow PAM, EPA, AOAC
and Zweig publications. The analysts have not compiled in-house residue
methods.
Chemists from the laboratory annually attend AOAC and Florida seminars
at which pesticide formulation and residue methodology are discussed. Cur-
rently, the residue chemists do not participate in AOAC collaborative
studies.
Analysts at the Texas laboratory feel that analytical methods are
needed for paraquat and glyphosphate. They also feel that they would
benefit from additional training in IR, AA, TLC techniques, and cross-
contamination screening methods.
The Texas laboratory appears adequately equipped to perform both for-
mulation and residue analysis. Additional staff (chemists and technicians)
will be needed as their formulation work develops. They will also need to
officially develop chain-of-custody and document control procedures if this
has not been done already.
Arkansas
The following discussion is limited to pesticide product analysis (see
footnote in _L_ General of this report section).
-------
VI-5
The Arkansas State Plant Board Chemical Laboratory in Little Rock is
responsible for the State-Federal grant agreement activities. William C.
Ware is the Laboratory Director and Chief Chemist. For daily operations,
the laboratory supervisor is Thomas B. Hall who holds a BS degree and has
22 years' experience in pesticide formulation work. Four other chemists
work in the formulation analytical laboratory. All have BS degrees; three
have 8 to 10 years' experience and one has about a year of formulation
testing experience.
Analytical functions in the Arkansas laboratory, beside formulations
analyses, include work with feeds, fertilizers, liming materials, pesticide
adjuvants, and soils. Routinely encountered pesticide products include
insecticides, herbicides, fungicides, rodenticides, and home and garden
mixtures.
The formulation laboratory is equipped with or has immediate access to
three analytical balances, a top-loading balance, pH/millivolt meter,
atomic absorption-unit, two IR spectrophotometers, two UV/visible spectro-
photometers, two gas chromatographs with a variety of detectors, and a
liquid chromatograph.
Gas chromatographic columns are seldom packed or coated in the lab-
oratory. The columns and/or packings are usually purchased from Applied
Science Laboratories, Inc. For routine GC sample analysis, internal stan-
dard techniques are used by chemists in the formulation laboratory.
An HPLC was purchased by the laboratory in March 1979. It has a gra-
dient capability, 254-nm wavelength, variable volume injection system and
heated compartment-type column temperature control. Peak response is mea-
sured by an electronic integrator. Analysts use internal standard tech-
niques for routine HPLC work.
Last year the laboratory analyzed 1,100 formulation samples for the
State; they did not analyze any samples for EPA. Custody of formulation
samples collected under the grant is practiced as follows. Samples are
-------
VI-6
officially sealed in plastic-lined bags by the inspector. When transferred
to the laboratory, the date of receipt and condition of sample and seal are
noted appropriately. The samples are locked in a laboratory cabinet with
limited key access until analysis is performed. Violative samples are
double-checked if the chief chemist so recommends. Finished non-violative
samples, standard solutions, and bulk or analytical reference standards are
not kept under lock and key when not in use. Analysts are not required to
officially reseal samples when analyses are complete. Sample records are
kept in a limited access locked filing cabinet in the EPA-supported chem-
ist's office.
The Arkansas laboratory participates in AAPCO Check Sample Program and
uses official AOAC or standard EPA, AWPA and Scott's methods to confirm all
potentially violative samples. Samples are tested by the original analyst
in true duplicate and, if available, on more than one subsample. A second
analyst does not normally recheck every analysis. Each analyst maintains a
set of commonly-used titrants and ^standardization or reagent blanks are
tested routinely as part of the verification procedure.
Principal sources for pesticide standards are EPA and manufacturers.
Both technical and analytical reference standards are maintained by the
formulation laboratory. Neat standards are replaced whenever analysis
shows a change in the standard. Dilute standards are prepared for each
instrumental analysis.
In addition to AOAC methods, the formulation section follows the tech-
niques published by EPA, Zweig (Analytical Methods for Pesticides and Plant
Growth Regulators) and FDA. Laboratory analysts have not compiled in-house
methods.
Analysts from the Arkansas laboratory attend AOAC meetings annually.
The laboratory is also a Collaborator participating in AOAC studies.
Arkansas considers chemical deficiencies, overformulations, and
cross-contamination as grounds for a violative formulation sample.
-------
VI-7
Laboratory analysts feel that they need additional training in chain-
of-custody procedures as well as analytical training in HPLC and TLC
techniques.
Arkansas has adequate professional staff and equipment to perform a
relatively large amount of formulation analyses. Their immediate staffing
needs appear to be technicians to support the five chemists. Training in
document control and sample custody is a high priority item also.
New Mexico
The New Mexico Department of Agriculture is responsible for pesticide
laboratory work associated with the State-Federal Enforcement Grant agree-
ment. The laboratory in Las Cruces is under the direction of Robert Martin
who is the State Chemist and an analyst in the formulation laboratory. His
associate, Floyd Highfill, resigned in November 1980 and has not been re-
placed. Currently, Mr. Highfill's assistant and Mr. Martin perform all
analyses. No technicians are assigned to assist in formulation analysis.
Routinely the laboratory analyzes insecticides, herbicides, home and
garden mixtures, antimicrobials (quaternary amine salts), and use-dilution
samples. In addition to this formulation work, the New Mexico laboratory
is involved with analysis of fertilizers, feeds, dairy products, petroleum
products, and residues. Last year the laboratory analyzed 80 formulation
samples for their State and 75 for EPA.
Equipment dedicated or readily available to the formulation analysts
includes two analytical balances, two pH/millivolt meters, an atomic ab-
sorption unit, IR and UV/visible spectrophotometers, three gas chromato-
graphs with various detectors and a liquid chromatograph.
Columns for gas chromatographic work are packed and coated in the lab-
oratory as well as purchased from Applied Science. Routine sample analysis
is done by external standard technique.
-------
VI-8
The HPLC unit has a UV detector, variable wavelength and loop-syringe-
type injection system. Peak response is normally measured by peak height,
and analysts employ external standard technique for routine sample analysis.
Excellent chain-of-custody procedures are practiced at the New Mexico
laboratory. Sealed samples (in plastic bags) are received at the labora-
tory, dated, and checked for condition. The samples are stored in .a locked
area with limited key access. Standard solutions, analytical and bulk
standard references, and sample documentation are also stored in locked
areas when not in use. Finally, when the analyst completes his work he
officially reseals all samples.
Currently, analysts in the New Mexico formulations laboratory do not
participate in the AAPCO Check Sample Program. However, all potentially
violative formulation analyses are confirmed by AOAC, CIPAC, EPA or AWPA1
methods. If no official or standard method is available, the analyst re-
sorts to retesting the sample by two or more independent methods and/or
relying on another chemist using a different methodology to confirm results
of the original analyst. Verification of potentially violative samples
involves true duplicate testing on more than one subsample, if available.
The analyst also uses ^standardization of titrants or determination of
reagent blanks as part of the verification procedure.
Reference standards for the formulation laboratory are obtained from
EPA (Beltsville) or manufacturers. Both technical and analytical reference
standards are kept by the laboratory. Neat standards are replaced at least
annually while dilute standards are prepared for instrumental analysis much
more often.
Routine pesticide formulation analysis is performed according to
methods published by AOAC, EPA, and Virginia Department of Agriculture, as
well as in-house.
Except for disinfectants, pesticide products are routinely screened
for organophosphates (TLC, GC-FPD), chlorinated hydrocarbons (TLC) and car-
bonates (GC-FID).
-------
VI-9
New Mexico considers a formulation pesticide sample to be violative if
it is chemically deficient, cross-contaminated or overformulated.
The New Mexico laboratory is well-enough equipped to perform a small
sample load. Another chemist and supporting technicians would increase
overall laboratory capability. More participation in AOAC and other
methods validation and development meetings and training programs appears
appropriate also.
Oklahoma
The Oklahoma Department of Agriculture is responsible for pesticide
laboratory functions in accordance with the State-Federal Pesticide
Enforcement Grant agreement with EPA. The Agricultural Laboratory at 50 NE
23rd Street in Oklahoma City, Oklahoma 73105 is under the direction of
Kendall Jeffress. The Pesticide Formulation Supervisor and senior analyst
in the pesticide laboratory is David Warrick. Mr. Warrick holds a BS de-
gree and has 6 years' experience in pesticide product analysis. He is
assisted by two chemists with college training and some experience and a
technician with college training and a years' experience.
The laboratory analysts routinely encounter such pesticide products as
insecticides, herbicides, fungicides, rodenticides, plant growth regula-
tors, baits, home and garden mixtures, antimicrobials, repellents, devices
and pressurized containers. Additionally, the laboratory analytical func-
tions include work with pesticide residues, feeds, fertilizers, dairy
products, meats, and animal health (Brucellosis and EIA). Last year the
Oklahoma laboratory analyzed 463 formulation samples for their own state
program.
Laboratory equipment dedicated or available for formulation analytical
work includes an analytical and top-loading balance, pH meter, atomic ab-
sorption unit, IR spectrophotometer, UV/visible spectrophotometer, two gas
chromatographs and a liquid chromatograph. Most of the equipment is less
than 5 years old.
-------
VI-10
The gas chromatographs are equipped with a variety of detectors (FID,
EC, FPD and Hall). Columns are packed but not coated at the laboratory.
Supelco and Alltech are major suppliers of columns and/or packings. Ana-
lysts use external standard technique for routine GC sample analysis.
The HPLC has a gradient capacity, UV detector and wavelengths of 254
and 280 available. Peak response is normally measured by peak height, and
analysts use external standard technique for HPLC work.
Oklahoma has a good chain-of-custody procedure. Inspectors officially
seal formulation samples in plastic bags. Upon receipt at the laboratory,
samples are dated, inspected for condition and seal, and stored in a locked
area with limited key access. Standards and sample documents are also kept
under lock and key when not in use. After analysis is completed, chemists
are not required to officially reseal samples.
The laboratory quality-assurance program involves active participation
in the AAPCO Check Sample Program and confirmation of all potentially vio-
lative samples (if possible) using AOAC, EPS, AWPA, or other standard
methods. If official or standard methodology is not available, samples
methods are sought from other professionals in the Agricultural Laboratory
or samples are sent to another laboratory for analysis. Routinely, poten-
tially violative samples are analyzed in true duplicate and, if possible,
on more than one subsample. A second analyst often rechecks the sample
analysis using new dilute solutions. Determination of reagent blanks and
^standardization of titrants are also part of the Oklahoma laboratory
sample verification procedure.
Pesticide reference standards are obtained from EPA (Beltsville) and
manufacturers. Technical and analytical standards are maintained by the
Oklahoma laboratory. When standards appear to give inaccurate results they
are replaced. Dilute standards are prepared for instrumental analysis at
various times depending upon the pesticide.
-------
VI-11
Analysts have not compiled in-house analytical methods but rely upon
methods published by EPA, manufacturers, and various professional or tech-
nical journals. Laboratory personnel participate in AOAC collaborative
studies as Collaborators. They also occasionally attend annual AOAC
meetings.
Except for fertilizers, tank mixes, and dipping vats, pesticide for-
mulation products are screened for cross-contamination of organophosphates
(TLC method) and chlorinated hydrocarbons (TLC-AOAC 6.030 method).
