MIDWEST RESEARCH INSTITUTE
STUDY OF SAMPLING AND ANALYSIS PROCEDURES I DEHP IN
HUMAN AND ENVIRONMENTAL MEDIA
LITERATURE REVIEW
FINAL REPORT
TASK 37
June 23, 1981
EPA Prime Contract No. 68-01-5915
MRI Project No. 4901-A(37)
Prepared for
U.S. Environmental Protection Agency
Office of Pesticides and Toxic Substances
Field Studies Branch
401 M Street, S.W.
Washington, D.C. 20460
Attn: Ms. Sandra Strassman-Sundy
Task Manager (TS-798)
MIDWEST RESEARCH INSTITUTE 425 VOLKER BOULEVARD. KANSAS CITY, MISSOURI 64110
816 753-7600
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STUDY OF SAMPLING AND ANALYSIS PROCEDURES FOR DEHP IN
HUMAN AND ENVIRONMENTAL MEDIA
LITERATURE REVIEW
by
John M. Hosenfeld
Paul H. Cramer
Donna R. Rose
Kenneth L. Thomas
John E. Going
FINAL REPORT
TASK 37
June 23, 1981
EPA Prime Contract No. 68-01-5915
MRI Project No. 4901-A(37)
Prepared for
U.S. Environmental Protection Agency
Office of Pesticides and Toxic Substances
Field Studies Branch
401 M Street, S.W.
Washington, D.C. 20460
Attn: Ms. Sandra Strassman-Sundy
Task Manager (TS-798)
KESEAKCIH1 OMSTOTOTi 425 VOLKER BOULEVARD, KANSAS CITY, MISSOURI 64110 ° 816753-7600
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PREFACE
This final report presents the completed literature review of documents
on MRI Project No. 490]-A(37), “Study of Sampling and Analysis Procedures for
DEHP in Human and Environmental Media,” for the Environmental Protection
Agency (EPA Prime Contract No. 68-01-5915). Mr. John Hosenfeld served as
task manager for this literature review. The review was conducted by Mr. Paul
Cramer, Ms. Donna Rose, Mr. Kenneth Thomas, and Mr. Hosenfeld. The final re-
port was prepared by Mr. Hosenfeld.
ARCH INSTITUTE
ohn E. Going
Program Manager
lames L. Spigarelli, Director
Analytical Chemistry Department
iii
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CONTENTS
Preface. . . . . iii
1. Introduction 1
2. Summary 2
3. Results 3
A. Air 67
B. Biota 98
C. Blood (Plasma, Serum, Cells) 131
D. Food Commodities (Processed Foods, Fish, Milk). . 152
E. Plastic Products (Film, Pipe, Tubing) 166
F. Sediment 195
G. Seston 227
H. Soil 233
I. Tissue (Human, Experimental Organisms) 236
J. Urine 249
K. Water (Drinking, Waste, Ground, Process Effluent) 257
L. Miscellaneous 353
References . . . 364
V
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SECTION 1
INTRODUCTI ON
Bis(2-ethylhexyl)phthalate (DEHP) has wide-spread use as a plasticizer
because of its ability to soften resins and to facilitate the manufacture and
end use of plastic products. Products containing DEHP include items such as
food wrapping film, lubricants, medical products, and consumer goods. As a
result of the large production and distribution of plastics containing DEJIP,
a large portion of the United States population may be exposed to a chemical
that may present toxicological risks.
The Environmental Protection Agency (EPA) in response to a concern about
potential risk to a large population has initiated a study to investigate sam-
pling and analysis procedures for DEHP. The first phase of this study was to
review and evaluate a limited number of scientific articles for their rele-
vance in contributing acceptable data to the DEHP data base. The remainder
of this report presents the summary and results of this literature review.
The results section includes the review articles ordered by matrix.
1
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SECTION 2
SIJNMARY
A total of 76 documents were reviewed using a form devised to obtain
precise and consistent information from each source. The results of these
reviews are segmented by matrix into 12 different sections in this report.
A given review may therefore be included in two or more matrices depending
on the information in the original article.
The review of each document was divided into four areas: survey design,
sampling, analysis and quality assurance. The overall relevance of all the
documents to each of these areas ranged from not applicable to highly specific.
For example, within a specific document, the section on sampling may address
the problem of contamination in a highly enlightened manner while the quality
assurance section may be less than adequate. In general, there were very few
documents that could be classified as excellent and complete.
2
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SECTION 3
RESULTS
Most of the documents reviewed on this task were identified and obtained
from the following EPA studies.
- MRI Task 27: Survey of Monitoring Data on Selected Toxic Substances
- Versar Task 2: Materials Balance for Di(2-ethylhexyl)Phthalate
Additional papers not included in the above two sources were submitted
by EPA for review.
A reprint summary form shown in Figure 1 was developed to provide a basis
on which the documents could be reviewed. The reprint form was divided into
four areas: survey design, sampling, analysis and quality assurance. In each
of these areas, a list of items were specified that if mentioned in the docu-
ment would provide a means of assessing the value of that area. A set of
prompter questions were placed after each item for the reviewer’s convenience
to obtain a relevant response for that item. The objective of each review
was to state the concept, if any, for each of the four areas and to comment
on the merits of each. However, the survey design area served a dual purpose.
When a paper had a survey design that could be reviewed, the comment and sum-
mary sections were completed. In those papers where a survey was not part of
the report, such as occurred in a method development paper, the sununary section
was used to characterize the whole report, such as a method development or a
position paper.
The results of the document reviews are ordered according to matrix. The
reviews are included in all appropriate matrix sections such that a given re-
view might appear in two or more sections. Each review contains the title of
the document followed by the author, the year of publication, and a reference
number. The reference number is used as a cross-reference to the appendix
where the citation is listed alphabetically by author.
The listing for water, which included sources such as groundwater, waste-
water, etc., contained the largest share of the documents reviewed (37). Biota
contained 14 articles while air and sediment contained 12 reviews each. Nine
reviews were listed for blood and its associated components. Human tissue
and food commodities each had five reviews while urine, seston and soil had
three, two and one respectively. The section for plastic products included
11 reviews. Fly ash and solvents and reagents had one review each.
3
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An overview of all 76 articles reviewed for this report is shown in
Table 1 which contains the comments on and summaries of the documents reviewed.
This is followed by the complete reviews placed in the appropriate matrix sec-
tions which are alphabetically listed. The appendix lists the complete cita-
tion of the reviews and their location in this report.
4
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1
REPRINT SUMMARY FORM
Reprint No.
Journal (Abbreviated Title)
Author
I. Survey Design
Matrix________________________________
Selection of sampling sites - basis?
Sampling
plan - diurnal?,
seasonal?, primary vs. control sites?______
Problems
noted
Goal(s)
Comments
Summary - were
goals achieved and reason?____________________________
Figure 1
5
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2
Reprint No.
Author
II. Sampling
Container preparation - reported?
Collection procedure — reported?_
Storage conditions - reported?, validated?
Stability demonstrated? in matrix?______
Field blanks - used?, number?__________
Spiked blanks - used?, number?, level?_
Noted problems___________________________
Comments____________________________________
Summary _____________________
Figure 1 (continued)
6
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3
Reprint No.
Author
III. Analysis
A. Measurement Procedure
Cleanup/fractionation - reported__________
Recovery - reported?, established by step?
Recovery linear?_________________________
Interferences identified? method?______
Limit of detection?_____________________
Noted problems___________________________
B. Instrument
Linear response - stated?_______________
Stability of response - reported?_______
Noted problems___________________________
Comments____________________________________
Summary -- _____________________
Figure 1 (continued)
7
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4
Reprint No.
Author
IV. Quality Assurance
Method blank - used?, how often?, results?________________________
Control sample - used?, how often?, user prepared?, results?_________
Reference material (e.g., SRN) - used?, how often?, type and appli-
cable?, results?________________________________________________
Precision and accuracy defined?______________________________________
Replicates - used?, how often?, randomized?, results?_______________
Verification by different analytical method - used?, type?, how
often?, results?________________________________________________
Interlab verification? — results?_______________________________________
Noted problems__________________________________________________________
Comments
Summary___________________________________
Figure 1 (continued)
8
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TABLE I. COPIIIENTS AND SUWIARIES ON PAPERS RELATIVE TO BIS(2-ETHYLHEXYL)PIITHALATE
Sample design Sampling Analysis Quality assurance Reference
AiR
Comment: Five PVC film samples
were supplied by Borden but
only three were used. Repre-
sentativeness of these films
to other films in doubt since
only one film source was
studied.
Coimnent : All film from same
company.
Comment : Results reported were
corrected for percent recovery 1
film thickness and width. Re-
sults were variable and can-
not be considered quantitative
but only indicative of levels
a person may be exposed to
when cutting PVC film.
Comment : Nethod not very re-
producible as shown by number
of smoky versus clean runs,
and relative standard devia-
tions of results. Variability
of results are semiquantitative
at best. Repetition of test
runs only seems to show varia-
bility of method and does not
necessarily give a better
average value of organics re-
leased during the cutting
process.
2, Boettner
and Ball
(1980).
Sunmiary : PVC films supplied
by Borden Chemical were sur-
veyed for volatilization of
various compounds during the
cutting process. Supermarket
conditions were simulated.
Summary : Five PVC films were
obtained from Borden Chemical.
No real sampling involved.
Summary : PVC films were cut
with a hot-wire ( . 215°C) or
a cool rod (135°C) inside a
specially constructed hood.
The phthalates were collected
by rinsing the hood with 25 ml
of ethanol. The ethanol vol-
ume was reduced to I ml and
analyzed by CC/FIn.
Summary : Sampling hood rinsed
between runs to ensure no car-
ryover. Replicate runs were
made to obtain average values
of phthalate released during
cutting.
Comment : Sufficient detail
required to determine the
overall design is lacking.
Apparently information is
from a small part of a
larger study in which air
sampling was conducted for
a 1-year period.
Comment : Sampling procedures
were not detailed. Because
of this lack of information,
little confidence can be
placed in the representative-
ness of the sample.
Comment : This section con-
tains little information ex-
cept for the extraction method.
No conclusions can be made
about the applicability of the
method because validation pro-
cedures were not revealed.
Comment : A qualitative result
of “small analytical blanks”
and the lack of other QA data
can be used to characterize
the data as “uncertain.”
Sunimar : Air samples were
collected at three sites in
New York City No comment
was made as why these sites
were chosen or what rela-
tionship existed with the
nearby environment.
Summary : Air samples were
collected on glass fiber
filters. DEHP was extracted
but no details were given
about filter preparation,
blanks, etc.
Summary : Analysis was per-
formed by CC/MS after soxhiet
extraction of the filters.
Summary : QA procedures were
minimal (method blanks only).
3, Bove,
et al.
(1918).
(AIR continued)
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TABLE I I conLinued I
Comment : Experiment not de-
signed specifically for phtha-
lates. Since the number of
samples collected in Antwerp
is unknown, the comparison be-
tween urban and background
levels cannot be justified
on a design basis.
Summary : The goal of re-
porting on the organic com-
position of aerosols around
LaPaz was achieved. Samples
were collected near the Cosmic
Ray Laboratory at an altitude
of 5,200 in.
Comment : This paper is an in-
dustrial hygiene evaluation of
Boettner’s results (Paper No. 2)
of one film from one batch of
PVC film from one source.
Summary : The air in a room
containing a wrapping machine
using PVC film was sampled to
identify thermal degradation
products and assess potential
health hazards.
Summary : The paper recom-
mends a procedure for mini-
mizing phthalate contamina-
tion in blanks for air and
ocean biota samples.
Comment : Sampling lacked QA
provisions and was not de-
signed specifically for
phthalates Container prepa-
ration was not reported so the
level of contamination cannot
be determined and the data may
thus have a sampling contamina-
tion bias.
Sunsnary : Sampling in Bolivia
was conducted during six
14—day sampling periods using
high volume samplers equipped
with glass fiber filters.
Summary : No pertinent in-
formation concerning sam-
pling was reported.
Summary : Samples were stored
in Mason jars and aluminum
foil. Mason jars were cleaned
with detergent, rinsed with
distilled water and solvents,
and heated in an oven. Alumi-
num foil was heated to 320°C.
Comment : Method was not
optimized for phthalates.
Presence of pbtbalates may
be due to contamination.
The analytical results are
of questionable value.
Summary : Filters were ex-
tracted with benzene and
methanol, evaporated and
dissolved in ether. Ex-
tracts derivatized with
diazometbane and analyzed
by GC/MS. Phthalates were
detected in method blanks.
Summary : Biota samples were
macerated, extracted with
acetonitrile, and the extracts
dried with sodium sulfate.
The dried extracts were then
passed through a Florisil
column for cleanup prior to
analysis by GC/EC. Air
samples were eluted with
petroleum ether and diethyl-
ether and analyzed by GC/EC.
Comnwnt: Not designed spe-
cifically for phthalates.
Data should be viewed as qual-
itative because of lack of suf-
ficient QA data.
Summary : QA was primarily in
the form of method blanks.
The method blanks indicated
low levels (< 200 ppm) of
phthalates.
Comment : Paper deals only
with exposure values and is
of no value from the stand-
point of chemical analysis.
Summary : The paper basically
presents cleanup procedures to
eliminate phthalate contamina-
tion when preparing biota and
air samples for phthalate
analysis.
Sample design Sampling Analysis Quality assurance Reference
Comment : This section is of
minimal value.
7, Cautreels,
at al.
(1977).
9, Cook
(1980).
Comment : This section is
of minimal value.
Summary : Analysis was by
CC/MS.
Summary : No QA information
reported.
Comment : No information on Comment : Presents a reasonable Comment : Recoveries or other Comment : QA provisions re- 23, Giam
the source or number of samples sampling method but does not validations were not reported. ported were primarily those (1976d).
used in the experiment. Bas- mention field blanks. The analytical method itself is concerning elimination of con-
ically this paper is the same adequate. tamination.
as Paper No. 19 but also in-
cludes air sampling.
JR iued
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TABLE I (continued)
Sample design Sampling Analysis Quality assurance Reference
Comment : The mass balance
model was developed using a
combination of data and as-
sumptions. Author states
that atmospheric input to
the Gulf was the most im-
portant route but cautions
that “direct field measure-
ments are imporLant.”
Cousnent : This section only
briefly outlines the sampling
method and is of limited
value.
Comment : This section lacks
enough information to assess
its value.
Comment : None
25, Giam
(1977).
Summary : This paper deals
primarily with a mass-balance
model [ or estimation of
fluxes of DEUP in the Gulf of
tiexico. Sampling and analy-
sis is as in reference 27.
Summary : Water samples were
solvent extracted on site or
adsorbed on XAD-2 resin.
Biota samples were collected
by hook and line or trawl.
Sediment samples were col-
lected with a metal coring
device. Air was adsorbed
on Florisil or polyurethane.
Summary : Samples were ex-
tracted with organic solvents,
cleaned up by column chroma-
tography and analyzed by GC/
SC.
Sucanary : No QA data of signifi-
cance reported.
Comment : Paper relates re-
suits of comparison of three
adsorbents for air sampling.
An unknown number of grab sam-
ples were collected during a
scientific cruise in the Gulf
of Necixo.
Comment : Evaluates three ad-
sorbents for sampling air for
phthalates and chlorinated hy-
drocarbons. Provides suitable
sampling procedures but no
blanks or spiked blanks.
Comment : Analytical procedure
was adequate but recoveries or
other validations were not re-
ported.
Comment : None
26, Giam
(1978a).
Summary : The purpose of
this paper is to describe the
sampling techniques, labora-
tory analysis, and evaluation
of different adsorbents for
sampling atmospheric
phthalates.
Sununary : A method is presented
for sampling air through col-
umns filled with: Florisil,
XAD-2 resin, polyurethane foam.
Sample cartridges were sealed
and frozen for transportation.
Swanary : The adsorbents were
eluted with solvents and the
eluates cleaned up on a
Florisil column. Collection
efficiency was influenced by
moisture. Analysis was by
GC/EC.
Summary : QA provisions were
not reported.
Comment : Basically same in-
formation as other articles
by Giam. Grab samples ap-
parently collected.
Comment : This section is too
brief to be of value.
Comment : Too little informa-
tion provided to properly as-
sess this section.
Comment : None.
27, Giani
Ct al.
(1978).
Summary : The purpose of the
project was to analyze for
phthalate esters and chlori-
nated hydrocarbons in air,
water, sediment, and biota
samples predominantly from
the Gulf of Mexico.
Summary : Sampling methods are
brief. Sediment——metal coring
device. Biota--hook and line
or trawl. Water——extracted
directly or adsorbed oii XAO-2.
Air--adsorbed on Florisil or
polyurethane foam. Sediment
and biota samples frozen.
Summary : Samples were ex-
tracted with organic solvents
and cleaned up by column chro-
matography. Analysis was by
CC/SC. Recoveries of “90% or
better” were mentioned as wcll
as “background values of
50 ng.”
Summary : Appropirate QA in-
formation was not provided
(AIR continued)
-------
TABLE 1 (continued)
Comment : Although not spe-
cifiralLy stated it is in-
ferred that the sampling was
part of a multiple task ocean
sampling cruise of unknown pur-
pose. Grab samples taken dur-
ing cruise.
Comment : The collection pro-
cedure was adequate but should
have provided for field blanks
and other validations.
Comment : The analytical method
was sufficient but recoveries
and other validation parameters
should have been determined.
Comment : A previous paper
(t b. 23) alluded to careful
sample handling and labora-
tory techniques to minimize
contamination.
Summau: The purpose of this
paper was to report the con-
centration of DBP, DEHP, PCB,
and DDT residues in the at-
mosphere of the northwest
Gulf of Flexico. Sampling
was conducted for 24 hr at
a time for 10 days during a
sampling cruise.
Summary : Samples were col-
lected by drawing air through
precombusted glass-fiber
filters backed by two pre-
extracted polyurethane foam
plugs housed in aluminum
cartridges. The samples
were refrigerated until
analysis.
Summary : The filters and
plugs were extracted for
16 hr with petroleum ether,
concentrated, and cleaned up
on Floriail. Analysis was
by GC/EC.
Summary : No quality assurance
was presented
Comment : Differences between
organica in urban and rural
areas not really brought out
in article. Distribution of
sampling locations within in-
dustrial or urban areas is un-
known.
Comment : Samples collected and
provided to author by the Air
Resources Branch of the Ontario
tliniatry of the Environment.
Storage of the glasa fiber
filters after sampling but
before soxh let extraction
was not discussed and could
be a source of contamination.
Comment : Although methanol
reportedly more efficient in
extraction than cyclohexane,
no recoveries were given.
Other parameters were also
supposedly checked out but not
reported. Absence of actual
extraction efficiencies of
DEHP from particulate matter
casts doubt on the signifi-
cance of the data presented.
Comment : Qualitative infor-
mation for phthalatea is good
because of GC/IIS. Obvious de-
ficiencies in reporting method
blanks or recoveries casts
doubt not only on the origin
of the compounds but also the
accuracy of the data preaented.
41, ICarasek,
et al
(1918).
Summary : Survey designed os-
tensibly to compare differing
levels of organics associated
with airborne particulates
from urban and rural areas.
Summary : Forty-two Hi-Vol
glass filter samples were col-
lected in Welland, Ontario,
and 36 were collected in
Simcoe, Ontario, to provide
representative samples of
urban and rural environments.
Each sample was collected over
a 24-hr period.
Summary : Soxhlet extraction
of filters for 2 hr with
glass—distilled methanol,
roto-vaped to I ml and an-
alyzed by GC/FID and GC/IIS
(El and C!).
Summary : Use of method blanks
or control samples was not re-
ported. Retention indices very
constant over 13-day period of
analysis and quantitation good
to ± 10% from response-factored
integrated GC peak areas.
Sample design Sampling Analysis Quality assurance Reference
28, Giam,
et al
(1980).
(AIR continued)
-------
TABLE I (continued)
Comment : The results of a
single air sample are re-
ported. This study was not
designed specifically for
phthalates.
Comment : The sampling pro-
cedure is simple and straight-
forward.
Comment : Analytical procedures
used would suggest a high de-
gree of data reliability.
Comment : The preextraction of
the apparatus until clean
means that the plithalates
found were associated with the
source and not the result of
contamination.
Summary : The phthalates were
identified because they were
“unknowns” appearing in sam-
ples taken for PCB analysis.
Summary : Phthalates are col-
lected by pulling air through
glass fiber filter and ethylene
glycol traps.
Summary : After cleanup
through Florisil and solvent
exchange from ether to hex—
ane, samples are screened by
GC/EC and identity confirmed
by CC/KS.
Summary : Phthalate data from
this study is scant as stated
by the author, since identifi-
cation of the phthalates was
incidental to a PCB study.
Comment : The location of the
sampling site may have been
chosen to obtain a representa-
tive building air sample, but
reason is not stated.
Comment : Sampling procedures
used showed an understanding
of problems associated with
using hi-vol samplers.
Comment : The analysis pro-
cedures used are consistent
with compound identification
only.
Comment : The use of standards
and GC/HS analysis can indicate
a positive identification of
the airborne particles.
74, Weschler
(1980).
Summary : The purpose of
this project was to identify
organic compounds in indoor
aerosols. This was ac-
complished by sampling
aerosols in a Bell Lab-
oratories facility in
Holmdel, New Jersey.
Summary : Sampling was con-
ducted using an Anderson
four stage impactor wLth a
backup filter. Samples were
collected on glass fiber
filters. tlnexposed filters
were used as blanks.
Susimary : The filters were
extracted with methanol. The
extracts were filtered and re-
duced, then analyzed by CC/KS.
No data were presented.
Summary : Little was reported
concerning QA measures. Nethod
blanks were used and reference
materials were used to verify
retention times and spectra.
Sample design Sampling Analysis Quality assurance Reference
65, Thomas
(1913).
(AIR concluded)
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TABLE I (continued)
Sample design Sampling Analysis Quality assurance Reference
BIOTA
Comment : No specific infor-
mation given on the source of
biota samples other than the
Gulf of Ilexico.
Comment : Cleaning to reduce
contamination was extensive
and reduced procedural back-
ground levels to 25 ng for
dibutyl phthalate and 50 ng
for dl—(2-ethylhexyl)phthalate.
Laboratory materials (e.g.,
Teflon , Na 2 SO 4 , glasswool, etc.)
were also collected for DEIIP
analysis.
Comment : The method seems
quite adequate. This paper
provides a method specifically
for phthalates in biota.
Comment: This paper may provide
a procedure which may well
serve as a model for reducing
contamination but further QA
is needed to determine the
limits of the method. A se-
lected number of laboratory
materials were observed to
have various amounts of DEIIP.
Summary : The goal was to es-
tablish methodology necessary
for the determination of
phtbalate levels in open-
ocean biota. No sampling
information reported.
Summary : Containers and la-
boratory apparatus were sub-
jected to a thorough clean-
ing. Samples were stored at
or below 0°C.
Swmnary : The extracts were
separated into acid and
base/neutral fractions. The
fractions were cleaned up on
a Florisil column and analyzed
by GC/EC. Recoveries were
70 to 100%.
Summary : Method blanks were
run frequently to ascure low
contamination. Replicates
and precision and accuracy
were not reported. Verifi-
cation was by a different
column.
Comment : This report is con-
cerned mainly with the analyt-
ical results and their signif-
icance. Criteria used to select
sampling Sites S unknown. Ap-
parently grab samples were col-
lected to assess phthalate
loading in the Gulf.
Comment : See other Giam
articles for procedures.
Comment : See other Giam
articles for procedures.
Comment : None.
20, Giam,
et al.
(1976a).
Summary : The goal of this
project was to analyze se-
lected samples from the
Gulf of Mexico for
phthalates and to assess the
significance of the data. The
Mississippi River accounts for
only one-fourth of the total
DEHP loading. “The origins
of the remaining inputs have
not yet been determined.”
Summary : No information was
provided on sampling methods
(see earlier Giam articles).
Summary : No information was
given concerning the analyt-
ical procedures. The detec-
tion limit for phthalate was
reported as 0.1 ng/g.
Summary : No QA information
was reported as this was a
discussion of published data.
19, Giam,
et al.
(1915b).
(BIOTA continued)
-------
TABLE I (continued)
Comment: Design not part. of
report. Selected results of
10 biota, 9 water, and 6 sedi-
ment samples were reported.
Comment : The sampling pro-
cedures recommended are very
good Emphasis is on reduc-
ing possible sample contami-
nation.
Suimsary : Paper proposed
methods for very low back-
ground sampling and analy-
sis, as well as for evalua-
tion of procedures for biota,
sediment, and water.
Summary : Recommends cleaning
glass and metal with deter-
gent, water, solvent, and then
heating. Recommends heating
aluminum foil to 320°C over-
night and solvent extraction
XAD-2 resin. Also recommends
use of spiked samples.
Summary : Analytical procedure
covers only cleaning of glass-
ware and equipment.
Summary : Paper recommends
procedures for minimizing
contamiantion.
U’
Comment : The origin of one
sample is not given.
Comment : None.
Comment : Cannot be used to
quantitate individual
phthalates. Individual
phtbalates must be quanti—
tated by CC/EC, assuming
no contamination.
Comment : None.
22, Giam,
et at.
( 1916c).
Summary : The goal of the
study was to develop suitable
chemical derivatives for con-
firmation of the phthalate
ester plasticizers.
Summary : No sampling infor-
mation reported.
Summary : Presents method for
converting phthalates to
N-(2-chloroethyl)phthalimide.
Yield is 90%. Analysis by
GC/EC will give quantitation
for total phthalates only.
Response is linear from 0 to
I ng.
Summary : No QA procedures
reported.
Comment : No information on
the source or number of samples
used in the experiment. Bas-
ically this paper is the same
as Paper No. 19 but also in-
cludes air sampling.
Summary : The paper recom-
mends a procedure for mini-
mizing phthalate contamina-
tion in blanks for air and
ocean biota samples.
Comment : Presents a reasonable
sampling method but does not
mention field blanks.
Summary : Samples were stored
in tiason jars and aluminum
foil. Hason jars were cleaned
with detergent, rinsed with
distilled water and solvents,
and heated in an oven. Alumi-
num foil was heated to 320°C.
Comment : Recoveries or other
validations were not reported.
The analytical method itself is
adequate.
Summary : Biota samples were
macerated, extracted with
acetonitrile, snd the extracts
dried with sodium sulfate.
The dried extracts were then
passed through a Florisil
column for cleanup prior to
analysis by GC/EC. Air
samples were eluted with
petroleum ether and diethyl-
ether and analyzed by CC/EC.
Comment : QA provisions re-
ported were primarily those
concerning elimination of con-
tamination.
Susmiary : The paper basically
presents cleanup procedures to
eliminate phthalate contamina-
tion when preparing blots and
air samples for phthalate
analysis.
Sample design Sampling Analysis Quality assurance Relerente
Comment: Analytical method
Comment: The discussion of
21, Giam,
not reported.
the QA procedures is some-
what minimal. The recom-
mended procedure for mini-
mizing contamination in
blanks is quite good.
et a!.
( 1976b).
23, Giam
(1976d).
(BIOTA continued)
-------
PAnI C 1 (continued)
Comment : Origin of samples
given as the Gulf of Mexico.
Grab samples inferred to have
been collected.
Comment : The sampling pro-
cedure should have yielded
samples with a minimum of
phthalate contamination.
Comment : The analytical pro-
cedure seems quite acceptable
based on the recovery values
reported.
Comment : The only quality as-
surance provisions reported
were procedures to minimize
background in blanks. With
the addition of replicate
samples and spiked blanks the
method could be better evalu-
ated.
Summary : The purpose of
this paper was to report a
procedure for the analysis
of marine biota, water, and
sediment. No design was
reported.
Summau: Samples were col-
lected in containers cleaned
with detergent, rinsed with
water and acetone, and heated
to 320°C. Water samples were
passed through XAD-2 resin
column. Biota samples were
stored at or below 0°C.
Summary : Samples were ex-
tracted with acetonitrile,
CH 2 C1 2 -petroleum ether and
cleaned up on a Florisil
column. Recoveries of
phthalates were in the range
79 to 100%. Analysis was
by GC/EC with S ng DEHP
yielding 50% full scale de-
flection.
Summary : Procedures given to
minimize backgrouud in sample
blanks. Verification by GC/EC
using a different column. DEN?
levels of laboratory items re-
ported.
I.-’
a ’
Comment : The mass balance
model was developed using a
combination of data and as-
sumptions. Author states
that atmospheric input to
the Gulf was the most im-
portant route but cautions
that “direct field measure-
ments are important.”
Comment : This section only
briefly outlines the sampling
method and is of limited
value.
Comment : This section lacks
enough Information to assess
its value.
Comment : None
25, Giam
(1977).
Sunsuary : This paper deals
primarily with a mass—balance
model for estimation of
fluxes of DE IIP in the Gulf of
Mexico. Sampling and analy-
sis is as in reference 27.
Summary : Water samples were
solvent extracted on site or
adsorbed on XAD-2 resin.
Shots samples were collected
by hook and line or trawl.
Sediment samples were col-
lected with a metal coring
device. Air was adsorbed
on Florisil or polyurethane.
Summary : Samples were ex-
tracted with organic solvents,
cleaned up by column chroma-
tography and analyzed by OC/
EC.
Summary : No QA data of signifi-
cance reported.
Sample design Sampling Analysis Quality assurance Reference
24, Giam,
et al.
( 1976e).
(BIOTA continued)
-------
TABLE I (continued)
Sample design Sampling Analysis Quality assurance Reference
Comment : Basically same in-
formation as other articles
by Giam. Grab samples ap-
parently collected.
Comment : This section is too
brief to be of value.
Comment : Too little inlorma-
Lion provided to properly as-
sess this section.
Comment : None.
27, Clam
et al.
(1978).
Summary : The purpose of the
project was to analyze for
phthalate eaters and chlori-
nated hydrocarbons in air,
water, sediment, and biota
samples predominantly from
the Gulf of Ilexico.
Summary : Sampling methods are
brief. Sediment--metal coring
device. Biota-—Iiook and line
or trawl. Water--extracted
directly or adsorbed on XAD-2.
Air--adsorbed on Florisil or
polyurethane foam. Sediment
and biota samples frozen.
Summary : Samples were ex-
tracted with organic solvents
and cleaned up by column chro-
matography. Analysis was by
GC/EC. Recoveries of “90% or
better” were mentioned as well
as “background values of
50 mg.”
Summary : Appropirate QA in-
formation was not provided.
Comment : Survey design is
poor. Grab samples of 11 dif-
ference species caught at each
station—-some were indigenous
to an area; others were free
— ‘ swimmers. No correlation pos-
sible between sampling loca-
Lions because there was a lack
of uniformity of species be-
tween each location.
Comment : This section does
not cover the cleaning pro-
cedure and therefore cannot
be evaluated.
Comment : The analytical sec-
tion is marginal because re-
coveries or other validations
were not reported.
Comment : QA section is insuf-
ficient.
Summary : Marine biota sam-
ples were collected for
analysis to determine their
plithalate levels.
Summary : Samples were col-
lected by net or hook and
line and placed in cleaned
aluminum foil or cleaned
Mason jars and kept at or
below 0°C.
Summary : Samples were homoge-
nized and extracted with aceto-
nitrile. Reextracted into
methylene chloride-petroleum
ether. Concentrated extracts
were cleaned up on Florisil
and analyzed by GC/EC.
Swmnary : Verification by
chemical derivatization.
29, Giam,
et al.
(1918).
(BIOTA continued)
-------
PA i (continuedi
Summary : Controlled labora-
tory studies of the uptake
and metabolism of DEIIP in
aquatic organisms in a model
ecosystem was performed.
No monitoring data presented.
Summary : Sampling of the
model ecosystem was not
discussed.
Comment : Total recovery for
method not discussed but
broken down Into recoveries
for DEHP and each metabolite.
Ilajor degradative pathways
inferred to be through hy-
drolysis of the ester groups
to produce the monoester, then
phthalic acid, and finally
phthallc anhydride.
Summary : A 9 uatic organisms
exposed to ‘ 4 C-!abeled DEIIP
spiked water and analyzed
by homogenization and ex-
traction with ether, TLC
separation and subsequent
scintillation counting.
Identities of metabolites
determined by chromatog-
raphy (TLC) with known
standards. Actual method
recoveries not generated
for DEIIP but rather re-
suits expressed in percent
of metabolites found versus
percent DEIIP remaining.
Comment : Use of 14 C-labeled
DEIIP virtually eliminates
the need for extensive quai-
ity assurance measures in
terms of method blanks.
Summary : No method
blanks, control samples,
or other standard quality
assurance measures were
taken because of the nature
of the radioactive metabolism
expeimenta performed.
Comment : Sites were selected
and grab samples collected in
the vicinity of a DEIIP plant.
“Vicinity” not delineated.
The impact of the factory
has not been determined by
this preliminary investi-
gation.
Comment : Fish caught at
spawning time; normal where-
abouts unknown.
Comment : Results corrected
for background but not for
recovery. Author calls iden-
tification of DEIIP by CC as
being “tentative.”
Comment : Results should be
viewed as qualitative at
best.
55, Persson,
et al.
(1978).
Summary : Samples of fish,
plankton, freshwater and
soil anthrapods, and soil ob-
tained in the vicinity of a
DEHP plant were analyzed for
DEW’.
Summary : Sampling methods
were not discussed.
Summary : Samples were dried
with Na 2 SO 4 and soxhlet ex-
tracted with hexane. Ex-
tracts cleaned up with alumina
and analyzed by GC/FID on two
columns.
Summary : Quality assurances
measures not described but
background level defined at
0.2 ppm and recovery at 40%.
Comment : No actual field survey Comment . None.
conducted
Sample design Sampling Analysis Quality assurance Reference
49, Metcalf,
et. al.
(1973).
(BIOTA continued)
-------
TABLE I (continued)
Sample design Sampling Analysis Quality assurance Reference
Comment : Design inferred to
be a monitoring of the open
lake and tributatires near
sewage trealment plants.
Comment : Composite sampler
rubber tubing replaced with
glass tubing to prevent con-
tamination. Water and sedi-
ment sampling procedure ap-
peared to eliminate source of
contamination. Fish sam-
ples may have been contami-
nated while taking a filet or
when stored in aluminum foil
if the foil was not rinsed
with solvent.
Comment : A well-defined ana-
lytical scheme was used to
separate the analytes from
the matrix. Although not
specifically stated except
for Na 2 SO 4 , mention of the
decontamination procedures
used, if any, would remove
any doubt about the validity
of the data.
Comment : Sample fortification
and recovery results mentioned
in table of contents but miss-
ing from the report. Results
can be considered somewhat
quantitative since method
blanks not reported.
58, Schacht
(1974).
I- ’
¼0
Summary : Survey design os-
tensibly formed to determine
levels of various pesticides
in Lake Hichigan, and their
source, but no information
given as to actual design
formulation. Grab samples of
sediment and fish and 24-hr
water composites were col—
lected over a 3-year period.
Summary : Water samples col-
lected in glass bottles. Both
grab samples and composite
(24 hr) samples taken. Fish
obtained from local fishermen
and stored frozen in aluminum
foil. Sediment samples taken
in glass jars by hand or with a
Ponar dredge.
Summary : “FWPCA Hethod for
Chlorinated Hydrocarbon Pesti-
cides in Water and Wastevater”
used with some modifications.
Results not corrected for re-
covery.
Summary : Spike recovery and
detection limits data were re-
ported, but use of method
blanks was not.
Comment : Survey designed to
point out differences in or-
ganic contamination between
populated and unpopulated
areas. Isle Royale selected
because of remoteness from in-
habited or industrial areas,
the lake on the island has no
direct connection to Lake
Superior and no internal coni-
biistion engines have been used
on the island.
Comment : Chance for contam-
ination in both fish and water
sampling could lead to high
results.