Oklahoma considers chemical deficiency, overformulation, and cross-
contamination to be violative. The laboratory uses AAPCO guidelines for
determining either deficiencies or overformulations.
Laboratory analysts feel that training in verification procedures
would be helpful. They also believe there is a need for more training in
HPLC techniques and in specific product analysis of phenolic disinfectants
and pressurized containers.
Staff and equipment at the Oklahoma laboratory appear adequate to per-
form a moderate amount of formulation analysis. As workload increases
another chemist would be helpful to increase overall laboratory capability.
Louisiana
The Louisiana Department of Agriculture, Feed and Fertilizer Labora-
tory at Louisiana State University in Baton Rouge is responsible for acti-
vities of the State-Federal Pesticide Enforcement Grant agreement with EPA.
The Laboratory Director is Herschel Morris and the Pesticide Formulation
Supervisor and senior analyst is John B. McDevitt, Jr. Mr. McDevitt holds
an MS degree and has 31 years' experience in pesticide product analysis.
His two laboratory associates have BS degrees with 29 and 1 year's exper-
ience, respectively.
-------
VI-12
The laboratory did not report the number of pesticide formulation
samples analyzed for either the State or EPA last year. They did report
that the laboratory routinely analyzes such pesticide products as insecti-
cides, herbicides, fungicides, rodenticides, anti-fouling paints, baits,
home and garden mixtures, antimicrobials, repellents and pressurized con-
tainers. Additionally, the Feed and Fertilizer Laboratory is engaged in
analyses of water, meat, pesticide residues, and, as its name implies,
feeds and fertilizers.
Laboratory equipment available for pesticide formulation work includes
an analytical and a top-loading balance, pH meter, atomic absorption unit,
IR and UV/visible spectrophotometers, a gas chromatograph with various de-
tectors and integrator accessories, and two liquid chromatographs. A
GLC/mass spectrometer is also available at another laboratory on the LSU
campus.
Gas chromatograph columns are packed and coated at the formulation
laboratory. Analysts routinely use external standard technique for analy-
sis of formulations.
One HPLC has a UV, RI and fluoro-type detector with available wave-
lengths of 254, 280, 360, 410, 440, and 550. The other HPLC has a UV de-
tector and an available wavelength of 254. Peak response for HPLC is nor-
mally measured by peak height, and analysts use external standard tech-
niques for routine sample analysis.
Chain-of-custody and document-control procedures in the Louisiana lab-
oratory have recently been upgraded. Samples are officially sealed in
plastic bags by inspectors for transport to the laboratory. At the lab-
oratory the sample is dated, and the condition of the seal and sample are
checked by the Grant Project Director. Until recently, samples (sealed or
unsealed) were not stored in locked areas when not in the analyst's imme-
diate possession. Standards and references have never been placed under
lock and key when not in use. Sample records are now being kept under room
lock at the Louisiana Department of Agriculture.
-------
VI-13
Analysts participate in the AAPCO Check Sample Program and analyze and
confirm analysis using official AOAC or standard EPS or AWPA methods.
Samples are neither done in true duplicate nor verified for more than one
subsample. A second analyst does not perform a check analysis on poten-
tially violative samples. Verification procedure does include restandardi-
zation of titrants or determination of reagent blanks.
Pesticide reference standards are obtained from the EPA or from spe-
cific manufacturers. Neither technical nor analytical reference standards
are maintained by the laboratory. No procedure (timetable) has been estab-
lished for replacing standards or for preparing dilute standards for in-
strumental analysis.
Analysts rely on methods published by EPA, manufacturers, or profes-
sional or technical journals. They do not participate in AOAC collabora-
tive studies and seldom attend AOAC annual meetings.
The Louisiana laboratory has a limited capability for formulation an-
alysis because only a single gas chromatograph is available for three chem-
ists' use. The laboratory needs to establish a chain-of-custody and docu-
ment control procedure. More participation in AOAC and other methods val-
idation and development meetings and training programs appear appropriate
also.
-------
VI-14
REGION VI
Chemist/Other Scientists
Chemists/Other Scientists
Ph. D
M.S.
B.S.
B.A.
Total
Technician/Support
Clerical Support
Administrative
Total - all Staff
Analytical Balances
Top Loading Balances
pH Meter
Atomic Absorption Specs.
Infrared Spectrometers
UV/Vis. Spectrometers
Electrodeposition
Gas Chromatographs
Liquid Chromatographs
GC/Mass Spec.
Other
Internal Standards
External Standards
Column pkg. capabil . (GLC)
In-lab
Purchased
Texas Arkansas New Mexico
Formul. Residues Formul. Residues Formul. Residues
2 5
2 5
2 5
2-a 2-b 2-a 1-d
1-a 1-b 1-d
1-a 1-b 1-d
1-a l-d
1-a 2-a
1-a 1-b 2-d
2-a 2-b 2-d
1-a l-d
Yes
Yes
Packed
Yes Yes
STAFF
1
1
2
2
EQUIPMENT
1-a 1-d
2-d
1-d
1-a
1-d
3- a
METHODOLOGY
Yes
Packed, Coated
Yes
Oklahoma
Formul. Residues
1
College trng
2
1
3
.
1-a
1-d
1-a
1-d
1-a
1-d
2-d
1-d
Yes
Packed
Yes
Louisiana
Formul. Resic
1
2
3
3
1-a
2-d
2-d
1-d
1-d
1-d
1-a
2-a
1-e
Yes
Pack, Coat
CHAIN-OF-CUSTODY SAMPLES
Sealed Samples
Plastic Bag Enclosure
Inspector
Laboratory
Receipt Inspec. of sample
Security of samples
Storage
Yes
Yes
Yes
Poor
Poor
Yes
Yes
Yes
Yes
Excellent
Excellent
Yes
Yes
Good
Good
Yes
Yes
Poor
Poor
QUALITY ASSURANCE
Check Sample programs
EPA
AAPCO
Southern Assn FFPCO
USDA/FSQS
Analysis Verification
Formulations
Residues
Standard Sources
Beltsville EPA
EPA/RTP
Manufacturer
Commercial
Methods
AOAC
FDA- P AM
EPA Formulation Methods
NEIC
ZWEIG
In-house
Methods Development
Samples per year
Yes
IPQAP
FDA
Good
Various Columns/detectors
Yes Yes
FDA
Yes Yes
Yes
Yes Yes
Yes Yes
Yes
Yes
Yes Yes
AOAC, Florida
New Program S=1100
Good
Yes
Yes
Yes
Yes
Virginia Agr.
Yes
Yes
Good
Yes
Yes
Yes
Journals
AOAC In-house AOAC
S=80,EPA=75
S=463
Yes
Fair
Yes
Yes
Yes
Yes
Journals
Yes
In-house
Equipment Use C«de: a = Formulations Lab, dedicated
d = Available in Lab elsewhere
b = Residue Lab. dedicated
e = Available outside Lab.
c = Formulations/Residues Shared
-------
VII-1
STATE PESTICIDE FORMULATIONS AND RESIDUES LABORATORIES
ANALYTICAL SCIENTIFIC CAPABILITIES
EPA REGION VII
GENERAL
Currently, Iowa and Kansas are the only States in Region VII that have
cooperative Pesticide Enforcement Grant agreements with the EPA. These
grants include laboratory analytical services. Both states responded to
the PEPIR laboratory questionnaire; program evaluation for Kansas and Iowa
pesticide laboratories are presented below.
OVERVIEW OF LABORATORY CAPABILITIES
Iowa and Kansas have an adequate capability for analyzing pesticide
residue and formulation samples. In Iowa, four chemists are assigned to
pesticide formulation analyses, and four chemists plus a laboratory assis-
tant are involved in residue work. The professional staff education level
at the Iowa laboratory is predominantly the BS or BA; two chemists have MS
degrees and a chemist in the Residue Section has a PhD degree. Senior
scientists in both residue and formulation laboratories have 6 years of
specific experience. Their co-workers have 4 years' (or less) experience.
Kansas has a smaller staff of two chemists doing formulation and one
doing residue work. Both chemists in the formulation section have BS de-
grees; one has 7 years' experience while the other has 1. The residue
chemist has a PhD and 6 years' experience in pesticide analyses.
Both Kansas and Iowa pesticide laboratories appear to be of adequate
size and are well equipped. Each laboratory has analytical/top-loading
balances, pH meters, atomic absorbers, infrared spectrometer, UV/visible
spectrophotometers, gas chromatographs, and high-pressure liquid chroma-
tographs. The Kansas laboratory also has electrodeposition equipment
while Iowa has a GLC/mass spectrometer, fluorometer, auto-tinator and an
auto-analyzer.
-------
VII-2
The staff of both laboratories typically use AOAC and EPA methods of
analyses. They participate in the EPA Sample Check Program to maintain a
good quality control over samples analyzed. Whenever possible, the collec-
tion and analyses of pesticide samples are scheduled year-round rather than
on a sporadic basis. This serves to maintain efficient use of their mini-
mal laboratory staff.
According to the PEPIR laboratory questionnaire, Iowa is interested in
advanced training for the staff in procedures for evaluating cross-
contamination of formulations. Kansas has an interest in additional train-
ing in electrodeposition and HPLC techniques. Both laboratories expressed
a need for training in verification procedures.
SPECIFIC STATE LABORATORY CAPABILITIES
Attached to this detailed analysis is an itemized tabulation of the
Kansas and Iowa laboratory capability.
Kansas
The Kansas State Board of Agriculture Laboratory is the agency respon-
sible for activities associated with the State-Federal Pesticide Enforce-
ment Agreement. Mr. Marvin L. Schreiber is the Laboratory Director of the
facilities at 2524 West Sixth Street, Topeka, Kansas 66606. Mr. Oliver 0.
Bennett, Jr. is the supervisor in the formulation section and the senior in
the two-man formulation laboratory. He holds a BS degree in chemistry and
has 7 years' experience in pesticide product analysis. Mr. Bennett's as-
sociate, Leonard Murphy, also holds a BS degree in chemistry and has 1
year's experience in formulation analysis. Dr. Jesse R. Wood occupies the
only position in the residue laboratory section. He has 6 years' experience.
The Kansas Agricultural Laboratory is involved with analyses of pesti-
cide products, residues, animal remedies, and veterinary Pharmaceuticals.
Pesticide formulation products encountered routinely by the Kansas labora-
tory include insecticides, herbicides, fungicides, rodenticides, baits,
-------
VII-3
repellents, antimicrobials, home and garden mixtures, and various types of
pressurized containers. Pesticide residue samples analyzed routinely for
herbicides or insecticides include water, soil, and vegetation. Last year
the Kansas laboratory analyzed 663 pesticide products for their state pro-
gram and 38 samples for EPA.
The formulation and residue laboratory share instrumentation but have
separate space for storage, cleaning, and preparation of samples. Equip-
ment available includes four analytical balances, two top-loading balances,
a pH meter, Infrared and UV/visible spectrophotometers, electrodeposition,
two gas chromatographs, and a liquid chromatograph. At a nearby facility
the laboratory also has access to an atomic absorption unit.
The gas chromatographs are equipped with a variety of detectors (FID,
EC, Hall, EPD) and data system/chart recorders. One unit also has an HP
7671A autosampler. Chromatographic columns are packed and coated at the
laboratory as well as purchased through Supelco or Applied Science. An-
alysts use internal standard technique for routine formulation work and
external standard technique for residue analysis.
The HPLC instrument has gradient capability, UV and flourescent de-
tectors, and variable wavelength. The instrument has a loop-type injection
system with a microprocessor-controlled heating block oven. Peak response
is measured by either peak height or integration using a standard GC in-
tegrator. Routine sample analysis usually employs internal technique for
formulation and external for residue.
Chain-of-custody procedures at the Kansas laboratory are excellent.
Formulation and residue samples are collected and officially sealed in
plastic bags by inspectors. At the laboratory the samples are dated as to
receipt, and inspected for condition and seal. Formulation samples are
stored in a locked area with limited key access. Residue samples are
locked in a refrigerator. Once samples are unsealed for analysis, they are
either kept in the immediate possession of the analyst or stored in the
locked areas. All solutions, standards, and sample records are also kept
under lock and key when not in use.
-------
VII-4
The formulation laboratory section participates in both EPA and AAPCO
Check Sample Programs. However, satisfactory arrangements have not been
made yet for participation in a residue Check Sample Program. Potentially
violative formulation samples are confirmed using official AOAC, CIPAC,
EPA, or AWPA methods. Routinely, the formulation chemists perform analysis
in true duplicate on potentially violative samples. The samples are ver-
ified on more than one subsample (if possible), and a second chemist rou-
tinely rechecks analytical results using new dilute standard solutions.
Each formulation chemist restandardizes titrants or determines reagent
blanks as part of the sample-result verification procedure. Confirmation
of pesticide residue results typically involves three or four identifica-
tions on gas chromatographic columns of different polarities.
Pesticide standards for both formulation and residue work in the
Kansas laboratory are obtained from EPA (Beltsville) or manufacturers.
Neat standards for formulation work are replaced or reassayed annually (for
organophosphates) or every 2 years (for carbamates and most organochlor-
ines). In the residue laboratory, neat standards replacement depends upon
stability so there is no set schedule for reassay.
Formulation chemists used analytical methods described in published
manuals by AOAC, EPA, and industry. In residue analysis the procedures
followed are those published by FDA and industry. No in-house methods for
formulation or residue analysis have been compiled.
Analysts from the residue and formulation laboratory annually attend
AOAC meetings. Formulation chemists also participate in AOAC collaborative
studies as a Collaborator.
There are numerous specific pesticides or groups of pesticides for
which analysts believe either formulation or residue methods are needed.
In formulation work these include Monuron-Trichloroacetate, pelleted Rozol,
isooctyl esters of 2,4-D pyrethins in multicomponent dusts, Delnav, peanut
formulations of strychnine, Meta-Systox-R, and technical chlordane in
soils. In residue work these include Permethrin, C isooctyl ester, T iso-
octyl ester and Furadan plus 3 hydroxyfuradon.
-------
VII-5
Except for disinfectants and tank samples, pesticide products are
screened for cross-contaminations. The general method used for organo-
phosphate, chlorinated hydrocarbon, and carbamate cross-contamination
screening tests is TLC and GLC.
Kansas considers chemical deficiencies and cross-contaminations as
major criteria for judging formulation samples as potentially violative.
Analysts feel that training is needed in such procedural areas as
verification techniques and courtroom presentations. Technical training
needs felt by the staff to be beneficial are electrodeposition and HPLC
methodology.
The Kansas laboratory appears well equipped to perform both residue
and formulation analysis. Another chemist in each group, or one to be
cross-shared, and technician support would improve the overall capability
of the laboratory to handle larger analytical loads.
Iowa
The Chemical Laboratory Division of the Iowa Department of Agriculture
has both a formulation and a residue laboratory responsible for analyzing
pesticide enforcement samples collected under the grant administered by
EPA. Mr. Dwight Harder is the pesticide laboratory supervisor. His office
and the two laboratories are located in the Henry A. Wallace Building, Des
Moines, Iowa 50319. Mr. Harter's telephone number is (515) 281-8610. Mr.
Roger Bishop is the Pesticide Formulation Laboratory supervisor. The Residue
Analysis laboratory supervisor is Dr. Ronald Krahn. Both supervisors have
6 years' experience in their respective analytical fields. Mr. Bishop's
formulation staff includes three chemists; one has an MS degree and the
others have BS degrees. Dr. Krahn1s residue group consists of three chem-
ists and a laboratory assistant. One chemist has an MS degree, the others
have BA degrees, and the assistant has a high school education.
-------
VII-6
In addition to identifying pesticide formulations and residues, the
Iowa Chemical Laboratory analyzes fertilizers, feeds, vitamins, drugs in
feeds and dairy products. Types of formulation products analyzed routinely
include: insecticides, herbicides, fungicides, rodenticides, mollusk baits,
home and garden mixtures, antimicrobials, insect repellents and various
types of pressurized containers. Residue samples encountered include drink-
ing water, surface water (lakes and rivers), animal tissues, aquatic organ-
isms, soil, sediment, vegetation, animal feeds, and food items. The lab-
oratory is equipped to perform organohalogen and organophosphorus screening
and herbicide residue analyses as well as element-specific screening for
compounds containing nitrogen and phosphorus. Last year, Iowa analyzed 125
pesticide formulation samples for their State program and 107 samples for
EPA under the State Cooperative Agreement.
The Iowa laboratory is equipped with or has easy access to a top-
loading and six analytical balances, two pH/millivolt meters, a Beckman
atomic absorption and an IR spectrometer, UV/visible spectrophotometer,
five gas chromatographs, two liquid chromatographs, a GLC/mass spectro-
photometer, fluorometer, auto-tinator and Technicon auto-analyzer. Some of
the instrumentation is more than 10 years old but apparently functional;
this includes two of the analytical balances, the atomic absorption equip-
ment, the IR spectrometer, one of the BC's and the auto-tinator. -Two of
the gas chromatographs are equipped with auto-sampling units. Columns are
packed and coated at the laboratory as well as purchased commercially.
They also have a Perkin-Elmer Series 3 high-performance liquid chromato-
graph with a gradient and UV detector capability (LC-65T).
Iowa uses both internal and external standard techniques for pesticide
formulation work and only external standards for the residue laboratory
analyses.
The Iowa laboratory maintains excellent chain-of-custody over samples.
Formulation and residue samples are sealed upon collection by inspectors
and enclosed in plastic bags for transfer to the laboratory. Controls for
the incoming samples include logging the date received, observing the con-
dition of the sample and seal, and placing all samples under lock and key
-------
VII-7
when not in use. Unsealed samples are also placed under lock and key when
they are not in the analyst's immediate possession. There is limited ac-
cess to the locked sample storage area. Bulk analytical and technical
reference standards are stored separately under lock and key, as are sample
records, documentation, work sheets and notebooks. Residue samples are
stored in a locked freezer until analysis.
Iowa participates in the EPA and AAPCO formulation Check Sample Pro-
grams. The laboratory does not participate in any pesticide residue pro-
gram. All potentially violative formulation samples are confirmed in the
Iowa laboratory by appropriate AOAC, CIPAC, EPA or AWPA methods. If a
standard method is not available and extractions are involved, the analysts
perform multiple extractions to ensure complete recovery. Internal stan-
dards are used when possible and often the analysis is rerun using a dif-
ferent GC column. Analysis of potentially violative formulations are per-
formed by the original analyst in true duplicate, routinely verified
through subsampling and checked by a second analyst. They do not use an
independently maintained set of titrants for each chemist. The second ana-
lyst uses new dilute standard solutions, and titrants are restandardized
and blanks analyzed to evaluate reagents. All pesticide residues are con-
firmed by quantisation on another GC column and on a specific detector if
available. , \
v
Beltsville EPA laboratory or specific manufacturers supply the Iowa
laboratory with pesticide reference standards. The laboratory maintains
both technical and analytical reference standards for formulation work
which are replaced or reassayed every 1 to 5 years depending upon the
chemical. Dilute residue standards are prepared at intervals up to 2 years
for instrumental analysis.
The formulation and residue laboratories routinely use AOAC Journal/
Manual methods. Additionally, the residue laboratory uses PAM I and II
while the formulation laboratory refers to methods published by EPA and
TSD. The Iowa laboratory has also prepared a compilation of in-house
methods for formulation and residue analyses.
-------
VII-8
Although the formulation laboratory staff are involved in AOAC activi-
ties at the Associate Referee and Collaborator level, they seldom attend
the annual meetings. Both formulation and residue staff have attended the
EPA workshops presented periodically at the Denver Federal Center.
Iowa believes methodology is needed in formulation for use-dilutions
and line sulfur. They believe residue methods are needed for carbamates,
1080 and general herbicides in vegetation and soil. They are also seeking
some guidance in developing a written quality-assurance document so it can
be used in the Iowa laboratory to govern day-to-day operations.
Pesticide formulations are screened routinely for cross-contamination.
The only exception to this practice occurs when the Iowa laboratory cannot
obtain a technical standard for the screening work. Generally the screen-
ing methods involve thin-layer chromatographs for organophosphates and
chlorinated hydrocarbon pesticides.
Chemical deficiencies, overformulation and cross-contamination are
considered by the Iowa formulation laboratory to be major causes of vio-
lative samples. The staff of both the formulation and residue laboratory
have had some experience testifying in public hearings or similar enforce-
ment actions; however, capability for efficacy or toxicology testing is not
available in the Iowa laboratory, so witness expertise is limited to ana-
lytical findings.
Routinely, the Iowa laboratory analyzes tank-mix pesticide samples.
Analytical areas for pesticide residue and formulation work are shared
because of limited instrumentation; however, sample preparation, glassware
storage and cleaning, and sample cleanup are strictly separated.
Iowa felt that there were several areas of training that would be
beneficial to their staff. Technical training in verification of residues
and cross-contamination of formulations are top priority items. For spe-
cific product analyses, they would like to have training offered that deals
-------
VII-9
with fertilizer-pesticide combinations and with analyses of 2,4-D residues
in vegetation.
In summary, the Iowa laboratory appears to be well-equipped and has
the capability to perform high-quality pesticide analyses. An increase in
analytical workload is limited by the small staff; thus, additional staff-
ing appears to be Iowa's major need.
-------
VII-10
REGION VII
Chemist/Other Scientists
Chemists/Other Scientists
Ph. 0
M.S
B.S.
B.A.
Total
Technician/Support
Clerical Support
Administrative
Total - all Staff
Analytical Balances
Top Loading Balances
pH Meter
Atomic Absorption Specs.
Infrared Spectrometers
UV/Vis. Spectrometers
Electrodeposi tion
Gas Chromatographs
Liquid Chromatographs
GC/Hass Spec.