Comment : Sample preparation
procedures delineated but
analysis by CC not discussed
in detail other than operat-
ing parameters. Sample prepa-
ration not specifically de-
signed for phthalates. Lack
of recoveries for method, es-
pecially with the indicated
cleanup steps, leaves room
for considerable analyte
losses as well as further
contamination.
Comment : Four different labs
used in these analyses but re-
sults not compared. Not knowii
if identical samples were an-
alyzed by each lab. These
facts cast considerable
doubt on whether the analytical
data are equivocable.
Summary : Selected sites in
Lake Superior were sampled
for fish and water in order
to determine background
levels of contaminants.
These were compared with
samples taken from a re-
mote area.
Summary : Fish caught using
deep water nets and either
eviscerated on site and
then stored on ice or simply
wrapped and stored on ice
until processing.
Summary : Fish samples homog-
enized with Na 2 SO 4 , extracted,
subjected to GPC and Florisil,
and silicic acid if PCBs pres-
ent, then analyzed by GC/EC.
Summary : No mention of blanks
or spikes was made. Use of
four different labs was sup-
posed to “minimize analytical
error.”
64, Swain
(1978).
(BIOTA continued)
-------
TABLE 1 (continued)
Sample design Sampling Analysis Quality assurance Reference
Comment : A good synopsis of
the persistance that a sel-
ected list of organics have
in Lake Huron. A literature
and data review of monitoring
data for the lake and its
inputs.
Comment : None.
Comment : None.
Comment : None.
71 , U.S.
EPA (1971b).
Summary : This report re-
lates the sources of organic
compounds entering Lake Huron
and describes their potential
impact on the environment.
The report was used as a means
to propose a total ban on PCB,
aidrin, dieldrin, VDT, and its
derivatives.
Summary : Sampling method not
described.
Summary : Analysis methods not
mentioned. DEUP found range
from < I to 1.4 pg/Liter in
water samples.
Summary : No quality assurance
mentioned.
(BIOTA concluded)
0
-------
TABLE I (continuedl
Sample design Sampling Analysis Quality assurance Reference
BL000 (PLASMA. SERUM. CELLS )
Comment Although not stated,
simple grab samples appear to
have been collected from tub-
ing and other plastic apparatus
used in a perfused liver experi-
ment, then from other plastic
products used in medicine, e.g.,
blood bags.
Summary : Limited survey of
plasticizers extracted from
plastic devices by biological
systems. Accumulation and
metabolism of the plasti-
cizers was also examined.
Comment : Grab samples taken
from transfused and nontrans-
fused subjects. Although not
stated, the samples appear to
have been collected on an op-
portunistic basis.
Comment : Procedure used to
control/eliminate contamina-
tion not stated.
Summary : No sampling was
done per se. Outdated whole
blood was purchased from a
nearby blood bank. Human
tissue was obtained from
patients at Johns Hopkins
Hospital. White rat tissue
and blood was obtained from
Johns hopkins University.
Comment : The problem of con-
tamination is not mentioned.
Since no collection procedures
were mentioned addressing this
problem, the results should be
considered qualitative.
Comment : Analytical procedures
not weLl defined. No pro-
cedures were given for any
kind of tissue. Lack of
method description for tis-
sue and general mode of
detection used for blood
analysis leaves ample room
for criticism of results.
Summary : Chloroform extracts
of neutral and acidified blood
were applied to TLC plates or
DOWEX-l. The eluent was spec-
torphotouietrically examined
for phthalates.
Comment : Phthallc acid and
other DEHP metabolies also
analyzed.
Comment : Credibility of the
data is in doubt because of
the minimal QA measures re-
ported.
Summary : Minimal quality as-
surance measures were reported,
i.e., no blanks or spiked sam-
ples were mentioned.
Comment : Blood values were
subtracted from tissue values.
Summary : DEHP found in
stored blood, patient’s
blood who had received
transfusions. DEHP metab-
olites also found.
Summary : Blood sampled from
patients, and after storage
and/or transfusion to deter-
mine source of phthalates in
patients blood.
Summary : CC column: 3% SE-30
on Gas chrom Q. No instrument
or detector mentioned.
Summary : Assay of samples in-
cluded blood not in contact
with PVC, blood in contact with
PVC for increasing time spans,
metabolites found in urine,
fat, and other tissues.
h - i
36, Jaeger
and Rubin
(1910).
37, Jaeger
and Rubin
(1972).
(BLOOD continued)
-------
TABLE I (continued)
Comment ; Logical progression
of studies. Each study based
on results of a previous
study. Grab samples taken in
each case.
Swniaary : Original experiments
designed to determine levels
of DEIIP in blood in a liver
perfusion system. Additional
experiments performed to de-
termine levels in blood and
various tissues exposed to
DEIIP by virtue of blood trans-
fusions, operations, or hemo—
dialysis. Attempts were also
made to determine metabolites.
Comment : Grab samples taken
from blood bags. Unknown if
all bags were from same manu-
facturer or if had the same
lot number.
Summary : Sampling methods
not discussed.
Comment: No mention of random-
ness of selection or procedures
to reduce contamination.
Comment : Analytical methods
not explained. Purity of
solvents and reagents used
(if any) not reported. Lack
of reporting recoveries and
analytical methods indicate
that any results reported
should be reviewed as un-
substantiated.
Summary : Analysis method for
liquids reported as TLC of an
unknown organic extract. Tis-
sue analyzed by unknown method.
Comment : Extraction scheme
could be improved with a
fractionation/cleanup step.
Summary : Ilethod blanks used in
the analysis of the liquids in
the liquid perfusion system and
in the tissue analysis. No dis-
cussion of use of spiked samples
to determine recoveries.
Comment : Data may be question-
able because of minimal QA.
Summary : Platelets and
plasma were from DEIIP
contaminated blood
storage bags.
Summary : Spiked blanks used,
platelet concentrates stored in
plastic blood bags were sampled.
Summary : GC analysis (de-
tector unspecified) of DEHP
from human blood platelets.
Summary : Method blank is the
only QA mentioned and the re-
sults were corrected for it.
Comment : This study is of
significance in determining
the possible fate of phthalates
ingested orally The author
cautions one to use care in
interpreting the data since
ester hydrolysis of the 14 C-
labeled carbonyl group of the
phihalates may affect the emis-
sion patterns observed.
Comment : Unknown whether one
group of animals went through
all collection phases or a
separate group of animals used
for each specific phase.
Comment : Recovery and quenching
data should have been reported.
Otherwise the results are con-
sidered qualitative.
Comment : An unspecified com-
parison with control groups
was made to account for
“slight” radioactivity after
12 to 24 hr. It is uncertain
as to what this statement re-
fers or its relevance.
44, Kitanaka,
et al. (1977)
Summary : This project was de-
signed to determine the effects
of phthalic acid esters on the
body. Rats and mice were ad-
ministered radioactive
phthalates.
Summary : Phthalates with a
carbon-14 tag were administered
to rats and mice Urine, feces,
and tissues were collected at
specific times after administra-
tion of the ‘ 4 C-phthalaies.
Summary : The various excrements, Summary : QA provisions were not
body fluids, tissues, and organs reported.
were measured for radioactivity
to determine which organs con-
tained phthalates and their
relative concentrations with
:tt
Comment : None.
Sample design Sampling Analysis Quality assurance Reference
Comment : Quality assurance
measures skimpy at best.
38, Jaeger
and Rubin
(1973a).
39, Jaeger
and Rubin
(1973b).
-------
TABLE 1 (continued)
Comment : Limited survey--
blood obtained from local
blood bank.
Summary : No real design
used other than obtaining
an unspecified number of
grab samples of blood which
had been exposed to plas-
ticizers.
Comment : Glass tubes to col-
lect blood from plastic bags
probably had a rubber septum
cap and could have caused more
contamination Blood had been
stored in plastic bags for 24
days.
Summary : Blood samples were
taken from transfusion blood
bags (from a local blood bank)
with evacuated glass tubes and
cryoprecipites were kept
frozen in the plastic bags un-
til analysis.
Comment : Cleaning of glass-
ware not elaborated upon.
What is a “negligible” amount
of DE IIP? What kind of caps
were on the glass tubes used
for blood storage?
Comment : Also analyzed for
triglycerides and attempted
to make a correlation between
those levels and DEIIP levels.
Absence of method recoveries
implies that the results gen-
erated can be considered semi-
quantitative.
Summary : Plasma was extracted,
the phthalates salted out, and
the extract analyzed by GC/FID.
Comment : Manipulation of
sample during workup not
detailed enough. Con-
tamination could come from
many sources. GC detector
not specified.
Comment: Lack of QA mea-
sures leads to the conclusion
that the results should be
considered as qualitative in
nature or semiquantitative at
best. Used two columns in
the CC analysis to corroborate
identity of DEUP.
Summary : No indication of
the use of method blanks, con-
trol samples, or any other QA
measures other than the use of
a DEHP standard in the CC analy-
sis and the use of dipentyl-
phthalate or dipropylphthalate
as an internal standard.
Summary : Sixteen patients
subjected to hemodialysis
and seven control physi-
cians and nurses were sam-
pled to determine the mi-
gration of DEUP into the
blood during hemodialysis.
Summary : Clean glass sy-
ringes were used to draw
blood from the patients
during dialysis. Samples
were stored in glass tubes
at dry ice temperatures un-
til analysis.
Swmsary : Ten milliliters
of blood were blended with
ethanolum, the sediment re-
moved, water added to the
ethsnolum solution and then
extracted with 5 ml of hex-
ane. Extract analyzed by
CC.
Suassary : Method blank and use
of control patients were the
only quality assurance measures
taken.
Sample design Sampling Analysis Quality assurance Reference
Comment : Grab samples of
blood taken from exposed and
control people. Design is
limited because samples ap-
parently collected from
people in only one hospital.
41, Marcel
(1913).
54, Ono,
et al.
(1915).
Comment : Use of glass sy-
ringes to draw blood adds
some credibility to analy-
sis but author should have
expanded on use of blanks and
should have done percent re-
coveries.
(BLOOD continued)
-------
TABLE I (continued)
Sample design Sampling Analysis Quality assurance Reference
I ’ . )
Comment : Very limited survey--
can be considered a prelim—
nary assessment of DEJIP ex-
posure through blood traiis—
fusions. Grab samples taken
from blood bags and control
bottles.
Swmnar! : DEHP elevated in
patients transfused with
blood stored in plastic.
Comment : Sampling restricted
to patients in a Japanese hos-
pital; plastic bags and anti-
coagulant under examination
were from a single manufacturer.
No mention was made of pro-
cedures designed to limit poten-
tial contamination, therefore,
validity of the data is un-
certain.
Summary : Blood collected
from patients who had un-
dergone massive transfu-
sions from “plastic bag”
stored blood, from glass
bottles and from patients
who had no transfusions.
Comment : Chromatography and
detection of DEUP not discussed
in depth. FID limited sensi-
tivity of method.
Summary : DEIIP extracted from
matrices by HeOII:CIIC1 3 and
subjected to silica gel col-
umn cleanup (except for anti-
cosgiilants). Determination
of DEIIP by GC/FID. Used di-n-
octyl phthalate as internal
standard. Recoveries of 83
to 100% are considered good
for this matrix and the low
blank levels are also sig—
ni ficant.
Comment : Quality assurance
limited to recoveries from
spiked blood stored Ilk glass
bottles. The use of di—n-
octyl phthalate as an in-
ternal standard raises a ques-
tion about the accuracy of the
data because no mention was
made about blank of this com-
pound.
Swmuary : Radioactive 14 C-
labeled DEHP used for deter-
mination of where IJEUP
stored in blood (red blood
cells or plasma). DEHP mostly
associated with plasma
-lipoprotein.
57, Sasakawa,
and lIitou ,i
(1978).
Comment : Grab samples taken
from a variety of foodstuffs,
some plastic products, and
blood from 13 people. Random-
ness, relationship among or
to products and distribution
among sample population is
unknown.
Comment : None.
Comment : Procedures given
were very sketchy.
Comment : Data cannot be
considered quantitative.
66, Tomita,
et al.
(1977).
Summary : Analyses for DEIIP
and other phthalates were
done in response to litera-
ture reports of widespread
environmental contamination
(in Japan) of pht.halalic
acid esters.
Swmnary : No information on
sampling.
Summary : Florisil fractionation
method and analyses by CC/MS and
GC/EC were used.
Summary : No identifiable
quality assurance stated.
(BLOOD continued)
-------
TABLE 1
VAflhl rnMhlnnTTlPS
(PRACRSSRI1 FOOI1S FISIL IIILKI
1% )
U ’
Comment : Directed specifi-
cally towards phthalate
esters. Grab samplea col-
lected from 10 large bodiea
of water apparently near
large urban/industrial com-
plexes.
Summary : Design was to col-
lect fish from various dis-
trict offices to analyze for
tbe presence of phthalates.
This paper presents metbods
only.
Comment : Deaign was adequate
but not statistically defensi-
ble. Crab aamples were col-
lected by each district but
procedure for selection of
samples not presented.
Comment : Field blanks should
have been reported to deter-
mined if there was any sampling
bias.
Summary : The aampling plan was
to collect the samples as close
to the point of catch as possi-
ble. Samples were wrapped in
phthalate ester-free aluminum
foil and frozen if necessary
prior to shipment. No field
blanks or spiked blanks were
uaed.
Comment : This report does not
adequately address sampling
conditions.
Comment : The method is de-
signed specifically for
phthalate esters and Is quite
comprehensive including aev-
eral tips for eliminating con-
tamination. It was noted
though that experimentation
shows only 50 to 60% recovery
of diisodecylphthlate and that
the chromatography is inade-
quate.
Summary : The analytical method
described uses CC with a 3% OV-
101 glass column.
Comment : A number of problems
rendered the results invalid
for the most part.
Comment : The QA provisions
are fairly good in view of the
program. Should have done
replicates.
Summary : This is a method only
and no results were reported.
QA consisted of method blanks.
Summary : Major processed
foods were sampled to deter-
mine if phthalstes were en-
tering the food supply through
the processing, packaging,
handling, and transportation
chain.
Summary : This report does
not give the sampling pro-
cedures.
Summary : Analytical method
was mentioned by reference
only.
Summsry : Quality assurance
measures reported were method
blanks only and these were
above an acceptable limit for
two of the five laboratories.
‘ ‘ , .. “
Sample design Sampling Analysis Quality assurance Reference
5, Bureau
of Foods,
(1912).
6, Bureau
of Foods
(1915).
Comment : The quality assurance
results are not good and these
data can be considered as weak.
(FOOD COMMODITIES continued)
-------
TABLE I (continued)
Sample design Sampling Analysis Quality assurance Rcfereiice
Couiment : Grab samples taken
from “a sample of commercial
pooled milk” and apparatus in
use at the laboratory.
Comment : None.
Comment : This method is out-
dated. The chance for contami-
nation is high, and the detec-
tion limit is probably above
reasonable levels.
Comment : QA was sufficient
for this study.
8, Cetbulis
and Ard
(1967).
Summar!: A method for isolat-
ing and detecting dioctylphtha—
late from milk was developed.
Summary : No information was
given on the sampling pro-
cedure.
Summary : The lipids were ex-
tracted by dialysis, separated
on an alumina column and the
phthalates isolated by TLC.
Recovery of DOP was determined
to be about 60%.
Summary : The equipment, so!—
vents, and other chemicals were
checked. Only the plastic tub-
ing showed definite indication
of DOP although the author did
not believe the milk contacted
the plastic tubing. Confirma-
tion of the TLC results was by
IR.
Comment : Grab samples taken
from a variety of foodstuffs,
some plastic products, and
t’. blood from 13 people. Random-
a’ ness, relationship among or
to products and distribution
among sample population is
unknown.
Summary : Analyses for DEIIP
and other phthalates were
done in response to litera-
ture reports of widespread
environmental contamination
(in Japan) of phthalalic
acid esters.
Summary : No information on
sampling.
Summary : Florisil fractionation
method and analyses by CC/hIS and
GC/EC were used.
Summary : No identifiable
quality assurance stated.
Comment : None.
Comment:
Procedures given
Comment:
Data
cannot
be
66,
Tomita,
were
very
sketchy.
considered
quantitative.
et
al
(1977).
(FOOD COHIIODITIES continued)
-------
TABLE 1 (conlinued)
Sample design Sampling Analysis Quality assurance Reference
Coioment : Twnety-one grab sam-
ples of fish collected.
Comment : Since the col-
lection procedure and
storage conditions used
by the “outside sources”
(Environment Canada) were
not reported, contamination
of the fresh fish is possi-
ble and thus the analytical
results may not reflect the
actual level in these fish.
Comment : An extended awl “old
fashioned’ cleanup but identi-
fication procedures good
Since background levels quanti-
tated and overall recoveries
done at two levels with mod-
erate recoveries (60 to 65%),
data would seem to be fairly
reliable.
Comment : Since recoveries
are only moderate this method
should riot be classified as
strictly quantitative but
rather as semiquantitative.
76, Williams
( 1973a).
— I
Summary : Fish obtained by
Environment Canada or from
local markets.
Summary : Fish purchased at
local markets and supplied
by outside sources.
Summary : One hundred grams of
fish sample chopped and macer-
ated with hot liexane. Sub-
jected to liquid—liquid par-
titioning, acid-base cleanup,
and other silica gel cleanup.
Quantitation using instrumen-
tion given above. Reagent
blanks considered to be back-
ground level. Levels found
at less than twice background
level reported as trace; other
values corrected for background
level.
Summary : Quality assurance
directed towards establish-
ing background level. An
unknown number of spiked
samples used to show re-
covery (60 to 65%). Re-
coveries for both levels
(0.1 to 0.5 ppm) not re-
ported separately but
rather reported together
as a range.
(FOOD COMMODITIES concluded)
-------
TABLE I (continued)
Sample design Sampling Analysts Quality assurance Reference
PLASTIC PRODUCTS (FILII. PIPE. TUBIN(fl
Comment : Five PVC Ellis samples
were supplied by Borden but
only three were used. Repre-
sentativeness of these films
to other films in doubt since
only one film source was
studied.
Comment : All Ellis from same
company.
Comment : Results reported were
corrected for percent recovery,
film thickness and width. Re-
sults were variable and can-
not be considered quantitative
but only indicative of levels
a person may be exposed to
when cutting PVC film.
Comment : Hethod not very re-
producible as shown by number
of smoky versus clean runs,
and relative standard devia-
tions of results. Variability
of results are semiquiantitative
at best. Repetition of test
runs only seems to show varia-
bility of method and does not
necessarily give a better
average value of organics re-
leased during the cutting
process.
2, Boettner
and Ball
(1980).
I’. )
Sunim : PVC films supplied
by Borden Chemical were sur-
veyed for volatilization of
various compounds during the
cutting process. Supermarket
conditions were simulated.
Summary : Five PVC films were
obtained from Borden Chemical.
No real sampling involved.
Suannar! : PVC films were cut
with a hot-wire (% 215°C) or
a cool rod (135°C) inside a
specially constructed hood.
The phthalates were collected
by rinsing the hood with 25 ml
of ethanol. The ethanol vol-
ume was reduced to I ml and
analyzed by GC/FID.
Summary : Sampling hood rinsed
between runs to ensure no car-
ryover. Replicate runs were
made to obtain average values
of phthalate released during
cutting.
Comment : The sampling plan did
not cover field blanks and
therefore does not permit as-
sessment of contamination but
only indicates changes in the
phthalate level.
Comment : Detection limits
were reported to be 10 P8/
liter but the analytical In-
strument used is not speci-
fied. The analytical method
was not reported and there-
fore cannot be assessed.
Summary : Potable water from
PVC pipe was sampled for a
variety of organic pollutants.
Sunwiary : Samples were col-
lected in amber bottles washed
in detergent followed by rinses
in tap and deionized water then
in pesticide grade hexane and
baked 1 hr at 400°C.
Summary : No cleanup was
reported, nor was sample
preparation reported. It
is assumed that the method
was the standard EPA B/N
method. Detection limit was
10 pg/liter.
Summary : Little information
reported on QA provisions.
The use of spiked samples was
mentioned but the specific
compounds or levels used was
not reported.
Comment : A static lab setup
was used to simulate pipe ex-
posure.
Comment : The QA information
provided is of little value.
11, De-
partment
of Health
Services
and De-
partment
of In-
dusti ral
Relations
(1980).
(PLASTIC PRODUCTS continued)
-------
TABLE 1 (continued)
Sample design Sampling Analysis Quality assurance Reference
Comment : Although not stated,
simple grab samples appear to
have been collected from tub-
ing and other plastic apparatus
used in a perfused liver experi-
ment, then from other plastic
products used in medicine, e.g.,
blood bags.
Summary : Limited survey of
plasticizers extracted from
plastic devices by biological
systems. Accumulation and
metabolism of the plasti-
cizers was also examined.
Comment : Grab samples taken
from transfused and nontrans-
fused subjects. Although not
stated, the samples appear to
have been collected on an op-
portunistic basis.
Comment : Procedure used to
control/eliminate contamina-
tion not stated.
Summary : No sampling was
done per Se. Outdated whole
blood was purchased from a
nearby blood bank. Human
tissue was obtained from
patients at Johns Hopkins
Hospital. White rat tissue
and blood was obtained from
Johns Hopkins University.
Comment : The problem of con-
tamination is not mentioned.
Since no collection procedures
were mentioned addressing this
problem, the results should be
considered qualitative.
Comment : Analytical procedures
not well defined. No pro-
cedures were given for any
kind of tissue. Lack of
method description for tis-
sue and general mode of
detection used for blood
analysis leaves ample room
for criticism of results.
Summary : Chloroform extracts
of neutral and acidified blood
were applied to TLC plates or
DOWEX-I. The eluent was spec-
torphotometrically examined
for phthalates.
Comment : Phthalic acid and
other DEHP metabolies also
ama lyzed.
Coninent : Credibility of the
data is in doubt because of
the minimal QA measures re-
ported.
Summary : Minimal quality as-
surance measures were reported,
i.e., no blanks or spiked sam-
ples were mentioned.
Comment : Blood values were
subtracted from tissue values.
Suimnary : DEHP found in
stored blood, patient’s
blood who had received
transfusions. DEHP metab-
olites also found.
Summary : Blood sampled from
patients, and after storage
and/or transfusion to deter-
mine source of phthalates in
patients blood.
Summary : CC column: 3% SE-30
on Gas chrom Q. No instrument
or detector mentioned.
Summary : Assay of samples in-
cluded blood not in contact
with PVC, blood in contact with
PVC for increasing time spans,
metabolites found in urine,
fat, and other tissues.
36, Jaeger
and Rubin
(1910).
37, Jaeger
and Rubin
(1972).
(PLASTIC PRODUCTS continued)
-------
TABLE I (continued)
Comment : Logical progression
of studies. Each study based
on results of a previous
study Grab samples taken in
each case.
Summary : Original experiments
designed to determine levels
of DEHP in blood in a liver
perfusion system Additional
experiments performed to de-
termine levels in blood and
various tissues exposed to
DEIIP by virtue of blood trans-
fusions, operations, or hemo—
dialysis. Attempts were also
made to determine metabolites.
Comment : This is a limted
in—house survey of pharma-
ceutical articles used at
the Royal Danish School of
Pharmacy. Grab samples used
to provide data to support a
new chromatographic technique.
Summary : Commonly used
pharmaceutical articles were
tested for phtbalate
content.
Summary : Sampling methods
not discussed.
Summary : Pharmaceutical
articles were presumably
obtained from in-house
sources and were to be
tested for phthalate
content.
Comment : Analytical methods
not explained. Purity of
solvents and reagents used
(if any) not reported. Lack
of reporting recoveries and
analytical methods indicate
that any results reported
should be reviewed as un-
substantiated.
Summary : Analysis method for
liquids reported as TLC of an
unknown organic extract. Tis-
sue analyzed by unknown method.
Comment : tlethod “3” found to be
most accurate--analyst dealing
with percent levels of di—
“isononyl” phthalate (38%)
Comparison of methods adds
credibility data generated.
Summary : Three methods of
analysis were compared: (I)
extraction (soxhiet) with
ether, ether removed and resi-
due weighed (plasticizer);
(2) dissolved in TUF and
methanol added to precipitate
PVC, residue weighed for
PVC and solution analyzed by
CC for phthalates; (3) dis-
solved in TIIF and analyzed by
CC for phthalates.
Summary : Method blanks used in
the analysis of the liquids in
the liquid perfusion system and
in the tissue analysis. No dis-
cussion of use of spiked samples
to determine recoveries.
Comment : Although use of blanks
not mentioned, the levels of
phthalates found were usually
so high that it would be un-
likely they were caused by
contamination.
Summary : Duplicates used for
every sample as well as two
analytical columns to identify
the various phthalates adds
considerable credibility to the
results reported.
Comment : None.
Sample design Sampling Analysis Quality assurance Reference
Comment : Quality assurance
measures skimpy at best.
0
Comment : None.
38, Jaeger
and Rubin
(1913a).
45, Lerche
and Noerch
(1973).
(PlASTIC PRODUCTS continued)
-------
TABLE I (continued)
Sample design Sampling Analysis Quality assurance Reference
Comment: Only one type of
tubing used in experiments.
Correlation between this one
tubing and other approved
tubing is therefore uncer-
tain.
Comment : Procedures to mini-
mize or determine background
DEIIP not. detailed, thus data
should be viewed with caution.
Comment : Purity of petroleum
ether not discussed; nor was
preparation of sodium sulfate
or florisil. These facts
leave doubt as to possibility
of contamination. Cutting sip
the tubing and working it in
the fluids, however, does not
really represent normal ex-
posure of the solutions to PVC
tubing, thus the data presented
will not reflect normal exposure
by consumption of the milk.
Comment : Results compared
against Wildbretts (1973)
findings in German PVC tub-
ing. Wildbrett looked [ or
total phthalate concentra-
tion by spectrophotometric
methods. Data generated
in the present study can
be viewed only as quali-
tative and only as a con-
firmation of the fact that
phthalates leach from dairy
tubing.
53, Iteuller
and Bradley
(1980).
I - ’
Summary : Survey designed to
examine phthalate migration
from PVC dairy tubing into
water, milk, and various
cleaners at various tem-
peratures
Summary : Duplicate 10 cm of
Tygon tubing weie submerged
for consecutive times in cov-
ered beakers containIng 500 ml
of the solution to be tested.
Immersion periods were chosen
to represent an average daily
exposure Lime of dairy tubing
in actual use.
Summary : Solutions under study
were extracted three times with
petroleum ether, the extract
dried with Na2SO4L, subjected to
florisil cleanup rand aceto-
nitrite partitioning if neces-
sary) and analyzed by GCIEC.
Summary : With the exception
of duplicate samples, few
quality assurance measures
were taken in terms of method
blanks or spiked samples.
(PLASTIC PRODUCTS continued)
-------
TABLE I (continued)
Comment : Noted to be a pre-
liminary, not an all—inclusive
survey and analysis program.
This study is a combination
of a literature survey and
the “llontgomery report,”
the purpose of which is
to present information to
a state agency pointing
out the hazards of licens-
ing the use of plastic
pipe in potable water sys-
tems. The results of this
study should be viewed with
caution as it may be biased.
Note: See also Review No. 62.
Comment : PVC, CPVC, and ABS
samples analyzed. No large
scale tests of water contami-
nation ever done. Water
through PVC and CPVC only.
Erratic sample selection,
large number of treatments.
Comment : DEHP found in PVC,
CPVC. No method of any kind
mentioned, some suggestion
that DEIIP may be present in
1120 as mucells.
Comment : Variation in re-
suits not accounted for.
DEIIP found as high as 246
pg/liter. DEIIP and DBP
levels found fluctuated
sharply; absence of pat-
tern suggests analytical
difficulty.
Summary : The study was de-
signed to identify kinds of
materials present in plastic
pipe and associated health
hazards, through a literature
and patent survey, and ex-
tremly limited analysis of
pipe and water samples.
Study was performed for
Local 467 Plumbers and
Steamfitters Union, AFL—
do.
Summary : Water samples
involved three types of
leach tests from two
pipes, three water types,
two temperatures, two
pipe joint cements, two
joint qualities. “Sam-
ples” were prepared in
the lab, not taken from
“real” situations.
Suimnary : DEIIP more likely
leached from older pipe,
many analysis problems.
Summary : DEHP present, but in
widely fluctuating amounts.
The entire program suggests
DEIIP will present analytical
difficulties.
Sample design Sampling Analysis Quality assurauice Reference
56, Reid,
et al.
(1980).
(PLASTIC PRODUCTS continued)
-------
TABLE 1 (continued)
Comment: Very limited survey--
can be considered a prelim-
nary assessment of DEIIP ex-
posure through blood trans-
fusions. Grab samples taken
from blood bags and control
bottles.
Summary : DEIIP elevated in
patients transfused with
blood stored in plastic.
Comment : This paper is a
study review.
Comment : Sampling restricted
to patients in a Japanese hos-
pital; plastic bags and anti-
coagulant under examination
were from a single manufacturer.
No mention was made of pro-
cedures designed to limit poten-
tial contamination, therefore,
validity of the data is un-
certain.
Summary : Blood collected
from patients who had un-
dergone massive transfu-
sions from “plastic bag”
stored blood, from glass
bottles and from patients
who had no transfusions.
Comment : Sampling not spe-
cifically designed for
phthalates. Equilibration
of water in PVC pipes prob-
ably not representative of
conditions encountered diir—
ing normal use.
Comment : Chromatography and
detection of DEIIP not discussed
in depth. FID limited sensi-
tivity of method.
Summary : DERP extracted from
matrices by HeOH:CIIC1 3 and
subjected to silica gel col-
umn cleanup (except for anti-
coagulants). Determination
of DEUP by GC/FID. Used di-n-
octyl phthalate as internal
standard. Recoveries of 83
to 1007. are considered good
for this matrix and the low
blank levels are also sig-
nificant.
Comment : Extraction procedure
not fully described Unknown
extraction efficiencies and
lack of field blanks casts
considerable doubt on low
level findings ( 100 ppb).
Comment : Quality assurance
limited to recoveries from
spiked blood stored in glass
bottles. The use of di-n-
octyl phthalate as an in-
ternal standard raises a ques-
tion about the accuracy of the
data because no mention was
made about blank of this com-
pound.
Summary : Radioactive 14 C-
labeled DEIIP used for deter-
mination of where DEHP
stored in blood (red blood
cells or plasma). DEIIP mostly
associated with plasma
-lipoprotein.
Comment : Report indicates
that further work would be
necessary to confirm the
validity of the phthalate
numbers. Results can be con-
sidered as only qualitative.
Summary : Water in newly
constructed house with PVC
pipe plumbing was tested
for various organic con-
taminants.
Summary : Grab samples were
taken in 40 ml VOA vials from
three different “hose bibs” in
a newly constructed house.
Summary : CS 2 and toluene
extracts of water samples
were analyzed for phthalate
esters by GC/FID and GC/EC.
Summary : No quality as-
surance measures were re-
ported other than CC/uS
identification of DEHP. Re-
port indicates that the study
was not designed to look at
phthalates.
Sample design Sampling Analysis Quality assurance Reference
57, Sasakawa,
and tlitomi
(1978).
62,
Sode rquist
(1980).
(PLASTIC PRODUCTS continued)
-------
Coniment : Three types of tubing
from unspecified source(s) may
not be representative of all
PVC tubing.
Comment : The three types
of tubing tested cannot be
considered to represent
all PVC tubing in use at
that time, nor can the
data generated be con-
sidered monitoring data.
Comment : The general mode
of detection would allow for
substantial occurrences of
interferences and would not
identify specific phthalates.
solution, etc.) indicates
that any blank levels present
would probably not have been
detected. The lack of ex-
traction recoveries however
cast considerable doubt as to
the accuracy of the data gen-
erated for migration.
Comment : The reporting of
milligram levels of total
phthalates in the ethanol
extracts of 100 ml of test
solution (milk, cleaning
Summary : No design
discussed.
Summary : Three types of
tubing were tested.
Summary : General nonspecific
spectrophotometric method for
determination of phthalates.
Summary : Blanks and recoveries
not mentioned in the articles.
Method used for high parts per
million levels.
(PLASTIC PRODUCTS concluded)
TABLE I (continued)
Sample design Sampling Analysis Quality assurance Reference
15, Wildbrett
(1973).
-------
TABLE 1 (continued)
Sample design Sampling Analysis Quality assurance Reference
SEDIMENT
Comment : The location of
sites for the collection of
grab samples was influenced
by the effluent plume move-
ment. Other sampling cri-
teria, e.g , temporal or
replicate sampling, was not
discussed.
Comment : With the exception
of QA samples and procedure
for cleaning equipment the
sampling seems quiLe adequate.
Comment : In view of the lack
of reported recoveries and the
mentioned interferences this
section is of questionable
value.
Comment : QA section was of no
value.
4, Brownlee
and Strachan
(1976).
Ln
Summary : The dispersion of
organics from the mill ef-
fluent was monitored by sam-
pling at various distances
from the outfall.
Comment : The design involved
collection of grab samples
from river and near-shore
waters. Criteria not deline-
ated for selection of sampling
sites.
Swmnary : Water was collected
using teflon and S.S. appa-
ratus. Seston retained on a
Nucleopore filter while sedi-
ment was collected with a
Shipek sampler.
Comment : The sampling method
seems quite adequte and thus
the samples should be repre-
sentative of the environment.
Summary : Due to the nature
of the study no attempt was
made to optimize for
phthalates. Instrument re-
sponse linearity was not re-
ported. No attempt appears
to have been made to determine
the recoveries of the compounds
reported.
Comment : The extraction method
is good based on high recoveries
but additional validation should
have been reported so that the
entire analytical method could
be assessed.
Sunanary : No quality assurance
provisions, blanks, spikes, or
replicates were reported.
Comment : The method blanks
are indicative of minimal
contamination but the accuracy
and verification of the data
are unknown.
10, Corcoran
and Curry
(1978).
Summary : Samples of water,
particulate matter, and sed-
iment were collected in 1975
from the lower Mississippi
River and northeast Gulf of
Mexico to determine the dis-
tributio.i and concentration
of various phthalic acid
esters.
Summary : After cleanup, glass-
ware and aluminum foil were ex-
tracted and checked by GC for
phthalate levels. Water samples
were taken at the surface, mid-
depth, and close to the bottom
using an all metal Niskin-type
sampler
Summary : Water samples were
filtered through glass fiber
filters, passed through XAD-2
resin. Eluted from XAD-2 with
diethyl ether, dried, and ex-
tracted with hexane. Glass
fiber filters were extracted
with hexane and cleaned up
on Florisil. Analysis was
by GC/EC. Recovery was 98%.
Summary : Glassware and alumi-
num foil was extracted after
cleaning. No detectable levels
were observed.
(SEDIMENT continued)
-------
TABLE I ( -nntin.u ifl
Comment : This report is con-
cerned mainly with the analyt-
ical results and their signif-
icance. Criteria used to select
sampling sites is unknown. Ap-
parently grab samples were col-
lected to assess phthalate
loading in the Gulf.
Summary : The goal of this
project was to analyze se-
lected samples from the
Gulf of Ilexico for
phthalates and to assess the
significance of the data. The
Nississippi River accounts for
only one-fourth of the total
DEUP loading. “The origins
of the remaining inputs have
not yet been determined.”
Comment : Design not part of
report Selected results of
10 biota, 9 water, and 6 sedi-
ment samples were reported.
Comment: See other Giam
articles for procedures.
Summary : No information was
provided on sampling methods
(see earlier Giam articles).
Comment : The sampling pro-
cedures recommended are very
good. Emphasis is on reduc-
ing possible sample contami-
nation.
Comment : See other Giam
articles for procedures.
Summary : No information was
given concerning the analyt-
ical procedures. The detec-
tion limit for phthalate was
reported as 0.1 ng/g.
Comment : Analytical method
not reported.
Comment : None. 20, Giam,
et al.
(1976a).
Summary ; No QA information
was reported as this was a
discussion of published data.