Other
Internal Standards
External Standards
Column pkg. capabil.(GLC)
In-lab
Purchased
Sealed Samples
Plastic Bag Enclosure
Inspector
Laboratory
Receipt Inspec. of sample
Security of samples
Storage
Check Sample programs
EPA
AAPCO
Southern Assn FFPCO
USOA/FSQS
Analysis Verification
Formulations
Residues
Standard Sources
Beltsville EPA
EPA/RTP
Manufacturer
Commercial
Methods
AOAC
FDA-PAM
EPA Formulation Methods
NEIC
ZWEIG
In-house
Methods Development
Samples per year
Kansas
Formulations Residues
STAFF
1
2
2 1
2 1
EQUIPMENT
3-a 1-b
1-a 1-b
1-a
1-d
1-a
1-a
1-a
1-a 1-b
1-a
Iowa
Formulations Residues
1
1 1
2
1 2
4 4
1
4 S.
4-d
1-b
2-d
1-d
1-a
1-c
1-a 1-d 3-b
2-d
1-c
Auto-analyzer-d Auto-tinator-d
METHODOLOGY
Yes
Yes
Pack, coat Pack, coat
Yes Yes
CHAIN-OF-CUSTODY SAMPLES
Yes Yes
Yes Yes
Yes Yes
Excellent
Excellent
QUALITY ASSURANCE
Yes
Yes
Good
Good
Yes Yes
Yes
Yes
Yes
Yes Yes
Yes
Flourometer- d
Yes
Yes Yes
Pack, coat Pack. coat
Yes Yes
Yes Yes
Yes Yes
Yes Yes
Excellent
excellent
i
Yes Yes
Good
Good
Yes Yes
Yes
Yes
Yes Yes
Yes
Yes
In-house AOAC
S-125, EPA- 107
Equipment Jse Code: a = Formulations Lab, dedicated
d = Available in Lab elsewhere
b = Residue Lab, dedicated
e = Available outside Lab.
c = Formulations/Residues Shared
-------
VIII-1
STATE PESTICIDE FORMULATIONS AND RESIDUES LABORATORIES
ANALYTICAL SCIENTIFIC CAPABILITIES
EPA REGION VIII
GENERAL
Montana and South Dakota are continuing their enforcement grant agree-
ment with the EPA while Utah has just received its EPA grant. Laboratory
questionnaire responses have been received from all three of these states
and capabilities of the respective laboratories are evaluated herein.
North Dakota, Wyoming and Colorado currently do not have grants for lab-
oratory analytical services.
OVERVIEW OF LABORATORY CAPABILITIES
The laboratory staffs from the three grant states in Region VIII range
from two permanently assigned persons in Montana to a staff of four chem-
ists each in South Dakota and Utah. Formulation and residue analyses in
South Dakota and Utah are done by the same staff chemists. These chemists
have an average of 10 to 20 years' experience in pesticide work. _In Mon-
tana a chemist with 2 years' experience in the formulation laboratory and a
newly-hired technician (1 year experience) perform the pesticide analyses.
Occasionally other chemists assist in the pesticide work, although they are
not employees hired under the grant. Generally the laboratories are small
and adequately equipped to perform limited pesticide analyses. There is a
wide variance in available instrumentation, chain-of-custody procedures,
quality-assurance programs, and methodology.
The State chemist in South Dakota and senior chemist in Montana hold
PhD degrees. Their supporting staff have BS/BA or MA degrees. In Utah all
four chemists have BS degrees.
Because of the wide variation in equipment on hand, there is a great
difference in sample loads. Montana analyzed approximately 160 pesticide
-------
VIII-2
samples for EPA plus check and collaborative study samples last year. Last
year South Dakota analyzed more than 500 state samples and 25 formulation
samples for EPA. Utah was not in the grant program last year but did ana-
lyze about 280 pesticide samples for the state.
All three grant states in Region VIII are interested in improving
methodology and receiving training in selected analytical techniques for
pesticides. Topics of common interest include training in high-pressure
liquid chromatography and GLC techniques.
SPECIFIC STATE LABORATORY CAPABILITIES
Attached to this detailed analysis is a comparative tabulation of ca-
pabilities in the Region VIII state pesticide laboratories operating under
EPA grants.
Montana
The laboratory is jointly operated by the Montana Department of Agri-
culture and the Agricultural Experiment Station on the Montana State Uni-
versity campus. The laboratory program is administered by the Environmen-
tal Management Division of the Montana Department of Agriculture. Mr.
Laszlo Torma is the Laboratory Director with offices at McCall Hall, Mon-
tana State University, Bozeman, Montana 59717. Mr. Torma1s telephone num-
ber is (406) 994-3383. Dr. Lynn Hageman is the Pesticide Formulation
laboratory supervisor. He is assisted by a laboratory technician who has a
BS degree and approximately 1 year's experience in the formulation labora-
tory. When workload requires additional help in pesticide analyses, other
chemists from the Department assist Dr. Hageman and his technician.
In addition to pesticide formulation work, the laboratory is engaged
in analyses of pesticide residues, fertilizers, feeds, biological mater-
ials, diagnostic samples, and a variety of agricultural products. Specific
and detailed information about residue analyses was not provided in the
questionnaire information submitted by Montana; therefore, the following
-------
VIII-3
discussion has only limited reference to residue laboratory capabilities
and extensive discussion on the formulation laboratory in Montana.
A variety of pesticide products are routinely encountered for analysis
in the Montana laboratory. They include insecticides, herbicides, fungi-
cides, rodenticides, antimicrobials, and repellents. Last year the formu-
lation laboratory analyzed 162 pesticide samples for the EPA. This.did not
include several series of check samples or samples from a collaborative
study. They analyzed only service samples for the state.
Laboratory equipment includes four analytical balances, two of which
are at least 25 years old, two top-loading balances, and two pH/millivolt
meters, one available but not dedicated to the formulation laboratory work.
Other available equipment includes a commercial and another home-made
atomic absorption instrument, a spectrophotometer, auto-analyzer and chlor-
ide titrater. Equipment dedicated to the formulation laboratory includes
an analytical and top-loading balance, an IR spectrometer, a UV/visible
spectrometer, three gas chromatographs (another is also available), and two
liquid chromatographs.
The gas chromatographs are equipped with ECD, TSD, FID and capillary
column, and FPD detectors as well as CDS 111 integrator accessories. Col-
umns are packed at the laboratory and occasionally coated at the laboratory
also. Often the columns and packing are purchased from the Applied Science
Company.
Montana appears to practice good chain-of-custody procedures. Samples
are sealed by the inspector and placed in plastic bags for shipment to the
laboratory. Upon receipt, the date is recorded along with sample condi-
tion, and the seal is checked. All samples which are unsealed and not in
the immediate possession of the analyst are kept under lock and key.
Standard solutions, reference standards, records, documents, work sheets,
and notebooks are also kept under lock and key when not in use. Access to
the locked sample storage area is limited to authorized personnel only.
-------
VIII-4
Montana participates in the AAPCO Check Sample Program for pesticide
formulations. In the past year the laboratory analyzed eight check sam-
ples. Whenever possible, official AOAC or standard EPA, AWPA or similar
methods are used by Montana to verify and confirm all potentially violative
samples. The analyst performs true duplicate tests to determine results of
potentially violative samples. The samples are routinely verified for more
than one subsample whenever possible. A second analyst performs a check
analysis for the potentially violative sample.
Reference standards are obtained from EPA Beltsville or the pesticide
manufacturer. The Montana laboratory maintains both technical and analyti-
cal reference standards. Dilute standards are prepared for each and every
instrumental analysis.
In addition to AOAC methods, the laboratory uses methods developed
in-house, by EPA, and by pesticide companies. Personnel in the laboratory
participate in AOAC as Associate Referees and Collaborators. They attend
the AOAC meeting annually.
With the exception of herbicides and carbamates, pesticides are rou-
tinely screened by Montana for cross-contamination. For organophosphates,
the method used for screening is GLC-FPD; for chlorinated hydrocarbons,
they use TLC, GLC with FID, and GLC with ECD.
Montana considers chemical deficiency, overformulation and cross-
contamination as being violative. None of the staff have had experience as
a witness in a court action.
Montana does some residue analyses. Instrumentation used is shared
with the formulation work; however, the sample preparation and associated
work is performed in separate work areas.
Training that Montana believes would be beneficial to the staff in-
cludes verification techniques, safety, and courtroom (witness) procedures.
Specific analytical technique training considered by Montana to be of high
-------
VIII-5
priority is HPLC, GLC, and screening for cross-contaminants. Product an-
alysis training which is believed to be beneficial to the Montana staff
involves techniques for analyzing baits, especially 1080 and strychnine,
pressurized containers, and disinfectants.
In summary, the Montana laboratory appears to be understaffed and op-
erating with a minimum of dedicated equipment. Their methods and associated
laboratory activities appear to be adequate to perform limited high-quality
analyses.
South Dakota
The South Dakota State Chemical Laboratory in Vermillion, South Dakota
57069 operates a pesticide formulation and residue laboratory under an EPA
grant. Dr. Joel M. Padmore is the state chemist and laboratory director.
His telephone number is (605) 624-3281 or 677-5258. Mr. Duane Henson
serves as the supervisor of both the formulation and residue laboratories.
He is assisted by another chemist who is also the drug laboratory super-
visor, Mr. Don Frasch. Mr. Henson holds a BA degree in chemistry and has
15 years' experience in pesticide analyses. Mr. Frasch has an MA; he and
Dr. Padmore have approximately 17 years' experience in pesticide formula-
tion and residue work.
In addition to identifying pesticide formulations and residues, the
South Dakota laboratory analyzes fertilizers, feeds, dairy products, water,
and various narcotics. Types of formulation products analyzed routinely
include insecticides, herbicides, fungicides, plant growth regulators, ro-
denticides, home and garden mixtures, antimicrobials, insect repellents,
and various types of pressurized containers.
Last year the South Dakota laboratory analyzed 500 state samples and
25 EPA samples for formulation. Additionally, they analyzed 15 pesticide
residue samples for their state program.
-------
VIII-6
Equipment dedicated or readily available to the laboratory includes
three analytical balances and three top-loading balances, several pH me-
ters, two atomic absorption instruments, two IR spectrometers, two
UV/visible spectrometers, two gas chromatographs, and two liquid chromato-
graphs. A Perkin Elmer NMR is also available at the University for the
pesticide laboratory use.
Gas chromatograph accessories include FID and FID-EC detectors. Col-
umns are either packed and coated in the laboratory or purchased from
Applied Science Laboratories.
Chain-of-custody procedures used by South Dakota are as follows:
Samples are tagged and sealed by the inspector upon collection. The sam-
ples are transferred to the laboratory in plastic bags. Upon receipt, the
plastic bags are discarded; the sample condition, seal, and date are
checked and recorded. Samples that are unsealed are kept under lock and
key when not in the immediate possession of the analyst. The samples are
stored in a locked area with limited key access. Standard solutions and
reference standards are not stored under lock and key. Records and analy-
tical documentation are not under lock and key when not in use either.
The laboratory does not participate in the AAPCO Check Sample-Program.
However, they do use AOAC or other standard procedures to confirm all po-
tentially violative samples. Additional checks for result verification are
done by analyzing spiked samples and standard additions. Although poten-
tially violative samples are analyzed in true duplicate testing, the re-
sults are neither verified by subsampling analyses nor checked by another
chemist.
Reference standards are obtained from either NEIC or the pesticide
manufacturer. Both technical and analytical references are maintained by
the South Dakota laboratory. Dilute standards are prepared every 2 to 3
weeks for instrumental analysis. Occasionally, the dilute standards are
prepared more often, especially as needed for violative samples.
-------
VIII-7
The laboratory uses in-house and EPA methods of analysis. They have
not prepared a compilation of in-house methods.
South Dakota participates in AOAC as a Collaborator and staff from the
laboratory attend the annual pesticide meeting.
Pesticide formulations are not routinely screened for cro.ss-
contamination; however, upon special request, this type of analysis is
done. Nevertheless, South Dakota considers cross-contamination, chemical
deficiencies, and overformulation to be violative.
Residue and formulation analyses are done in the same general area.
According to the laboratory director, separation of the sample preparation
for these different activities will, hopefully, be corrected within a few
months.
The South Dakota laboratory staff recognize a need for training in
chain-of-custody procedures, HPLC methods, GLC techniques, and residue an-
alyses. With respect to product analyses, they feel training in analysis
of pressurized containers and pesticide combinations would be beneficial.
In conclusion, it appears that the South Dakota laboratory is under-
staffed and some laboratory facility changes are needed (separate residue
and formulation preparation/work areas). Improvement in chain-of-custody
procedures and violative sample verification is needed. The laboratory is
equipped to perform regulatory analyses of pesticide samples.
Utah
The Utah Department of Agriculture recently signed a State-EPA agree-
ment and received an EPA grant to assist in the operation of their pesti-
cide formulation and residue laboratories. Mr. H. Kent Francis is the
state chemist and laboratory director. His offices and the laboratory are
in the laboratory building, State Capitol, in Salt Lake City, Utah 84114.
Mr. Francis1 telephone number is (801) 553-4128. The Pesticide Formulation
-------
VIII-8
laboratory supervisor is Mr. Barr Chn'stensen. Mr. Grant Miller supervises
activities in the pesticide residue section. Another chemist, Mr. Tony
Day, assists Messrs. Francis, Miller and Christensen in pesticide analyses
performed by the Utah laboratory.
All four chemists have BS degrees. They work as a team, performing
either pesticide formulation or residue analyses as needed. State chemist
Francis has 20 years' experience in pesticide analytical work. His asso-
ciates have 15 years' (Miller), 10 years' (Christensen) and 2 years' (Day)
experience in this specialty.
In addition to pesticide and formulation analyses, the laboratory
functions include analyses of commercial fertilizers, feeds, food, dairy
products, meats, and bedding materials. The laboratory is also involved in
toxicological studies.
Routine pesticide products analyzed by the Utah laboratory include
insecticides, herbicides, fungicides, plant growth regulators, rodenti-
cides, mollusk baits, home and garden mixtures, antimicrobials, and
repellents.
Last year Utah was not in the grant program, so the pesticide analy-
tical work was done solely for the state. They analyzed 30 formulations
and 250 residue samples.
The laboratory appears underequipped to perform any extensive formu-
lation or residue work. They have single pieces of the following equipment
dedicated to pesticide work: analytical and top-loading balances, pH/mil-
livolt meter, atomic absorption unit, IR spectrometer, UV/visible spectrom-
eter, gas chromatograph, and a liquid chromatograph. Most of the equipment
is at least 10 years old, but reported to be functional. No backup instru-
mentation appears available, The gas chromatographic instrument is
equipped with a two-electron capture and flame photometric detector as well
as an integrator accessory. Columns are neither packed nor coated in the
laboratory. All columns and packing are purchased from the Tracer Company.
-------
VIII-9
Chain-of-custody procedures in practice in Utah are as follows. Nor-
mally the inspector collects a sample, places it in a plastic bag and sends
it to the laboratory unsealed. The laboratory staff records the date re-
ceived and schedules the required analyses. There are no lock and key pro-
cedures used for samples, standards, or documents.
Utah participates in the AAPCO Check Sample Program. They analyzed
five check samples last year. All laboratory samples are analyzed by AOAC
or other official/standard procedures. True duplicates are not performed
on potentially violative samples. No subsampling techniques are employed
and analyses are not checked by a second chemist when potentially violative
samples are identified.
Pesticide reference standards are obtained by the Utah laboratory from
the EPA or from chemical manufacturers. Neither technical nor analytical
reference standards are maintained by the Utah laboratory.
Laboratory personnel participate as Collaborators in the AOAC. They
attend the pesticide meetings annually.
Utah considers four conditions as violative: chemical deficiencies,
overfemulations, cross-contaminations, and net-weight deficiencies.
Utah recognized the need for training in sampling and storage of pes-
ticides. They also believe a high priority for future training should in-
clude analytical techniques in HPLC, AA, GLC, cleanup procedures, and
screening for cross-contaminants. With respect to specific product analy-
ses, they feel training would be beneficial in the techniques for evalua-
ting carbamates and phenolic disinfectants.
Overall, the Utah laboratory appears to be underequipped. There is
apparently no backup instrumentation to use during equipment "downtime".
The experienced staff recognizes the need for changing and improving some
quality-assurance practices and their chain-of-custody procedures. The
laboratory is staffed with experienced professionals and minimally equipped
ID-perform limited formulation and residue analyses.
-------
VIII-10
REGION VIII
Chemist/Other Scientists
Chemists/Other Scientists
Ph. D
M.S
B.S.
B.A.
Total
Technician/Support
Clerical Support
Administrative
Total - all Staff
Analytical Balances
Top Loading Balances
pH Meter
Atomic Absorption Specs.
Infrared Spectrometers
UV/Vis. Spectrometers
Electrodeposition
Gas Chromatographs
Liquid Chromatographs
GC/Mass Spec.
Montana
Formulations Residues
STAFF
1
1
1
2
EQUIPMENT
1-a 3-d
1-a 1-d
2
2
1-a
1-a
3-a 1-d
2-a 1-d
Other Chloride Titrater-Auto Analyzer
Spec. 20
South Dakota
Formulations Residues
1 (both labs)
1 (both labs)
1 (both labs)
3
3 (one vacancy)
1-a 1-d 1-e
2-a 1-d
1-a 1-e
1-a 1-e
1-d 1-e
1-a 1-e
1-a 1-d
1-a 1-d
NMR
Utah
Formulations Residues
4 (both labs)
4
4
1-a
1-a
1-a
1-a
1-a
1-a
1-a
1-a
METHODOLOGY
Internal Standards
External Standards
Column pkg. capabil.(GLC)
Yes
Yes
Yes
In-lab
Purchased
Sealed Samples
Plastic Bag Enclosure
Inspector
Laboratory
Receipt Inspec. of sample
Security of samples
Storage
Packed, sometimes coates
Yes
CHAIN-OF-CUSTODY
Yes
Yes
Yes
Yes
Excellent
Excellent
Coat, pack
Yes
SAMPLES
Yes
Yes
Yes
Yes
Good
Good
No
Yes
No
Yes
Yes
Limited
Limited
Poor
QUALITY ASSURANCE
Check Sample programs
EPA
AAPCO
Southern Assn FFPCO
USDA/FSQS
Analysis Verification
Formulations
Residues
Standard Sources
Beltsville EPA
EPA/RTP
Manufacturer
Commercial
Methods
AOAC
FDA-PAM
EPA Formulation Methods
NEIC
ZWEIG
In-house
Methods Development
Samples per year
Yes
Good
Yes
Yes
Yes
Yes
Yes
Yes
In-house-AOAC
EPA- 162
No
Fair
NEIC
Yes
Yes
Yes
Yes
Yes
In-house-AOAC
S-500, EPA 25, S-15
Yes
Fair
Yes
Yes
Yes
Yes
Yes
In-house-AOAC
S-30
Equipment Use Code:
a = hormulations Lab, dedicated
u = Available in Lab elsewhere
b = Residue Lab. dedicated
e = Available outside Lab.
c = Formulations/Residues Shared
-------
IX-1
STATE PESTICIDE FORMULATIONS AND RESIDUES LABORATORIES
ANALYTICAL SCIENTIFIC CAPABILITIES
EPA REGION IX
GENERAL
Currently, all states in Region IX have pesticide enforcement grants
in effect. However, Arizona is funded only for support of investigations
and compliance by the Pesticide Control Board, and there is no direct lab-
oratory support. Laboratory support for Guam and other far Pacific islands
enforcement grants is provided by the University of Hawaii laboratory as a
part of the Hawaii enforcement grant. Capabilities of the state pesticide
laboratories in Region IX are summarized below.
OVERVIEW OF LABORATORY CAPABILITIES
The state laboratories in Region IX are for the most part well-staffed
with qualified personnel. The only current large program need among the
granted states is for a residue capability at the Nevada Department of
Agriculture Laboratory or elsewhere in Nevada. California, Nevada, and
Hawaii had ongoing state-mandated pesticide analysis capability prior to
inception of the EPA grant program. California and Nevada have used grant
funds to upgrade instrumentation and expand personnel; Hawaii has purchased
new equipment. Grant monies have also been used to attend training courses
and attend professional meetings by all three states. Staffing is probably
at an optimal level for all three states unless major program expansion is
projected.
From the inception of the grants in California, Hawaii, and Nevada,
Region IX Pesticide Product Laboratory personnel worked closely with the
state laboratories in order to develop and improve their capability and
expertise. Personnel from the three state laboratories attended training
in the now closed San Francisco laboratory and, in turn, obtained onsite
assistance by EPA Region IX staff.
-------
IX-2
The states in Region IX are well equipped through both State purchases
and EPA-funded instrumentation. Upgrading and replacement of worn out or
obsolete instruments will be an ongoing need in all states. Also, automa-
tion and data systems will continue to be in need where state laboratories
want to increase efficiency and achieve full state-of-the-art data handling.
The overall Region IX sample workload for formulations samples ana-
lyzed under the grant program approached 1,000 samples in fiscal year
1979. An additional 1,500 formulation samples were analyzed in California
under state-mandated procedures. Projected fiscal year 1980 outputs will
be similar.
The residue workload in the Region IX State grant enforcement program
is unknown at this time but probably approaches 800 to 1,000 samples per
year for California and Hawaii combined.
SPECIFIC STATE LABORATORY CAPABILITIES
Attached to this detailed analysis are comparative tabulations of the
Region IX State laboratory capabilities.
California
The California Department of Food and Agriculture operates the state
pesticide laboratory in Sacramento. Mr. George Tichelaar is the laboratory
director. He is assisted by Mr. Joe Audi no who serves as the pesticide
formulation supervisor.
The formulation staff currently consists of seven people, including
six professionals. Five of the professionals have 3 years' experience or
less. One chemist, of many year's experience, has recently left the lab-
oratory, which has severely curtailed methods development and innovative
problem solving in the laboratory. The formulation supervisor has had many
years' experience, but none of the laboratory staff are participating as
AOAC Associate Referees; however, the staff does routinely participate as
Collaborators.
-------
IX-3
The staffing and experience of the residue staff (including field lab-
oratories) is unknown at this time.
Formulation products routinely encountered at the California labora-
tory include insecticides, herbicides, fungicides, plant growth regulators,
rodenticides, baits, home and garden mixtures, antimicrobials, repellents
and pressurized containers.
In addition to pesticide formulation analyses, the laboratory is rou-
tinely engaged in analyzing feed, fertilizers, dairy products, crop resi-
dues and meat. The laboratory also has a large and active worker-safety
program.
The formulation laboratory is well equipped with instrumentation pur-
chased under both state and EPA grant funds. The section is dedicated
solely to formulation analysis; there is no routine sharing of these in-
struments with the residue section.