Comment : The discussion of
the QA procedures is some-
what minimal. The recom-
mended procedure for mini-
mizing contamination in
blanks is quite good.
Summary : Paper proposed
methods for very low back-
ground sampling and analy-
sis, as well as for evalua-
tion of procedures for biota,
sediment, and water.
Summa!i: Recommends cleaning
glass and metal with deter-
gent, water, solvent, and then
heating. Recommends heating
aluminum foil to 320°C over-
night and solvent extraction
XAD-2 resin. Also recommends
use of spiked samples.
Suimnary : Analytical procedure
covers only cleaning of glass-
ware and equipment.
Suimnary : Paper recommends
procedures for minimizing
contamiantion.
Sample design Sampling Analysis Quality assurance Reference
a’
21, Giam,
et al.
( 1976b).
(SEDIMENT continued)
-------
TABLE I (continued)
Sample design Sampling Analysis Quality assurance Reference
Comment : Origin of samples
given as the Gulf of Plexico.
Grab samples inferred to have
been collected
Comment : The sampling pro-
cedure should have yielded
samples with a minimum of
phthalate contamination.
Comment : The analytical pro-
cedure seems quite acceptable
based on the recovery values
reported.
Comment : The only quality as-
surance provisions reported
were procedures to minimize
background in blanks. With
the addition of replicate
samples and spiked hlanks the
method could be helter evalu-
ated.
ta
-J
Summary : The purpose of
this paper was to report a
procedure for the analysis
of marine biota, water, and
sediment. No design was
reported.
Comment : The mass balance
model was developed using a
combination of data and as-
sumptions. Author states
that atmospheric input to
the Gulf was the most im-
portant route but cautions
that “direct field measure-
ments are important.”
Summary : Samples were col-
lected in containers cleaned
with detergent, rinsed with
water and acetone, and heated
to 320°C. Water samples were
passed through XAD-2 resin
column. Biota samples were
stored at or below 0°C.
Comment : This section only
briefly outlines the sampling
method and is of limited
value.
Summary : Samples were ex-
tracted with acetonitrile,
Ch1 2 C1 2 —petroleum ether and
cleaned up on a Florisil
column. Recoveries of
phthalates were in the range
19 to 100%. Analysis was
by GC/EC with S ng DEIIP
yielding 50% full scale de-
flection.
Comment : This section lacks
enough information to assess
its value.
Summary : Procedures given to
minimize background in sample
blanks. Verification by GC/EC
using a different column. DEHP
levels of laboratory items re-
ported.
Comment : None
25, Giam
(1911).
Summary: This paper deals
primarily with a mass—balance
model for estimation of
fluxes of 0 5 1 W in the Gulf of
Mexico. Sampling and analy-
sis is as in reference 21.
Sunsn y: Water samples were
solvent extracted on site or
adsorbed on XAD-2 resin.
Riots samples were collected
by hook and line or trawl.
Sediment samples were col-
lected with a metal coring
device. Air was adsorbed
on Florisil or polyurethane.
Summary : Samples were ex-
tracted with organic solvents,
cleaned up by column chroma-
tography and analyzed by GC/
SC.
Summary : No QA data of signifi-
cance reported.
24, Giam,
et al.
(1976e).
(SEDIMENT continued)
-------
TABLE I (continued)
Sample design Sampling Analysis Quality assurance Reference
Comment : Basically same in-
formation as other articles
by Giam. Grab samples ap-
parently collected.
Comment : This section is too
brief to be of value.
Comment : Too little informa-
tion provided to properly as-
sess this section.
Comment : None.
21, G am
et al.
(1978).
Summary : The purpose of the
project was to analyze for
phthalate esters and chlori-
nated hydrocarbons in air,
water, sediment, and biota
samples predominantly from
the Gulf of Mexico.
Summary : Sampling methods are
brief. Sediment--metal coring
device. Biota-—hook and line
or trawl. Water--extracted
directly or adsorbed on XAD-2.
Air—-adsorbed on Florisil or
polyurethane foam. Sediment
and biota samples frozen.
Summary : Samples were ex-
tracted with organic solvents
and cleaned up by column chro-
matography. Analysis was by
GC/EC. Recoveries of “90% or
better” were mentioned as well
as “background values of
50 ag.”
Summary : Appropirate QA in-
formation was not provided
Co
Comment : Design was based
on grab sample collection
from a single point in the
river.
Summary : The study was de-
signed to present data on
organics in sediment in
Charles River system.
Comment : The lack of a col—
lection procedure to limit
contamination is a serious
fault of this study.
Summary : A weighted brass
tube with a teflon flap col-
lected mud from the river
bottom. The mud was taken
to the lab where processing
began without delay.
Comment : Extraction and analy-
sis procedures are somewhat
complete in themselves and
reference is made to addi-
tional sources of information.
Summary : After the dried
samples were extracted on a
Soxhlet apparatus, one batch
was gradient eluted from an
alumina column. A second
batch was pentane-extracted
from methylene chloride.
After an initial GC screen
the samples were analyzed by
GC/HS andfor l OUIS.
Comment : Very little infor-
mation given, so results are
questionable.
Summary : The absence of DEIIP
was noted in blank analyses.
33, Rites
and Biemann
(1975).
(SEDIMENT continued)
-------
TABLE I (continued)
Sample design Sampling Analysis Quality assurance Reference
Comment : Grab samples col-
lected to assess influence of
chemical point sources on
river systems. Study I ap-
pears to have been a single
sampling of multiple points
along a river system. Tem-
poral differences investi-
gated in study 2 with 5 of
13 sites resampled.
Conunent : Samples preserved im-
mediately after collection Is
an effective procedure for min-
imizing artifacts. Without men-
tion of container preparation,
the validity of the samples
is quesitonable because of the
unknown possibility of con-
tamination from the sampling
equipment.
Comment : Blanks were run through
cleanup procedure and showed
no contamination. Solvents
used were nanograde but were
not concentrated and checked
by GC for contamination; thus,
would still be some room for
phthalate contamination.
Comment : Low levels of DEPIP
reported could conceivably
be due to contamination and
its presence in the waste-
water. Quantitative identi-
fication good, however, be-
cause of the use of MS. Lack
of method recoveries also in-
dicates results are semiquan—
titative in nature.
L.J
Summary : Survey designed to
provide samples for detailed
organic analysis by various
sample concentration tech-
niques and GC/IIS.
Comment : Design inferred to
be a monitoring of the open
lake and tributatires near
sewage treatment plants.
Summary : Water samples were
cooled to refrigerator temper-
ature and those for solvent ex-
traction were acidified and
solvent added; sediments were
frozen after collection.
Comment : Composite sampler
rubber tubing replaced with
glass tubing to prevent con-
tamination. Water and sedi-
ment sampling procedure ap-
peared to eliminate source of
contamination. Fish sam-
ples may have been contami-
nated while taking a filet or
when stored in aluminum foil
if the foil was not rinsed
with solvent.
Summary : Grab water sample
were extracted in the bottle
overnight by stirring. Some
extracts were cleaned up using
silica gel followed by basic
extraction cleanup. Analysis
of the extracts were carried
out by GC using EC, FID, or
MS and authentic standards.
Comment : A well-defined ana-
lytical scheme was used to
separate the analytes from
the matrix. Although not
specifically stated except
for tla 2 SO 4 , mention of the
decontamination procedures
used, if any, would remove
any doubt about the validity
of the data.
Summary : Minimal quality as-
surance procedures were re-
ported.
Comment : Sample fortification
and recovery results mentioned
in table of contents but miss-
ing from the report. Results
can be considered somewhat
quantitative since method
blanks not reported.
58, Schacht
(1974).
Summary : Survey design os-
tensibly formed to determine
levels of various pesticides
in Lake Michigan, and their
source, but no information
given as to actual design
formulation Grab samples of
sediment and fish and 24-hr
water composites were col-
lected over a 3-year period.
Summary : Water samples col-
lected in glass bottles. Both
grab samples and composite
(24 hr) samples taken. Fish
obtained from local fishermen
and stored frozen in aluminum
foil. Sediment samples taken
in glass jars by hand or with a
Ponar dredge.
Summary : “FWPCA Method for
Chlorinated Hydrocarbon Pesti-
cides in Water and Wastewater”
used with some modifications.
Results not corrected for re-
covery.
Summary : Spike recovery and
detection limits data were re-
ported, but use of method
blanks was not.
34, Mites,
et a!.
(1979).
(SEDIMENT continued)
-------
TABLE I (continued)
Comment : No actual design
discussed; however, grab
samples were apparently col-
lected along entire river and
probably representative of
the river system at the time
of sample collection. An
attempt to collect replicate
samples was not accurate be-
cause of temporal and spatial
differences in returning to
the site.
Comment : Sampling procedures
used probably reduced any
potential for contamination
and the samples collected
represent the actual en-
vi ronment.
Comment: Good recovery (90
to llO’/) combined with a
fractionation and cleanup
step indicate a meaningful
analysis.
Comment : Overall, the min-
imal contamination and the
verification by two analyti-
cal methods can support con-
fidence in the data.
Summary : Sediment samples
were taken from the Rhine,
Issel , and Heuse Rivers in
the Netherlands for the
determination of DE1IP and
DHP levels (32 samplIng
stations). Twelve samples
were taken from a nearby
nature-reserve and one
from a landfill.
Suaimary : Samples collected
with a hydro-blos dredge and
stored at -30°C after freeze-
drying. Some sites sampled
months apart to determine any
temporal variations.
Summary : Sediment was freeze-
dried, soxhlet extracted con-
centrated and detected by LC
system. GC determinations re-
quired florisil cleanup.
Summary : Number of blanks
and spikes not discussed.
Reduction of contamination
solved by rinsing lab equip-
ment with hexane. Method
recovery mentioned as being
quantitative.
Comment : A good synopsis of
the persistance that a sel-
ected list of organics have
in Lake Huron. A literature
and data review of monitoring
data for the lake and its
inputs.
Comment : None
Comment : None.
Comment : None.
11, u.s.
EPA (1977b).
Summary : This report re-
lates the sources of organic
compounds entering Lake Huron
and describes their potential
impact on Lhe environment.
The report was used as a means
to propose a total ban on PCB,
aidrin, dieldrin, DDT, and its
derivatives.
Summary : Sampling method not
described.
Summary : Analysis methods not
mentioned. DEIIP found range
from < 1 to 1.4 pg/liter in
water samples.
Summary : No quality assurance
mentioned.
Sample design Sampling Analysis Quality assurance Reference
59, Schwartz,
et al.
(1979).
(SEDIMENT concluded)
-------
TABLE I (continued)
Sample design Sampling Analysis Quality assurance Reference
SESTON
Comment : The location of
sites for the collection of
grab samples was influenced
by the effluent plume move-
ment. Other sampling cri-
teria, e.g., temporal or
replicate sampling, was not
discussed.
Comment : With the exception
of QA samples and procedure
for cleaning equipment the
sampling seems quite adequate.
Comment : In view of the lack
of reported recoveries and the
mentioned interferences this
section is of questionable
value.
Comment : QA section was of no
value.
4, Brownlee
and Strachan
(1976).
- Is
I- ’
Summary : The dispersion of
organics from the mill ef-
fluent was momitored by sam-
pling at various distances
from the outfall.
Comment : The design involved
collection of grab samples
from river and near-shore
waters. Criteria not deline-
ated for selection of sampling
site.
Summary : Water was collected
using teilon and 5.5. appa-
ratus. Seston retained on a
Nucleopore filter while sedi-
ment was collected with a
Shipek sampler.
Comment : The sampling method
seems quite adequte and thus
the samples should be repre-
sentative of the environment.
Summary : Due to the nature
of the study no attempt was
made to optimize for
phthalates. Instrument re-
sponse linearity was not re-
ported. No attempt appears
to have been mmde to determine
the recoveries of the compounds
reported.
Comment : The extraction method
is good based on high recoveries
but additional validation should
have been reported so that the
entire analytical method could
be assessed.
Summary : No quality assurance
provisions, blanks, spikes, or
replicates were reported.
Comment : The method blanks
are indicative of minimal
contamination but the accuracy
and verification of the data
are unknown.
10, Corcoran
and Curry
(1978).
Summary : Samples of water,
particulate matter, and sed-
iment were collected in 1915
from the lower Flississippi
River and northeast Gulf of
Mexico to determine the dis-
tribution and concentration
of various phthalic acid
esters.
Summary : After cleanup, glass-
ware and aluminum foil were ex-
tracted and checked by GC for
phthalate levels Water samples
were taken at the surface, mid—
depth, and close to the bottom
using an all metal Niskin-type
sampler.
Surmaary : Water samples were
filtered through glass fiber
filters, passed through XAD-2
resin. Eluted From XAD-2 with
diethyl ether, dried, and ex-
tracted with hexane. Glass
fiber filters were extracted
with hexane and cleaned up
on Florisil. Analysis was
by GC/EC. Recovery was 98%.
Summary : Glassware and alumi-
num foil was extracted after
cleaning. No detectable levels
were observed.
(SESTON concluded)
-------
TABLE I (continued)
Sample design Sampling Analysis Quality assurance Reference
SOIL
Comment : Sites were selected
and grab samples collected in
the vicinity of a DEIIP plant.
“Vicinity” not delineated.
The impact of the factory
has not been determined by
this preliminary investi-
gation.
Comment : Fish caught at
spawning time; normal where-
abouts unknown.
Comment : Results corrected
for background but not for
recovery. Author calls Iden-
tification of DEJIP by CC as
being “tentative.”
Comment : Results should be
viewed as qualitative at
best.
55, Persson,
et al.
(1978).
Summary : Samples of fish,
plankton, freshwater and
soil anthrapods, and soil ob-
tained in the vicinity of a
DEIIP plant were analyzed for
DEIIP.
Summary : Sampling methods
were not discussed.
Summary : Samples were dried
with Na 2 SO 4 and soxhiet ex-
tracted with hexane. Ex-
tracts cleaned up with alumina
and analyzed by CC/lID on two
columns.
Summary : Quality assurances
measures not described but
background level defined at
0.2 ppm and recovery at 40%.
(SOIL concluded)
-------
TABLE I (continued)
Sample design Sampling Analysis Quality assurance Reference
TISSUE fiIJJIIAN. EXL’ERIMENTAL ORGANISIIS )
Comment : Unspecified number
of grab samples collected.
Summary : This paper reports
the finding of three phtha—
lates in Rhine River water
by element specific CC/MS.
Comment : None.
Summary : No information
given
Comment : Not enough infor-
mation given to evaluate an-
alytical method.
Summary : CC/MS operated as
a halogen-specific detector.
Comment : None.
Summary : None reported.
17,
Freudentha 1
(1978).
Comment : Although not stated,
simple grab samples appear to
have been collected from tub-
jog and other plastic apparatus
used in a perfused liver experi-
ment, then from other plastic
products used in medicine, e.g.,
blood bags.
Comment : Procedure used to
control/eliminate contamina-
tion not stated.
Comment : Analytical procedures
not well defined. No pro-
cedures were given for any
kind of tissue. I.ack of
method description for tis-
sue and general mode of
detection used for blood
analysis leaves ample room
for criticism of results.
Comment : Credibility of the
data is in doubt because of
the minimal QA measures re-
ported.
Summary : Limited survey of
plasticizers extracted from
plastic devices by biological
systems. Accumulation and
metabolism of the plasti-
cizers was also examined.
Summary : No sampling was
done per se. Outdated whole
blood was purchased from a
nearby blood bank. Human
tissue was obtained from
patients at Johns Hopkins
Hospital. White rat. tissue
and blood was obtained from
Johns Hopkins University.
Summary : Chloroform extracts
of neutral and acidified blood
were applied to TLC plates or
DOWEX-l. The eluent was spec-
torphotometrically examined
for phthalates.
Sunasary : Minimal quality as-
surance measures were reported,
i.e., no blanks or spiked sam-
pies were mentioned.
36, Jaeger
and Rubin
(1970).
(TISSUE continued)
-------
TABLE I (continued)
Comment : Logical progression
of studies. Each study based
on results of a previous
study. Grab samples taken in
each case.
Comment : Analytical methods
not explained. Purity of
solvents and reagents used
(if any) not reported. Lack
of reporting recoveries and
analytical methods indicate
that any results reported
should be reviewed as un-
substantiated.
Summary : Original experiments
designed to determine levels
of DE IIP in blood in a liver
perfusion system. Additional
experiments performed to de-
termine levels in blood and
various tissues exposed to
DEIIP by virtue of blood trans-
fusions, operations, or hemo-
dialysis. Attempts were also
made to determine metabolites.
Comment : This study is of
significance in determining
the possible fate of phthalates
ingested orally. The author
cautions one to use care in
interpreting the data since
ester hydrolysis of the C-
labeled carbonyl group of the
phthalates may affect the emis-
sion patterns observed.
Summary : Sampling methods
not discussed.
Comment: Unknown wheLher one
group of animals went through
all collection phases or a
separate group of animals used
for each specific phase.
Sussnary : Analysis method for
liquids reported as TLC of an
unknown organic extract. Tis-
sue analyzed by unknown method.
Conanent : Recovery and quenching
data should have been reported.
Otherwise the results are con-
sidered qualitative.
Summary : Method blanks used in
the analysis of the liquids in
the liquid perfusion system and
in the tissue analysis. No dis-
cussion of use of spiked samples
to determine recoveries.
Comment : An unspecified com-
parison with control groups
was made to account for
“slight” radioactivity after
12 to 24 hr. It is uncertain
as to what this statement re-
fers or its relevance.
44, K ltanaka,
et al. (1911)
Summary : This project was de-
signed to determine the effects
of phthalic acid esters on the
body. Rats and mice were ad-
ministered radioactive
phtha l ates
Susunary : Phthalates with a
carbon-14 tag were administered
to rats and mice. Urine, feces,
and tissues were collected at
specific times after administra-
tion of the 11 C-phthalates.
Suasnary : The various excrements,
body fluids, tissues, and organs
were measured for radioactivity
to determine which organs con-
tained phthalates and their
relative concentrations with
respect to time.
Summary : QA provisions were not
reported.
Comment : None.
Sample design Sampling Analysis Quality assurance Reference
Comment : Quality assurance
measures skimpy at best.
38, Jaeger
and Rubin
( 1913a).
(TISSUE continued)
-------
TABLE 1 ‘ •‘••—
Comment : Background of autopsy
subjects, randomness or dis-
bution of this sample popula-
tion were not. given. Appears
that the samples are grab
specimens.
Swmnary : Samples from avail-
able accident victims from
three Canadian cities were
taken for analysis of DBP
and DEIIP. No survey design
used as such.
Comment : No indication of
what kind of instruments
were used to take the tissue
samples or how they were
prepared for taking the
samples leaves room for pos-
sible contamination.
Summary : Human adipose tis-
sue was collected during
autopsies on accident victims,
placed in glass jars, and
frozen until analysis. The
sample jars were carfully
cleaned but no mention was
made of how the actual tissue
samples were taken.
Comment : Typical tissue pro-
cedure. Also applicable to
PCBs and other organochiorine
pesticides.
Summary : Tissue samples (5 g)
were blended, the extract fil-
tered, concentrated to dryness,
redissolved and applied to a
ulorisil column. The resulting
extract was analyzed by CC/EC.
Recoveries show that method
worked best at 5 ppm level and
was only semiquantitative at
the I ppm level (40% recovery).
Comment : Quality assurance
measures apparently taken
but could use expansion.
Use of blanks and spikes at
two levels indicates the
data generated was meaning-
ful.
Summary : Quality assurance
measures employed consisted of
an unknown number of solvent
blanks and sample spikes at I
and 5 ppm. No DEHP was found
in the solvent blanks but DBP
was found at a constant but
unspecified level. Further
cleanup of these pooled sam-
pies by TLC was done with
verification by CC/KS.
Sample design Sampling Analysis Quality assurance Reference
48, lIes,
et al.
(1974).
L.n
(TISSUE concluded)
-------
TABLE 1 (continued)
Sample design Sampling Analysis Quality assurance Reference
Comment : Grab samples taken
from trana fused and nontrans—
fused subjects. Although not
stated, the samples appear to
have been collected on an op-
portunistic basis.
Summary : DEHP found in
stored blood, patient’s
blood who had received
transfusions. DEHP metab-
olites also found.
Comment : Logical progression
of studies. Each study based
.P’ on results of a previous
‘ study. Grab samples taken in
each case.
Comment : The problem of con-
tamination is not mentioned.
Since no collection procedures
were mentioned addressing this
problem, the results should be
considered qualitative.
Summary : Blood sampled from
patients, and after storage
and/or transfusion to deter-
mine source of phthslates in
patients blood.
Comment : Phthslic acid and
other DEHP metsbolies also
analyzed.
Suassary : CC column: 3% SE-30
on Gas chrom Q. No instrument
or detector mentioned.
Comment : Analytical methods
not explained. Purity of
solvents and reagents used
(if any) not reported. Lack
of reporting recoveries and
analytical methods indicate
thst sny results reported
should be reviewed as un-
substantiated.
Comment : Blood values were
subtracted from tissue values.
Susssary : Assay of samples in-
cluded blood not in contact
with PVC, blood in contsct with
PVC for increasing time spans,
metabolites found in urine,
fat, and other tissues.
Summary : Original experiments
designed to determine levels
of DEHP in blood in a liver
perfusion system. Additional
experiments performed to de-
termine levels in blood and
various tissues exposed to
UEHP by virtue of blood trans-
fusions, operations, or hemo-
dialysis. Attempts were also
made to determine metsbolites.
Summary : Sampling methods
not discussed.
Summsry : Analysis method for
liquids reported as TLC of am
unknown organic extract. Tis-
sue analyzed by unknown method.
Summary : Method bisnks used in
the snslysis of the liquids in
the liquid perfusion system and
in the tissue analysis. No dis-
cussion of use of spiked samples
to determine recoveries.
Comment : None.
31, Jaeger
and Rubin
(1912).
38, Jaeger
and Rubin
(1913s).
Comment : Quality assursnce
measures skimpy at best.
(URINE continued)
-------
TABLE I (continued)
Sample design Sampling Analysis Quality assurance Reference
Comment : This study is of
significance in determining
the possible fate of phthalates
ingested orally. The author
cautions one to use care in
interpreting the data since
ester hydrolysis of the 14 C-
labeled carbonyl group of the
pbthalates may affect the emis-
sion patterns observed.
Comment : Unknown whether one
group of animals went through
all collection phases or a
separate group of animals used
for each specific phase.
Comment : Recovery and quenching
data should have been reported
Otherwise the results are con-
sidered qualitative.
Comment : An unspecified com-
parison with control groups
was made to account for
“slight” radioactivity after
12 to 24 hr. It is uncertain
as to what this statement re-
farm or its relevance.
44, Kltanaka,
et al. (1977)
Summary : This project was de-
signed to determine the effects
of phthalic acid esters on the
body. Rats and mice were ad-
ministered radioactive
phtha lates.
Summary : Phthalates with a
carbon-14 tag were administered
to rats and mice. Urine, feces,
and tissues were collected at
specific times after administra-
tion of the 34 C-phthalates.
Summary : The various excrements,
body fluids, tissues, and organs
were measured for radioactivity
to determine which organs con-
tained phthalates and their
relative concentrations with
respect to time.
Summary : QA provisions were not
reported.
1
(URINE concluded)
-------
TABLE I (continued)
Sample design Sampling Analysis Quality assurance Reference
WATER (DRINKING. WASTE. GROUND, PROCESS EFFLUENT )
Comment : The location of
sitrs for the collection of
grab samples was influenced
by the effluent plume move-
ment. Other sampling cri.—
teria, e.g., temporal or
replicate sampling, was not
discussed.
Comment ; With the exception
of QA samples and procedure
for cleaning equipment the
sampling seems quite adequate.
Comment : In view of the lark
of reported recoveries and the
mentioned interferences this
section is of questionable
value.
Comment : QA section was of no
value.
4, Brownlee
and Strachan
(1976).
Summary : The dispersion of
organics from the mill ef-
fluent was monitored by sam-
pling at various distances
from the outfall.
Summary : Water was collected
using teflon and S.S. appa-
ratus. Seston retained on a
Nucleopore filter while sedi-
ment was collected with a
Shipek sampler.
Sunanary: Due to the nature
of the study no attempt was
made to optimize for
phthalates. Instrument re-
sponse linearity was not re-
ported. No attempt appears
to have been made to determine
the recoveries of the compounds
reported.
Summary : No quality assurance
provisions, blanks, spikes, or
replicates were reported.
Comment : The design involved
collection of grab samples
from river and near-shore
waters. Criteria not deline-
ated for selection of sampling
sites.
Comment : The sampling method
seems quite adequte and thus
the samples should be repre-
sentative of the environment.
Comment : The extraction method
is good based on high recoveries
but additional validation should
have been reported so that the
entire analytical method could
be assessed.
Comment : The method blanks
are indicative of minimal
contamination but the accuracy
and verification of the data
are unknown.
10, Corcoran
and Curry
(1978).
Summary : Samples of water,
particulate matter, and sed-
iment were collected in 1975
from the lower hlississippi
River and northeast Gulf of
hlexico to determine the dis-
tribution and concentration
of various phthialic acid
esters.
Summary : After cleanup, glass-
ware and aluminum foil were ex-
tracted and checked by GC for
phthalate levels. Water samples
were taken at the surface, mid-
depth, and close to the bottom
using an all metal Niskin-type
sampler.
Summary : Water samples were
filtered through glass fiber
filters, passed through XAD—2
resin. Eluted from XAD-2 with
diethyl ether, dried, and ex-
tracted with hexane. Glass
fiber filters were extracted
with hexane and cleaned up
on Florisil. Analysis was
by GC/EC. Recovery was 98%.
Summary : Glassware and alumi-
num foil was extracted after
cleaning. No detectable levels
were observed.
(WATER continued)
-------
TABLE 1 (continued)
Sample design Sampling Analysis Quality assurance Reference
Coimnent : A static lab setup
was used to simulate pipe ex-
posure.
Comment : The sampling plan did
not cover field blanks and
therefore does not permit as-
sessment of contamination but
only indicates changes in the
phthalate level
Comment : Detection limits
were reported to be 10 pg/
liter but the analytical in-
strument used is not speci-
fied. The analytical method
was not reported and there-
fore cannot be assessed.
11, De-
partment
of health
Services
and De-
partment
of In-
dustiral
Relations
(1980).
Summary : Potable water from
PVC pipe was sampled for a
variety of organic pollutants.
Summary : Samples were col-
lected in amber bottles washed
in detergent followed by rinses
in tap and deionized water then
in pesticide grade hexane and
baked 1 hr at 400°C.
Summary : No cleanup was
reported, nor was sample
preparation reported. It
is assumed that the method
was the standard EPA B/N
method. Detection limit was
10 pg/liter.
Summary : Little information
reported on QA provisions.
The use of spiked samples was
mentioned but the specific
compounds or levels used was
not reported.
Comment : The only part of
the article dealing with
phthalates is the landfill
study. The experiment was not
designed for specific com-
pounds but was limited to de-
termining dump-site leachables
from one test well.
Comment : The collection method
is not designed specifically
for phthalates. No field
blanks were reported. The
value of the sampling method
could be significantly im-
proved by the use of field
blanks and spiked blanks.
Comment : The analytical
method leaves much to be
desired. No method blanks
or limits of detection
were reported. Recovery of
organic matter was reported
to be less than 10%.
Comment : This section appears
to be of minimal value.
12, Dunlap,
et at.
(1976a).
Summary : Project designed to
identify organic pollutants
contributed to ground water
by municipal solid waste near
Norman, Oklahoma.
Summary : Collection was on ac-
tivated carbon columns which
were then drained and sealed
with solvent-washed aluminum
foil.
Summary : The activated carbon
columns were extracted with
CUd 3 and C 2 H 5 0 1 1. The ex-
tracts were reduced and fur-
ther separated. The fractions
were analyzed by CC/MS. Quan-
titation was estimated.
Summary : A control well
up-gradient of the landfill
was used to provide background
levels. No other standard QA
procedures were used.
Comment : The QA information
provided is of little value.
(WATER continued)
-------
TABLE I (continued)
Comment : This article is
essentially the same as
the other by Dunlap (No. 12)
The experimental design was
limited to determining dump-
site leachable from one test
well. A control site was
utilized.
Summary : The study was to
investigate organic pol-
lutants contributed to
groundwater by a landfill
near Norman, Oklahoma.
Comment : The survey design
was applicable to monitoring
studies used to determine, in
general, pollutants in a water
system. Replicate or random
sampling would have added
significantly to the design.
Comment : Collection method not
optimized for pbthalales, but
the sampling procedure was sound
and used a field blank.
Summary : Samples were col-
lected on activated carbon
columns. A third column was
prepared and treated the
same as the other two. This
column served as a blank
Comment : Sampling method was
adequate; however, a more
stringent cleaning procedure
and the use of field blanks
would provide significant
improvement.
Comment : Analytical method
was not optimized for
phthalates. Extraction ef-
ficiencies were not reported
and overall recoveries were
low. The method is of ques-
tionable value.
Summary : Samples were ex-
tracted from activated car-
bon with CIIC1 2 and C 2 H 5 011,
and reduced. The reduced cx-
extracts were run by CC/MS and
then further fractionated and
rerun by CC/MS. Author states
that results should be viewed
as “estimates” of probable
groundwater contamination.
Comment : Analytical protocol
is widely accepted, although
some of the recoveries were
low.
Comment : No replicates used.
A field blank gave results
similar to those of the con-
trol sample. The QA reported
should have included other
validations such as precision
and accuracy. Results should
be viewed as qualitative.
Summary : Quality assurance
provisions were in the form
of a control well up-gradient
and a method blank (third
activated carbon column).
Comment : Not enought in-
formation was provided to
adequately assess QA pro-
cedures. However, overall
design of study would sug-
gest that the data was
highly relevant.
Sunsna : The purpose of
the survey was to deter-
mine the identities and
semiquantitative concen-
trations of organic com-
pounds and inorganic ele-
ments present in waterways
around industrial centers.
Two hundred four sites were
sampled. Control sites up-
stream from discharge points
were utilized.
Summ : Samples were col-
lected in glass and polyethyl-
ene containers. Glass bot-
tles were heated to 3500
overnight. Polyethylene con-
tainers were rinsed with
nitric acid, then distilled
water. All containers were
rinsed three times with sam-
ple. Samples were refrigerated
pending analysis
Summary : VOA samples were
stripped and trapped on Tenax
before flashing into CC. Other
samples were extracted into
chloroform and separated into
acid and base/neutral frac-
tions. Extraction efficiencies
for amines was 41 to lO0 .
Analysis of organics was by
CC/MS. Techniques used were
state-of-the-art at the time
of the surveys.
Summary : Method blanks were
used but it was not reported
how often. Internal standards
were used. Evaluation of dif-
ferent sorptive materials,
optimization of extraction
solvents, and conditions are
indicative of a well planned
study.
Sample design Sampling Analysis Quality assurance Reference
U i
0
13, Dunlap,
et al.
(1976b).
15, Ewing,
et al.
(1911).
(WATER continued)
-------
TABLE I (continued)
Coimnent : Survey not de-
signed specifically for
phthlates. The experiment
was limited to grab sampling.
Comment : The sampling method
was not optimized for phtha-
lates and did not provide
blanks. Sampling method would
require further validation.
Comment : Concentrating diethyl
ether extracts by evaporation
may be hazardous. The method
Is of limited value since re-
coveries were based on the use
of pure compounds to represent
classes.
Comment : Could not account
for presence of dioctyl
phthalate. Produced blanks
free of DOP although the
method for preparing blanks
was not adequately reported.
No quant.itation of plume
values. Background levels
of 10 to 15 pg/liter which
may invalidate findings.
Summary : Sampling was con-
ducted on eight occasions in
the effluent plume of a Kraft
paper mill near Red Rock,
Ontario, to determine the ef-
fective zone of persistence of
dissolved organic compounds.
Summary : Samples were col-
lected from the center of a
dye-marked plume and acidified.
Summary : Loaded XAO-2 columns
were eluted with diethyl ether
and concentrated to I ml. Ex-
tracts were analyzed by
GC/FID and GC/HS. Recoveries
reported to be 80 to 1O0 .
Sunuaary : QA was primarily
method blanks which reportedly
showed no dioctylpht.halate.
Comment : Unspecified number
i—i of grab samples collected.
Comment : None.
Comment : Not enough infor-
mation given to evaluate an-
alytical method.
Comment : None.
17,
Freudentha 1
(1978).
Summary : This paper reports
the finding of three phtha-
lates in Rhine River water
by element specific CC/MS.
Summary : No information
given.
Summary : GC/HS operated as
a halogen—specific detector.
Summary : None reported.
Comment : Sample collection
was adequate to define the
effectiveness of the treatment
systems studied, but the re—
suits probably do not apply to
all wastewaler treatment sys-
tems.
Comment : The sampling pro-
cedure was considered inade-
quate. The uncertainty of
using aliquots stored in poiy-
ethylene cast doubt on source
of phthalates reported.
Comment : No method validation
results such as recoveries were
reported. The validity of the
analytical procedure is there-
fore questionable.
Comment : No quantitation was
done on phthalates identified.
Not enough information was
provided to assess the quality
assurance provisions.
Suuunary : The goals were to
develop analytical techniques,
identify compounds, and pro-
vide specific compound data
to help determine wastewater
treatment effectiveness for
extractable and volatile com-
pounds in domestic waste-
waters.
Summary : Samples were col-
lected in glass containers
and stored at 4°C. Aliquots
also stored frozen in poly-
ethylene containers. No field
blanks or field spikes reported
used.
Summary : Samples were ex-
tracted into pesticide grade
methylene chloride using
liquid-liquid extraction.
Separated into acid and base!
neutral fractions. Analyzed
by GC/FID and CC/MS.
Summary : QA was primariy in
the form of control samples.
Identification was by CC/MS
with spectra matched against
standard spectra in the EPA-
Battelle computer files and
the NIH mass spectral search
system.
Sample design Sampling Analysis Quality assurance Reference
16, Fox
(1976).
18,
Garrison,
(1976).
(WATER continued)
-------
TABLE I (continued)
Sample design Sampling Analysis Quality assurance Reference
Comment : This report is con-
cerned mainly with the analyt-
ical results and their signif-
icance. Criteria used to select
sampling sites is unknown. Ap-
parently grab samples were col-
lected to assess phthalate
loading in the Gulf.
Comment : See other Giam
articles for procedures.
Comment : See other Giam
articles for procedures.
Comment : None.
20, Clam,
et a!.
(1976a).
Summacy : The goal of this
project was to analyze se-
lected samples from the
Gulf of Mexico for
phthalates and to assess the
significance of the data. The
Mississippi River accounts for
only one-fourth of the total
DEIIP loading. “The origins
of the remaining inputs have
not yet been determined.”
Comment : Design not part of
report. Selected results of
10 biota, 9 water, and 6 sedi-
ment samples were reported.
Summary : No information was
provided on sampling methods
(see earlier Giam articles).
Comment : The sampling pro-
cedures recommended are very
good Emphasis is on reduc-
ing possible sample contami-
nation.
Suasnary : No information was
given concerning the analyt-
ical procedures. The detec-
tion limit for phthalate was
reported as 0.1 ng/g.
Comment : Analytical method
not reported.
Summary : No QA information
was reported as this was a
discussion of published data.
Comment : The discussion of
the QA procedures is some-
what minimal. The recom-
mended procedure for mini-
mizing contamination in
blanks is quite good.
Summary : Paper proposed
methods for very low back-
ground sampling and analy-
sis, as well as for evalua-
tion of procedures for biota,
sediment, and water.
Swmnary : Recommends cleaning
glass and metal with deter-
gent, water, solvent, and then
heating. Recommends heating
aluminum foil to 320°C over-
night and solvent extraction
XAD-2 resin. Also recommends
use of spiked samples.
Suninary : Analytical procedure
covers only cleaning of glass-
ware and equipment.
Summary : Paper recommends
procedures for minimizing
contamiantion.