The formulation section has five dedicated gas chromatographs, primar-
ily equipped for flame-ionization analysis, but also with thermionic
(nitrogen-phosphorus) and thermal conductivity. A Halie specific detector
is not currently directly available. The section also has a dedicated
liquid chromatograph with gradient capability and a variable wavelength
detector. All chromatographs are tied to a central Hewlett-Packard data
system. The formulation section also has new UV/visible and infrared
spectrophotometers. The infrared spectrophotometer is tied to an automatic
file search program for compound identification. Atomic absorption, gas
chromatography/mass-spectroscopy and x-ray diffraction are also available
through cross-sharing with other laboratory sections.
Residue instrumentation information is not available at this time.
California has good chain-of-custody control of samples from inspector
collection through the laboratory. Formulation samples are officially
sealed by inspectors and enclosed in plastic bags. Upon arrival at the
laboratory, the incoming samples are checked for data as well as condition
-------
IX-4
of seal and sample. Samples and standards are kept in locked storage when
not in the immediate possession of the analyst. Records, work sheets, and
other sample documentation are not kept under lock and key.
The California Laboratory currently analyzes approximately 2,100 for-
mulation samples per year, 1,500 of those collected and analyzed using
state procedures, the remainder according to EPA protocols. This,repre-
sents 25 samples/analyst/month. Basically, producer-establishment samples
are identified as EPA grant samples, whereas, market surveillance samples
are collected and analyzed under state authority.
The California laboratory is analyzing the full range of pesticides
regulated under FIFRA, as amended, except for anti-foul ing paints. The
State laboratory does not test devices or perform any efficacy testing.
Use-dilution samples are analyzed routinely. All required formulations are
screened for cross-contamination.
The full range of the California testing program in the residue area
is unknown at this time.
The supervisor from the California laboratory has attended the
EPA/NEIC sponsored training course "Enforcement Procedures and Screening
for Cross-Contamination". The laboratory staff have also spent at least 1
week in the San Francisco Pesticide Product Laboratory reviewing EPA pro-
cedures and methodology. It would be desirable for all analysts in the
California laboratory to attend an "Enforcement Laboratory Procedures"
course as soon as it is practical, and at least within the next 3 years.
Other training, highly recommended, includes advanced techniques in HPLC,
gas-chromatography, and cross-contamination screening.
In summary, California's laboratory is well equipped, staffed with
capable people, and conducts a good pesticide program. Analytical work
could be strengthened with improvement in carbamate and other related res-
idue analyses. An additional HPLC for the formulation laboratory would
also be desirable considering the number of samples analyzed and the im-
portance »of this technique in contemporary state-of-the-art formulation
analysis.
-------
IX-5
The California laboratory also should consider devoting a halogen spe-
cific detector (e.g., microconductimetric) to formulation analysis.
Nevada
The state pesticide laboratory is one of the facilities of the Nevada
State Department of Agriculture. Mr. Harlan Specht is the laboratory di-
rector. The analytical staff currently consists of two full-time persons
including the supervisor. The supervisory chemist has had 8 years expe-
rience, the chemist has 2 years. Both individuals are quite competent.
The supervisory chemist serves as an AOAC Associate Referee for the analy-
sis of tank-mix samples.
The Nevada laboratory is well equipped considering the size and scope
of the program. Most of the major equipment is new, having been bought
with EPA grant funds. Only the atomic absorption and infrared spectropho-
tometers are more than 5 years old. The Nevada Laboratory has two gas
chromatographs, one with flame ionization and thermionic detectors and the
other with flame-ionization and electron-capture. Both instruments are
equipped with printer-plotter data stations. The laboratory also has a
liquid chromatograph with gradient capability and a variable wavelength
detector. The liquid chromatograph also has its own printer-plotter data
station. Other available equipment includes a relatively new Perkin Elmer
scanning UV/visible spectrophotometer and a Beckman pH/millivolt meter.
Chain-of-custody procedures for samples at the Nevada laboratory are
as follows. Inspectors officially seal product samples upon collection.
These samples are enclosed in plastic bags and retained as such in the lab-
oratory. Incoming samples are dated and checked for condition and seal at
the laboratory. When analyses are complete, all samples are officially
resealed. During the period of analysis, unsealed samples are not kept
under lock and key when not in the immediate possession of the analyst.
Analytical and technical reference standards and sample documentation
(worksheets, records, notebooks) are not stored in locked areas when not in
use.
-------
IX-6
Currently, the Nevada laboratory only has capability for formulation
analysis. A residue capability is not projected at this time, except pos-
sibly through some other agency such as the Department of Health or the
University of Nevada. The laboratory is currently analyzing 100 formula-
tion samples per year (both producer establishment and market surveillance),
all under the EPA grant program. This represents 10 samples/ chemist/month,
assuming one-half time devoted to fertilizer analysis under state authority.
The staff routinely analyzes all types of pesticides except anti-foul ing
paints, repellents and devices. All required formulations are screened for
cross-contamination. The laboratory routinely analyzes use-dilution (tank-mix)
samples.
Representatives from the Nevada laboratory have attended EPA/NEIC train-
ing courses on procedures and cross-contamination. Future training that
should be considered a high priority for the Nevada staff includes advanced
techniques in HPLC and gas-chromatography.
In summary, the Nevada laboratory has a competent staff and is well
equipped to perform a relatively large pesticide analytical load. In the
near future, the laboratory should consider replacing the P.E. 337 infrared
spectrophotometer which is 12 years old, because servicing and reliability
may become a problem.
Hawaii
The pesticide laboratory is at the University of Hawaii, Department of
Agricultural Biochemistry in the College of Tropical Agriculture, Honolulu.
Dr. John W. Hylin is the laboratory director. He is assisted by Yoshihiko
Kawano who serves as the pesticide formulation supervisor and associate
chemist in the laboratory. In all, the formulation section currently con-
sists of two full-time analysts, occasionally supplemented by personnel
from other sections and/or students. The pesticide supervisor (responsible
for formulations and residues) has more than 20 years' direct experience,
is involved in the AOAC collaborative program, and publishes regularly in
scientific journals. The chemist has more than 5 years' experience and is
-------
IX-7
considered quite knowledgeable in the field. The supervisor performs check
and special project analyses, but the chemist performs most of the routine
testing.
Currently, five analysts comprise the residue section, three chemists
and two technicians. The senior chemist has 10 years' experience. One
chemist is devoted to operation of the gas chromatograph-mass spectrometer.
The residue staff is involved in other pesticides monitoring and research
projects besides the grant enforcement program.
The laboratory is fairly well equipped, instrumentation having been
acquired with both state and EPA funds. The section has new infrared and
UV/visible spectrophotometers that are cross utilized with other functions,
if necessary. Currently, residues and formulations share four gas chroma-
tographs with the flame-ionization detectors on two of the instruments
being used primarily for formulation analysis. The pesticide section also
is equipped for halide detection (microconductimetric and electroncapture),
nitrogen detection (thermionic) and phosphorus/sulfur detection (flame
photometric). All data reduction is done manually. The pesticide unit
does not currently have a dedicated liquid chromatograph, and is presently
borrowing an instrument from another laboratory section, if necessary. The
laboratory is currently planning to purchase a liquid chromatograph for the
pesticide unit with fiscal year 1980 grant funds.
The laboratory has a gas chromatograph-mass spectrometry unit, 6 years
old, which is used primarily for residue identification. The instrument is
apparently in need of major upgrading and repair.
Laboratory staff from Hawaii have attended or plan to attend several
EPA/NEIC-sponsored training courses including: procedures in cross-
contamination, HPLC, and residue analysis. Another course which would be
beneficial to these analysts is an "Enforcement Laboratory Procedures"
course which is offered by EPA periodically.
-------
IX-8
The formulation section currently analyzes about 200 formulations per
year, about half being collected and analyzed under the EPA grant program.
This represents 10 samples/analyst/month, assuming one-half time devoted by
the supervisor. All types of pesticide products are being routinely ana-
lyzed, including antimicrobials, anti-fouling paints and repellents. Oc-
casionally user-dilution samples are analyzed. All required samples are
screened for organophosphate and organochlorine contaminations. Efficacy
testing is not locally available.
It is estimated that approximately 300 to 400 residue samples are ana-
lyzed per year, the bulk representing crop samples. The laboratory occa-
sionally analyzes water (drinking and receiving), fish and soils. Chlori-
nated hydrocarbons, organophosphates and phenoxy herbicides are regularly
screened for, in addition to analysis of special pesticides.
In summary, the Hawaii laboratory is staffed with a competent team of
analysts who perform a relatively large workload of pesticide analyses.
Although much of the laboratory equipment is new, the gas chromatograph/
mass spectrometer is in need of upgrading and repair; concurrently, the
data system should also be upgraded. A dedicated HPLC for the pesticide
section is needed (this may be in the process of being purchased with
fiscal year 1980 funds). The instrument should have gradient elution ca-
pability and have a variable (or multiple) wavelength detector.
-------
IX-9
REGION IX
Chemist/Other Scientists
Call forma
Formulations Residues
Nevada
Formulations Residues
Hawaii
Formulations Residues
STAFF
Chemists/Other Scientists
Ph D
M S.
B S.
B.A
Total
Technician/Support
Clerical Support
Administrative
Total - all Staff
Analytical Balances
Top Loading Balances
pH Meter
Atomic Absorption Specs
Infrared Spectrometers
UV/Vis. Spectrometers
Electrodeposition
Gas Chromatographs
Liquid Chromatographs
GC/Mass Spec.
Other
Internal Standards
External Standards
Column pkg. capabil.(GLC)
In-lab
Purchased
Sealed Samples
Plastic Bag Enclosure
Inspector
Laboratory
Receipt Inspec. of sample
Security of samples
Storage
4-a
1-a
2-a
2-d
1-a
1-a
1-a
6-a
1-a
1-d
X-ray Diffraction-d
Yes
EQUIPMENT
1-d
1-a 1-d
1-d
1-d
1-a
1-a
1-d
METHODOLOGY
Yes
Packed
Yes
Yes
Yes
Yes
Good
Good
Yes
CHAIN-OF-CUSTODY SAMPLES
Yes
Yes
Yes
Poor
Good
2-a
1-a
1-a
1-d
1-a
2-a
2-a 2-d
1-d
1-d
automatic titrimeter-a
Yes
Packed, coated
Yes
Yes
Yes
Yes
Excellent
Excellent
QUALITY ASSURANCE
Check Sample programs
EPA
AAPCO
Southern Assn FFPCO
USDA/FSQS
Analysis Verification
Formulations
Residues
Standard Sources
Beltsville EPA
EPA/RTP
Manufacturer
Commercial
Methods
AOAC
FDA-PAM
EPA Formulation Methods
NEIC
ZWEIG
In-house
Methods Development
Samples per year
Yes
Yes
Excellent
Yes
Yes
Yes
Yes
Yes
AOAC, In-house
S=K97, EPA 573
Yes
Yes
Excellent
Yes
Yes
Yes
Yes
Yes
Yes
AOAC, In-house
EPA=100
Yes
Excellent
EPA Reg X
Yes
Yes
Yes
Yes
AOAC
S=200
Equipment Use Code
a = Formulations Lab, dedicated
d = Available in Lab elsewhere
b = Residue Lab dedicated
e = Available outside Lab
c = Formulations/Residues Shared
-------
X-l
STATE PESTICIDE FORMULATIONS AND RESIDUES LABORATORY
ANALYTICAL SCIENTIFIC CAPABILITIES
REGION X
GENERAL
Washington, Oregon, and Idaho have pesticide enforcement grants in
Region X. Alaska does not currently have a grant, but there is some pros-
pect of placing a grant in fiscal year 1980. State pesticide laboratory
capabilities for Washington, Oregon, and Idaho are described below.