¼ ”
I ’. )
21, Giam,
et a!.
(l976b).
(WATER continued)
-------
TABLE 1 (continued)
Sample design Sampling Analysis Quality assurance Reference
Comment : Origin of samples
given as the Gulf of Mexico.
Grab samples inferred to have
been collected.
Comment : The sampling pro-
cedure should have yielded
samples with a minimum of
phthalate contamination.
Comment : The analytical pro-
cedure seems quite acceptable
based on the recovery values
reported.
Comment : The only quality as-
surance provisions reported
were procedures to minimize
background in blanks. With
the addition of replicate
samples and spiked blanks the
method could be better evalu-
ated.
Summary : The purpose of
this paper was to report a
procedure for the analysis
of marine biota, water, and
sediment. No design was
reported.
Summary : Samples were col-
lected in containers cleaned
with detergent, rinsed with
water and acetone, and heated
to 320°C. Water samples were
passed through XAD-2 resin
column. Biota samples were
stored at or below 0°C.
Summary : Samples were ex-
tracted with acetonitrile,
CH 2 C1 2 -petroteum ether and
cleaned up on a Florisil
column. Recoveries of
phthalates were in the range
19 to 100%. Analysis was
by GC/EC with 5 ng OEHP
yielding 50% full scale de-
flection.
Summary : Procedures given to
minimize background in sample
blanks. Verification by GC/EC
using a different column. DEHP
levels of laboratory items re-
ported.
Comment : The mass balance
model was developed using a
combination of data and as-
sumptions. Author states
that atmospheric input to
the Gulf was the most im-
portant route but cautions
that “direct field measure-
ments are important.”
Comment : This section only
briefly outlines the sampling
method and is of limited
value.
Comment : This section lacks
enough information to assess
its value.
Comment : None 25, Giam
(1977)
Summary : This paper deals
primarily with a mass—balance
model for estimation of
fluxes of DEHP in the Gulf of
Mexico. Sampling and analy-
sis is as in reference 27.
Susmiary : Water samples were
solvent extracted on site or
adsorbed on XAD-2 resin.
Biota samples were collected
by hook and line or trawl.
Sediment samples were col-
lected with a metal coring
device. Air was adsorbed
on Florisil or polyurethane.
Summary : Samples were ex-
tracted with organic solvents,
cleaned up by column chroma-
tography and analyzed by GC/
EC.
Summary : No QA data of signifi-
cance reported.
24, Giam,
et al.
(1976e).
LB
(WATER continued)
-------
TABLE 1 (conLinued
Comment : Basically same in-
formation as other articles
by Clam. Grab samples ap-
parently collected.
Summary : The purpose of the
project was to analyze for
phtha late esters and chlori-
nated hydrocarbons in air,
water, sediment, and biota
samples predominantly from
the Gulf of Mexico.
Comment : This section is too
brief to be of value.
Summary : Sampling methods are
brief. Sediment—-metal coring
device. Biota--hook and line
or trawl. Water—-extracted
directly or adsorbed on XAD—2.
Air-—adsorbed on Florisil or
polyurethane foam. Sediment
and biota samples frozen.
Comment : Too little informa-
tion provided to properly as-
sess this section.
Summary : Samples were ex-
tracted with organic solvents
and cleaned up by column chro-
matography. Analysis was by
GC/EC. Recoveries of “90% or
better” were mentioned as well
as “background values of
50 ng.”
Comment : None. 27, Giam
et al.
(1978).
Summary : Appropirate QA in-
formation was not provided.
Comment : Grab samples of river
water were collected to show
that CC/MS is a powerful survey
technique to identify the
general nature of organic
pollutants.
Summary : The characteriza-
tion of the major organic
pollutants was achieved by
GC/MS and LC identification
and quantitation.
Comment : Sampling consisted of
collection of grab samples.
SLwm ary : Other than the pro-
cedure for collecting the sam-
ple, no comments were made
about stability, blanks, con-
tainer preparation, etc.
Summary : Analysis was per-
formed by GC/IIS with 0.17, OV-l
column.
Summary : Use of distilled
water as a procedure blank
was the only QA mentioned.
30, Mites
and Biemann
(1912).
Comment : Survey design
limited to grab sampling and
did not address seasonal or
spatial variation in the rivers.
Comment : Number of samples
collected is unknown as is
the preparation and subse-
quent storage conditions all
of which add an unknown to
the data.
Comment : The validity of the
DEIIP data and its source is
open to question.
Summary : Two rivers were
sampled to determine the in-
fluences of a factory and
five urban areas.
Summary : Four liter water sam-
ples were collected.
Summary : Only information
given was that samples were
analyzed by CC/MS.
Summary : No information re-
ported.
Sample design Sampling Analysis Quality assurance Reference
U i
Comment : Minimal method valida- Comment : Information given
tion information given, was minimal and the results
should be termed “tentative.”
Comment : Lack of method valida-
tion.
31, Mites
(1973a).
(WATER continued)
-------
TABLE I (continued)
Comment : This is a position
paper to describe the merits
of CC/MS analysis.
Summary : Author presented
evidence to demonstrate “the
power of modern analytical
methods for the identification
and determination of organic
pollutants at the fractional
parts per billion level in
water.”
Comment : Crab samples cal-
lected to assess influence of
chemical point sources on
river systems. Study 1 ap-
pears to have been a single
sampling of multiple points
along a river system. Tem-
poral differences investi-
gated In study 2 with 5 of
13 sites resampled.
Comment : Information is min-
imal. Reader is referred to
reference 30.
Summary : The analytical re-
sults of duplicates collected
at two depths from three sites
were reported but whether
other samples were collected is
unknown.
Comment : Samples preserved im-
mediately after collection is
an effective procedure for min-
imizing artifacts. Without men-
tion of container preparation,
the validity of the samples
is queaitonable because of the
unknown possibility of con-
tamination from the sampling
equipment.
Comment : Extraction scheme
was reported in refereiice 30.
Summary : Samples were analyzed
by CC/US and phthalates quanti-
tated by IIPLC.
Comment : Blanks were run through
cleanup procedure and showed
no contamination. Solvents
used were nanograde but were
not concentrated and checked
by GC for contamination; thus,
would still be some room for
phthalate contamination.
Comment : Duplicate results
reported at a given depth
agreed within 0.1 ppb. Lack
of information other than
“procedural blaiik showed
only very small amounts of
material” means that data
should be considered qual-
itative.
Sumin : A procedural blank
was analyzed by GC/MS. Quan-
titation of the phthalates was
by IIPLC compared to an internal
standard.
Comment : Low levels of DEHP
reported could conceivably
be due to contamination and
its presence in the waste—
water. Quantitative identi-
fication good, however, be-
cause of the use of PIS. Lack
of method recoveries also in-
dicates results are semiquan-
titative in nature.
Summary : Survey designed to
provide samples for detailed
organic analysis by various
sample concentration tech-
niques and CC/US
Summary : Water samples were
cooled to refrigerator temper-
ature and those for solvent ex-
traction were acidified and
solvent added; sediments were
frozen after collection.
Summary : Crab water sample
were extracted in the bottle
overnight by stirring. Some
extracts were cleaned up using
silica gel followed by basic
extraction cleanup. Analysis
of the extracts were carried
out by CC using EC, FID, or
MS and authentic standards.
Sunsnary : Minimal quality as-
surance procedures were re-
ported.
Sample design Sampling Analysis Quality assurance Reference
32, Mites
(I973b).
34, Hites,
et al.
(1979).
(WATER continued)
-------
TABLE 1 (continued)
Sample design Sampling Analysis Quality assurance Reference
Comment : The design is ade-
quate for identification of
groundwater contamination, but
should have included randomiza-
tion or replication to have a
complete experimental design.
Comment : The quality of the sam-
pling portion of this project
could have been improved by using
blanks and field blanks.
Comment : Adquate extraction/
cleanup technique but validation
results are needed to determine
the effectiveness and limits of
the method.
Comment: Quality assurance as
reported was minimal, although
a comparison of the blank and
sample results was made.
Summary : The goal of finding
evidence of groundwater contam-
ination and Identifying major
organic pollutants contributed
by a landfill near Norman,
Oklahoma, was reached by sam-
pling groundwater from five
wells drilled at the site,
Lap-gradient, and down—gradient.
Summary : Groundwater was pumped
through an all-glass and Teflon
system containing an activated
carbon trap. Glassware was
washed with detergent and chromic
acid and rinsed with water and
acetone.
Summary : Carbon was extracted
with chloroform for 36 hr in a
Soxhiet extractor. The extract
was dried with Na 2 SO 4 , fraction-
ated, and analyzed by GC/IIS.
Summary : A method blank was
done on activated carbon.
Comment: In one case
tinterstate Hill) the sta—
bilization pond bad a reten-
tion time of at least 3 months
and no attempt was made to
take a sample of that “slug”
after treatment.
Comment : Use of plastic bot-
tles casts doubt on validity
of any phthalate data reported.
Comment: Data table for com-
pounds identified in paper
mill effluents list only “a
dioctyl phthalate.” Listed
as unconfirmed with no
levels specified.
Comment : None.
42, Keith,
et al.
(1976a).
Sunsnary : Study was designed to
follow a given slug of waste—
water through the treatment
system used at that facility.
Summary : Grab and composite
samples were collected at
two paper mills before and
after treatment if possible.
Each plant was sampled twice
2 years apart.
Summary : Grab samples were
extracted with pesticide grade
chloroform as were the carbon
filters. After concentration
the extracts were analyzed by
GC/FID and GC/MS. Some samples
were methylated.
Sunmiary : Minimal quality as-
surance measures reported.
Data reported are unconfirmed
and tentative at best.
Comment : Detailed sampling
procedures given in EPA
reports. Activity and clean-
liness of carbon used in CAN
samples could be a source of
erratic extraction efficiencies
and contamination.
Comment : New Orleans samples
quantitated using GC/FID peak
areas—-results for 10 cities
in NORS quantitatedusing RGC
(KS) peak areas. 1.ack of re-
covery data for extraction ef-
ficiency of DEHP from carbon
adds a degree of error to the
analytical method.
Summary : Survey design for
NORS not discussed but data
presented is monitoring data
for several cities
Summary : Samples of various
drinking water supplies were
concentrated using CAM samplers
with carbon and XAD-2 resin
cartridges.
Summary : Carbon chloroform
extracts from CAN samples
analyzed by GC/FID and CC/MS.
Soxhiet extractions were car-
ried out in a special room
designed to minimize contami-
nation.
Summary : Solvent blanks and
carbon blanks generated, but
data not presented on whether
blanks were subtracted from
values in tables.
40, Jorque
(1973).
Comment : Survey design for
National Organics Recon-
naissance Survey (NORS).
Inferred that a single sam-
pling period was used to
characterize the organic
contact of drinking water
from various cities.
Comment : Method blanks ex-
amined for interfering back-
ground components by FID and
MS but values not reported.
Actual recoveries for effec-
tiveness of carbon filters
not given. Data reported can
be considered only as semi—
quantitative.
43, Keith,
et al.
(1976).
‘er ””
-------
TABLE I (contiiiued
Comment : The survey design
appears adequate for an in-
dication of the level of
pollutants in the systems
studied.
Comment : The description
of sampling methods is in-
adequate.
Comment : The analytical pro-
cedure was quite adequate. The
emphasis of the paper is not,
however, on the chemical analy-
Comment : None. 46, Levins,
et al.
(1979).
Summary : Influents to POTWs
were sampled in hartford,
Connecticut; St. Louis,
Missouri; Atlanta, Georgia;
and Cincinnati, Ohio to de-
termine the relative signifi-
cance of the major source
type-—residential, commercial,
industrial--contributions of
priority pollutants.
Summary : Samples were col-
lected manually using 2-liter
stainless steel buckets.
Swmnary : Samples were analyzed
by the EPA screening protocol
for priority pollutants. The
detection limit for phthalates
was 10 pg/liter and the re-
were 42 to 74%.
Summary : The EPA “QA Program
for the Analysis of Chemical
Constituents,” (1918) was used.
Ui
-4
Comment : No actual field survey Comment : None.
conducted.
Comment : Total recovery for
method not discussed but
broken down into recoveries
for DEHP and each metabolite
Major degradative pathways
inferred to be through hy-
drolysis of the ester groups
to produce the monoester, then
phthalic acid, and finally
phtbalic anhydride.
Comment : Use of 14 C-labeled
DEJIP virtually eliminates
the need for extensive qual-
ity assurance measures in
terms of method blanks.
49, Metcalf,
et al.
(1973).
Summary : Controlled labora-
tory studies of the uptake
and metabolism of DEIIP in
aquatic organisms in a model
ecosystem was performed.
No monitoring data presented.
Summary : Sampling of the
model ecosystem was not
discussed.
Summary : A9uatlc organisms
exposed to ‘ 4 C-labeled DEHP
spiked water and analyzed
by homogenization and ex-
traction with ether, TLC
separation and subsequent
scintillation counting.
Identities of metabolites
determined by chromatog-
raphy (TLC) with known
standards. Actual method
recoveries not generated
for DEIIP but rather re-
suits expressed in percent
of metabolites found versus
percent DEHP remaining.
Summary : No method
blanks, control samples,
or other standard quality
assurance measures were
taken because of the nature
of the radioactive metabolism
expeiments performed.
Sample design Sampling Analysis Quality assurance Reference
sis.
(WATER continued)
-------
TABLE 1 (continued)
Comment: No survey design
di sctissed.
Comment : Sampling of river(s)
not discussed
Comment : Use of these sep-
aration modes with an li v de-
tector provides the basis
for a very sensitive
method for the determina-
tion of phthalate esters in
river water. The method
is a viable one for samples
which do not require cleanup.
Recovery for extraction of
DEUP from water not reported
so final results may be ques-
tionable.
Comment : liethod blanks were
not reported nor were results
from any spiked samples.
River water results (‘s. 10 ppb)
may reflect some contamina-
tion and unknown extraction
efficiency.
I -n
Summary : LC method applied
to analysis of river water
of unknown origin. No actual
survey design implied.
Suaaaary : Unknown river sampled
in an unknown manner.
Suimaary : System A (normal
hexane phase) eluted
phthalates in order of de-
creasing chain length or
increasing polarity.
System B (reversed phase,
methanol) eluted phthalates
in order of increasing chain
length or decreasing polarity;
System C (GPC, chloroform)
governed by steric exclusion
effects and eluted phthalates
in order of decreasing chain
length.
Summary : Filters used to
filter sample were preextracted
with hexane. Other solvents
used for extraction or for the
LC eluent system were redistilled
before use.
Comment : Survey designed to
assess phtha late contamina-
tion in river, well, and
treated city water of
Tokyo. Data generated can
be considered as monitoring
data for areas involved.
Comment : Bottle preparation,
sample storage, etc., not
reported. Since bottle prepa-
ration and sampling methods
were not reported, contamina-
tion could have occured before
sampling.
Comment : Ether distilled
twice before use; acid also
distilled; Na 2 SO 4 rinsed
with distilled ether and
dried at 200°C. Caution
taken to avoid contamina-
tion of reagents used adds
credibility to the analy-
sis. However, lack of re-
coveries indicates results
reported may only be semi-
quantitative.
Comment : No mention of sample
collection procedures, bottle
preparation procedures, or
method blanks casts doubt
on validity of these findings.
52, Horita,
et at.
(1914).
Sumamry : Sample sites ranged
from upper tributary streams,
to raw water, to the city
treatment system. City and
suburban wells were also
sampled.
Suassary : No actual sampling
methods were reported; only
locations.
Summary : Water samples
were adjusted to a p 1 1 of
2 with I IC 1 and extracted
three times with ether. Ex-
tract was dried, concentrated
to 0.5 ml and analyzed by dual
column CC/FID.
Summary : Although the ex-
istence of DEHP and DIIP was
verified in the samples, no
mention was made of method
blanks or control samples.
Sample design Sampling Analysis Quality assurance Reference
SI, Hon
(1916).
LIATED “ inu ’
-------
TABLE 1 (continued)
Sample design Sampling Analysis Quality assurance Reference
Comment ; Design inferred to
be a monitoring of the open
lake and tributatires near
sewage treatment plants.
Comment : Composite sampler
rubber tubing replaced with
glass tubing to prevent con-
tamination. Water and sedi-
ment sampling procedure ap-
peared to eliminate source of
contamination. Fish sam-
ples may have been contami-
nated while taking a filet or
when stored in aluminum foil
if the foil was not rinsed
with solvent.
Comment : A well-defined ana-
lytical scheme was used to
separate the analytes from
the matrix. AlLhough not
specifically stated except
for Na 2 SO 4 , mention of the
decontamination procedures
used, if any, would remove
any doubt about the validity
of the data.
Comment : Sample fortification
and recovery results mentioned
in table of contents but miss-
ing from the report. Results
can be considered somewhat
quantitative since method
blanks not reported.
58, Schacht
(1974).
Summaq : Survey design os-
tensibly formed to determine
levels of various pesticides
in Lake Michigan, and their
source, but no information
given as to actual design
formulation. Grab samples of
sediment and fish and 24—hr
water composites were col-
lected over a 3-year period.
Summary : Water samples col-
lected in glass bottles. Both
grab samples and composite
(24 hr) samples taken. Fish
obtained from local fishermen
and stored frozen in aluminum
foil. Sediment samples taken
in glass jars by hand or with a
Ponar dredge.
Summary : “FWPCA Method for
Chlorinated Hydrocarbon Pesti-
cides in Water and Wastewater”
used with some modifications.
Results not corrected for re-
covery.
Summary : Spike recovery and
detection limits data were re-
ported, but use of method
blanks was not.
Comment : March samples taken
were more widely spaced than
the first two groups. Eleven
sampling points over 80 miles.
Comment : Both blanks are Im-
portant in this type of survey
and should have been reported.
Any report of phthalates in the
samples, especially low level,
should be viewed cautiously in
light of the apparent absence
of bottle and field blanks.
Comment : Details of analytical
procedure given in Paper No.
30. Procedure not specifically
designed for phthalates.
Comment : Method blanks only
Indication of quality assur-
ance measures. Absence of
field blank a significant
omission.
60, Sheldon
and lutes
(1978).
Summary : Survey design based
on industrial discharge loca-
tions along the Delaware
River and samples taken during
different seasons. Designed
to identify organic compounds
in Delaware River and trace
compounds to their discharge
point.
Summary : Grab samples cal-
lected in 1-gal. glass amber
bottles with Teflon® lined
caps. Samples preserved in
field and returned to lab as
soon as possible for vorkup.
No indication of the use of
field blanks.
Summary : General methylene
chloride extraction with
silica gel cleanup and identi-
fication by CC/MS using au-
thentic standards Di(2-ethyl-
hexyl)adipate also found.
Summary : Quality assurance
limited to use of method
blanks for cleanup and con-
centration only. No recovery
data given. Method refered
to as primarily qualitative.
(WATER continued)
-------
TABLE I (continued)
Sample design Sampling Analysis Quality assurance Reference
Comment : “The sampling scheme
was designed to account [ or
retention times between the
various sampling locations,
as well as for the tidal
movements in the river.”
Design was adequate to give
an indication of problem,
but continuous rather than
once a week sampling would
have been better.
Comment : Samples preserved on
site with C11 2 C1 2 and IIC1 No
bottle preparation given.
Absence of bottle preparation
measures and field and/or
bottle blanks subtracts a de-
gree of credibility from the
low level ( I ppb) results.
Comment : Ilethod employed not
specifically designed for
phthalates but rallier used
for a wide range of Industrial
organic chemicals.
Comment : Use of field blanks
and method blanks not men-
tioned. DEIIP was not one of
the seven compounds for which
extraction efficiencies were
established. Contamination of
reagents could conceivably ac-
count for low level findings
of DEHP.
61, Sheldon
and lutes
(1979).
0
Summary : Sampling designed
to trace the movement of
various industrial chemicals
from their origin, through
the river, and into
Philadelphia’s drinking
water supply
Summary : Twenty-four hour com-
posite sample taken from chem—
cal plant effluent. All others
were composites of individual
grab samples collected at a
particular site. Another set
collected weekly over a period
of 10 weeks.
Summary : Analytical tech-
niques used were only sum-
marized. Recoveries reported
for seven target compounds
but not for DEUP. high
levels of DEIIP reported (100
to 200 ppb) may not be
quantitative but do indicate
that DEHP was being discharged
from industries in the area.
Summary : Solvent extraction ef-
ficiencies (from preextracted
water samples) measured for 7
of the 84 compounds identified
in the water samples taken.
Spiked samples from four loca-
tions analyzed in triplicate
for percent recoveries(> 15%).
Reported concentration values
were corrected for solvent
extraction efficiencies (not
for DEHP) and had errors of
less than ± 20%, excluding
sampling errors.
Comment : Experimental design
can be described as only sup-
plying inferrential data for
the water treatment system.
Comment : Extensive distillation
and reagent cleaning procedures
assured the validity of the sam-
ples taken.
Comment : Despite the variety
of instrumentation used for
identification of the com-
pounds found, the data
table indicates that di—
octyl phthalate was only a
tentative identification.
In addition, the author
reviewed the data presented
as only “qualitative in
nature.”
Comment : Despite the QA
measures taken, the data
for dioctyl phthalate
is considered a tentative
identification based on
mass spectrum only and
is only assigned a con—
ceiitration based in ab-
solute terms.
Summary : Survey designed
to determine organic con-
taminant levels in
Philadelphia drinking
water after treatment,
in storage, and in the
water distribution sys-
tem. Study presents
monitoring data from
2/75 to i/li
Summary : Water from several
points in Philadelphia’s drink-
ing water system was passed
through an XAD-2 lIRE or a CLLE
for time periods ranging from
5 to over 24 hr.
Summary : Ether extracts of
XAD—2 resin columns and
chloroform extracts from
the continuous liquid-
liquid extracts were
analyzed by CC and GC/IIS
on several different
columns.
Summary : Extensive use of
solvent and resin blanks as-
sures presence of only those
compounds which were actually
extracted from the water.
Data not reported for those
compounds also seen in blanks.
63, Suffet,
et al.
(1980).
(WATER continued)
-------
TABLE I (continued)
Comment : Survey designed to
point out differences in or-
ganic contamination between
populated and unpopulated
areas. Isle Royale selected
because of remoteness from in-
habited or industrial areas,
the lake on the island has no
direct connection to Lake
Superior and no internal coni-
bustlon engines have been used
on the island.
Comment : Chance for contam-
ination in both fish and water
sampling could lead to high
results.
Comment : Sample preparation
procedures delineated but
analysis by CC not discussed
in detail other than operat-
ing parameters. Sample prepa-
ration not specifically de-
signed for phthalates. Lack
of recoveries for method, es-
pecially with the indicated
cleanup steps, leaves room
for considerable analyte
losses as well as further
contamination.
Comment : Four different labs
used in these analyses but re-
suits not compared. Not known
if identical samples were an-
alyzed by each lab. These
facts cast considerable
doubt on whether the analytical
data are equivocable.
Summa y: Selected sites in
Lake Superior were sampled
for fish and water in order
to determine background
levels of contaminants
These were compared with
samples taken from a re-
mote area.
Comment : Design was not
explained in detail but
data would serve as moni-
toring data for New Orleans.
Summary : Fish caught using
deep water nets and either
eviscerated on site and
then stored on ice or simply
wrapped and stored on ice
until processing.
Comment : The minisample con-
sisted of a sample column con-
structed of PVC. Samples
taken with this sampler were
probably contaminated with
phthalates in the field.
Summary : Fish samples homog-
enized with Na 2 SO 4 , extracted,
subjected to CPC and Florisil,
and silicic acid if PCBs pres-
ent, then analyzed by GC/EC.
Comment : Absence of recovery
values indicates data only
semiquantitative in nature.
Values are the “highest con-
centration values” as mea-
sured by the method and are
not absolute concentration
values.
Summary : No mention of blanks
or spikes was made. Use of
four different labs was sup-
posed to “minimize analytical
error.”
Comment : The data are only
semiquantitative because of
the lack of recoveries and
incomplete detail on method
blanks.
61, U.S.
EPA (l974c).
Summary : Survey designed to
characterize water supplies
in the New Orleans area by
sampling water at three water
treatment plants in the area.
Summary : Water samples were
concentrated by using mega
samplers, CAll samplers, and
minisamplers. Additional
samples were concentrated on
XAD-2 resin and triplicate
I-liter grab samples were
extracted with tetralin.
Summary : Chloroform extracts
of the activated carbon used in
the various samplers were an-
alyzed by GC and CC/hIS. Com-
pounds were identified by
CC/KS and quantitated versus
authentic standards by GC/FID.
Summary : hlethod blanks were
apparently used but were not
reported in detail.
Sample design Sampling Analysis Quality assurance Reference
64, Swain
(1918).
0 ’
(WATER continued)
-------
TABLE I (continued)
Sample design Sampling Analysis Quality assurance Reference
Comment : This is only a
compilation of the compounds
identified in Cincinnati tap
water (1913-1975). Analyti-
cal methods are only mentioned
in passing. No judgement of
the reliability of the
phthalate data can be made.
Comment : None
I
Comment : None.
Comment : None.
68, U.S.
EPA (1915a).
Summary : None.
Summary : None.
Summary : None.
Summary : None.
Comment : Data only reported.
Methodology not discussed.
Comment : None.
Comment : None
Comment : None
69, U.S.
EPA (1975b).
Summary : Survey designed to
totally characterize the or-
ganic content of finished
water supplied in the U.S.
Summary : None.
Summary : None.
Suimnary : None.
0” Comment : Criteria to select
t ) sites was not reported. Tem-
poral and replicate sampling
could provide a better study.
Comment : No special cleanup
was used; however, the authors
state that blanks in the same
kinds of containers did not
indicate contamination.
Comment : The extremely high
recovery for DEIIP indicates a
probable contamination problem.
This makes the value of these
data questionable.
Comment : The authors state
that the phthalate results
be used “with appropriate
caution.”
70, U.S.
EPA (1915).
Summary : Report contains a
comprehensive list of pol-
lutants and their levels
2 months after the Safe
Drinking Water Act became
law.
Summary : Grab samples of
drinking water, just prior
to and several hours after
chlorination as well as
carbon filter extracts.
Summary : GC/FJD of ethyl ether
extracts of water samples pre-
served with CHC1 3 (2.5 ml/liter
samples) Soxhlet extraction of
carbon.
Summary : No quality assurance
mentioned for DEHP analysis—-
extensive EPA QA/QC procedure
described for other priority
pollutants and pesticides.
Comment : A good synopsis of
the persistance that a sel-
ected list of organics have
in Lake Huron. A literature
and data review of monitoring
data for the lake and its
inputs.
Comment : None.
Comment : None.
Comment : None.
71, U.S.
EPA (1911b).
Summary : This report re-
lates the sources of organic
compounds entering Lake Huron
and describes their potential
impact on the environment.
The report was used as a means
to propose a total ban on PCB,
a ldrin, dieldrin, DDT, and its
derivatives.
Summary : Sampling method not
described.
Summary : Analysis methods not
mentioned. DEJIP found range
from C I to 1.4 pg/liter in
water samples.
Summary : No quality assurance
mentioned.
kTEI inu
-------
TARTS I (continued)
Sample design Sampling Analysis Quality assurance Reference
Comment: The selection of the
plants to be samples was based
on need to characterize the
waste effluent from this in-
dustry.
Summary : Effluent pollutants
were identified, quantified,
and assigned to a significance
category.
Comment : Survey design ap-
pears adequate based on the
selection criteria given and
the replicate plants sampled.
However, no information given
about how representative the
sampled plants were with the
entire industry.
Suasnary : A category of en-
vironmental significance was
assigned to all pollutants
detected in the 19 samples.
Summary : Verification phase
sampling method, but not spe-
cified.
Comment : No direct sampling
methods given.
Comment : No analytical methods CommentS None.
were specified.
Summary : In data tables, DEMP
was detected in majority of
samples analyzed; categorized,
however, as “pollutant of un-
known environmental significance.”
Comment : This section is of
minimal value.
Summary : DEUP considered “9”
category, or pollutant of un-
known environmental signifi-
cance in one table--in another
table DE IIP is classified as
environmentally significant.
DEHP not detected during
verification phase. Spe-
cific methods never men-
tioned.
Summary : No QA reported.
Comment : The lack of infor-
mation raises a question
about data validity.
Comment : No information given.
C’
12, U.S.
EPA (1980).
13, U.S.
EPA (1981).
Summary : Nineteen effluent
water samples taken from
representative subcategories
of the timber processing in-
dustry.
Summary : No QA mentioned.
(WATER concluded)
-------
TABLE I (continued)
Sample design Sampling Analysis Quality assurance Refereiice
Fly Ash
MISCELLANEOUS
Conuneiit : Not designed for
phthalates or as a representa-
tive sample of the total
plants available.
Summary : The purpose of the
project was to identify or-
ganic compounds in fly ash
from municipal incinerators
in Japan, Canada, and the
Netherlands.
Comment : The authors had no
control over samples collected
in Japan and the Netherlands.
Summary : Grab samples were col-
lected and placed in containers
cleaned with Alconox, rinsed
with hot water, d.i. water, and
heated to 350°C 1 hr. Samples
were stored in closed contain-
ers at room temperature and
protected from UV and visible
light.
Comment : Authors did not re-
port recoveries and the data
may be considered semtquianti-
tative.
Summary : Samples were ex-
tracted with B&J grade benzene
and concentrated to 100 p1.
Sample extracts were analyzed
by GC/FID and GC/PIS.
Comment : Two large peaks
identified as phthalate
esters were present in
method blank but not
column blank. Study would
Lherefore be of little value
[ or phthalate data.
Summary : A method blank was
used in the QA; however,
phthalates were found in the
method blank.
14, Eiceman,
et al.
(1979).
(MISCELLANEOUS continued)
-------
TABLE I (continued)
Sample design Sampling Analysts Quality assurance Reference
Laboratory Media
Comment : Scope of survey urn-
iled to those chemicals com-
mercially available to this
author (Japan). Results can-
not be considered monitoring
data
Comment : No actual sampling
done.
Coimnent : Water and organic
solvent phthalate results
probably fairly accurate.
Results for solid reagents
and other materials probably
much less accurate due to
testing procedure. No re-
coveries given; this de-
tracts from the credibility
of the results.
Comment : No recoveries
given so actual levels re-
ported may not be accurate.
However, use of solvent
blanks indicates that
phthalates were present.
Summary : Commonly used
solvents, chemicals, and la-
boratory equipment were in-
cluded in this survey of
laboratory sources of
phthalate contamination.
Summary : Samples or organic
solvents, water, solid re-
agents, aluminum foil and
other materials were acquired
to test for the extent of DSP
and DEHP contamination. All
were tested as received from
manufacturers.
Summary : Five liters of each
water sample were extracted,
the extract reduced, and then
analyzed by GC/FID. Each or-
ganic solvent (100 ml) was
evaporated to dryness, re-
dissolved and then analyzed
by GC/FID. Each powdered
reagent was soaked in 100
to 300 ml of 1:1 CIIC1 3 MeOII,
filtered, reduced in volume,
and analyzed by GC/FID.
Aluminum foil, rubber
stoppers, etc., were simi-
larly immersed in solvent
and the resultant extract
analyzed by GC/FID.
Summary : Solvents used in the
determination of phthalate con-
centration of other mateials were
redistilled and proven to be
phthalate free. Actual levels
of DRP and DEIIP in some of the
materials Like rubber stoppers,
aluminum foil, etc., are prob-
ably not quantitative due to
lack of procedural recoveries.
Medical Survey
Comment : Medical and physi-
ological survey--no methods
or chemical data mentioned.
Comment : None.
Comment : None.
Comment : None.
SO, Milkov,
et al.
(1973).
Summary : None.
Summary : None.
Summary : None.
Summary : None.
35, Ishida
(1980).
(MISCELLANEOUS continued)
-------
TABLE 1 (continued)
Sample design Sampling Analysis Quality assurance Reference
Comment : None.
Comment : None.
Comment : None.
Coninent : None.
Summary : None.
Summary : None.
Swmnary : None.
(NISCELLANEOUS concluded)
Position Paper
Sunimar : The document is a
statement of arguments for
the necessity of an environ-
mental impact report before
the use of plastic pipe is
approved for potable water
systems by and for the
State of California. No
applicable information for
the subject task. Note:
See also Reviews Nos. 56
and 62.
1, Adams 1
and
Broadwel I
(1980).
0 ’
-------
A. AIR
This section presents the reviews on 12 articles designated for inclu-
sion under this matrix.
SURVEY DESIGN
Information to determine the overall design for most of the articles was
generally lacking. One article (65) contained the results of a single air
sample while others (3, 7, 27, 28, and 41) reported the results on 10 or more
air samples. However, the relationship of the samples to the environment
(i.e., time or space) was often not provided in sufficient detail. No men-
tion was made of efforts to randomize or replicate the collection of samples.
SAMPLING
Procedures used to collect the samples were described very briefly in
most articles. When the sampling was described, mention of quality assurance
samples such as field blanks or spiked blanks were the most frequently omitted
items. Thus contamination by the sampling equipment could not be ruled out as
a source of DEHP. Only one aritcie (2) mentioned the use of field blanks.
ANALYSIS
The methods for extraction of the analyte from the collection media were
reported in most articles (3, 7, 23, 25, 26, 27, 28, 65, and 74). However,
only two papers (27 and 65) reported any recovery or response data. In princi-
ple the analytical procedures were adequate but more information was needed
to assess the validity of the reported methods.
QUALITY ASSURANCE
Little, if any, information was presented for this section in most of
the articles. A significant QA result that was reported in only five articles
(2, 7, 23, 65, and 74) was the use of method blanks. Verification by other
methods such as second column or GC/MS were mentioned in only two of these
articles (23 and 65). Origin of the DEHP is therefore unsubstantiated in all
articles for the air matrix except 23 and 65.
67
-------
Thermal Degradation Products from PVC Film in Food-Wrapping Operations
Boettner and Ball (1980), Ref. No. 2
SURVEY DESIGN
Sampling sites : Not applicable.
Sampling plan : Not applicable.
Problems : Not reported.
Goal(s) : To test the levels of various compounds volatilized during cut-
ting of the PVC film by the hot-wire method and the cool rod method.
Comments : Five PVC film samples were supplied by Borden but only three
were used. Representativeness of these films to others is in doubt since
only one film source was studied.
Summary : PVC films supplied by Borden Chemical were surveyed for various
compounds volatilized during the cutting process. Supermarket conditions were
simulated.
SAMPL ING
Container preparation : Not applicable.
Collection procedure : Specially designed hood enclosed the film and cut-
ting wires. High boiling compounds were washed from the hood with solvents.
Volatile compounds collected “in an impinger, charcoal tube, or other sampling
device.”
Storage conditions : Not applicable.
Stability demonstrated : Not applicable.
Field blanks : Hood blanks were generated.
Spiked blanks : Not applicable.
Problems : “Smoky” cuts were not reproducible.
Comments : All film from same company and cleanliness of the hood pose
problems of representativeness and contamination.
Summary : Five PVC films were obtained from Borden Chemical. No real
sampling involved.
68
-------
Boettner and Ball (1980)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not applicable.
Recovery : Hood rinse after known amounts of phthalates were vola-
tilized showed 80% recovery for DEHA and 77% recovery for DEHP.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/FID on 1% SE-30.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Results reported were corrected for percent recovery, film
thickness and width. Results were variable and cannot be considered quanti-
tative but only indicative of levels a person may be exposed to when cutting
PVC film.
Summary : PVC films were cut with a hot—wire C ”. 215°C) or a cool rod
(135°C) inside a specially constructed hood. The phthalates were collected
by rinsing th hood with 25 ml of ethanol. The ethanol volume was reduced to
1 ml and anlyzed by GC/FID.
QUALITY ASSURANCE
Method blank : Hood rinsed between cuts to ensure no sample carryover.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Micrograms per cut reported; relative standard
deviations to 100%.
Replicates : Three to nine runs for each film.
Method verification : Not reported.
69
-------
Boettner and Ball (1980)
Interlab verification : Not reported.
Problems : Some cuts were smoky and resulted in high levels; no apparent
way to minimize variations.
Comments : Method not very reproducible as shown by number of smoky ver-
sus clean runs, and relative standard deviations of results. Variability of
results indicates results are semiquantitative at best. Repetition of test
runs only seems to show variability of method and does not necessarily give a
better average value of organics released during the cutting process.
Summary : Sampling hood rinsed between runs to ensure no carryover.
Replicate runs were made to obtain average values of phthalate released dur-
ing cutting.
70
-------
Airborne di-Butyl and di-(2-Ethylhexyl)phthalate at Three New York City
Air Sampling Stations
Bove et al. (1978), Ref. No. 3
SURVEY DESIGN
Sampling sites : Samples were collected from three New York City aero-
metric sampling stations (Tilden High School Station, Brooklyn (74 samples
analyzed); Seaview Hospital Station, Staten Island (138 samples analyzed);
Andrew Jackson High School Station, Queens (16 samples analyzed)). Three
long-term high volume samples collected at Sterling Forest, New York.
Sampling plan : Monthly average concentrations reported. Frequency of
single samples is unknown. Sterling Forest samples compared to New York City
samples for dibutyl phthalate (DBP) and DEHP.
Problems : Not reported by author.
Goal(s) : Not stated.
Comments : Sufficient detail required to determine the overall design is
lacking. Apparently information is from a small part of a larger study in
which air sampling was conducted for a 1-year period.
Summary : Air samples were collected at three sites in New York City.
No comment was made as to why these sites were chosen or what relationship
existed with the nearby environment.
SANPL ING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Sampling procedures were not detailed. Because of this lack
of information, little confidence can be placed in the representativeness of
the sample.
Summary : Air samples were collected on glass fiber filters. DEHP was
extracted, but no details were given about filter preparation, blanks, etc.
71
-------
Bove et al. (1978)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Glass filters placed in a Soxhiet extractor
and refluxed for 6 hr with benzene (B&J). Filtered through a fritted-glass
Buchner funnel (ASTM 10-20) and benzene removed in all-glass rotary evaporator.
Residue transferred to 10-mi vial with B&J methylene chloride (MeCl 2 ). Solvent
removed by warming under a stream of filtered dry N 2 .
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : Gas Chromatography/Mass Spectrometry (GC/MS).
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : This section contains little information, except for the ex-
traction method. No conclusion can be made about the applicability of the
method because validation procedures were not revealed.
Summary : Analysis was performed by GC/MS after soxhiet extraction of
the filters.
QUALITY ASSURANCE
Method blank : Mention is made of “small analytical blanks.”
Control sample : Apparently none.
Reference material : Internal standard added before GC/MS analysis.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
72
-------
Bove et al. (1978)
Problems : Not reported.
Comments : A qualitative result of t sma1l analytical blanks” and the
lack of other QA data can be used to characterize the data as “uncertain.”
Summary : QA procedures were minimal (method blanks only).
73
-------
Comparison Between the Organic Fraction of Suspended Hatter at a Background
and an Urban Station
Cautreels et al. (1977), Ref. No. 7
SURVEY DESIGN
Sampling sites : Sampling was conducted near LaPaz, Bolivia, and near
Antwerp, Belgium, to compare levels at a remote site with those of an urban
site.
Sampling plan : Sampling in Bolivia for six 14-day periods. The article
does not mention the sampling time in Belgium.
Problems : Not reported.
Goal(s) : To report on the organic composition of aerosol in order to
establish background levels.
Comments : Experiment not designed specifically for phthalates. Since
the number of samples collected in Antwerp is unknown, the comparison between
urban and background levels cannot be justified on a design basis.
Summary : The goal of reporting on the organic composition of aerosols
around LaPaz was achieved. Samples were collected near the Cosmic Ray Labor-
atory at an altitude of 5,200 m.
SANPLING
Container preparation : Not reported.
Collection procedure : Collected with a high volume sampling unit as de-
scribed by Dams and Heindryckx using Whatman glass fiber filters.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Sampling lacked QA provisions and was not designed specific-
ally for phthalates. Container preparation was not reported so the level of
contamination cannot be determined and the data may thus have a sampling con-
tamination bias.
Summary : Sampling in Bolivia was conducted during six 14-day sampling
periods using high volume samplers equipped with glass fiber filters.
74
-------
Cautreels et al. (1977)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Successive Soxhiet extractions of the filter
with benzene and methanol. Four hours with each solvent. Extract evaporated
under vacuum at < 40°C and redissolved in ether. Inorganic compounds eliminated
with water. Acidic compounds derivatized with diazomethane in ether.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : 0.1 pg for phthalates.
Problems : Not reported.
Instrument : GC/MS, 3 m 4% Dexil 500.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Possible contamination by phthalates during sample
handling.
Comments : Method was not optimized for phthalates. Presence of phthal-
ates may be due to contamination. The analytical results are of questionable
value.
Summary : Filters were extracted with benzene and methanol, evaporated,
and dissolved in ether. Extracts derivatized with diazomethane and analyzed
by GC/MS. Phthalates were detected in method blanks.
QUALITY ASSURANCE
Method blank : Method blanks on glass fiber filters yielded low levels
(< 200 ppm) of phthalates.
Control sample : Not reported.
Reference material : Calibration curves determined using three standard
mixtures.
Precision and accuracy : Relative standard deviation (RSD) of quantitative
results < 10%.
Replicates : Not reported.
75
-------
Cautreels et al. (1977)
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Possible contamination of samples during sample handling.
Comments : Not designed specifically for phthalates. Data should be
viewed as qualitative because of lack of sufficient QA data.
Summary : QA was primarily in the form of method blanks. The method
blanks indicated low levels (< 200 ppm) of phthalates.
76
-------
Industrial Hygiene Evaluation of Thermal Degradation Products from PVC Film
in Meat-Wrapping Operations
Cook (1980), Ref. No. 9
SURVEY DESIGN
Sampling sites : Room containing meat wrapper.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s): To evaluate potential health hazards from thermal degradation
products of PVC film in meat-wrapping operations.
Comments : This paper is an industrial hygiene evaluation of Boettner’s
results (Paper No. 2) of one film from one batch of PVC film from one source.
Summary : The air in a room containing a wrapping machine using PVC film
was sampled to identify thermal degradation products and assess potential health
hazards.
SAMPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : This section is of minimal value.
Summary : No pertinent information concerning sampling was reported.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
77
-------
Cook (1980)
Limit of detection : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported
Instrument : GC/MS.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : This section is of minimal value.
Summary : Analysis was by GC/MS.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Paper deals only with exposure values and is of no value from
the standpoint of chemical analysis.
Summary : No QA information reported.
78
-------
Control of Blanks in the Analyis of Phthalates in Air and Ocean Biota Samples
Giam (1976d), Ref. No. 23
SURVEY DESIGN
Sampling sites : Not applicable.
Sampling plan : Not applicable.
Problems : Not applicable.
Goal(s) : To present a procedure to reduce phthalate contamination in
blanks for air and ocean biota samples.
Comments : No information given on the source or number of samples used
in the experiment. Basically, this paper is the same as Paper No. 19 but it
also includes air sampling.
Summary : The paper recommends a procedure for minimizing phthalate con-
tamination in blanks for air and ocean biota samples.
SAMPLING
Container preparation : Bottles are cleaned with detergent, rinsed with
distilled water and distilled acetone, and heated in an oven to 320°C.
Collection procedure : Not reported.
Storage conditions : Mason jars and aluminum foil. Stored at or below
0°C.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Presents a reasonable method for cleaning equipment but does
not mention field blanks.
Summary : Samples were stored in Mason jars and aluminum foil. Mason
jars were cleaned with detergent, rinsed with distilled water and solvents,
and heated in an oven. Aluminum foil was heated to 320°C.
79
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Giam (1976d)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Biota samples macerated for 2 minutes and
extracted with acetonitrile. The extracts are dried with sodium sulfate and
cleaned up on a Florisil column. Air samples eluted with petroleum ether and
diethyl ether.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : DEHP, 5 ng = 50% FSD.
Problems: Not reported.
Instrument : GC/EC, 2 m x 6 mm OD glass column, 3% SE-30 on Gas Chrom Q
(100/120); 2 in x 6 mm OD glass column, 1.5 % SP-2250 and 1.95% SP-2401 on
Supelcon AW-DMCS (100/120).
Linear reponse : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Recoveries or other validation were not reported. The analyt-
ical method itself is adequate.
Summary : Biota samples were macerated, extracted with acetonitrile, and
the extracts dried with sodium sulfate. The dried extracts were then passed
through a Florisil column for cleanup prior to analysis by GC/EC. Air sam-
ples were eluted with petroleum ether and diethyl ether and analyzed by GC/EC.
QUALITY ASSURANCE
Method blank : “Background level for procedure is about 1 ng.”
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : GC/EC second column.
80
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Giam (1976d)
Interlab verification : Not reported.
Problems : Not reported.
Comments : QA provisions reported were primarily those concerning elim-
ination of contamination.
Summary : The paper basically presents cleanup procedures to eliminate
phthalate contamination when preparing biota and air samples for phthalate
analysis.
81
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Estimation of Fluxes of Organic Pollutants to the Marine Environment -
Phthalate Plasticizer Concentration and Fluxes
Giam (1977), Ref. No. 25
SURVEY DESIGN
Sampling sites : Not applicable.
Sampling plan : Not applicable.
Problems : Not applicable.
Goal(s) : Develop a mass balance model for fluxes of DEHP.
Comments : The mass balance model was developed using a combination of
data and assumptions. Author states that atmospheric input to the Gulf was
the most important route but cautions that “direct field measurements are
important.”
Summary : This paper deals primarily with a mass balance model for es-
timation of fluxes of DEHP in the Gulf of Mexico. Sampling and analysis as
in reference 27.
SANPLING
Container preparation : Not reported.
Collection procedure : Water was solvent extracted or passed through XAD-2
resin. Sediment with metal coring device; biota by hook and line or trawl.
Air through columns of Florisil or polyurethane foam.
Storage conditions : Biota and sediment frozen.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : This section only briefly outlines the sampling method and
is of limited value.
Summary : Water samples were solvent extracted on site or adsorbed on
XAD—2 resin. Biota samples were collected by hook and line or trawl. Sedi-
ment samples were collected with a metal coring device. Air was adsorbed on
Florisil or polyurethane.
82
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Giam (1977)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Extraction with organic solvents, separation
by column chromatography.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/EC; column not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : This section lacks enough information to assess its value.
Summary : Samples were extracted with organic solvents, cleaned up by
column chromatography, and analyzed by GC/EC.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Chemical derivatization.
Interlab verification : Not reported.
Problems : Not reported.
Comments : None.
Summary : No QA data of significance reported.
83
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Measurement of Phthalate Esters in Marine Air
Giam (1978), Ref. No. 26
SURVEY DESIGN
Sampling sites : The Gulf of Mexico.
Sampling plan : March-April 1977.
Problems : Not reported.
Goals : Evaluate different adsorbants for sampling atmospheric pollutants.
Comments : Paper relates results of comparison of three adsorbents for
air sampling. An unknown number of grab samples were collected during a sci-
entific cruise in the Gulf of Mexico.
Summary : The purpose of this paper is to describe the sampling tech-
niques, laboratory analysis, and evaluation of different adsorbents for sam-
pling atmospheric phthalates.
SAMPLING
Container preparation : Florisil heated to 320°C and packed in glass col-
umns. XAD-2 extracted with methanol, benzene, acetonitrile, and acetone-
petroleum ether and then packed in glass columns. Polyurethane rinsed with
water and extracted with acetone and petroleum ether.
Collection procedure : Sample tubes mounted at bow of ship; sample col-
lected for 24 hr.
Storage conditions : Sample cartridges sealed and frozen.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not used for sampling.
Problems : Moist marine air may affect trapping efficiency.
Comments : Evaluates three adsorbents for sampling air for phthalates and
chlorinated hydrocarbons. Provides suitable sampling procedures but no men-
tion of blanks or spiked blanks.
Summary : A method is presented for sampling air through columns filled
with Florisil, XAD—2 resin, and polyurethane foam. Sample cartridges were
sealed and frozen for transportation.
84
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Giam (1978)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Florisil eluted with diethyl ether and con-
centrated with isooctane. XAD-2 eluted with acetonitrile and methylene
chloride-petroleum ether. Polyurethane plugs extracted with petroleum ether.
Cleaned up on Florisil.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : DEHP, 10-20 ng.
Problems : Not reported.
Instrument : GC/EC, 6’ x 1/4” 3% OV-17 at 230°C.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Analytical procedure was adequate but recoveries or other
validations were not reported.
Summary : The adsorbents were eluted with solvents and the eluates
cleaned up on a Florisil column. Collection efficiency was influenced by
moisture. Analysis was by GC/EC.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
85
-------
Giam (1978)
Problems : Not reported.
Comments : None.
Summary : QA provisions were not reported.
86
-------
Phthalate Ester Plasticizers: A New Class of Marine Pollutant
Giam et al. (1978a), Ref. No. 27
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Results were reported on samples collected from the
Mississippi Delta (36), Gulf Coast (19), Open Gulf (10), Gulf of Mexico (28),
and North Atlantic (15).
Problems : Not reported.
Goal(s) : To analyze for phthalate esters and chlorinated hydrocarbons in
air, water, sediment, and biota samples predominately from the Gulf of Mexico.
Comments : Basically same information as other articles by Giam. Grab
samples apparently collected.
Summary : The purpose of the project was to analyze for phthalate esters
and chlorinated hydrocarbons in air, water, sediment, and biota samples pre-
dominately from the Gulf of Mexico.
SAMPLING
Container preparation : Not reported.
Collection procedure : Sediment collected with metal coring devices.
Water extracted directly or adsorbed on XAD-2. Biota collected with hook and
line or trawl. Air adsorbed on Florisil or polyurethane foam.
Storage conditions : Sediment and biota frozen.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : This section is too brief to be of value.
Summary : Sampling methods are brief. Sediment collected by metal coring
device. Biota collected by hook and line or trawl. Water extracted directly
or adsorbed on XAD-2. Air adsorbed on Florisil or polyurethane foam. Sedi-
ment and biota samples frozen.
87
-------
Giam et al. (1978a)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Extraction with organic solvents. Cleanup
by column chromatography.
Recovery : “90% or better.”
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Instrument : GC/EC, column not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Too little information provided to properly assess this section.
Summary : Samples were extracted with organic solvents and cleaned up by
column chromatography. Analysis was by GC/EC. Recoveries of “90% or better”
were mentioned as well as “background values of 50 ng.”
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Chemical derivatization.
Interlab verification : Not reported.
Problems : Not reported.
Comments : None.
Summary : Appropriate QA information was not provided.
88
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Phthalate Esters, PCB and DDT Residues in the Gulf of Mexico Atmosphere
Giam et al. (1980), Ref. No. 28
SURVEY DESIGN
Sampling sites : Northwest Gulf of Mexico.
Sampling plan : 24 hr at a time during March and April 1977. (Results
on 10 samples were reported.)
Problems : Not reported.
Goal(s) : Report the concentration of DBP, DEHP, PCB, and DDT residues in
the atmosphere of the northwest Gulf of Mexico.
Comments : Although not specifically stated, it is inferred that the
sampling was part of a multiple task ocean sampling cruise of unknown pur-
pose. Grab samples taken during cruise.
Summary : The purpose of this paper was to report the concentration of
DBP, DEll !’, PCB, and DDT residues in the atmosphere of the northwest Gulf of
Mexico. Sampling was conducted for 24 hr at a time for 10 days during a sam-
pling cruise.
SAMPLING
Container preparation : Not reported.
Collection procedure : Precombusted glass-fiber filters backed by two
pre-extracted polyurethane foam plugs housed in aluminum cartridges. Sampler
operated at 450 £ mm 1 on the bow of the ship.
Storage conditions : Refrigerated.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : The collection procedure was adequate but should have provided
for field blanks and other validations.
Summary : Samples were collected by drawing air through precombusted
glass-fiber filters backed by two preextracted polyurethane foam plugs housed
in aluminum cartridges. The samples were refrigerated until analysis.
ANALYSI S
Measurement procedure
Cleanup/fractionation : Filters and foam plugs extracted 16 hr with
petroleum ether, concentrated, and cleaned up on Florisil.
Recovery : Not reported.
89
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Giam et al. (1980)
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/EC, 3% OV-17 at 230°C.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : The analytical method was sufficient, but recoveries and
other validation parameters should have been determined.
Summary : The filters and plugs were extracted for 16 hr with petroleum
ether, concentrated, and cleaned up on Florisil. Analysis was by GC/EC.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : A previous paper (No. 23) alluded to careful sample handling
and laboratory techniques to minimize contamination.
Summary : No quality assurance was presented.
90
-------
Analysis of Complex Organic Mixtures on Airborne Particulate Matter
Karasek et al. (1978), Ref. No. 41
SURVEY DESIGN
Sampling sites : Industrial, urban versus rural areas in Ontario, Canada.
Sampling plan : Forty-two samples representing an industrial, urban area
and 36 representing a rural environment.
Problems : Not reported.
Goal(s) : Development of method which would rapidly and practically pro-
vide qualitative and quantitative information for a wide range of organic com-
pounds found in atmospheric particulate samples.
Comments : Differences between organics in urban and rural areas not
really brought out in article. Distribution of sampling locations within
industrial or urban areas is unknown.
Summary : Survey designed ostensibly to compare differing levels of or-
ganics associated with airborne particulates from urban and rural areas.
SAMPLING
Container preparation : Not reported.
Collection procedure : Hi-Vol apparatus recommended by Air Pollution
Measurement Committee (APMC).
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Samples collected and provided to author by the Air Resources
Branch of the Ontario Ministry of the Environment. Handling and storage of
the glass fiber filters before and after sampling but before Soxhiet extraction
was not discussed and could be a source of contamination.
Summary : Forty—two Hi-Vol glass filter samples were collected in Welland,
Ontario, and 36 were collected in Simcoe, Ontario, to provide representative
samples of urban and rural environments. Each sample was collected over a
24-hr period.
91
-------
Karasek et al. (1978)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : Gas Chromatography/Flame Ionization Detector (GC/FID) and
GC/MS. Special column (10 ft) of Carbowax (0.2%) on acid-washed Chromosorb W.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Although methanol reportedly more efficient in extraction than
cyclohexane, no recoveries were given. Other parameters were also supposedly
checked out but not reported. Absence of actual extraction efficiencies of
DEHP from particulate matter casts doubt on the significance of the data pre-
sented.
Summary : Soxhiet. extraction of filters for 2 hr with glass-distilled
methanol, roto-vaped to 1 ml, and analyzed by GC/FID and GC/MS Electron
Impact (El) and Chemical Ionization (CI).
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Retention index was ±1%; quantitation ±10%.
Replicates : Not reported.
Method verification : GC/MS used for verification of compounds suspected
to be present from GC/FID retention indices.
Interlab verification : Not reported.
92
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Karasek et al. (1978)
Problems : Not reported.
Comments : Qualitative information for phthalates is good because of
GC/MS. Obvious deficiencies in reporting method blanks or recoveries cast
doubt not only on the origin of the compounds but also the accuracy of the
data presented.
Summary : Use of method blanks or control samples was not reported. Re-
tention indices very constant over 13-day period of analysis, and quantitation
good to ±10% from response-factored integrated GC peak areas.
93
-------
Quantitative Determination and Confirmation of Identity of Trace Amounts of
Dialkyl Phthalates in Environmental Samples
Thomas (1973), Ref. No. 65
SURVEY DESIGN
Sampling sites : Near municipal incinerator. The samples for this proj-
ect were obtained from a study of PCBs and incinerators.
Sampling plan : Single site adjacent to municipal incinerator.
Problems : Not reported.
Goal(s) : Detailed study of dialkylphthalates.
Comments : The results of a single air sample are reported. This study
was not designed specifically for phthalates.
Summary : The phthalates were identified because they were “unknowns”
appearing in samples taken for PCB analysis.
SAMPLING
Container preparation : Reagents and apparatus preextracted with hexane
or acetone:benzene (9:1) until “clean” by GC/EC.
Collection procedure : Air pulled through a glass fiber filter and then
three ethylene glycol traps in series at 1.7 ft 3 /inin.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : The sampling procedure is simple and straightforward.
Summary : Phthalates are collected by pulling air through glass fiber
filter and ethylene glycol traps.
ANA.LYSIS
Measurement procedure
Cleanup/fractionation : Florisol (25 cm). Serial dilution with
hexane, 2% ether/75% hexane, ether. Phthalates in third (ether) fraction.
Recovery : > 90% from ethylene glycol traps; 100% from chromato-
graphic cleanup.
94
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Thomas (1973)
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : 10 ag for dialkylphthalates.
Problems : Not reported.
Instrument : GC, Varian Model 1200, unspecified EC detector. GC/MS, Pye
104 interfaced to El MS-30; GC: 6 ft x 1/4 in. glass column, 3% SE-30 on
Chromosorb W(AW-DMCS, 60/80 mesh), isothermal 210°C, injector 230°, detector
225°, nitrogen carrier 25 mi/mm; MS: helium flow 40 mi/mm.
Linear response : 100 to 1,000 ng.
Stability of response : Response decreases as run time increases.
Problems : GC/EC decrease in detector sensitivity with prolonged
running necessitates frequent injection of standards.
Comments : Analytical procedures used would suggest a high degree of data
reliability.
Summary : After cleanup through Florisil and solvent exchange from ether
to hexane, samples were screened by GC/EC and identity confimed by GC/MS.
QUALITY ASSURANCE
Method blank : All reagents and apparatus were preextracted until free
from contaminants as indicated by GC/EC.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : GC/EC for screening; GC/MS for confirmation.
Interlab verification : Not reported.
Problems : Not reported.
Comments : The preextraction of the apparatus until clean means that the
phthalates found were associated with the source and not the result of contam-
ination.
Summary : Phthalate data from this study is scant as stated by the author
since identification of the phthalates was incidental to a PCB study.
95
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Characterization of Selected Organics in Size—Fractionated Indoor Aerosols
Weschler (1980), Ref. No. 74
SURVEY DESIGN
Sampling sites : Bell Laboratories, Holmdel, New Jersey, sixth floor,
central corridor.
Sampling plan : 400 hr per sample for the six “sets” of samples.
Problems : Contamination from impactor blower required modification.
Goal(s) : To identify organic compounds in indoor aerosols.
Comments : The location of the sampling site may have been chosen to
obtain a representative building air sample, but the reason is not stated.
Summary : The purpose of this project was to identify organic compounds
in indoor aerosols. This was accomplished by sampling aerosols in a Bell
Laboratories facility in Holmdel, New Jersey.
SANPLING
Container preparation : Aluminum plates cleaned ultrasonically with de-
tergent followed by rinses with distilled water and ethanol.
Collection procedure : Samples were collected on glass fiber filters us-
ing an Anderson Model 65-000 four-stage cascade impactor with backup filter.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Blanks prepared from u.nexposed collection media.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Sampling procedures used showed an understanding of problems
associated with using hi-vol samplers.
Summary : Sampling was conducted using an Anderson four-stage impactor
with a backup filter. Samples were collected on glass fiber filters. Unex-
posed filters were used as blanks.
ANALYSI S
Measurement procedure
Cleanup/fractionation : Filters were extracted for 24 hr with meth-
anol. The extracts were filtered and reduced by evaporation.
96
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Weschler (1980)
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/MS, 120 x 0.2 cm glass column with 3% OV-1O1.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : The analysis procedures used are consistent with compound
identification only.
Summary : The filters were extracted with methanol. The extracts were
filtered and reduced, then analyzed by GC/MS. No data were presented.
QUALITY ASSURANCE
Method blank : Unexposed filters treated in same way as exposed filters.
Reference material : Authentic standards from Aldrich Chemical Company,
Pfaltz and Bauer, and Supelco.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : The use of standards and GC/MS analysis can indicate a posi-
tive identification of the airborne particles.
Summary : Little was reported concerning QA measures. Method blanks were
used, and reference materials were used to verify retention times and spectra.
97
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B. BIOTA
Fourteen articles were reviewed for this matrix and are included in this
section.
SURVEY DESIGN
The overall design of most articles could not be easily determined with
the exception of articles 58 and 64. Selected results were presented in arti-
cles 21 and 24 while an attempt at monitoring was mentioned as being conducted
in the vicinity of a DEHP plant in artcle 55. Two articles, 20 and 25, as-
sessed the significance of selected data and presented a mass balance model
which was not validated. Analytical methodology or results of selected samples
were presented in articles 19, 21, 22, 23, 24, 27, and 29 in which little in-
formation was given about a sampling plan. Results of specific sampling loca-
tions were reported in article 29 but the data are compounded with both in-
digenous and free swimming biota. Results of a laboratory metabolism study
and a literature review are given in articles 49 and 71.
SAMPLING
The sampling preparation and collection procedures described for this
matrix ranged from no information (20, 22, 49, 55, and 71) to somewhat exten-
sive (19, 21, 23, 24, 58, and 64). Some cursory information was presented in
three articles (25, 27, and 29). However, in no article was mention made of
field blanks which is important to establish the origin of the DEHP determined.
ANALYSIS
In principle, the analytical methods reported were adequate in seven
articles (19, 22, 23, 24, 55, 58, and 64). Articles 55 and 58 were unique in
that recovery and detection limit data were reported. Some information was
given in three articles (27, 29, and 49) while none was given in four articles
(20, 21, 25, and 71). More information was generally needed to assess the
validity of the reported methods.
QUALITY ASSU1 ANCE
One article (19) reported the results of method blanks and the use of
two column verification. Two articles (58 and 64) reported additional infor-
mation based on interlab verification but failed to mention method blanks or
replicate analyses. Minimal QA data were reported in three articles (21, 23,
and 24) however, procedures to minimize contamination were mentioned in some
detail. Insufficient information was presented in six articles (20, 22, 25,
27, 29, and 71). Only one article (49) eliminated the need for extensive QA
by the use of 14 C-labeled DEHP.
98
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Sensitive Method for Determination of Phthalate Ester Plasticizers in Open-
Ocean Biota Samples
Giam et al. (1975b), Ref. No. 19
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Results given for muscle (10), liver (1), whole (2), and
gill (1) for an unknown number of spade fish, croaker, trout, shark, catfish,
shrimp, sting ray, eel, and blue crab.
Problems : Not reported.
Goal(s) : Establish methodology necessary for the determination of
phthalate levels in open-ocean biota.
Comments : No information given on the source of biota samples other
than the Gulf of Mexico.
Summary : The goal was to establish methodology necessary for the deter-
mination of phthalate levels in open-ocean biota. No sampling information re-
ported.
SAMPLING
Container preparation : Mason jars and aluminum foil cleaned with clean-
ing solution (Micro International Products Corporation), distilled water, and
distilled acetone, and heated to 320°C for 10 hr.
Collection procedure : Not reported.
Storage conditions : Samples kept at or below 0°C.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Spiked tissue samples were mentioned.
Problems : Not reported.
Comments : Cleaning to reduce contamination was extensive and reduced
procedural background levels to 25 ng for dibutylphthalate and 50 ng for di-
(2-ethylhexyl)phthalate. Laboratory materials, e.g., Teflon®, Na 2 SO 4 , glass-
wool, etc., were also collected for DEHP analysis.
Summary : Containers and laboratory apparatus were subjected to a thorough
cleaning. Samples were stored at or below 0°C.
99
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Giam et al. (1975b)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Extracts were separated into acid and base!
neutral fractions and cleaned up through a Florisil column.
Recovery : Spiked tissue samples yielded 70 to 100% recoveries.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : DBP, 1 ppb.
Problems : Lipids and tissue components eluting from Florisil with
ether/petroleum ether caused a background problem in chromatography.
Instrument : GC/EC, 6 ft x 1/4 in. OD glass column, 3% SE-30 on Gas
Chrom Q (100/200); 6 ft x 1/4 in. OD glass column, 1.5% SP—2250 and 1.95%
SP-2401 on Supelcon AW-DMCS (100/200).
Linear response : 5 ng DEHP, 50% full-scale deflection; linearity
not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : The method seems quite adequate. This paper provides a method
specifically for phthalates in biota.
Summary : The extracts were separated into acid and base/neutral frac-
tions. The fractions were cleaned up on a Florisil column and analyzed by
GC/EC. Recoveries were 70 to 100%.
QUALITY ASSURANCE
Method blank : Reported as “frequent” method blanks.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not repotted.
Replicates : Not reported.
Method verification : Different column.
100
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Giam et al. (1975b)
Interlab verification : Not reported.
Problems : Not reported.
Comments : This paper may provide a procedure which will serve as a
model for reducing contamination, but further QA is needed to determine the
limits of the method. A selected number of laboratory materials were ob-
served to have various amounts of DEHP.
Summary : Method blanks were run frequently to assure low contamination.
Replicates and precision and accuracy were not reported. Verification was by
a different column.
101
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Concentration and Fluxes of Phthalates, DDTs, and PCBs to the Gulf of Mexico
Giam et al. (1976a), Ref. No. 20
SURVEY DESIGN
Sampling sites : Thirty-five stations in the Mississippi River Delta and
the Gulf of Mexico.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : To analyze selected samples from the Gulf of Mexico for
phthalates.
Comments : This report is concerned mainly with the analytical results
and their significance. Criteria used to select sampling stations is un-
known. Apparently grab samples were collected to assess phthalate loading
in the Gulf.
Summary : The goal of this project was to analyze selected samples from
the Gulf of Mexico for phthalates and to assess the significance of the data.
The Mississippi River accounts for only one-fourth of total DEHP loading.
“The origins of the remaining inputs have not yet been determined.”
SAMPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : See other Giam articles for procedures.
Summary : No information was provided on sampling methods.
102
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Giam et al. (1976a)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : 0.1 ng/g phthalates.
Problems : Not reported.
Instrument : Not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : See other Giam articles for procedures.
Summary : No information was given concerning the analytical procedures.
The detection limit for phthalates was reported as 0.1 ng/g.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : None.
Summary : No QA information was reported as this was a discussion of
published data.
103
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Problems in Analysis of Organic Pollutants in Open-Ocean Samples
Giam et al. (1976b), Ref. No. 21
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : To propose methods for very low background sampling and analy-
sis, as well as for evaluation of procedures.
Comments : Design not part of report. Selected results of 10 biota,
9 water, and 6 sediment samples were reported.
Summary : Paper proposed methods for very low background sampling and
analysis, as well as for evaluation of procedures for biota, sediment, and
water.
SAMPLING
Container preparation : Glass and metal cleaned with detergent, water,
solvent, and heat. Aluminum foil heated to 320°C. XAD-2 resin extracted.
Collection procedure : Biota collected by hook and line or diving.
Plankton collected with nets. Sediment collected with corers. Water with
XAD-2 column.
Storage conditions : Biota, frozen. Plankton and sediment, precleaned
Mason jars with aluminum foil-lined caps.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Recommended use of spiked samples.
Problems : Not reported.
Comments : The sampling procedures recommended are very good. Emphasis
is on reducing possible sample contamination.
Summary : Recommends cleaning glass and metal with detergent, water, sol-
vent, and then heating. Recommends heating aluminum foil to 320°C overnight
and solvent extraction with XAD-2 resin. Also recommends use of spiked
samples.
104
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Giam et al. (1976b)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Proposes thorough cleaning of equipment but
does not report method for sample cleanup.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : 25 ng DBP and 50 ng DEHP.
Problems : Not reported.
Instrument : Not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Analytical method not reported.
Summary : Analytical procedure covers only cleaning of glassware and
equipment.
QUALITY ASSURANCE
Method blank : Recommends use of method blanks.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Mentioned ttsatisfyingll results.
Comments : The discussion of QA procedures is somewhat minimal. The rec-
ommended procedure for minimizing contamination in blanks is quite good.
Summary : Paper recommends procedures for minimizing contamination.
105
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Confirmation of Phthalate Esters from Environmental Samples by Derivatization
Giam et al. (1976c), Ref. No. 22
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Results of one starfish given.
Problems : Not reported.
Goal(s) : To develop suitable chemical derivatives for confirmation of
the phthalate ester plasticizers and the synthesis and application of N-(2-
chloroethyl)phthalimide for confirmation.
Comments : The origin of the one sample was not reported.
Summary : The goal of the study was to develop suitable chemical deriva-
tives for confirmation of the phthalate ester plasticizers.
SANPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : None.
Summary : No sampling information reported.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Derivatization of phthalates, treated with
KOH in MeOH and gently heated 1 hr. Cooled and 2-chioroethylamine hyrochlo-
ride added. Acidified, evaporated to dryness, and heated to 200°C for 1/2 hr.
Recovery : 90% yield of imicle based on quantity of esters.
Linear recovery : Not reported.
106
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Giam et al. (1976c)
Interferences : Not reported.
Limit of detection : “Background of 30 ng or less.”
Problems : Not reported.
Instrument : GC/EC, 6 ft x 1/4 in. OD glass column, 3% SE-30 on Gas
Cb.rom Q (100/200).
Linear response : Shown by graph.
Stability of response : Not reported.
Problems : Not reported.
Comments : Cannot be used to quantitate individual phthalates. Individ-
ual phthalates must be quantitated by GC/EC, assuming no contamination.
Summary : Presents method for converting phthalates to N-(2-chloroethyl)-
phthalimide. Yield is 90%. Analysis by GC/EC will give quantitation for
total phthalates only. Response is linear from 0 to 1 ng.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : None.
Summary : No QA procedures reported.
107
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Control of Blanks in the Analysis of Phthalates in Air and Ocean Biota Samples
Giam (1976d), Ref. No. 23
SURVEY DESIGN
Sampling sites : Not applicable.
Sampling plan : Not applicable.
Problems : Not applicable.
Goal(s) : To present a procedure to reduce phthalate contamination in
blanks for air and ocean biota samples.
Comments : No information given on the source or number of the samples
used in the experiment. Basically this paper is the same as Paper No. 19 but
it also includes air sampling.
Summary : The paper recommends a procedure for minimizing phthalate con-
tamination in blanks for air and ocean biota samples.
SAMPLING
Container preparation : Bottles are cleaned with detergent, rinsed with
distilled water and distilled acetone, and heated in an oven to 320°C.
Collection procedure : Not reported.
Storage conditions : Mason jars and aluminum foil. Stored at or below
0°C.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Presents a reasonable method for cleaning equipment but does
not mention field blanks.
Summary : Samples were stored in Mason jars and aluminum foil. Mason
jars were cleaned with detergent, rinsed with distilled water and solvents,
and heated in an oven. Aluminum foil was heated to 320°C.
ANALYS IS
Measurement procedure
Cleanup/fractionation : Biota samples macerated for 2 minutes and
extracted with acetonitrile. The extracts were dried with sodium sulfate and
cleaned up on a Florisil column. Air samples eluted with petroleum ether and
diethyl ether.
108
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Giam (1976d)
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : DEHP, 5 ng = 50% FSD.
Problems: Not reported.
Instrument : GC/EC, 2 m x 6 mm OD glass column, 3% SE-30 on Gas Chrom Q
(100/120); 2 m x 6 mm OD glass column, 1.5 % SP-2250 and 1.95% SP-2401 on
Supelcon AW-DMCS (100/120).
Linear reponse : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Recoveries or other validations were not reported. The an-
alytical method itself is adequate.
Summary : Biota samples were macerated, extracted with acetonitrile, and
the extracts dried with sodium sulfate. The dried extracts were then passed
through a Florisil column for cleanup prior to analysis by GC/ECD. Air sam-
ples were eluted with petroleum ether and diethyl ether and analyzed by GC/ECD.
QUALITY ASSURANCE
Method blank : ?tBackground level for procedure is about 1 ag.”
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : GC/EC second column.
Interlab verification : Not reported.
Problems : Not reported.
Comments : QA provisions reported were primarily those concerning elim-
ination of contamination.