OVERVIEW OF LABORATORY CAPABILITIES
The grant-funded state laboratories in Region X with laboratory opera-
tion are well staffed with qualified personnel. Washington was one of the
pilot states to receive grant funds and has been acknowledged as one of the
more successful state laboratory operations, although the overall program
is not as large as some of the other states. Region IX Pesticide Product
staff (through an Inter-Regional Agreement) worked closely with both Wash-
ington and Oregon to organize laboratory programs with respect to required
procedures, methodology, and instrumentation during the initial phases of
the grants. This liaison and cooperation has continued with the transfer
of EPA's responsibility to NEIC. Both Oregon and Washington have bought
considerable equipment to upgrade their laboratory operations. Equipment
purchase culminated in 1979 with Oregon's purchase of a Hewlett-Packard
gas-chromatograph/mass-spectrometer.
The overall sample workload in Region X is about 800 formulation
samples per year, of which about 190 are samples analyzed under the grant
program. Thus, the bulk of the state sampling and analysis is still per-
formed using state procedures. The overall extent of the residue output is
unknown at this time, but is probably somewhat less than the formulation
output. The bulk of the residue sampling and analysis is in conjunction
with intrastate food and commodities.
-------
X-2
SPECIFIC STATE LABORATORY CAPABILITIES
Attached to this detailed analyses are comparative tabulations of the
Region X state laboratory capabilities.
Washington
The state pesticide laboratory is part of the Washington State Depart-
ment of Agriculture (WSDA) facilities. It is in Yakima and the laboratory
director is H. Dal Antles. The current staff of the WSDA laboratory (Pes-
ticide Section) consists of three chemists and one technician. A certain
amount of rotation occurs among staff from other sections of the labora-
tory. Two chemists have less than 1 year's specific experience, although
the technician has more than 4 years' experience.
The laboratory is fairly well equipped although some of the instru-
ments are old. Two gas chromatographs are available, one Barber-Colman
with flameionization detectors, for formulation analysis, is 10 years old;
the other (Nuclear Chicago) for residue analysis is equipped with electron-
capture, alkaline bead, and flame ionization. The Barber-Colman is inter-
faced with a Hewlett-Packard printer-plotter for data acquisition. The
laboratory has a relatively new Hewlett-Packard liquid chromatograph (HPLC)
with gradient capability and a variable wave-length detector. The HPLC
also has its own printer-plotter data system.
Other instrumentation in the laboratory includes an Orion 701 pH/mil-
livolt meter (6 years old), Perkin-Elmer 303 atomic-adsorption spectro-
photometer (11 years old), Perkin-Elmer infrared spectrophotometer (5 years
old) and several UV/visible spectrophotometers, the newest of which is
eight years old. All of the spectrophotometers are cross-utilized between
the pesticide group and other sections of the laboratory.
The WSDA laboratory analyzes about 625 formulation samples per year,
approximately 80% for the state-funded program, the remainder identified as
grant samples. Overall, Washington analyzes approximately 25 samples/month/
-------
X-3
analyst. The laboratory is experienced in the routine analysis of most
pesticides regulated under FIFRA, as amended, except anti-fouling paints,
plant growth regulators, and devices. The laboratory routinely analyzes
use-dilution mixtures. All appropriate grant pesticide samples are
screened for cross-contamination using approved procedures.
The extent of the residue program is unknown at this time. The lab-
oratory routinely analyzes receiving waters, tissues, soils, vegetation,
and commodities; chlorinated hydrocarbons, organophosphates and phenoxy
herbicides are routinely analyzed. GC/MS capability is not locally
available.
The supervising chemist of the Washington pesticide laboratory has
attended several EPA/NEIC-sponsored training courses including a procedures
and cross-contamination course as well as an HPLC analysis course. Other
staff have attended EPA-sponsored courses on advanced gas chromatography
and residue techniques. Future training should include participation by
all analysts in an "Enforcement Laboratory Procedures" training course.
In summary, the Washington laboratory is well equipped and staffed to
perform pesticide analyses. There appears to be no absolutely necessary
equipment needs; however, the following observation is made.
The Barber Col man 5000 gas-chromatograph is 10 years old and will
probably become unserviceable in the near future. It would be desirable to
obtain a second gas chromatograph dedicated to formulation analysis with
flame-ionization detectors. It would also be expeditious to add a micro-
conductimetric (Hall) halogen specific detector, if possible, to this new
instrument. This Hall detector would prove useful in the formulations sec-
tion and provide a good backup detector to the electron-capture detector.
The State Department of Agriculture operates the pesticide laboratory
in Salem, Oregon. Dr. H. Michael Wehr is the laboratory director. The
-------
X-4
formulation laboratory is supervised by James E. Launer. Its staff con-
sists of three chemists with more than 45 combined years of experience.
The supervisory chemist, who also performs analyses, has received on-site
training at both the San Francisco Pesticide Product Laboratory and at
Beltsville Chemistry Laboratory. The supervisor also serves as an
Associate Referee for the AOAC; he is considered an expert in the field.
The degree of expertise of the remainder of the staff is unknown.
The residue section is supervised by Alfred C. Cornwell. The section
consists of five chemists with more than 50 years of combined experience.
The residue section is considered well-qualified and operating at state-
of-art.
The formulation section has one shared Hewlett-Packard gas chromato-
graph with dual flame-ionization detectors and two liquid chromatographs,
one of which is equipped with gradient capability and a variable wave-
length detector. The gas chromatograph is tied to a printer-plotter for
automatic data reduction. The formulation section also has infrared,
UV/visible and atomic absorption spectrophotometers, all of which are
relatively new. The analytical balance (two single-pan and two double-pan)
are all more than 12 years old, as is the pH/millivolt meter.
\
The residue section maintains three gas chromatographs primarily
equipped for electron capture (ni63), flame photometric and alkali bead.
Two of the chromatographs are interfaced with Hewlett-Packard printer-
plotters for data reduction. Presumably, liquid chromatography is avail-
able from the formulation section, if necessary. The residue section has
recently purchased a Finnegan 1020 gas chromatograph/mass spectrometer with
a full data system that will be installed in February 1980. This instru-
ment will provide support primarily for confirmation and, in some cases,
analyses for most pesticide enforcement and monitoring activities in Oregon.
The USDA Laboratory currently is analyzing about 180 formulation samples
per year. Five samples were analyzed for the state of Idaho, Department of
Agriculture in 1979. Approximately 60% of the Oregon samples were sampled
and analyzed under state protocols. Overall, Oregon analyses about 10
-------
X-5
samples/month/analyst. The laboratory has experience in the analysis of
most pesticides analyzed under FIFRA, as amended. Required products are
also screened for cross-contamination. The formulation section has occa-
sionally analyzed use-dilution samples.
The residue section routinely analyzes all types of matrices including
waters, tissues, fish, soils, and commodities. Feeds, dairy products,
oils, paints, and vegetation are also analyzed. The laboratory has capa-
bility for organohalogen, organophosphorus, and carbamate screening, in
addition to phenoxy herbicides. The total number of residue samples ana-
lyzed per year is unknown at this time, but is probably close to 500 sam-
ples/year, the bulk being commodities and vegetation. Approximately 100
residue samples/year are analyzed directly for use/misuse and other inci-
dent investigations.
Representatives from the Oregon laboratory have attended HPLC and
cross-contamination courses sponsored by EPA/NEIC. Other training that
should be considered in the near future includes advanced techniques in
residue analysis and gas-chromatography as well as a course in "Enforcement
Laboratory Procedures".
In summary, the Oregon laboratory appears adequately staffed and
equipped to perform pesticide analyses. Equipment needs would be classi-
fied as desirable, but not absolutely necessary. Among these is the "need"
for a dedicated gas chromatograph with FID capability. This will minimize
possible contamination if the current instrument is also used for residue
analysis. All four analytical balances and the pH/millivolt meters are 12
years or older. Consideration should be given to replacement, if servi-
cing, calibration, and reliability become problems.
-------
X-6
REGION X
Chemist/Other Scientists
Chemists/Other Scientists
Ph. D
H.S
B.S.
B.A.
Total
Technician/Support
Clerical Support
Administrative
Total - all Staff
Analytical Balances
Top Loading Balances
pH Meter
Atomic Absorption Specs.
Infrared Spectrometers
UV/Vis. Spectrometers
Electrodeposition
Gas Chromatographs
Liquid Chromatographs
GC/Mass Spec.
Other
Internal Standards
External Standards
Column pkg. capabil. (GLC)
In- lab
Purchased
Sealed Samples
Plastic Bag Enclosure
Inspector
Laboratory
Receipt Inspec. of sample
Security of samples
Storage
Check Sample programs
EPA
AAPCO
Southern Assn FFPCO
USOA/FSQS
Analysis Verification
Formulations
Residues
Standard Sources
Beltsville EPA
EPA/RTP
Manufacturer
Commercial
Methods
AOAC
FDA- PAH
EPA Formulation Methods
HE 1C
ZWEIG
In-house
Methods Development
Samples per year
Washington
Formulations Residues
STAFF
1
1
1 1
3 1
1 1
4 2
EQUIPMENT
2-d 1-c 1-d
1-d
1-d 1-c
1-d
1-c
2-d 1-c
1-a 1-b
1-c
METHODOLOGY
Yes
Yes
Packed
Yes Yes
CHAIN OF CUSTODY SAMPLES
Yes Yes
Yes Yes
Yes Yes
Yes Yes
Good Good
Good Good
QUALITY ASSURANCE
Yes
Yes
Good
GLC. thin layer
Yes Yes
FDA
Yes Yes
Yes Yes
Yes
Yes
Yes Yes
Yes Yes
AOAC, In-house
S=525, EPA=107
Oregon
Formulations Residues
1 2
2 3
3 5
3 5
3-a 1-b
2-a 1-b
1-a 1-b
1-a
1-a
1-a
1-a
4-b
2-a
1-a
Polarograph-a
Yes
Yes
Packed, coated
•Yes Yes
Yes Yes
Yes Yes
Yes Yes
Good Good
Good Good
Yes Yes
Yes
Yes
Good
2nd column, other detectors
Yes Yes
USDA
Yes Yes
Yes
Yes Yes
Yes
Yes
Yes Yes
AOAC, In-house
S-95 EPA-77 Idaho-5
Equipment Use Code: a: Formulations Lab, dedicated
d: Ava in Lab elsewhere
b: Residue Lab. dedicated
e: Available outside Lab.
c: Formulations/Residues Shared
-------
APPENDIX
ANALYTICAL AND TESTING ACTIVITIES
PEPIR QUESTIONNAIRE
PESTICIDE LABORATORY PROFILE
-------
PESTICIDE LABORATORY PROFILE
I. GENERAL
A. Organization
1. Region, State or Agency:
2. Address of Laboratory:
4.
5.
6.
7.
Telephone:
FTS? Yes
No
Laboratory Director:
Pesticide Formulation Supervisor:
Residue Analysis Supervisor:
Organizational Structure of Laboratory:
(attach copy if appropriate)
1.
2.
3.X
4.
5.
1.
2.
3.
4.
8. Analytical Staff (include both professional and technician,
part-time and full-time)
a. Pesticide Formulation Section
Name Title Education
Name
b. Pesticide Residue Section
Title
Education
Years of
specific
Experience
Years of
specific
Experience
-------
B. Function
1. Analytical functions of laboratory in addition to pesticide
formulation and residue analysis, i.e., fertilizers, feeds,
crop residues, etc.
What types of pesticide formulation products are routinely
encountered for analysis?
a. Insecticides
b. Herbicides
c. Fungicides
d. Plant Growth Regulators _
e. Rodenticides
f. Anti-foul ing Paints
g. Slug and Snail Baits
h. Home and Garden Mixtures
i. Antimicrobials :
j. Insect Repellents
k. Animal Repellents
1. Pressurized Containers
m. Devices
n. Others (list)
(1) Phenolics
(2) Quaternary Amine Salts
(3) Available Chlorines
What types of pesticide residue samples are routinely encountered
for analysis?
a. Waters, drinking
b. Waters, discharge
Waters, lake & river
Animal tissues
i. Other matrices (specify):
c.
:
d.
e.
Fish & marine org. _
f. Soil, sediment, etc.
g. Vegetation
h. Fouds, feeds
(specify)
j. Type analyses:
Organohalogen screen
Organophosphorous screen
Herbicides
Miscellaneous (name):
Element specific screens:
N P S Other
r.r /S.
-------
4. Approximately hew many pesticide formulation samples were
analyzed in the last year: For State:
For EPA:
For other states: (designate specific
states)
II. Instrumentation:
A. Description
Code: Enter "1" if dedicated to Pesticide Formulation
Section
HOD
2" if dedicated to Pesticide Residue Section
3" if cross utilized for residues and formulations
4" if available elsewhere in the laboratory
IIOII
IIA II
lien
5" if readily-available outside of laboratory (i.e.,
at nearby university or private laboratory).
Instrument Code Manufacturer Model Age
1. Analytical Balance
2. Top-loading Balance
3. pH/Mi111 volt Meter
4. Atomic Absorption
5." Infra-red Spect.
6. UV/VIS Spect.
7. Electrodeposition
-------
Instrument
8. Gas Chrcmatograph
Code Manufacturer
Model Age
9. Liquid Chromatograph
10. GLC/Mass Spec
11. Others:
B. Chromatographic Capability
1. Gas Chrcmatography
a
For each gas chrcmatograph, give type of detector(s)
available and data acquisition accessories. Mark with
an asterisk (*) those chromatographs with oven program-
ming capability.
Mfr./Hodel
Dectector(s) Data Acquisition Accessory Autosamp' r
(1)
(2)
(3)
(4)
(5)
-------
b. Columns
Formulation:
(1) Are column packings coated at laboratory?
Yes No
(2) Are columns packed at the laboratory?
Yes No
(3) If columns and/or packings are purchased, who
is the major supplier?
(4) List the basic columns used in the laboratory
for pesticide formulation and residue analysis:
Loading
Support Length Pi am.
Tubing
Residue:
c. Techniques
(1) For routine sample analysis, indicate which technique
is usually employed?
Internal Standard External Standard
Pesticide Form. Lab
Pesticide Residue Lab
(2) High Performance Liquid Chrcmatograph'
a. For each liquid chromatograph, give the designated informati
(1) Mfr./Model:
Gradient Capability: Yes
Detector (mfr./Model):
No
-------
Type (UV, RI, fluor, etc.)
Variable Wavelength UV: Yes No
If "No", what wavelengths are
available?
Type of Injection System:
Type of Column Temperature Control:
Auto sampler: Yes No
(2) Mfr./Model:
Gradient Capability: Yes No
Detector (Mfr./Model
Type (UV, RI, fluor, etc.)
Variable Wavelength UV: Yes No
If "No", what wavelengths are
available?
Type of Injection System:
Type of Column Temperature Control:
Auto sampler: Yes No
(3) Mfr./Model:
Gradient Capability: Yes No
Detector (Mfr./Model
Type (UV, RI, fluor, etc.)
Variable Wavelength UV: Yes No
If "No", what wavelengths
available?
Type of Injection System:
Type of Column Temperature Control:
Auto sampler: Yes No
-------
b. List the primary HPLC columns used in laboratory
for pesticide analysis:
Source Packing Part. Size Length Piam.
(1)
(2)
(3) -.
(4)
(5)
(6)
c. How is peak response normally measured? (Check)
(1) Peak Height:
(2) Integration: Type(s) of Integrator(s)
d. For routine sample analysis, which technique is usually
employed? A. Formulations B. Residues
(1) Internal Standard:
(2) External Standard: :
III. CHAIN OF CUSTODY
A. Are samples normally officially sealed by the Inspector upon
collection? A. Formulation: Yes No
B. Residues: Yes No
B. Are plastic bags used to enclose sample?
Formulations Residues
By Inspector: Yes No Yes No
By Laboratory: Yes No Yes No
C. Are incoming samples noted as to:
Date of Receipt: Yes No
Condition of Sample: Yes No
Condition of Seal: Yes No
-------
8
D. Are unsealed samples kept under lock and key when not in the
analyst's irrmediate possession? Yes No
E. Are samples and standard solutions kept under lock and key
when not in use? Yes Mo
F. Are all samples officially resaaled by the analyst upon com-
pletion of analysis? Yes No
G. Is the sample storage area locked with limited key access?
Yes No
H. Are bulk analytical and technical reference standards stored
under lock and key? Yes No
I. Are active sample records, documentation, work sheets and note-
books kept under lock and key when not in use? Yes No
•>
J. Are residue samples stored in a freezer until analysis?
Yes No Locked: Yes No
IV. QUALITY ASSURANCE
A. Check Sample Analysis
1. Does the laboratory participate in a Check Sample
Program for pesticide formulations? EPA Yes No
AAPCO Yes No
2. In which check sample programs does the Pesticide Residue
section participate?
B. Verification and Check Analyses for Pesticide Formulations and Residues
1. Are official AOAC, CIPAC EPA, or AWPA methods used to confirm all
potentially violative formulation samples,- if applicable?
Yes No
2. If official or standard formulation methodology is not
available or appropriate, what steps are taken by the
original analyst to confirm potential violative samples?
-------
3. Are analyses on potentially violative formulation samples
performed by the original analyst in true duplication, i.e.:
with newly prepared standard and sample solutions for each
result? Yes Mo
4. Are potentially violative samples routinely verified for
more than one subsample, if available? Yes No
5. Is a check analysis performed by a second analyst for every
potentially violative sample? Yes No
6. If "Yes" to £5, are new dilute standard solutions used by
the second analyst? Yes Mo
7. Does each analyst maintain his or her set of commonly used
titrants? Yes No
8. Is restandardization of titrants or determination of
reagent blanks performed as part of the verification
procedure for potentially violative samples, if appro-
priate? Yes No
9. Any additional remarks concerning confirmation and/or
check analysis?
10. How are pesticide residue results confirmed?
C. Pesticide Reference Standards - Formulation
1. What are the principal sources of pesticide standards
used? .
Other sources used
2. Are both technical and analytical reference standards
maintained by the Formulation Laboratory? Yes No
3. How often are neat standards replaced or reassayed?
-------
10
4. How often are dilute standards prepared for instrumental
analysis?
a. For every analysis:
b. Every so often: How often?
c. Only for potentially violative samples:
D. Pesticide Reference Standards - Residue
1. What are the principal sources of pesticide standards
used?
Other sources used
2. How often are neat standards replaced or reassayed?
3. How often are dilute standards prepared for instrumental
analysis?
a. For every analysis:
b. Every so often: How often?
c. Only for potentially violative samples:
E. Methodology
1. What methods are routinely used for pesticide residue a,nd formu-
lation analysis?
Source Formulation Residue
2. Has the laboratory prepared a compilation on in-house
methods: Formulation? Yes No Residue? Yes No
3. Do personnel in the laboratory participate in AOAC Col-
laborative studies?
Formulation Residue
a. As a General Referee:
b. As Associate Referee:
c. .As Collaborator:
-------
n
4. Does someone represent the Pesticide Sections at the Annual Fall
or Spring A.O.A.C. Meetings?
Formulation Residue
a. Every year:
b. Occasionally:"
c. Seldom:
d. Never:
Do laboratory personnel attend any other regional or national
meetings at which pesticide formulation or residue methodology
is discussed (e.g., ACS/Div. of Pest. Chem., Southern Asso. of
Feed Fertilizer & Pesticide Control Officials Chemist's Seminars,
Florida Pesticide Residue Conference)? Yes No
Names:
6. For which specific pesticides or groups of pesticides do you feel
formulation or residue methods, are needed (or need to be improved)?
Formulation:
1- 2.
3- 4.
5. 6.
7- 8.
Residue:
1.
2.
3.
4.
F. Written Procedures
Is there currently a "Quality Assurance" document in use by
your laboratory governing your day-to-day operations?
Formulation: Yes No Residue: Yes ' No
-------
2
V. SCREENING FOR CROSS-CONTAMINATION
A. Are pesticide formulations routinely screened for cross-contamination?
Yes No
Approximate percent found contaminated?
B. If "Yes", what typss of samples are not screened?
C. What general methods are used when screening for:
1. Organophosphates:
2. Chlorinated Hydrocarbons:
3. Carbamates:
4. Others:
D. Does the Pesticide Formulation Section currently have thin-layer
chromatography capability?
a. Experience: Yes Mo
b. Supplies: Yes No
VI. GENERAL
A. Which of the following does the formulation laboratory consider as
being potentially violative?
1. Chemical Deficiencies:
2. Overformulations:
3. Cross-Contaminations:
4. Net-weight deficiencies:
5. Other:
B. (Optional) What are the defective sample criteria for the
laboratory with respect to formulation analysis?
-------
C. Have laboratory personnel had witness experience with respect
to their analytical findings or otherwise as experts in the
field of pesticides?
Formulations Residue
1. Appreciable experience:
2. Some experience:
3. No experience: .
D. Are labels or copies thereof routinely prepared and submitted for
each formulation sample? Yes No
E. Is local or immediate capability available for efficacy or
toxicology testing of pesticide formulations?
Efficacy: Yes No Toxicology: Yes No
»
F. Has the laboratory had occasion to analyze use-dilution (tank-mix)
pesticide samples?
Routinely:
Occasionally:
Seldom:
Never:
G. Are pesticide residue and formulation analyses performed in
the same general area?
Sample preparation: Yes No
Sample cleanup: Yes No
Instrumentation: Yes No
Glassware storage/cleaning: Yes No
VII. TRAINING
A. In what procedural areas do you feel that training would be of
benefit to your staff? (Such as chain-of-custody, reporting,
verification procedures, etc.)
1.
2.
3.
4.
-------
14
For what general analytical techniques do you feel that training
would be of benefit to your staff? (Such as TLC, HPLC, AA, GLC,
screening for cross-contamination, microbiological analyses, etc.)
Formulations
2.
3.
4.
Residues
1.
2.
3.
4.
C. For what types of specific product analyses do you feel training
would be of benefit to your staff? (Such as phenolic disinfectants,
paints, pressurized containers, fertilizer-pesticide combinations,
etc.)
1. _
2. _
3. _
4. _
5.
------- |