Summary : The paper basically presents cleanup procedures to eliminate
phthalate contamination when preparing biota and air samples for phthalate
analysis.
109
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Trace Analyses of Phthalates (and Chlorinated Hydrocarbons) in Marine Samples
Giam (1976e), Ref. No. 24
SURVEY DESIGN
Sampling sites : Gulf of Mexico.
Sampling plan : Selected results reported on 10 biota, 9 water, and 6
sediment sames and some laboratory materials (e.g., teflon, Na 2 SO 4 , etc.).
Problems : Not reported.
Goal(s) : To analyze marine samples for phthalates a’nd chlorinated hydro-
carbons.
Comments : Origin of samples given as the Gulf of Mexico. Grab samples
inferred to have been collected.
Summary : The purpose of this paper was to report a procedure for the
analysis of marine biota, water, and sediment. No design was reported.
SAMPLING
Container preparation : Equipment cleaned with detergent, rinsed with
water and acetone, heated to 320°C for 10 hr.
Collection procedure : Water aspirated through precleaned copper tubing
into a glass carboy, then passed through Amberlite XAD-2 resin.
Storage conditions : Biota at or below 0°C. Others not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : The sampling procedure should have yielded samples with a mm-
imum of phthalate contamination.
Summary : Samples were collected in containers cleaned with detergent,
rinsed with water and acetone, and heated to 320°C. Water samples were passed
through XAD-2 resin column. Biota samples were stored at or below 0°C.
110
-------
Giam (1976e)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Biota macerated, extracted with acetonitrile,
methylene chloride-petroleum ether. Water eluted with acetonitrile and ex-
tracted with inethylene chloride-petroleum ether. Sediment extracted with ace-
tonitrile, methylene chloride-petroleum ether. All through Florisil.
Recovery : From XAD-2 - DMP (abbrevation not specified): 79.8 to
85.7%; DBP: 94.1 to “.‘ 100%; DEll?: 88.5 to 97.3%.
Linear recovery : Not reported.
Interferences : By GC: DBP and Aroclor 1254 interfere with each
other, and DEHP and Aroclor 1260 interfere with each other.
Limit of detection : 5 ng DEHP = 50% full-scale deflection.
Problems : Coelution with Aroclors.
Instrument : GC/EC. Biota: 1.8 m x 0.64 cm OD glass, 3% SE-30 on Gas
Chrom Q (100/120); water and sediment: 1.8 m x 0.64 cm OD, 3% SE-30 on
Chromosorb WHP (100/120); confirmation: 1.8 m x 0.64 cm OD, 1.5 ¼ SP-2250
and 1.95% SP-2401 on Supelcon AW-DMCS (100/120).
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : The analytical procedure seems quite acceptable based on the
recovery values reported.
Summary : Samples were extracted with acetonitrile, methylene chloride-
petroleum ether, and cleaned up on a Florisil column. Recoveries of phthal-
ates were in the range 79 to 100%. Analysis was by GC/ECD with 5 ng DEHP
yielding 50% full-scale deflection.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
111
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Giam (1976e)
Replicates : Not reported.
Method verification : GC/EC using a different column.
Interlab verification : Not reported.
Problems : Not reported.
Comments : The only quality assurance provisions reported were procedures
to minimize background in blanks. With the addition of replicate samples and
spiked blanks the method could be better evaluated.
Summary : Procedures given to minimize background in sample blanks.
Verification by GC/EC using a different column. DEHP levels of laboratory
items reported.
112
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Estimation of Fluxes of Organic Pollutants to the Marine Envirorunent -
Phthalate Plasticizer Concentration and Fluxes
Giam (1977), Ref. No. 25
SURVEY DESIGN
Sampling sites : Not applicable.
Sampling plan : Mean concentration of water (31), sediment (34), air
(16), and biota (20) samples were reported.
Problems : Not applicable.
Goal(s) : Develop a mass balance model for fluxes of DEHP.
Comments : The mass balance model was developed using a combination of
data and assumptions. Author states that atmospheric input to the Gulf was
the most important route but cautions that t?direct field measurements are im-
portant.”
Summary : This paper deals primarily with a mass balance model for es-
timation of fluxes of DEHP in the Gulf of Mexico. Sampling and analysis as
in reference 27.
SAMPLING
Container preparation : Not reported.
Collection procedure : Water was solvent extracted or passed through XAD-2
resin. Sediment with metal coring device; biota by hook and line or trawl.
Air through columns of Florisil or polyurethane foam.
Storage conditions : Biota and sediment frozen.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : This section only briefly outlines the sampling method and
is of limited value.
Summary : Water samples were solvent extracted on site or adsorbed on
XAD-2 resin. Biota samples were collected by hook and line or trawl. Sedi-
ment samples were collected with a metal coring device. Air was adsorbed on
Florisil or polyurethane.
113
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Giam (1977)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Extraction with organic solvents, separation
by column chromatography.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/EC; column not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : This section lacks enough information to assess its value.
Summary : Samples were extracted with organic solvents, cleaned up by
column chromatography, and analyzed by GC/EC.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Chemical derivatization.
Interlab verification : Not reported.
Problems : Not reported.
Comments : None.
Summary : No QA data of significance reported.
114
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Phthalate Ester Plasticizers: A New Class of Marine Pollutant
Giam et al. (1978a), Ref. No. 27
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Results were reported on samples collected from the
Mississippi Delta (36), Gulf Coast (19), Open Gulf (10), Gulf of Mexico
(28), and North Atlantic (15).
Problems : Not reported.
Goal(s) : To analyze for phthalate esters and chlorinated hydrocarbons in
air, water, sediment, and biota samples from the Gulf of Mexico.
Comments : Basically same information as other articles by Giam. Grab
samples apparently collected.
Summary : The purpose of the project was to analyze for phthalate esters
and chlorinated hydrocarbons in air, water, sediment, and biota samples pre-
dominately from the Gulf of Mexico.
SANPL ING
Container preparation : Not reported.
Collection procedure : Sediment collected with metal coring devices.
Water extracted directly or adsorbed on XAD-2. Biota collected with hook and
line or trawl. Air adsorbed on Florisil or polyurethane foam.
Storage conditions : Sediment and biota frozen.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : This section is too brief to be of value.
Summary : Sampling methods are brief. Sediment collected by metal coring
device. Biota collected by hook and line or trawl. Water extracted directly
or adsorbed on XAD-2. Air adsorbed on Florisil or polyurethane foam. Sedi-
ment and biota samples frozen.
115
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Giam et al. (1978a)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Extraction with organic solvents. Cleanup
by column chromatography.
Recovery : “90% or better.”
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Instrument : GC/EC, column not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Too little information provided to properly assess this section.
Summary : Samples were extracted with organic solvents and cleaned up by
column chromatography. Analysis was by GC/EC. Recoveries of “90% or better”
were mentioned as well as “background values of 50 ng.”
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Chemical derivatization.
Interlab verification : Not reported.
Problems : Not reported.
Comments : None.
Summary : Appropriate QA information was not provided.
116
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Phthalate Ester Plasticizers, DDT, DDE & Polychiorinated Biphenyls in Biota
from the Gulf of Mexico
Giam et al. (1978), Ref. No. 29
SURVEY DESIGN
Sampling sites : Northwestern Gulf of Mexico. Near-shore areas which
have generally higher levels of contamination.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : Determine phthalate levels in Gulf biota.
Comments : Survey design is poor. Grab samples of 17 different species
caught at each station—-some were indigenous to an area; others were free
swimmers. No correlation possible between sampling locations because there
was a lack of uniformity of species between each location.
Summary : Marine biota samples were collected for analysis to determine
their phthalate levels.
SAMPLING
Container preparation : Not reported.
Collection procedure : Net or hook and line.
Storage conditions : Wrapped in precleaned foil or placed in cleaned
Mason jars; frozen and kept at or below 0°C.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : This section does not cover the cleaning procedure and there-
fore cannot be evaluated.
Summary : Samples were collected by net or hook and line and placed
in cleaned aluminum foil or cleaned Mason jars and kept at or below 0°C.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Homogenized and extracted with acetonitrile.
Reextracted into methylene chloride-petroleum ether. Cleanup on Florisil.
Recovery : Not reported.
117
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Giam et al. (1978)
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : 0.1 ng/g.
Problems : Not reported.
Instrument : GC/EC; column not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : The analytical section is marginal because recoveries or other
validations were not reported.
Summary : Samples were homogenized and extracted with acetonitrile. Re-
extracted into methylene chloride-petroleum ether. Concentrated extracts were
cleaned up on Florisil and analyzed by GC/EC.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Alkaline hydrolysis and chemical derivatization.
Interlab verification : Not reported.
Problems : Not reported.
Comments : QA section is insufficient.
Summary : Verification by chemical derivatization.
118
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Uptake and Fate of Di-2-ethylhexyl Phthalate in Aquatic Organisms and in a
Model Ecosystem
Metcalf (1973), Ref. No. 49
SURVEY DESIGN
Sampling sites : Not applicable.
Sampling plan : Unknown number of fish, snail, clam, Daphnia, and Elodea
were used in DEHP uptake experiments.
Problems : Not reported.
Goal(s) : To study the metabolism and possible bio-magnification of DEHP
in a variety of aquatic organisms and its ecological behavior in food chains
of a laboratory model ecosystem.
Comments : No actual field survey conducted.
Summary : Controlled laboratory studies of the uptake and metabolism of
DEHP in aquatic organisms in a model ecosystem were performed. No monitoring
data presented.
SAMPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : None.
Summary : Sampling of the model ecosystem was not discussed.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Thin-layer chromatography (TLC).
Recovery : 14 C-labeled DEHP used in study. Scintillation counting
used to detemine amount of DEHP left and any evidence of metabolism.
Linear recovery : Not reported.
119
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Metcalf (1973)
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : Not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Total recovery for method not discussed but broken down into
recoveries for DEIIP and each metabolite. Major degradative pathways inferred
to be through hydrolysis of the ester groups to produce the monoester, then
phthalic acid, and finally phthalic anhydride.
Summary : Aquatic organism exposed to 14 C-labeled DEHP spiked water and
analyzed by homogenization and extraction with ether, TLC separation, and sub-
sequent scintillation counting. Identities of metabolites determined by chro-
matography (TLC) with known standards. Actual method recoveries not generated
for DEHP but rather results expressed in percent of metabolites found versus
percent DEHP remaining.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Use of ‘ 4 C-labeled DEHP virtually eliminates the need for ex-
tensive quality assurance measures in terms of method blanks.
Summary : No method blanks, control samples, or other standard quality
assurance measures were taken because of the nature of the radioactive metab-
olism experiments performed.
120
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DEHP in the Vicinity of an Industrial Area in Finland
Persson (1978), Ref. No. 55
SURVEY DESIGN
Sampling sites : Sites near DEHP factory.
Sampling plan : Unspecified number “of fish, net plankton, freshwater
arthropods, soil arthropods, and soil were obtained. .
Problems : Not reported.
Goal(s) : Determination of DEHP levels in the vicinity of a DEHP manu-
facturing plant.
Comments : Sites were selected and grab samples collected in the vicinity
of DEHP plant. “Vicinity” not delineated. The impact of the factory has not
been determined by this preliminary investigation.
Summary : Samples of fish, plankton, freshwater and soil arthropods, and
soil obtained in the vicinity of a DEIIP plant were analyzed for DEIIP.
SAMPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Fish caught at spawning time; normal whereabouts unknown.
Summary : Sampling methods were not discussed.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Alumina.
Recovery : 40% at unknown level.
Linear recovery : Not reported.
Interferences : Not reported.
121
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Persson (1978)
Limit of detection : 0.1 ppm for unknown sample size.
Problems : Not reported.
Instrument : Varian 2800 GCJFID on two columns: 3% SE-30 and 1% DC-560.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Results corrected for background but not for recovery. Author
calls identification of DEHP by GC “tentative.”
Summary : Samples were dried with sodium sulfate and Soxhlet extracted
with hexane. Extracts cleaned up with alumina and analyzed by GC/FID on two
columns.
QUALITY ASSURANCE
Method blank : Background level from chemicals and apparatus reported to
be 0.2 ppm.
Control sample : 40% recovery obtained from somewhere but not discussed.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Results should be viewed as qualitative at best.
Summary : Quality assurance measures not described but background level
defined at 0.2 ppm and recovery at 40%.
122
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Pesticides in the Illinois Waters of Lake Michigan
Schacht (1974), Ref. No. 58
SURVEY DESIGN
Sampling sites : Lake Michigan; streams feeding into the lake; sources
of contamination (sewage, etc.) being dumped into feed stream.
Sampling plan : Samples of sediment (50) and water (45) were collected
from tributaries, streams, near-shore, and off-shore stations in and around
sewage treatment plants and associated waters. Fish samples (255) were col-
lected from the lake.
Problems : Not reported.
Goal(s) : Determination of levels of pesticides discharged as well as
levels then found in Lake Michigan water, sediment, and fish. Phthalates
were secondary to the major goal.
Comments : Design inferred to be a monitoring of the open lake and tribu-
taries near sewage treatment plants.
Summary : Survey design ostensibly formed to determine levels of various
pesticides in Lake Michigan and their source, but no information given as to
actual design formulation. Grabs of sediment, fish and 24-hr water composites
were collected over a 3-year period.
SANPLING
Container preparation : Glass bottles with aluminum foil liners, rinsed
with Nanograde hexane.
Collection procedure : Fish from commercial fishermen; water by grab
sampling and composite samplers; sediments collected directly in glass bot-
tles or by use of a Ponar dredge.
Storage conditions : Fish frozen; sediment stored at ambient; water not
reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Composite sampler rubber tubing replaced with glass tubing to
prevent contamination. Water and sediment sampling procedure appeared to elim-
inate source of contamination. Fish samples may have been contaminated while
taking a filet or when stored in aluminum foil if the foil was not rinsed with
solvent.
123
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Schacht (1974)
Summary : Water samples collected in glass bottles. Both grab samples
and composite (24 hr) samples taken. Fish obtained from local fishermen and
stored frozen in aluminum foil. Sediment samples taken in glass jars by hand
or with a Ponar dredge.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Florisil standard column; sodium sulfate
heated overnight at 450°C.
Recovery : Fish, 85 to 95%; sediments, 90%; water, 90%. Spike
levels not reported, however.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Fish, 10 ppb; sediment, 1 ppb; water, 100 ppt
(all DEHP data).
Problems : Not reported.
Instrument : Varian 204; 62 Ni 255°; column 200-210°, inj. 225°. Pesticide
analysis: 1/8 in. x 8 m column, 2.0% QF-1 and 1.25% OV-17 on 100/200 mesh
Supelcoport. For DEIIP: 1/8 in. x 1 m column, 4% QF-1 and 2.0% OV-17.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : A well-defined analytical scheme was used to separate the ana-
lytes from the matrix. Although not specifically stated except for sodium
sulfate, mention of the decontamination procedures used, if any, would remove
any doubt about the validity of the data.
Summary : “FWPCA Method for Chlorinated Hydrocarbon Pesticides in Water
and Wastewater” used with some modifications. Results not corrected for re-
covery.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
124
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Schacht (1974)
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Two columns (not specified); one more, one less
polar than specified, were used.
Interlab verification : Yes, but no other information.
Problems : Not reported.
Comments : Sample fortification and recovery results mentioned in table
of contents but missing from the report. Results can be considered somewhat
quantitative since method blanks not reported.
Summary : Spike recovery and detection limit data were reported, but use
of method blanks was not.
125
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Chlorinated Organic Residues in Fish, Water, and Precipitation from the
Vicinity of Isle Royale, Lake Superior
Swain (1978), Ref. No. 64
SURVEY DESIGN
Sampling sites : Lake Superior sites chosen near populated areas and also
in deep lake region. Compared with data from sites on an “untouched” lake on
Isle Royale.
Sampling plan : Eight whitefish and 17 trout obtained from Isle Royale
area. Ten whitefish and 30 trout obtained from Lake Superior.
Problems : Not reported.
Goal(s) : Determination of baseline levels of selected contaminants in
sport or commercially valuable fish in the nearshore waters of Lake Superior.
Comments : Survey designed to point out differences in organic contamina-
tion between populated and unpopulated areas. Isle Royale selected because
of remoteness from inhabited or industrial areas, the lake on the island has
no direct connection to Lake Superior, and no internal combustion engines
have been used on the island.
Summary : Selected sites in Lake Superior were sampled for fish and water
in order to determine background levels of contaminants. These were compared
with samples taken from a remote area.
SAMPLING
Container preparation : Gallon glass container for water; fish wrapped in
something but not reported what.
Collection procedure : Deep water trawls or gill nets. Fish eviscerated
immediately or held on ice. No procedure reported for water.
Storage conditions : Fish were frozen. Storage conditions for water were
not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Chance for contamination in both fish and water sampling could
lead to high results.
Summary : Fish caught using deep water nets and either eviscerated on
site and then stored on ice or simply wrapped and stored on ice until process-
ing.
126
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Swain (1978)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Fish: GPC (SX-3), toluene:ethyl acetate,
1:3, then Florisil cleanup. If PCB’s present, further silicic acid column
separation used. Water extracts: Subjected to micro-Florisil cleanup if
necessary.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : 0.1 pg/g.
Problems : Not reported.
Instrument : GC/EC, 6 ft x 4 mm glass with 1.5% OV-17/2% OV-210 on Q.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Sample preparation procedures delineated but analysis by GC
not discussed in detail other than operating parameters. Sample preparation
not specifically designed for phthalates. Lack of recoveries for method, es-
pecially with the indicated cleanup steps, leaves room for considerable ana-
lyte losses as well as further contamination.
Summary : Fish samples homogenized with sodium sulfate, extracted, sub-
jected to GPC and Florisil, and silicic acid if PCBs present, then analyzed
by GC/EC.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Error estimates are indicated as ± two standard
error units.
Replicates : Not reported.
127
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Swain (1978)
Method verification : Not reported.
Interlab verification : Four different labs for fish, two for water.
Problems : Not reported.
Comments : Four different labs used in these analyses but results not
compared. Not known if identical samples were analyzed by each lab. These
facts cast considerable doubt on whether the analytical data are equivocable.
Summary : No mention of blanks or spikes was made. Use of four different
labs was supposed to “minimize analytical error.”
128
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Organic Contaminants - Lake Huron
EPA (1977b), Ref. No. 71
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Not reported.
Problems : Environmental analysis is a still developing “state-of-the-
art.”
Goal(s) : Not reported.
Comments : A good synopsis of the persistance that a selected list of or-
ganics have in Lake Huron. A literature and data review of monitoring data
for the lake and its inputs.
Summary : This report relates the sources of organic compounds entering
Lake Huron and describes their potential impact on the environment. The re-
port was used as a means of proposing a total ban on PCB, aldrin, dieldrin,
DDT, and its derivatives.
SAMPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : None.
Summary : Sampling method not described.
129
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EPA (1977b)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : Not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : None.
Summary : Analysis methods not mentioned. DEHP found ranging from < 1 to
1.4 pg/liter in water samples.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : None.
Summary : No quality assurance mentioned.
130
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C. BLOOD (PLASMA, SERUM, CELLS )
Nine articles were reviewed for this matrix and are included in this
section.
SURVEY DESIGN
Information to determine the overall design for these articles was lim-
ited. A restricted sampling was reported in seven articles (36, 37, 39, 47,
54, 57, 66). Two articles (38 and 44) involved a series of grab samples dur-
ing laboratory experiments. Random or replicate sampling, distribution or
relationship of sample population was uncertain in all articles.
SAMPLING
Equipment preparation and collection procedures ranged from insufficient
or no information in four articles (36, 37, 38, and 66) to brief information
in five articles (39, 44, 47, 54, and 57). One article (39) did mention
field blanks and spikes but other information on equipment preparation was
not given. Contamination from use of rubber stoppers in the sampling equip-
ment may account for the presence of DEHP (47).
ANALYSIS
The analytical methods when reported were adequate. Some information
was provided in nine articles (36, 37, 38, 39, 44, 47, 54, 57, and 66) with
recovery data stated in three of them (37, 39, and 57). Confirmation by
GC/MS was performed in only one article (66). Lack of a complete method with-
out any validation leaves room for criticism of the results.
QUALITY ASSURANCE
In five articles (36, 39, 44, 47, and 66) little, if any, information
was presented. The remaining four articles (37, 38, 54, and 57) reported the
use of method blanks and, with one excpetion (38), each reported the use of
control samples. The results in these articles (37, 38, 54, and 57) have more
credibility than the others reported under this matrix, but all articles could
be improved with further QA.
131
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Plasticizers from Plastic Devices: Extraction, Metabolism, and Accumulation
by Biological Systems
Jaeger and Rubin (1970), Ref. No. 36
SURVEY DESIGN
Sampling sites : Based on exposure to plastic tubing and storage devices.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : To determine the extent of extraction, metabolism, and accumu-
lation of plasticizers from plastic devices by biological systems.
Comments : Although not stated, single grab samples appear to have been
collected from tubing and other plastic apparatus used in a perfused liver
experiment, then from other plastic products used in medicine, e.g., blood
bags.
Summary : Limited survey of plasticizers extracted from plastic devices
by biological systems. Accumulation and metabolism of the plasticizers was
also examined.
SAMPLING
Container preparation : Not reported.
Collection procedure : Not applicable.
Storage conditions : Not applicable.
Stability demonstrated : Not applicable.
Field blanks : Not applicable.
Spiked blanks : Not applicable.
Problems : Not reported.
Comments : Procedures used to control/eliminate contamination not stated.
Summary : No sampling was done se. Outdated whole blood was pur-
chased from a nearby blood bank. Human tissue was obtained from patients at
Johns Hopkins Hospital. White rat tissue and blood were obtained from Johns
Hopkins Hospital.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Dowex-1 for blood extract; also used TLC.
132
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Jaeger and Rubin (1970)
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : Gilford spectrophotometer at 260 nm or 280 urn.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Analytical procedures not well-defined. No procedures were
given for any kind of tissue. Lack of method description for tissue and gen-
eral mode of detection used for blood analysis leaves ample room for criticism
of results.
Summary : Chloroform extracts of neutral and acidified blood were applied
to TLC plates or Dowex-1. The eluent was spectrophotometrically examined for
phthalates.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Credibility of the data is in doubt because of the minimal QA
measures reported.
Summary : Minimal quality assurance measures were reported; i.e., no
blanks or spiked samples were mentioned.
133
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Migration of Phthalate Ester Plasticizer from Polyvinyl Chloride Blood Bags
into Stored Human Blood and Its Localization in Human Tissues
Jaeger and Rubin (1972), Ref. No. 37
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Not defined but samples were collected from 6 units
of stored blood, unspecified number of fresh blood and urine samples, 13
autopsy subjects who had received blood, and 7 autopsy subjects who had not.
Problems : Not reported.
Goal(s) : Determination of DEHP in blood stored in PVC bags.
Comments : Grab samples taken from transfused and nontransfused subjects.
Although not stated, the samples appear to have been collected on an oppor-
tunistic basis.
Summary : DEHP found in stored blood, and patient’s blood who had received
transfusions. DEHP metabolites also found.
SAMPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : The problem of contamination is not mentioned. Since no col-
lection procedures were mentioned addressing this problem, the results should
be considered qualitative.
Summary : Blood sampled from patients, and after storage and/or transfu-
sion to determine source of phthalates in patient’s blood.
ANALYS IS
Measurement procedure
Cleanup/fractionation : Blood lyophilized, chloroform extract washed
with saline. Extract dried, reconstituted with methanol, centrifuged, dried,
reconstituted with hexane.
134
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Jaeger and Rubin (1972)
Recovery : 60 to 90%.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : Not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Phthalic acid and other DEHP metabolites also analyzed.
Summary : GC column: 3% SE-30 on Gas Chrom Q. No instrument or detector
mentioned.
QUALITY ASSURANCE
Method blank : Ranged from 20 to 60 pg.
Control sample : Fresh blood in glass.
Reference material : Not reported.
Precision and accuracy : Reproducibility ±10%.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Blood values were subtracted from tissue values.
Summary : Assay of samples included blood not in contact with PVC, blood
in contact with PVC for increasing time spans, metabolites found in urine,
fat, and other tissues.
135
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Extraction, Localization, and Metabolism of Di-2-ethylhexyl Phthalate from
PVC Plastic Medical Devices
Jaeger and Rubin (1973a), Ref. No. 38
SURVEY DESIGN
Sampling sites : Based on possible exposure to DEHP.
Sampling plan : Stepwise investigation after DEHP found in a liver per-
fusion system. Grab sampis of tubing, blood bags, rat whole-body homogenate,
rat liver and lung were collected and analyzed.
Problems : Not reported.
Goal(s) : Determination of phthalate levels in various types of fluids
and tissues subjected to DEHP and other plasticizers.
Comments : Logical progress of studies. Each study based on results of a
previous study. Grab samples taken in each case.
Summary : Original experiments designed to determine levels of DEHP in
blood in a liver perfusion system. Additional experiments performed to deter-
mine levels in blood and various tissues exposed to DEHP by virtue of blood
transfusions, operations, or hemodialysis. Attempts were also made to deter-
mine metabolites.
SANPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : In one part of the study different temperatures were
used to determine effect of temperature on migration rate of DEHP from tubing.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : None.
Summary : Sampling methods not discussed.
ANALYSIS
Measurement procedure
Cleanup/fractionation : TLC.
Recovery : Not reported.
136
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Jaeger and Rubin (1973a)
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : TLC.
Linear response : Not reported.
Stability of response : Not reported
Problems : Not reported.
Comments : Analytical methods not explained. Purity of solvents and
reagents used (if any) not reported. Lack of reporting recoveries and ana-
lytical methods indicates that any results reported should be viewed as unsub-
stantiated.
Summary : Analysis method for liquids reported as TLC of an unknown or-
ganic extract. Tissue analyzed by unknown method.
QUALITY ASSURANCE
- Method blank : Used for liquid analysis of perfusion system and in tissue
analysis (20 to 60 Jg DEHP).
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : ±10% for tissue analysis.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Quality assurance measures skimpy at best.
Summary : Method blanks used in the analysis of the liquids in the liquid
perfusion system and in the tissue analysis. No discussion of use of spiked
samples to determine recoveries.
137
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Di-2-ethylhexyl Phthalate, a Plasticizer Contaminant of Platelet Concentrates
Jaeger and Rubin (1973b), Ref. No. 39
SURVEY DESIGN
Sampling sites : Five random units of human platelet concentrate.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : Ascertaining whether blood (and its components) stored in plas-
tic bags become contaminated with plasticizers.
Comments : Grab samples taken from blood bags. Unknown if all bags
were from some manufacturer or if had the same lot number.
Summary : Platelets and plasma were from DEIIP-contaminated blood storage
bags.
SAMPLING
Container preparation : Not reported.
Collection procedure : Platelet concentrates stored in blood bags.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Yes, one.
Spiked blanks : Yes, but level not reported.
Problems : Not reported.
Comments : No mention of randomness of selection or procedures to reduce
contamination.
Summary : Spiked blanks used; platelet concentrates stored in plastic
blood bags were sampled.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Lyophilized samples extracted with 2:1
CHC1 3 :MeOH, saline washed, organic phase silicic acid treated, filtered,
dried, taken up with MeOH.
Recovery : 60 to 98%.
Linear recovery : Not reported.
138
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Jaeger and Rubin (1973b)
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC unspecified, 3% SE-30 on Gas Chrom Q, conditions unspeci-
fied.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Extraction scheme could be improved with a ±ractionation/
cleanup step.
Summary : GC analysis (detector unspecified) of DEHP from human blood
platelets.
QUALITY ASSURANCE
Method blank : Yes, “clean.”
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Data may be questionable because of minimal QA.
Summary : Method blank is the only QA mentioned, and the results were
corrected for it.
139
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Studies on Absorption, Distribution & Excretion of Phthalates
Kitanaka et al. (1977), Ref. No. 44
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Samples collected from mice and rats given radiolabeled
phthalates. Unspecified number of urine, feces, blood, kindey, liver, fat,
and spleen samples were collected from test animals.
Problems : Not reported.
Goal(s) : Determine the distribution and levels over time of radioactive
phthalates and the effects of the phthalates on the body.
Comments : This study is of significance in determining the possible fate
of phthalates ingested orally. The author cautions one to use care in inter-
preting the data since ester hydrolysis of the 14 C-labeled carbonyl group of
the phthalates may affect the emission patterns observed.
Summary : This project was designed to determine the effects of phthalic
acid esters on the body. Rats and mice were administered radioactive
phthalates.
SAMPLING
Container preparation : Not reported.
Collection procedure : Test animals were anesthetized, exsanguinated, and
eviscerated. Metabolic cages used to collect urine and feces.
Storage conditions : Processing began immediately after collection.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Unknown whether one group of animals went through all collec-
tion phases or a separate group of animals used for each specific phase.
Summary : Phthalates with a carbon-14 tag were administered to rats and
mice. Urine, feces, and tissues were collected at specific times after admin-
istration of the ‘ 4 C-phthalates.
140
-------
Kitanaka et al. (1977)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : Liquid scintillation counter.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Recovery and quenching data should have been reported. Other-
wise the results are considered qualitative.
Summary : The various excrements, body fluids, tissues, and organs were
measured for radioactivity to determine which organs contained phthalates and
their relative concentrations with respect to time.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
141
-------
Kitanaka et al. (1977)
Comments : An unspecified comparison with control groups was made to
account for “slight” radioactivity after 12 to 24 hr. It is uncertain as to
what this statement refers or its relevance.
Summary : QA provisions were not reported.
142
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Determination of Di-2-ethylhexyl Phthalate Levels in Human Blood Plasma and
Cryoprecipitates
Marcel (1973), Ref. No. 47
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : Measurement of DEHP levels in blood and cryoprecipitates stored
in plastic bags.
Comments : Limited survey--blood obtained from local blood bank.
Suimnary : No real design used other than obtaining an unspecified number
of grab samples of blood which had been exposed to plasticizers.
SAIIPLING
Container preparation : Used evacuated glass tube .
Collection procedure : Not reported.
Storage conditions : Cryoprecipitates kept frozen until analysis.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Glass tubes used to collect blood from plastic bags probably
had a rubber septum cap and could have caused more contamination. Blood had
been stored in plastic bags for 24 days.
Summary : Blood samples were taken from transfusion blood bags (from a
local blood bank) with evacuated glass tubes and cryoprecipitates were kept
frozen in the plastic bags until analysis.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Chloroform added to blood, shaken, and 2.5 ml
of 0.75% NaC1 added. Layers separated overnight. Chloroform layer removed.
Recovery : Not reported.
Linear recovery : Not reported.
143
-------
Marcel (1973)
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/FID. Either 4 ft diethylene glycol succinate at 195°C
or 2 ft dimethylsilicone gum at 175°C at 2°C/mm to ?.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Also analyzed for triglycerides and attempted to make a corre-
lation between those levels and DEIIP levels. Absence of method recoveries im-
plies that the results generated can be considered semiquantitative.
Summary : Plasma was extracted, the phthalates salted out, and the ex-
tract analyzed by GC/FID.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Internal standard.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Two GC columns.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Lack of QA measures leads to the conclusion that the results
should be considered as qualitative in nature or semiquantitative at best.
Used two columns in the GC analysis to corroborate identity of DEIIP.
Summary : No indication of the use of method blanks, control samples, or
any other QA measures other than the use of a DEHP standard in the GC analysis
and the use of dipentylphthalate or dipropylphthalate as an internal standard.
144
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Migration of Plasticizer from Hemodialysis Blood Tubing - Preliminary Report
Ono et al. (1975), Ref. No. 54
SURVEY DESIGN
Sampling sites : Sixteen patients undergoing hemodialysis selected be-
cause of prolonged exposure to plastic dialysis materials.
Sampling plan : Control and DEHP exposed subjects had samples of blood
taken.
Problems : Not reported.
Goal(s) : To quantitate the amount of DEHP in blood from patients under-
going hemodialysis.
Comments : Grab samples of blood taken from exposed and control people.
Design is limited because samples apparently collected from people in only
one hospital.
Summary : Sixteen patients subjected to hemodialysis and seven control
physicians and nurses were sampled to determine the migration of DEHP into the
blood during hemodialysis.
SAMPLING
Container preparation : Glass syringes used to draw blood “carefully
cleaned” and found to contain “negligible” amounts of DEHP.
Collection procedure : Glass syringes used.
Storage conditions : Stored in glass tubes at dry ice temperature.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Cleaning of glassware not elaborated upon. What is a “negli-
gible” amount of DEHP What kind of caps were on the glass tubes used for
blood storage?
Summary : Clean glass syringes were used to draw blood from the patients
during dialysis. Samples were stored in glass tubes at dry ice temperatures
until analysis.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Ethanolum used in initial extraction, water
added, then extracted with hexane.
Recovery : Not reported.
145
-------
Ono et al. (1975)
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : 5 ppb for 10 ml blood.
Problems : Not reported.
Instrument : GC/unknown detector, 2 m x 4 mm ID glass column with 2% OV-225.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Manipulation of sample during workup not detailed enough.
Contamination could come from many sources. GC detector not specified.
Summary : Ten milliliters of blood were blended with ethanoluin, the sedi-
ment removed, water added to the ethanolum solution, and then extracted with
5 ml of hexane. Extract analyzed by GC.
QUALITY ASSURANCE
Method blank : Run at least once and reported to have “negligible”
amounts of DEUP.
Control sample : Blood samples from seven healthy persons.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Use of glass syringes to draw blood adds some credibility to
analysis, but author should have expanded on use of blanks and should have
done percent recoveries.
Summary : Method blank and use of control patients were the only quality
assurance measures taken.
146
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Di-2-ethylhexyl Phthalate (DEHP) Content of Blood Components Stored in Plastic
Bags
Sasakawa and Mitomi (1978), Ref. No. 57
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : The contents of an unspecified number of blood storage
containers (bags and bottles) were sampled for DEHP levels.
Problems : Not reported.
Goal(s) : Determination of DEHP levels in blood stored in plastic bags
and correlation to patients who had undergone massive transfusions.
Comments : Very limited survey; can be considered a preliminary assess-
ment of DEHP exposure through blood transfusions. Grab samples taken from
blood bags and control bottles.
Summary : DEHP elevated in patients transfused with blood stored in
plastic.
SAMPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Blood stored at 5°C, plasma at -20°C, anticoagulants
at ambient--none verified.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Sampling restricted to patients in a Japanese hospital; plas-
tic bags and anticoagulant under examination were from a single manufacturer.
No mention was made of procedures designed to limit potential contamination;
therefore, validity of the data is uncertain.
Summary : Blood collected from patients who had undergone massive trans-
fusions from “plastic bag” stored blood, from glass bottles, and from patients
who had no transfusions.
147
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Sasakawa and Mitomi (1978)
ANALYSIS
Measurement procedure
Cleanup/fractionation : After extraction with MeOH:CHC1 3 (1:2),
silicic acid column used with 4% ethyl ether/hexane as eluant.
Recovery : 83 to 100% recovery for whole blood spiked with DEHP.
Blood used for recoveries was stored in glass bottles and contained less than
0.01 pg/mi DEHP.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : 0.1 pg/mi for method.
Problems : Not reported.
Instrument : GC/FID, 4 mm x 2 m glass with 5% SE-52.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Chromatography and detection of DEHP not discussed in depth.
Use of GC/FID limited sensitivity of method.
Summary : DEHP extracted from matrices by MeOH:CHC1 3 and subjected to
silica gel column cleanup (except for anticoagulants). Determination of DEHP
by GC/FID. Used di-n-octylphthalate as internal standard. Recoveries of 83
to 100% are considered good for this matrix, and the low blank levels are also
significant.
QUALITY ASSURANCE
Method blank : Blood stored in glass bottles used as blanks.
Control sample : Spiked whole blood samples from blood stored in glass
bottles used for method recovery.
Reference material : Di-n-octylphthalate used as an internal standard.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
148
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Sasakawa and Mitomi (1978)
Interlab verification : Not reported.
Problems : Not reported.
Comments : Quality assurance limited to recoveries from spiked blood
stored in glass bottles. The use of di—n-octylphthalate (DOP) as an internal
standard raises a question about the accuracy of the data because no mention
was made about blank of this compound.
Summary : Blood stored in glass bottles served as blanks and used for
spiked recoveries. An internal standard, DO?, was used. NOTE: Radioactive
14 C-labeled DEHP used for determination of where DEHP stored in blood (red
blood cells or plasma). DEHP mostly associated with plasma -lipoprotein.
149
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Phthalic Acid Esters in Various Foodstuffs and Biological Materials
Tomita et al. (1977), Ref. No. 66
SURVEY DESIGN
Sampling sites : 22 Japanese foods, 17 fatty foods, 38 nonfatty foods,
most from plastic containers.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : Determination of phthalate contamination in foods.
Comments : Grab samples taken from a variety of foodstuffs, some plastic
products, and blood from 13 people. Randomness, relationship among or to
products, and distribution among sample population is unknown.
Summary : Analyses for DEHP and other phthalates were done in response to
literature reports of widespread environmental contamination (in Japan) by
phthalic acid esters.
SANPLING
Container preparation : A comment notes that “extremely careful pretreat-
ment” of equipment and solvents is essential for accurate analysis. No proce-
dure given.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : None.
Summary : No information on sampling.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Acetonitrile or ethyl ether extraction fol-
lowed by Florisil fractionation.
Recovery : Not reported.
Linear recovery : Not reported.
150
-------
Tomita et al. (1977)
Interferences : Not reported.
Limit of detection : Stated that “significant values for. . .DEHP were
over.. .0.005 ppm.”
Problems : Not reported.
Instrument : GC/MS and GC/EC, column 2% DEGS-0.5% H 3 P0 4 ; other parameters
not specified.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Procedures given were very sketchy.
Summary : Florisil fractionation method and analyses by GC/MS and GC/EC
were used.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Data cannot be considered quantitative.
Summary : No identifiable quality assurance stated.
151
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D. FOOD COMMODITIES (PROCESSED FOODS, FISH, MILK )
This section presents the reviews on five articles designed for inclu-
sion under this matrix.
SURVEY DESIGN
Two articles (5 and 6) presented information on the source of the sam-
pies collected. The other three articles (8, 66, and 76) involved a series
of grab sample collections. Randomness, relationship and distribution of
sample population is unknown for all articles.
SAMPLING
Procedures used to collect samples were not described in three of the
five articles (6, 8, and 66). The remaining articles (5 and 76) state where
the samples were collected but only in one article (5) was container prepa-
ration mentioned. In all articles the validity of the results cannot be
established because there is a lack of sampling information about procedures
to eliminate contamination.
ANALYSIS
The methods reported ranged from outdated to very applicable. In princi-
ple, the analytical methods reported were quite adequate for two articles (5
and 76). One article (6) gave the method by reference, while another (66)
provided very little information. An outdated method was used in another
article (8).
QUALTIY ASSURANCE
Insufficient information was given in one article (66). The other arti-
cles gave the following information: use of method blanks (5, 6, 8, and 76);
verification by second column or detector (5, 6, 8, and 76); use of control
sample (8) and interlab verification (6) but with wide variances between the
labs. Origin of DEHP is therefore substantiated in each article except one
(66).
152
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Phthalate Esters in Fish
Bureau of Foods (1972), Ref. No. 5
SURVEY DESIGN
Sampling sites : Seven samples of fish from each location—-Mobile Bay,
Chesapeake Bay, Lake Erie (near Cleveland), Ohio River, Lake Michigan (near
Gary/Chicago), Galveston Bay, Lower Mississippi River, Long Island Sound or
New York Harbor, San Francisco Bay, and Puget Sound. Also an additional 14
samples (7 each from the Atlanta and New Orleans offices) of commercial pond-
grown catfish. Samples collected as close to the point of catch as possible.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : To sample and analyze fish from commercial fish farms and from
the waters in 10 industrial areas for phthalate esters. To determine the
prevalence of this contaminant in that portion of the food supply.
Comments : Directed specifically toward phthalate esters. Grab samples
collected from 10 large bodies of water apparently near large urban/industrial
complexes.
Summary : Design was to collect fish from various district offices and
to analyze for the presence of phthalates. This paper presents methods only.
SAMPLING
Container preparation : Aluminum foil previously determined to be
phthalate-free by laboratory analysis. Rinsed with petroleum ether.
Collection procedure : Collected samples as close to point of catch as
possible. Collected a variety of species. Samples were either fresh or
frozen whole or dressed. Location of catch was pinpointed as closely as pos-
sible. Any possible phthalate ester contamination was noted.
Storage conditions : May be frozen if necessary.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Field blanks should have been reported to determine if there
was any sampling bias.
Summary : The sampling plan was to collect the samples as close to the
point of catch as possible. Samples were wrapped in phthalate ester-free
aluminum foil and frozen if necessary prior to shipment. No field blanks or
spiked blanks were used.
153
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Bureau of Foods (1972)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Pesticide Analytical Manual (PAN) 1 141.12e(H)
and 142.21, PAN 1 212.13a. PAN 1 211.14d with the addition of the 50% ethyl
ether-petroleum ether eluant. If optional extraction 211.13f is used, PAM 1
211.14a (petroleum ether-acetonitrile partitioning) must be used prior to the
Florisil column (211.14d).
Recovery : Before analysis demonstrate recoveries of 75%.
Linear recovery : Procedure calls for demonstrating linearity and
reproducibility. Linearity from 5 to 20 ng using four-point curve.
Interferences : Not reported.
Limit of detection : 20 ng DEHP to give 60 to 80% full-scale deflec-
tion at 1 x 10 amps.
Problems : Not reported.
Instrument : GC, detector not reported. 6 ft x 4 mm ID glass, 3% OV-101
on 80/100 Chromasorb W(HP), “ 210°C isothermal adjusted so DEHP has a Ra
(retention relative to aidrin?) of ‘ ‘ 5.6; 120 mi/mm_N 2 ; inj. 215°C; DC voltage
adjusted so 20 ng DEHP gives 60 to 80% FSD at 1 x 10 amps.
Linear response : 5 to 20 ng.
Stability of response : Not reported.
Problems : Not reported.
Comments : The method is designed specifically for phthaiate esters and
is quite comprehensive including several tips for eliminating contamination.
It was noted though that experimentation shows only 50 to 60% recovery of di-
isodecylphthalate and that the chromatography is inadequate.
Summary : The analytical method described uses PAM procedures including
GC with a 3% OV-101 glass column.
QUALITY ASSURANCE
Method blank : Method recommends running complete set of method blanks
before analysis.
Control sample : Not reported.
Reference material : Not reported.
154
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Bureau of Foods (1972)
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Recommends confirming DEHP and diisooctylphthalate
on PAN 1 mixed column when possible.
Interlab verification : Not reported.
Problems : 50 to 60% recovery of diisodecylphthalate and poor chromatog-
raphy.
Comments : The QA provisions are fairly good in view of the program.
Should have done replicates.
Summary : This is a method only and no results were reported. QA con-
sisted of method blanks.
155
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Phthalate Esters in Food Survey: FY 1974
Bureau of Foods (1975), Ref. No. 6
SURVEY DESIGN
Sampling sites : Each of 17 FDA districts collected two samples each,
margarine, processed American cheese, meat (bacon, weiners, or ground beef),
ready-to-eat cereal, eggs, milk, white bread, canned corn, corn meal, and
canned beans. About half of local origin; the other half nationally recog-
nized brands.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : To determine if di-2-ethylhexylphthalate, diisooctylphthalate,
and diisodecylphthalate were entering the food supply through the processing,
packaging, handling, and transportation chain.
Comments : Design was adequate but not statistically defensible. Grab
samples were collected by each district but procedure for selection of samples
not presented.
Summary : Major processed foods were sampled to determine if phthalates
were entering the food supply through the processing, packaging, handling, and
transportation chain.
SMIPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : This report does not adequately address sampling conditions.
Summary : This report does not give the sampling procedures.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Pesticide Analytical Manual (PAN), Vol. 1.
Recovery : Not reported.
156
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Bureau of Foods (1975)
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Apparent lack of uniformity in reporting phthalate resi-
dues between labs involved. Possibility of contamination. One lab failed to
report DBP. Some milk samples soured before analysis. Data for DEHP could
not be treated statistically.
Instrument : GC.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Distortion of peak shape for DEHP after continued injec-
tions of fatty food extracts would invalidate quantitative measurements.
Comments : A number of problems rendered the results invalid for the most
part.
Summary : Analytical method was mentioned by reference only.
QUALITY ASSURANCE
Method blank : Method blanks used; no indication of how often. 1 to 3
ppm on a fat basis reported for two of the five labs.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Residues to be confirmed by GC using a second column.
Interlab verification : Not reported.
Problems : DEHP data could not be treated statistically because of the
difference in results between laboratories. 1 to 3 ppm on a fat basis for
method blanks from two of five labs.
Comments : The quality assurance results are not good, and these data can
be considered as weak.
Summary : Quality assurance measures reported were method blanks only,
and these were above an acceptable limit for two of the five laboratories.
157
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Method for Isolation and Detection of Dioctyl Phthalate from Milk Lipids
Cerbulis and Ard (1967), Ref. No. 8
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : Apparently to develop a method for isolating and detecting di-
octylphthalate in milk.
Comments : Grab samples taken from “a sample of commercial pooled milk”
and apparatus in use at the laboratory.
Summary : A method for isolating and detecting dioctylphthalate from mi lk
was developed.
SANPL ING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : None.
Summary : No information was given on the sampling procedure.
158
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Cerbulis and Ard (1967)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Extraction was by dialysis with distilled
water for 4 days at 2°C, changing the water three times daily. The nondialyz-
able fraction was lyophilized and extracted with petroleum ether six times,
filtered, evaporated, dissolved in CHC1 3 , and chromatographed on alumina col-
umn. Dissolved residue in benzene and subjected to TLC on Silica Gel G,
(petroleum ether-diethyl ether, acetic acid solvent).
Recovery : Recovery of fats from alumina column was 99.6%. Recovery
of DOP at 30 to 40 mg/liter was 60%.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : Infrared spectroscopy (IR).
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : This method is outdated. The chance for contamination is high,
and the detection limit is probably above reasonable levels.
Summary : The lipids were extracted by dialysis, separated on an alumina
column, and the phthalates isolated by TLC. Recovery of DOP was determined to
be about 60%.
QUALITY ASSURANCE
Method blank : All laboratory equipment used in the study was extracted
with petroleum ether and chloroform-methanol (2:1 v/v). Alumina was extracted
with ethanol-CHC1 3 -H 2 0 (5:2:2 v/v). Plastic tubing and bags cut into pieces
and extracted twice with solvents. Solvents evaporated and analyzed by TLC.
No DOP found in solvents. DOP found in plastic tubing and possibly in rubber
tubing. Milk apparently did not contact plastic.
Control sample : DOP gave same result by TLC.
Reference material : Flexol Plasticizer DOP from Union Carbide Chemicals
Company used as IR standard.
159
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Cerbulis and Ard (1967)
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : TLC and IR.
Interlab verification : Not reported.
Problems : Not reported.
Comment : QA was sufficient for this study.
Summary : The equipment, solvents, and other chemicals were checked.
Only the plastic tubing showed definite indication of DOP although the author
did not believe the milk contacted the plastic tubing. Confirmation of the
TLC results was by IR.
160
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Phthalic Acid Esters in Various Foodstuffs and Biological Materials
Tomita et al. (1977), Ref. No. 66
SURVEY DESIGN
Sampling sites : 22 Japanese foods, 17 fatty foods, 38 nonfatty foods,
most from plastic containers.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : Determination of phthalate contamination in foods.
Comments : Grab samples taken from a vareity of foodstuffs, some plastic
products and blood from 13 people. Randomness, relationships among or to
products, and distribution among sample population is unknown.
Summary : Analyses for DEHP and other phthalates were done in response to
literature reports of widespread environmental contamination (in Japan) by
phthalic acid esters.
SANPLING
Container preparation : A comment notes that “extremely careful pretreat-
ment” of equipment and solvents is essential for accurate analysis. No proce-
dure given.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : None.
Summary : No information on sampling.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Acetonitrile or ethyl ether extraction fol-
lowed by Florisil fractionation.
Recovery : Not reported.
Linear recovery : Not reported.
161
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Tomita et al. (1977)
Interferences : Not reported.
Limit of detection : Stated that “significant values for. . .DE]IP were
over.. .0.005 ppm.”
Problems : Not reported.
Instrument : GC/MS and GC/EC; column 2% DEGS-0.5% H 3 P0 4 ; other parameters
not specified.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Procedures given were very sketchy.
Summary : Florisil fractionation method and analyses by GC/MS and GC/EC
were used.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Data cannot be considered quantitative.
Summary : No identifiable quality assurance stated.
162
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Dibutyl- and Di-(2-ethylhyexy)phthalate in Fish
Williams (1973a), Ref. No. 76
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : “Fish from Canadian lakes and rivers were supplied by
Environment Canada; other samples purchased at local markets.”
Problems : Not reported.
Goal(s) : Preliminary survey of DBP and DEHP in fish available to
Canadian customers.
Comments : Twenty-one grab samples of fish collected.
Summary : Fish obtained by Environment Canada or from local markets.
SAMPLING
Container preparation : Not reported.
Collection procedure : Purchased at local markets and supplied from out-
side source.
Storage conditions : Canned fish at room temperature, others at -10°C.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Since the collection procedure and storage conditions used by
the “outside sources” (Environment Canada) were not reported, contamination of
the fresh fish is possible, and thus the analytical results may not reflect
the actual level in these fish.
Summary : Fish purchased at local markets and supplied by outside sources.
163
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Williams (1973a)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Acetonitrile partitioning, H 2 S0 4 cleanup of
petroleum ether extract, then silica gel.
Recovery : Spiked samples, 65 to 70% for DEHP, 60 to 65% for DBP.
Linear recovery : Not reported.
Interferences : Lipids.
Limit of detection : Background level from reagents, DEJIP = 15 ppb,
DBP = 10 ppb (based on 100-g fish sample).
Problems : Not reported.
Instrument : Two methods of detection: (1) GC/FID using two columns:
(a) 6 ft x 3.5 nun ID glass with 3% XE-60 and (b) 7 ft x 2 mm ID glass with
5% OV-101, and (2) GC/MS using 6 ft x 1/8 in. SS, 3% XE-60, Perkin-Elmer
(PE)-900 with. Hitachi Perkin-Elmer MS.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : An extended and “old fashioned” cleanup but identification
procedures good. Since background levels quantitated and overall recoveries
done at two levels with moderate recoveries (60 to 65%), data would seem to be
fairly reliable.
Summary : One hundred grams of fish sample chopped and macerated with hot
hexane. Subjected to liquid-liquid partitioning, acid-base cleanup, and other
silica gel cleanup. Quantitation using instrumentation given above. Reagent
blanks considered to be background level. Levels found at less than twice
background level reported as trace; other values corrected for background
level.
QUALITY ASSURANCE
Method blank : Used to establish background level.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
164
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Williams (1973a)
Replicates : Not reported.
Method verification : Two coluins for GC/FID and then GC/MS.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Since recoveries are only moderate, this method should not be
classified as strictly quantitative but rather as semiquantitative.
Summary : Quality assurance directed towards establishing background
level. An unknown number of spiked samples used to show recovery (60 to 65%).
Recoveries for both levels (0.1 to 0.5 ppm) not reported separately but rather
reported together as a range.
165
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E. PLASTIC PRODUCTS (FILM, PIPE, TUBING )
Eleven articles were reviewed for this matrix and are included in this
section.
SURVEY DESIGN
The overall design of most articles could not be easily determined.
Eight articles (2, 11, 36, 37, 38, 53, 57, and 75) appear to suggest that the
samples were collected on an opportunistic basis from items available or used
in laboratory experiments. Representativeness of these samples to its popu-
lation is therefore uncertain. The results reported in one article (45) were
used to support the presentation of a new analytical method. A study reveiw
article (62) and one article (56) describing a literature and patent search
with limited grab sampling were also included under this matrix.
SA}IPLING
In eight of the articles (36, 37, 38, 45, 53, 56, 57, and 62) no mention
was made of procedures to limit potential contamination. The collection of
vapors on a hood and a blank of that equipment was mentioned in article 2.
Although a cleaning procedure is described in article 11, the use of blanks
was not mentioned. Validity of the data could be questioned in all articles
except two but lack of other sampling information means that data are uncer-
tain.
ANALYS IS
Limited or no information was given in five articles (11, 38, 53, 56,
and 62). Article 57 provided an adequate method as indicated by high recovery
and low blank levels while the method in article 2 gave good recovery but var-
iable results. Article 37 indicated acceptable recoveries along with an ac-
ceptable method. A specific method capable of determining percent values was
given in article 45. A nonspecific detector was used in two articles (36 and
75).
QUALITY ASSURANCE
In five articles (2, 37, 38, 56, and 57) a method blank was used and
three articles (37, 56, and 57) also added a control sample. Other articles
did not mention the use of method blanks but did mention using controls (11),
duplicate samples (45), and method validation (53 and 62). Lack of method
blanks raises a question about validity of the data in these articles (1].,
45, 53, and 62) as does the reporting of little or no information in two arti-
cles (36 and 75).
166
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Thermal Degradation Products from PVC Film in Food-Wrapping Operations
Boettner and Ball (1980), Ref. No. 2
SURVEY DESIGN
Sampling sites : Not applicable.
Sampling plan : Not applicable.
Problems : Not reported.
Goal(s) : To test the levels of various compounds volatilized during cut-
ting of the PVC film by the hot-wire method and the cool rod method.
Comments : Five PVC film samples were supplied by Borden but only three
were used. Representativeness of these films to others is in doubt since
only one film source was studied.
Summary : PVC films supplied by Borden Chemical were surveyed for various
compounds volatilized during the cutting process. Supermarket conditions were
simulated.
SANPLING
Container preparation : Not applicable.
Collection procedure : Specially designed hood enclosed the film and cut-
ting wires. High boiling compounds were washed from the hood with solvents.
Volatile compounds collected “in an impinger, charcoal tube, or other sampling
device.
Storage conditions : Not applicable.
Stability demonstrated : Not applicable.
Field blanks : Hood blanks were generated.
Spiked blanks : Not applicable.
Problems : “Smoky” cuts were not reproducible.
Comments : All film from same company and cleanliness of the hood pose
problems of representativeness and contamination.
Summary : Five PVC films were obtained from Borden Chemical. No real
sampling involved.
167
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Boettner and Ball (1980)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not applicable.
Recovery : Hood rinse after known amounts of phthalates were vola-
tilized showed 80% recovery for DEHA and 77% recovery for DEHP.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/FID on 1% SE-30.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Results reported were corrected for percent recovery, film
thickness and width. Results were variable and cannot be considered quanti-
tative but only indicative of levels a person may be exposed to when cutting
PVC film.
Summary : PVC films were cut with a hot-wire C ”. 215°C) or a cool rod
(135°C) inside a specially constructed hood. The phthalates were collected
by rinsing th hood with 25 ml of ethanol. The ethanol volume was reduced to
1 ml and anlyzed by GC/FID.
QUALITY ASSURANCE
Method blank : Hood rinsed between cuts to ensure no sample carryover.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Micrograms per cut reported; relative standard
deviations to 100%.
Replicates : Three to nine runs for each film.
Method verification : Not reported.
168
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Boettner and Ball (1980)
Interlab verification : Not reported.
Problems : Some cuts were smoky and resulted in high levels; no apparent
way to minimize variations.
Comments : Method not very reproducible as shwon by number of smoky ver-
sus clean runs, and relative standard deviations of results. Variability of
results indicates results are semiquantitative at best. Repetition of test
runs only seems to show variability of method and does not necessarily give a
better average value of organics released during the cutting process.
Summary : Sampling hood rinsed between runs to ensure no carryover.
Replicate runs were made to obtain average values of phthalate released dur-
ing cutting.
169
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Final Report on Potential Health Hazards Associated with the Use of Plastic
Pipe in Potable Water Systems
Departments of Health Services and Industrial Relations, California (1980),
Ref. No. 11
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Unspecified number of samples collected at different dwell
times and flowing versus nonf lowing water.
Problems : Not reported.
Goal(s) : To determine the extent of health risks, if any, posed by the
use of plastic pipe systems in homes.
Comments : A static lab setup was used to simulate pipe exposure.
Summary : Potable water from PVC pipe was sampled for a variety of organic
pollutants.
SANPLING
Container preparation : Washed in detergent followed by rinses in tap
water, deionized water, and pesticide grade hexane. Baked > 1 hr at 400°C.
Collection procedure : Collected 1.65 liters of water in an “organic
free” graduated cylinder by opening a valve spout.
Storage conditions : Amber glass bottles stored at 4°C.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Spiked “samples” were used.
Problems : Not reported.
Comments : The sampling plan did not cover field blanks and therefore
does not permit assessment of contamination but only indicates changes in the
phthalate level.
Summary : Samples were collected in amber bottles washed in detergent
followed by rinses in tap and deionized water, then in pesticide grade hexane
and baked > 1 hr at 400°C.
170
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Departments of Health Services and Industrial Relations, California (1980)
ANALYS IS
Measurement procedure
Cleanup/fraction : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : DMP - 10 pg/liter; DBP - 10 pg/liter; BBP -
10 pg/liter; DEHP - 10 pg/liter; DOP - 10 pg/liter.
Problems : Not reported.
Instrument : Not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Detection limits were reported to be 10 pg/liter, but the ana-
lytical instrument used is not specified. The analytical method was not re-
ported and therefore cannot be assessed.
Summary : No cleanup was reported, nor was sample preparation reported.
Detection limit was 10 pg/liter.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Hot and cold tap water was collected prior to use.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
171
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Departments of
Comments:
Summary :
spiked samples
not reported.
Health Services and Industrial Relations, California (1980)
The QA information provided is of little value.
Little information reported on QA provisions. The use of
was mentioned, but the specific compounds or levels used were
172
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Plasticizers from Plastic Devices: Extraction, Metabolism, and Accumulation
by Biological Systems
Jaeger and Rubin (1970), Ref. No. 36
SURVEY DESIGN
Sampling sites : Based on exposure to plastic tubing and storage devices.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : To determine the extent of extraction, metabolism, and accumu-
lation of plasticizers from plastic devices by biological systems.
Comments : Although not stated, single grab samples appear to have been
collected from tubing and other plastic apparatus used in a perfused liver
experiment, then from other plastic products used in medicine, e.g., blood
bags.
Summary : Limited survey of plasticizers extracted from plastic devices
by biological systems. Accumulation and metabolism of the plasticizers was
also examined.
SAMPLING
Container preparation : Not reported.
Collection procedure : Not applicable.
Storage conditions : Not applicable.
Stability demonstrated : Not applicable.
Field blanks : Not applicable.
Spiked blanks : Not applicable.
Problems : Not reported.
Comments : Procedures used to control/eliminate contamination not stated.
Summary : No sampling was done p se. Outdated whole blood was pur-
chased from a nearby blood bank. Human tissue was obtained from patients at
Johns Hopkins Hospital. White rat tissue and blood were obtained from Johns
Hopkins Hospital.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Dowex-1 for blood extract; also used TLC.
173
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Jaeger and Rubin (1970)
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : Gilford spectrophotometer at 260 nm or 280 run.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Analytical procedures not well-defined. No procedures were
given for any kind of tissue. Lack of method description for tissue and gen-
eral mode of detection used for blood analysis leaves ample room for criticism
of results.
Summary : Chloroform extracts of neutral and acidified blood were applied
to TLC plates or Dowex-1. The eluent was spectrophotometrically examined for
phthalates.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Credibility of the data is in doubt because of the minimal QA
measures reported.
Summary : Minimal quality assurance measures were reported; i.e., no
blanks or spiked samples were mentioned.
174
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1igration of Phthalate Ester Plasticizer from Polyvinyl Chloride Blood Bags
into Stored Human Blood and Its Localization in Human Tissues
Jaeger and Rubin (1972), Ref. No. 37
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Not defined but samples were collected from 6 units
of stored blood, unspecified number of fresh blood and urine samples, 13
autopsy subjects who had received blood, and 7 autopsy subjects who had not.
Problems : Not reported.
Goal(s) : Determination of DEHP in blood stored in PVC bags.
Comments : Grab samples taken from transfused and nontransfused subjects.
Although not stated, the samples appear to have been collected on an oppor-
tunistic basis.
Summary : DEHP found in stored blood, and patient’s blood who had received
transfusions. DEHP metabolites also found.
SAMPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : The problem of contamination is not mentioned. Since no col-
lection procedures were mentioned addressing this problem, the results should
be considered qualitative.
Summary : Blood sampled from patients, and after storage and/or transfu-
sion to determine source of phthalates in patient’s blood.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Blood lyophilized, chloroform extract washed
with saline. Extract dried, reconstituted with methanol, centrifuged, dried,
reconstituted with hexane.
175
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Jaeger and Rubin (1972)
Recovery : 60 to 90%.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : Not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Phthalic acid and other DEHP metabolites also analyzed.
Summary : GC column: 3% SE-30 on Gas Chrom Q. No instrument or detector
mentioned.
QUALITY ASSURANCE
Method blank : Ranged from 20 to 60 pg.
Control sample : Fresh blood in glass.
Reference material : Not reported.
Precision and accuracy : Reproducibility ±10%.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Blood values were subtracted from tissue values.
Summary : Assay of samples included blood not in contact with PVC, blood
in contact with PVC for increasing time spans, metabolites found in urine,
fat, and other tissues.
176
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Extraction, Localization, and Metabolism of Di-2-ethylhexyl Phthalate from
Medical Devices
Jaeger and Rubin (1973a), Ref. No. 38
SURVEY DESIGN
Sampling sites : Based on possible exposure to DEHP.
Sampling plan : Stepwise investigation after DE1{P found in a liver per-
fusion system. Grab samples of tubing, blood bags, rat whole-body homogenate,
rat liver and lung were collected and analyzed.
Problems : Not reported.
Goal(s) : Determination of phthalate levels in various types of fluids
and tissues subjected to DEHP and other plasticizers.
Comments : Logical progress of studies. Each study based on results of a
previous study. Grab samples taken in each case.
Summary : Original experiments designed to determine levels of DEHP in
blood in a liver perfusion system. Additional experiments performed to deter-
mine levels in blood and various tissues exposed to DEHP by virtue of blood
transfusions, operations, or hemodialysis. Attempts were also made to deter-
mine metabolites.
SAMPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : In one part of the study different temperatures were
used to determine effect of temperature on migration rate of DEHP from tubing.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : None.
Summary : Sampling methods not discussed.
ANALYSIS
Measurement procedure
Cleanup/fractionation : TLC.
Recovery : Not reported.
177
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Jaeger and Rubin (1973a)
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : TLC.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Analytical methods not explained. Purity of solvents and
reagents used (if any) not reported. Lack of reporting recoveries and ana-
lytical methods indicates that any results reported should be viewed as unsub-
stantiated.
Sununary : Analysis method for liquids reported as TLC of an unknown or-
ganic extract. Tissue analyzed by unknown method.
QUALITY ASSURANCE
Method blank : Used for liquid analysis of perfusion system and in tissue
analysis (20 to 60 pg DEHP).
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : ±10% for tissue analysis.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Quality assurance measures skimpy at best.
Summary : Method blanks used in the analysis of the liquids in the liquid
perfusion system and in the tissue analysis. No discussion of use of spiked
samples to determine recoveries.
178
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Qualitative and Quantitative Gas Chromatographic Determination of Plasticizers
in Polyvinyl Chloride
Lerche and Moerch (1973), Ref. No. 45
SURVEY DESIGN
Sampling sites : Not applicable.
Sampling plan : Grab samples of in-house plastic products.
Problems : Not applicable.
Goal(s) : Determination of phthalate levels by a gas chromatographic
technique in some commonly used pharmaceutical articles.
Comments : This is a limited in-house survey of pharmaceutical articles
used at the Royal Danish School of Pharmacy. Grab samples used to provide
data to support a new chromatographic technique.
Summary : Commonly used pharmaceutical articles were tested for phthalate
content.
SAMPLING
Container preparation : Not applicable.
Collection procedure : Not applicable.
Storage conditions : Not applicable.
Stability demonstrated : Not applicable.
Field blanks : Not applicable.
Spiked blanks : Not applicable.
Problems : Not reported.
Comments : None.
Summary : Pharmaceutical articles were presumably obtained from in-house
sources and were to be tested for phthalate content.
179
-------
Lerche and Moerch (1973)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Method phthalate values were compared against manufac-
turers’ specification for a particular PVC article.
Linear recovery : Not applicable.
Interferences : Not reported.
Limit of detection : 0.05 mg/100 ml in the extract (i p1 mi) =
0.5 ng. 0.1% w/w for articles.
Problems : Not reported.
Instrument : GC/FID on 1.5 m x 4 mm glass, 3.8% OV-1 (and 3.8% OV-17).
Linear response : Not reported.
Stability of response : RDS = 2.9% for tubing III.
Problems : Front end of column sometimes became discolored from de-
posits of PVC; renewed as needed.
Comments : Method 3 found to be most accurate--analyst dealing with
percent levels of di “isononyl” phthalate (38%). Comparison of methods adds
credibility to data generated.
Summary : Three methods of analysis were compared: Ci) extraction
(Soxhlet) with ether, ether removed, and residue weighed (plasticizer); (2)
dissolved in T}EF and methanol added to precipitate PVC, residue weighed for
PVC, and solution analyzed by GC for phthalates; and (3) dissolved in TUF and
analyzed by GC for phthalates.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Dipentylphthalate used as an internal standard.
Precision and accuracy : For method 3: maximum difference between dupli-
cates was 0.8% of their PVC compound.
Replicates : Duplicates for every sample.
180
-------
Lerche and tloerch (1973)
tiethod verification : Use of two analytical columns added credibility to
identification of various phthalates.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Although use of blanks not mentioned, the levels of phthalates
found were usually so high that it would be unlikely they were caused by con-
tamination.
Summary : Duplicates used for every sample as well as two analytical col-
umns to identify the various phthalates add considerable credibility to the
results reported.
181
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Loss of Phthalic Acid Esters from Polyvinyl Chloride Tubing in Various Fluids
Mueller and Bradley (1980), Ref. No. 53
SURVEY DESIGN
Sampling sites : Not applicable.
Sampling plan : Not applicable. -
Problems : Not reported.
Goal(s) : Study to determine quantities of phthalates (DBP and DEHP) mi-
grating out of U.S. -manufactured PVC dairy tubing into water, milk, and aque-
ous solutions of chlorinated alkaline cleaners and sanitizers under simulated
use conditions.
Comments : Only one type of tubing used in experiments. Correlation
between this one tubing and other approved tubing is therefore uncertian.
Summary : Experiment designed to examine phthalate migration from PVC
dairy tubing into water, milk, and various cleaners at various temperatures.
SANPL ING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not applicable.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Procedures to minimize or determine background DEHP not de-
tailed; thus data should be viewed with caution.
Summary : Duplicate 10-cm squares of Tygon tubing were submerged for con-
secutive times in covered beakers containing 500 ml of the solution to be
tested. Immersion periods were chosen to represent an average daily exposure
time of dairy tubing in actual use.
182
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Mueller and Bradley (1980)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Fiorisil for all samples; also acetonitrile
partitioning for milk samples.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not identified but removed by Florisil.
Limit of detection : “ 1 ppb for 500-mi sample.
Problems : Not reported.
Instrument : HP 5700A GC/EC with 5% OV-1.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Purity of petroleum ether not discussed; nor was preparation
of sodium sulfate or Florisii. These facts leave doubt as to possibility of
contamination. Cutting up the tubing and working it in the fluids, however,
does not really represent normal exposure of the solutions to PVC tubing; thus
the data presented will not reflect normal exposure by consumption of the milk.
Summary : Solutions under study were extracted three times with petroleum
ether, the extrct dried with sodium sulfate, subjected to Florisil cleanup
(and acetonitrile partitioning if necessary), and analyzed by GC/EC.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Each sample had a duplicate.
Method verification : Not reported.
Interlab verification : Not reported.
183
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Mueller and Bradley (1980)
Problems : Not reported.
Comments : Results compared against Wildbrett’s (1973), reference No. 75,
findings in German PVC tubing. Data generated in the present study can be
viewed only as qualitative and only as a confirmation of the fact that phthal-
ates leach from dairy tubing.
Summary : With the exception of duplicate samples, few quality assurance
measures were taken in terms of method blanks or spiked samples.
184
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Preliminary Survey of Chemical Composition, Contamination and Associated
Health Hazard of Plastic Pipe for Potable Water Supply
Reid et al. (1980), Ref. No. 56
SURVEY DESIGN
Sampling sites : Pipe being considered for use in California for potable
water supply.
Sampling plan : Not reported.
Problems : Excessive number of possible compounds, which change even with
a given pipe or a single manufacturer.
Goal(s) : To assess the degree of public health hazard associated with
use of plastic pipe to transport potable water.
Comments : Noted to be a preliminary, not an all-inclusive survey and
analysis program. This study is a combination of a literature survey and the
“Montgomery report,” the purpose of which is to present information to a state
agency pointing out the hazards of licensing the use of plastic pipe in pota-
ble water systems. The results of this study should be viewed with caution as
it may be biased. Note: See also Ref. No. 62.
Summary : The study was designed to identify kinds of materials present
in plastic pipe and associated health hazards, through a literature and patent
survey, and extremely limited analysis of pipe and water samples. Study was
performed for Local 467 Plumbers and Steamfitters Union, AFL-CIO.
SAMPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : DEHP has half-life of over 1 year in water.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Insufficient samples taken to allow statistical significance.
Comments : PVC, CPVC, and ABS samples analyzed. No large scale tests of
water contamination ever done. Water through PVC and CPVC only. Erratic sam-
ple selection, large number of treatments.
Summary : Water samples involved three types of leach tests from two
pipes, three water types, two temperatures, two pipe joint cements, two joint
qualitites. “Samples” were prepared in the lab, not taken from “real” situa-
tions.
185
-------
Reid et al. (1980)
ANALYS IS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Qualitative only.
Linear recovery : Not reported.
Interferences : Solvent--large numbers of similar compounds diffi-
cult to resolve.
Limit of detection : Not reported.
Problems : Statistical validation of results was impossible partially
because of complexity of sampling situations.
Instrument : GC/MS (same as for priority pollutants).
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : DEHP found in PVC, CPVC. No method of any kind mentioned;
some suggestion that DEHP may be present in water as micells.
Summary : DEIIP more likely leached from older pipe; many analysis prob-
lems.
QUALITY ASSURANCE
Method blank : Yes, but results not reported.
Control sample : Used, but frequency not mentioned.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Used, but insufficient.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
186
-------
Reid et al. (1980)
Comments : Variation in results not accounted for. DEHP found as high as
246 pg/liter. DEHP and DBP levels fluctuated sharply; absence of pattern sug-
gests analytical difficulty.
Summary : DEIIP present, but in widely fluctuating amounts. The entire
program suggests DEHP will present analytical difficulties.
187
-------
Di-2-ethylhexyl Phthalate (DEHP) Content of Blood Components Stored in Plastic
Bags
Sasakawa and Mitomi (1978), Ref. No. 57
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : The contents of an unspecified number of blood storage
containers (bags and bottles) were sampled for DEIIP levels.
Problems : Not reported.
Goal(s) : Determination of DEHP levels in blood stored in plastic bags
and correlation to patients who had undergone massive transfusions.
Comments : Very limited survey; can be considered a preliminary assess-
ment of DEHP exposure through blood transfusions. Grab samples taken from
blood bags and control bottles.
Summary : DEHP elevated in patients transfused with blood stored in
plastic.
SAMPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Blood stored at 5°C, plasma at -20°C, anticoagulants
at ambient--none verified.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Sampling restricted to patients in a Japanese hospital; plas-
tic bags and anticoagulant under examination were from a single manufacturer.
No mention was made of procedures designed to limit potential contamination;
therefore, validity of the data is uncertain.
Summary : Blood collected from patients who had undergone massive trans-
fusions from “plastic bag” stored blood, from glass bottles, and from patients
who had no transfusions.
188
-------
Sasakawa and Mitoini (1978)
ANALYSIS
Measurement procedure
Cleanup/fractionation : After extraction with MeOH:CHC1 3 (1:2),
silicic acid column used with 4% ethyl ether/hexane as eluant.
Recovery : 83 to 100% recovery for whole blood spiked with DEIIP.
Blood used for recoveries was stored in glass bottles and contained less than
0.01 pg/mi DEHP.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : 0.1 pg/mi for method.
Problems : Not reported.
Instrument : GC/FID, 4 mm x 2 m glass with 5% SE-52.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Chromatography and detection of DEHP not discussed in depth.
Use of GC/PID limited sensitivity of method.
Summary : DEHP extracted from matrices by MeOH:CHC1 3 and subjected to
silica gel column cleanup (except for anticoagulants). Determination of DEHP
by GC/FID. Used di-n-octylphthalate as internal standard. Recoveries of 83
to 100% are considered good for this matrix, and the low blank levels are also
significant.
QUALITY ASSURANCE
Method blank : Blood stored in glass bottles used as blanks.
Control sample : Spiked whole blood samples from blood stored in glass
bottles used for method recovery.
Reference material : Di-n-octylphthalate used as an internal standard.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
189
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Sasakawa and Mitomi (1978)
Interlab verification : Not reported.
Problems : Not reported.
Comments : Quality assurance limited to recoveries from spiked blood
stored in glass bottles. The use of di-n-octylphthalate (DOP) as an internal
standard raises a question about the accuracy of the data because no mention
was made about blank of this compound.
Summary : Blood stored in glass bottles served as blanks and used for
spiked recoveries. An internal standard, DOP, was used. NOTE: Radioactive
‘ 4 C-labe].ed DEIIP used for determination of where DEHP stored in blood (red
blood cells or plasma). DEHP mostly associated with plasma -lipoprotein.
190
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Presence of Chemicals Associated with PVC/CPVC Plastic Pipe in Potable Water
Soderquist (1980), Ref. No. 62
SURVEY DESIGN
Sampling sites : Newly installed PVC pipes to test for methyethyi ketone,
tetrahydrofuran, dimethyforinamide, and cyclohexanone.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : From California Analytical Laboratories, Inc., report of May 15,
1980: Determination of levels of four contaminants in water from PVC pipe.
Comments : This paper is a study review.
Summary : Water in newly constructed house with PVC plumbing was tested
for various organic contaminants.
SAMPLING
Container preparation : Not reported.
Collection procedure : Grab samples from outside water spigots on house.
Storage conditions : Refrigeration.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Sampling not specifically designed for phthalates. Equilibra-
tion of water in PVC pipes probably not representative of conditions encoun-
tered during normal use.
Summary : Grab samples were taken in 40-mi VOA vials from three different
“hose bibs” in a newly constructed house.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
191
-------
Soderquist (1980)
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/FID on SP-2250 and GC/EC on pesticide colunui.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Extraction procedure not fully described. Unknown extraction
efficiencies and lack of field blanks cast considerable doubt on low level
findings ( 100 ppb).
Summary : CS 2 and toluene extracts of water samples were analyzed for
phthalate esters by GC/FID and GC/EC.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : GC/MS verification of the presence of DEHP.
Interlab verification : Not reported.
Problems : Author realized the sample vials and sampling protocol not
intended for phthalate analysis.
Comments : Report indicates that further work would be necessary to con-
firm the validity of the plithalate numbers. Results can be considered as only
qualitative.
Summary : No quality assurance measures were reported other than GC/MS
identification of DEHP. Report indicates that the study was not designed to
look at phthalates.
192
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Diffusion of Phthalic Acid Esters from PVC Milk Tubing
Wildbrett (1973), Ref. No. 75
SURVEY DESIGN
Sampling sites : Not applicable.
Sampling plan : Not applicable.
Problems : Not applicable.
Goal(s) : Not applicable.
Comments : Three types of tubing from unspecified source(s) may not be
representative of all PVC tubing.
Summary : No design discussed.
SAMPLING
Container preparation : Not applicable.
Collection procedure : A flow-through device used to pass milk through
PVC tubing.
Storage conditions : Not applicable.
Stability demonstrated : Not applicable.
Field blanks : Not applicable.
Spiked blanks : Not applicable.
Problems : Not reported.
Comments : The three types of tubing tested cannot be considered to repre-
sent all PVC tubing in use at that time, nor can the data generated be consid-
ered monitoring data.
Summary : Three types of tubing were tested.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Milk samples hydrolyzed, then extracted with
petroleum ether. Extract dissolved in MeOH, milk fat separated by freezing,
and remaining phthalates and fat residues saponified with lye, reextracted into
EtOH, and phthalate concentration determined at 284 rim. For cleaning solutions
and water, samples were acidified, extracted with petroleum ether, solvent
exchanged into EtOH, and analyzed spectrophotometrically.
Recovery : Not reported.
193
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Wildbrett (1973)
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : Spectrometer, 284 run.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : The general mode of detection would allow for substantial oc-
currences of interferences and would not identify specific phthalates.
Summary : General nonspecific spectrophotometric method for determination
of phthalates.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : The reporting of milligram levels of total phthalates in the
ethanol extracts of 100 ml of test solution (milk, cleaning solution, etc.)
indicates that any blank levels present would probably not have been detected.
The lack of extraction recoveries casts considerable doubt as to the accuracy
of the data generated for migration.
Summary : Blanks and recoveries not mentioned in the article. Method
used for high parts per million levels.
194
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F. SEDIMENT
This secton presents the reviews on 12 articles designated for inclusion
in this matrix.
SURVEY DESIGN
The overall design for the selection of sampling points for five arti-
cles (10, 20, 33, 58, and 59) was not stated but most were inferred to be
grab samples. Selected results were presented in three articles (21, 24, and
27), one of which (24) was a method development. The dispersion of effluent
from point sources was monitored in two articles (4 and 34). An untested
mass balance model was given in article 25. A literature review (71) gave a
synopsis of the persistence of selected organics in a lake and its influents.
SAMPLING
The collection procedure was described in seven articles (4, 10, 24, 33,
34, 58, and 59) but no mention was made of determining the cleanliness of the
equipment except for one article (10). No information was given in three
articles (20, 27, and 71) while a very brief outline was presented in article
27. One article (21) presented a description of procedures to reduce contami-
nation.
ANALYSIS
Seven articles (4, 10, 24, 33, 34, 58, and 59) presented details on
methods that appear in principle to be adequate. Four of these (4, 24, 33,
and 59) addressed the problem of interferences while three (24, 58, and 59)
presented recovery data. Information needed to assess the methods was minimal
in two articles (25 and 27). No information was given in another three arti-
cles (20, 21, and 71).
QUALITY ASSURANCE
Two articles (10 and 59) stated the use of method blanks and one of them
(59) also included method verification. Another article (58) added interlab
verification but omitted mention of any method blanks. No information was
given in five articles (4, 20, 25, 27, and 71). Assessing four articles (21,
24, 33, and 34) was not possible because of minimal information.
195
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Persistant Organic Compounds from a Pulp Mill in a Near-Shore Freshwater
Environment
Brownlee and Strachan (1976), Ref. No. 4
SURVEY DESIGN
Sampling sites : The majority of the sites near the northern shore of
Lake Superior were selected to be outside the area influenced by the effluent
plume.
Sampling plan : Each of the 15 stations were sampled at least once for
water and seston. A limited number of sediment samples were collected (ap-
parently four).
Problems : Not reported.
Goal(s) : Determine if any organic compounds present in the mill effluent
could be detected at significant distances (up to 5 km) from the effluent out-
fall.
Comments : The loction of sites for the collection of grab samples was
influenced by the effluent plume movement. Other sampling criteria, e.g.,
temporal or replicate sampling, was not discussed.
Summary : The dispersion of organics from the mill effluent was monitored
by sampling at various distances from the outfall.
SAMPLING
Container preparation : Not reported.
Collection procedure : Water aspirated using Teflon and s.s. apparatus.
Pressure filtered through precombusted (450°C) Nucleopore glass fiber filters
in a Teflon ad s.s. apparatus using N 2 purified through molecular sieves. A
portion extracted the same day. Seston retained on Nucleopore glass fiber
filters from water collection. Sediment collected by Shipek sampler.
Storage conditions : Water extracted same day as collected. Seston placed
in “clean” containers and stored frozen. Sediment stored frozen.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : With the exception of field blanks or spikes and a procedure
for cleaning equipment, the sampling seems quite adequate.
196
-------
Brownlee and Strachan (1976)
Summary : Water was collected using Teflon and s.s. apparatus and ex-
tracted on day of collection. Seston retained on a Nucleopore filter while
sediment was collected with a Shipek sampler; both sample types stored frozen.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Water made saline with precombusted (450°C)
sodium chloride and extracted with glass—distilled CC1 3 for 22 hr. Reduced to
small volume and stored in a “clean, sealed ampoule.” Taken to dryness at
60°C, methylated with diazomethane in ether-methanol. Solvent removed at 60°C.
Methylated extracts stored at 4°C in sealed ampoules until analysis. Seston
thawed and homogenized with glass-distilled CHC1 3 :CH 3 OH (2:1 v/v). Refluxed
1 hr and filtered. Made acidic with HC1, taken to dryness, methylated, and
stored under same conditions as water samples. Sediment was freeze-dried
and extracted 24 hr with glass-distilled Cd 3 . Extracts treated same as
water extracts.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Presence of ethyl esters of fatty and resin acids in
derivatized extracts. Artifacts of extraction procedure. Dioctylphthalate
and methyl ketodehydroabietate nearly coelute.
Limit of detection : 0.1 pg/liter in H 2 0, 10 pg/g dry weight of
seston, 0.1 pg/g dry weight of sediment.
Problems : Not reported.
Instrument : GC/FID, GC/MS.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : In view of the lack of reported recoveries and the mentioned
interferences this section is of questionable value.
Summary : Due to the nature of the study no attempt was made to optimize
for phthalates. Instrument response linearity was not reported. No attempt
appears to have been made to determine the recoveries of the compounds re-
ported.
197
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Brownlee and Strachan (1976)
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Apparently not used for phthalates.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Verification was by GC/MS.
Interlab verification : Not reported.
Problems : Not reported.
Comments : QA section was of no value.
Summary : No quality assurance provisions, blanks, spikes, or replicates
were reported.
198
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Phthalic Acid Esters in the Marine Environment
Corcoran and Curry (1978), Ref. No. 10
SURVEY DESIGN
Sampling sites : Lower Mississippi River (11 sites) and northeast Gulf
of Mexico (6 sites).
Sampling plan : Fall of 1975.
Problems : Not reported.
Goal(s) : Determining the distribution and concentration of various com-
mon phthalic acid esters.
Comments : The design involved collection of grab samples from river and
near—shore waters. Criteria not delineated for selection of sampling sites.
Summary : Samples of water, particulate matter, and sediment were col-
lected in 1975 from the lower Mississippi River and northeast Gulf of Mexico
to determine the distribution and concentration of various phthalic acid
esters.
SAMPLING
Container preparation : Cleaned with detergent and water, rinsed with
distilled water, and heated to 600°C. Extracted and checked by GC.
Collection procedure : Water collected with all-metal Niskin type sampler.
Samples taken of surface, mid—depth, and close to the bottom.
Storage conditions : Not reported for water. Glass fiber filters stored
frozen.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : The sampling method seems quite adequate and thus the samples
should be representative of the environment.
Summary : After cleanup, glassware and aluminum foil were extracted and
checked by GC for phthalate levels. Water samples were taken at the surface,
mid-depth, and close to the bottom using an all-metal Niskin type sampler.
199
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Corcoran and Curry (1978)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Water was filtered through glass fiber filters,
passed through XAD-2 resin. Eluted from XAD-2 with diethyl ether, dried, and
extracted with hexane. Filters extracted with hexane and cleaned up on Florisil.
Recovery : 98% for extraction from XAD-2 resin “with respect to the
various simple diesters of phthalic acid.”
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/EC.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : The extraction method is good based on high recoveries but
additional validation results should have been reported so that the entire
analytical method could be assessed.
Summary : Water samples were filtered through glass fiber filters, passed
through XAD-2 resin. Eluted from XAD-2 with diethyl ether, dried, and ex-
tracted with hexane. Glass fiber filters were extracted with hexane and
cleaned up on Florisil. Analysis was by GC/EC. Recovery was 98%.
QUALITY ASSURANCE
Method blank : All glassware was precleaned; “no detectable levels were
observed.”
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
200
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Corcoran and Curry (1978)
Ilethod verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : The method blanks are indicative of minimal contamination, but
the accuracy and verification of the data are unknown.
Summary : Glassware and aluminum foil was extracted after cleaning. No
detectable levels were observed.
201
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Concentration and Fluxes of Phthalates, DDTs, and PCBs to the Gulf of Mexico
Giam et al. (1976a), Ref. No. 20
SURVEY DESIGN
Sampling sites : Thirty—five stations in the Mississippi River Delta and
the Gulf of Mexico.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : To analyze selected samples from the Gulf of Mexico for
phthalates.
Comments : This report is concerned mainly with the analytical results
and their significance. Criteria used to select sampling stations is un-
known. Apparently grab samples were collected to assess phthalate loading
in the Gulf.
Summary : The goal of this project was to analyze selected samples from
the Gulf of Mexico for phthalates and to assess the significance of the data.
Th Mississippi River accounts for only one-fourth of the total DEHP loading.
‘ t The origins of the remaining inputs have not yet been determined.”
SAMPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : See other Giam articles for procedures.
Summary : No information was provided on sampling methods.
202
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Giam et al. (1976a)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : 0.1 ng/g phthalates.
Problems : Not reported.
Instrument : Not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : See other Giam articles for procedures.
Summary : No information was given concerning the analytical procedures.
The detection limit for phthalates was reported as 0.1 ng/g.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : None.
Summary : No QA information was reported as this was a discussion of
published data.
203
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Problems in Analysis of Organic Pollutants in Open-Ocean Samples
Giam et al. (1976b), Ref. No. 21
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : To propose methods for very low background sampling and analy-
sis, as well as for evaluation of procedures.
Comments : Design not part of report. Selected results on 10 biota,
9 water, and 6 sediment samples were reported.
Summary : Paper proposed methods for very low background sampling and
analysis, as well as for evaluation of procedures for biota, sediment, and
water.
SAMPLING
Container preparation : Glass and metal cleaned with detergent, water,
solvent, and heat. Aluminum foil heated to 320°C. XAD-2 resin extracted.
Collection procedure : Biota collected by hook and line or diving.
Plankton collected with nets. Sediment collected with corers. Water with
XAD-2 column.
Storage conditions : Biota, frozen. Plankton and sediment, precleaned
Mason jars with aluminum foil-lined caps.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Recommended use of spiked samples.
Problems : Not reported.
Comments : The sampling procedures recommended are very good. Emphasis
is on reducing possible sample contamination.
Summary : Recommends cleaning glass and metal with detergent, water, sol-
vent, and then heating. Recommends heating aluminum foil to 320°C overnight
and solvent extraction with XAD-2 resin. Also recommends use of spiked
samples.
204
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Giam et al. (1976b)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Proposes thorough cleaning of equipment but
does not report method for sample cleanup.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : 25 ng DBP and 50 ng DEIIP.
Problems : Not reported.
Instrument : Not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Analytical method not reported.
Summary : Analytical procedure covers only cleaning of glassware and
equipment.
QUALITY ASSURANCE
Method blank : Recommends use of method blanks.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Mentioned “satisfying” results.
Comments : The discussion of QA procedures is somewhat minimal. The rec-
ommended procedure for minimizing contamination in blanks is quite good.
Summary : Paper recommends procedures for minimizing contamination.
205
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Trace Analyses of Phthalates (and Chlorinated Hydrocarbons) in Marine Samples
Giam et al. (1976e), Ref. No. 24
SURVEY DESIGN
Sampling sites : Gulf of Mexico.
Sampling plan : Selected results reported in 10 biota, 9 water, 6 sedi-
ment samples and some laboratory materials (e.g., teflon, Na 2 SO 4 , etc.).
Problems : Not reported.
Goal(s) : To analyze marine samples for phthalates and chlorinated hydro-
carbons.
Comments : Origin of samples given as the Gulf of Mexico. Grab samples
inferred to have been collected.
Summary : The purpose of this paper was to report a procedure for the
analysis of marine biota, water, and sediment. No design was reported.
SAMPLING
Container preparation : Equipment cleaned with detergent, rinsed with
water and acetone, heated to 320°C for 10 hr.
Collection procedure : Water aspirated through precleaned copper tubing
into a glass carboy, then passed through Amberlite XAD-2 resin.
Storage conditions : Biota at or below 0°C. Others not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : The sampling procedure should have yielded samples with a mm-
imum of phthalate contamination.
Summary : Samples were collected in containers cleaned with detergent,
rinsed with water and acetone, and heated to 320°C. Water samples were passed
through XAD-2 resin column. Biota samples were stored at or below 0°C.
206
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Giam et al. (1976e)
ANALYSIS
Ileasurement procedure
Cleanup/fractionation : Biota macerated, extracted with acetonitrile,
methylene chloride-petroleum ether. Water eluted with acetonitrile and ex-
tracted with methylene chloride-petroleum ether. Sediment extracted with ace-
tonitrile, methylene chloride-petroleum ether. All through Florisil.
Recovery : From XAD-2 - DMP (abbreviation not specified): 79.8 to
85.7%; DBP: 94.1 to “ 100%; DEHP: 88.5 to 97.3%.
Linear recovery : Not reported.
Interferences : By GC: DBP and Aroclor 1254 interfere with each
other, and DEHP and Aroclor 1260 interfere with each other.
Limit of detection : 5 ng DEHP = 50% full-scale deflection.
Problems : Coelution with Aroclors.
Instrument : GC/EC. Biota: 1.8 m x 0.64 cm OD glass, 3% SE-30 on Gas
Chrom Q (100/120); water and sediment: 1.8 m x 0.64 cm OD, 3% SE-30 on
Chromosorb WHP (100/120); confirmation: 1.8 m x 0.64 cm OD, 1.5 % SP-2250
and 1.95% SP-2401 on Supelcon AW-DMCS (100/120).
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : The analytical procedure seems quite acceptable based on the
recovery values reported.
Summary : Samples were extracted with acetonitrile, methylene chloride-
petroleum ether, and cleaned up on a Florisil column. Recoveries of phthal-
ates were in the range 79 to 100%. Analysis was by GC/ECD with 5 ng DEHP
yielding 50% full-scale deflection.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
207
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Giam et al. (1976e)
Replicates : Not reported.
Method verification : GC/EC using a different column.
Interlab verification : Not reported.
Problems : Not reported.
Comments : The oniy quality assurance provisions reported were procedures
to minimize background in blanks. With the addition of replicate samples and
spiked blanks the method could be better evaluated.
Summary : Procedures given to minimize background in sample blanks.
Verification by GC/EC using a different column. DEIIP levels of laboratory
items reported.
208
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Estimation of Fluxes of Organic Pollutants to the Marine Environment -
Phthalate Plasticizer Concentration and Fluxes
Giam (1977), Ref. No. 25
SURVEY DESIGN
Sampling sites : Not applicable.
Sampling plan : Not applicable.
Problems : Not applicable.
Goal(s) : Develop a mass balance model for fluxes of DEHP.
Comments : The mass balance model was developed using a confirmation of
data and assumptions. Author states that atmospheric input to the Gulf was
the most important route but cautions that “direct field measurements are
important.”
Summary : This paper deals primarily with a mass balance model for es-
timation of fluxes of DEIIP in the Gulf of Mexico. Sampling and analysis as
in reference 27.
SANPLING
Container preparation : Not reported.
Collection procedure : Water was solvent extracted or passed through XAD-2
resin. Sediment with metal coring device; biota by hook and line or trawl.
Air through columns of Florisil or polyurethane foam.
Storage conditions : Biota and sediment frozen.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : This section only briefly outlines the sampling method and
is of limited value.
Summa y : Water samples were solvent extracted on site or adsorbed on
XAD-2 resin. Biota samples were collected by hook and line or trawl. Sedi-
ment samples were collected with a metal coring device. Air was adsorbed on
Florisil or polyurethane.
209
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Giam (1977)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Extraction with organic solvents, separation
by column chromatography.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/EC; column not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : This section lacks enough information to assess its value.
Summary : Samples were extracted with organic solvents, cleaned up by
column chromatography, and analyzed by GC/EC.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Chemical derivatization.
Interlab verification : Not reported.
Problems : Not reported.
Comments : None.
Summary : No QA data of significance reported.
210
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Phthalate Esters Plasticizer: A New Class of Marine Pollutant
Giam et al. (1978a), Ref. No. 27
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Results were reported on samples collected from the
Mississippi Delta (36), Gulf Coast (19), Open Gulf (10), Gulf of Mexico (28),
and North Atlantic (15).
Problems : Not reported.
Goal(s) : To analyze for phthalate esters and chlorinated hydrocarbons in
air, water, sediment, and biota samples from predominately the Gulf of Mexico.
Comments : Basically same information as other articles by Giam. Grab
samples apparently collected.
Summary : The purpose of the project was to analyze for phthalate esters
and chlorinated hydrocarbons in air, water, sediment, and biota samples pre-
dominately from the Gulf of Mexico.
SAMPLING
Container preparation : Not reported.
Collection
Water extracted
line or trawl.
procedure: Sediment collected with metal coring devices.
directly or adsorbed on XAD-2. Biota collected with hook and
Air adsorbed on Florisil or polyurethane foam.
Storage conditions : Sediment and biota frozen.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : This section is too brief to be of value.
Summary :
device. Biota
or adsorbed on
ment and biota
Sampling methods are brief. Sediment collected by metal coring
collected by hook and line or trawl. Water extracted directly
XAD-2. Air adsorbed on Florisil or polyurethane foam. Sedi-
samples frozen.
211
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Giam et al. (1978a)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Extraction with organic solvents. Cleanup
by column chromatography.
Recovery : “90% or better.”
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Instrument : GC/ECD, column not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Too little information provided to properly assess this section.
Summary : Samples were extracted with organic solvents and cleaned up by
column chromatography. Analysis was by GC/EC. Recoveries of “90% or better”
were mentioned as well as “background values of 50 ng.”
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Chemical derivatization.
Interlab verification : Not reported.
Problems : Not reported.
Comments : None.
Summary : Appropriate QA information was not provided.
212
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Identificaiton of Specific Organic Compounds in a Highly Anoxic Sediment by
Gas Chromatography-Mass Spectrometry and High Resolution Mass Spectrometry
Mites and Biemann (1975), Ref. No. 33
SURVEY DESIGN
Sampling sites : Sample collected from a section of the river with
little if any water column mixing.
Sampling plan : Samples collected from the Charles River beneath the
Harvard Bridge.
Problems : Not reported.
Goal(s) : Present further data on the Charles River system.
Comments : Design was based on grab sample collection from a single point
in the river.
Summary : The study was designed to present data on organics in sediment
in the Charles River system.
SAMPLING
Container preparation : Not reported.
Collection procedure : Coring device was a weighted brass tube with a
Teflon flap closing the bottom. The device was lowered into the water and
penetrated the soft mud about 7 cm. The mud was transferred to a beaker and
covered with aluminum foil.
Storage conditions : Samples were processed without delay.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : The lack of a collection procedure to limit contamination is a
serious fault of this study.
Summary : A weighted brass tube with a Teflon flap collected mud from the
river bottom. The mud was taken to the lab where processing began without
delay.
213
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Hites and Biemann (1975)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Two batches of sediment, 15 g each, were
dried in a desiccator, Soxhiet extracted with MeC1 2 , and evaporated to dryness.
The first batch was redissolved in MeC1 2 and gradient eluted from an alumina
column into 122 fractions with pentane, benzene, and methanol. The second
batch was dissolved in MeC1 2 and a pentane extract collected.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Elemental sulfur.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC, 6 ft x 0.125 in. SS packed with 3% OV-17 on a Gas Chrom
Q, temperature program 70 to 330°C at 12°C/mm, hold for 20 nan. GC/MS,
Perkin-Elmer 990 GC interfaced to a Hitachi RNU-GL mass spectrometer. URNS,
DuPont 21-11OB mass spectrometer.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Extraction and analysis procedure are somewhat complete in
themselves, and reference is made to additional sources of information.
Summary : After the dried samples were extracted on a Soxhlet apparatus,
one batch was gradient eluted from an alumina column. A second batch was
pentane-extracted from methylene chloride. After an initial GC screen, the
samples were analyzed by GC/MS and/or URNS.
QUALITY ASSURANCE
Method blank : Absence of DEHP noted.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
214
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Hites and Biemann (1975)
tlethod verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Very little information given so results are questionable.
Summary : The absence of DEJfP was noted in blank analyses.
215
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Potentially Toxic Organic Compounds in Industrial Wastewater and River Systems
Hites et al. (1979), Ref. No. 34
SURVEY DESIGN
Sampling sites : Study 1 - Upstream and downstream from specialty chem-
ical plant. Study 2 - Industrialized area of river and also source of drink-
ing water supply for several cities.
Sampling plan : Study 1 - Grab samples of water collected at clarifier
(1), upstream (2) and downstream (13); sediment (19) downstream only. Study
2 - Water collected near point sources and at two different seasons (13 in
August/October and 5 in March).
Problems : Not reported.
Goal(s) : To identify compounds discharged into receiving waters, those
already present, and those formed through in situ transformation.
Comments : Grab samples collected to assess influence of chemical point
sources in river systems. Study 1 appears to have been a single sampling of
multiple points along a river system. Temporal differences investigated in
study 2 with 5 of the 13 sites resampled.
Summary : Survey designed to provide samples for detailed organic analy-
sis by various sample concentration techniques and GC/MS.
SANPLING
Container preparation : Not reported.
Collection procedure : Water samples - amber bottles with Teflon—lined
caps; sediment - “dredge-type” sampler to collect and then stored in glass
jars with aluminum foil—lined caps.
Storage conditions : Water samples stored in refrigerator; samples for
solvent extraction were acidified to pH 2 and MeC1 2 added; sediments were
packed in dry ice.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Samples preserved immediately after collection--an effective
procedure for minimizing artifacts. Without mention of container preparation,
the validity of the samples is questionable because of the unknown possibility
of contamination from the sampling equipment.
216
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Hites et al. (1979)
Summary : Water samples were cooled to refrigerator temperature, and
those for solvent extraction were acidified and solvent added; sediments were
frozen after collection.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Study 2 - 5% deactivated silica gel and base
extraction. Study 1 - not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Fatty acids.
Limit of detection : 1 ppb.
Problems : Not reported.
Instrument : GC using EC, FID, and MS; columns: 180 cm x 2 mm glass with
3% SP-2100 and 25 m x 0.25 mm glass capillary with SE-52.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Blanks were run through cleanup procedure and showed no con-
tamination. Solvents used were nanograde but were not concentrated and
checked by GC for contamination; thus there would still be some room for
phthalate contamination.
Summary : Grab water samples were extracted in the collection bottle by
stirring overnight. Some extracts were cleaned up using silica gel followed
by basic extraction cleanup. Analysis of the extracts was carried out by GC
using EC, FID, or MS and authentic standards.
QUALITY ASSURANCE
Method blank : Used in cleanup procedure of Delaware River (Study 2)
extracts. Study 1 - not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : 20%.
217
-------
Hites et al. (1979)
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Low levels of DEHP reported could conceivably be due to con-
tamination plus its presence in the wastewater. Quantitative identification
good, however, because of the use of MS. Lack of method recoveries indicates
results are semiquantitative in nature.
Summary : Minimal quality assurance procedures were reported.
218
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Pesticides in the Illinois Waters of Lake Michigan
Schacht (1974), Ref. No. 58
SURVEY DESIGN
Sampling sites : Lake Michigan; streams feeding into the lake; sources
of contamination (sewage, etc.) being dumped into feed stream.
Sampling plan : Samples of sediment (50) and water (45) were collected
from tributaries, streams, near-shore, and off-shore stations in and around
sewage treatment plants and associated waters. Fish samples (255) were col-
lected from the lake.
Problems : Not reported.
Goal(s) : Determination of levels of pesticides discharged as well as
levels then found in Lake Michigan water, sediment, and fish. Phthalates were
secondary to the major goal.
Comments : Design inferred to be a monitoring of the open lake and tribu-
tatires near sewage treatment.
Summary : Survey design ostensibly formed to determine levels of various
pesticides in Lake Michigan and their source, but no information given as to
actual design formulation. Grabs of sediment, fish, and 24-hr water composites
were collected over a 3-year period.
SAMPLING
Container preparation : Glass bottles with aluminum foil liners, rinsed
with Nanograde hexane.
Collection procedure : Fish from commercial fishermen; water by grab sam-
pling and composite samplers; sediments collected directly in glass bottles or
by use of a Ponar dredge.
Storage conditions : Fish frozen; sediment stored at ambient; water not
reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Composite sampler rubber tubing replaced with glass tubing to
prevent contamination. Water and sediment sampling procedure appeared to elim-
inate source of contamination. Fish samples may have been contaminated while
taking a filet or when stored in aluminum foil if the foil was not rinsed with
solvent.
219
-------
Schacht (1974)
Summary : Water samples collected in glass bottles. Both grab samples
and composite (24 hr) samples taken. Fish obtained from local fishermen and
stored frozen in aluminum foil. Sediment samples taken in glass jars by hand
or with a Ponar dredge.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Florisil standard column; sodium sulfate
heated overnight at 450°C.
Recovery : Fish, 85 to 95%; sediments, 90%; water, 90%. Spike
levels not reported, however.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Fish, 10 ppb; sediment, 1 ppb; water, 100 ppt
(all DEHP data).
Problems : Not reported.
Instrument : Varian 204; 63 Ni 255°; column 200-210°, inj. 225°. Pesticide
analysis: 1/8 in. x 8 m column, 2.0% QF-1 and 1.25% OV-17 on 100/200 mesh
Supelcoport. For DEHP: 1/8 in. x 1 m column, 4% QF-1 and 2.0% OV-17.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : A well-defined analytical scheme was used to separate the ana-
lytes from the matrix. Although not specifically stated except for sodium
sulfate, mention of the decontamination procedures used, if any, would remove
any doubt about the validity of the data.
Summary : “FWPCA Method for Chlorinated Hydrocarbon Pesticides in Water
and Wastewater” used with some modifications. Results not corrected for re-
covery.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
220
-------
Schacht (1974)
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Two columns (not specified); one more, one less
polar than specified, were used.
Interlab verification : Yes, but no other information.
Problems : Not reported.
Comments : Sample fortification and recovery results mentioned in table
of contents but missing from the report. Results can be considered somewhat
quantitative since method blanks not reported.
Summary : Spike recovery and detection limit data were reported, but use
of method blanks was not.
221
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PAEs in Sediments
Schwartz et al. (1979), Ref. No. 59
SURVEY DESIGN
Sampling sites : Not reported for rivers other than from Rhine, Issel
and tleuse, but for the 12 samples taken from the nature reserve the copper
gradient was used as an indication of pollution at this Netherland site.
Sampling plan : Except for 2 of the 32 sites samples, “all sample sta-
tions were chosen at places where the movement of the river water was slug-
gish.
Problems : Not reported.
Goal(s) : Establish levels of DEHP and DMP in the three main rivers in
the Netherlands.
Comments : No actual design discussed; however, grab samples were ap-
parently collected along entire river and probably representative of the river
system at the time of sample collection. An attempt to collect replicate
samples was not accurate because of temporal and spatial differences in re-
turning to the site.
Summary : Sediment samples were taken from the Rhine, Issel, and Meuse
Rivers in the Netherlands for the determination of DEHP and DBP levels (32
sampling stations). Twelve samples were taken from a nearby nature reserve
and one from a landfill.
SANPLING
Container preparation : Glass jars washed with soap and water, rinsed
with hot water, acetone, then hexane.
Collection procedure : Used a Hydro-Bios dredge.
Storage conditions : Samples freeze-dried and stored at -30°C.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Homogeneity of samples taken not possible at some sites.
Replicate sampling at same site, months apart, often not done in exactly same
place.
Comments : Sampling procedures used probably reduced any potential for
contamination, and the samples collected represent the actual environment.
222
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Schwartz et al. (1979)
Summary : Samples collected with a Hydro-Bios dredge and stored at -30°C
after freeze-drying. Some sites sampled months apart to determine any tem-
poral variations.
ANALYSIS
Measurement procedure
Cleanup/fractionation : For GC method used Florisil column (7 g);
15% diethyl ether/hexane fraction collected.
Recovery : Overall recovery reported to be 90 to 110% for both
phthalates by the High Pressure Liquid Chromatography (HPLC) method.
Linear recovery : Not reported.
Interferences : Not identified for GC method, but removed by
Florisil.
Limit of detection : 10 ng at 233 rim - HPLC.
Problems : Percent of ethanol impurity in CH 2 C1 2 used as mobile
phase caused shifting retention volumes for phthalates.
Instrument : HPLC: Siemens Model S100 LC with multiple wavelength detec-
tor (5 pm LiChrosorb S160). GC: Pye Unicam 1O4GC with FID and EC (7 ft x 2 mm
glass with 4% OV-101).
Linear response : 0.1 to 15 pg/mi of hexane solution.
Stability of response : Not reported.
Problems : Not reported.
Comments : Good reocvery (90 to 110%) combined with a fractionation and
cleanup step indicate a meaningful analysis.
Summary : Sediment was freeze-dried, Soxhiet extracted, concentrated, and
detected by HPLC system. GC determination required Florisil cleanup.
QUALITY ASSURANCE
Method blank : Used to keep contamination below detection limit of 10 ng.
Control sample : Not reported.
Reference material : Not reported.
223
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Schwartz et al. (1979)
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : HPLC versus GC.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Overall, the minimal contamination and the verification by two
analytical methods can support confidence in the data.
Summary : Number of blanks and spikes not discussed. Reduction of con-
tamination solved by rinsing lab equipment with hexane. Method recovery men-
tioned as being quantitative.
224
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Organic Contaminants - Lake Huron
EPA (1977b), Ref. No. 71
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Not reported.
Problems : Environmental analysis is a still developing “state-of—the-
art.”
Goal(s) : Not reported.
Comments : A good synopsis of the persistance that a selected list of or-
ganics have in Lake Huron. A literature and data review of monitoring data
for the lake and its inputs.
Summary : This report relates the sources of organic compounds entering
Lake Huron and describes their potential impact on the environment. The re-
port was used as a means of proposing a total ban on PCB, aidrin, dieldrin,
DDT, and its derivatives.
SANPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : None.
Summary : Sampling method not described.
225
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EPA (1977b)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : Not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : None.
Summary : Analysis methods not mentioned. DEHP found ranging from < 1 to
1.4 pg/liter in water samples.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : None.
Summary : No quality assurance mentioned.
226
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G. SESTON
Two articles were reviewed for this matrix and are included in this sec-
tion.
SURVEY DESIGN
The overall design for the selection of sampling sites for one article
(10) was not delineated but inferred to be grab samples. The dispersion of
effluent from a point source was monitored in the other article (4). There
was no mention of randomness or replicate sampling in. either article.
SAMPLING
The collection procedure was described in both articles (4 and 10) but
no mention was made of determining the cleanliness of the equipment except
for article 10.
ANALYSIS
The two articles (4 and 10) presented details on methods that appear in
principle to be adequate.
QUALITY ASSURANCE
Method blanks were reported in one article (10) while no information was
given in the other (4).
227
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Persistant Organic Compounds from a Pulp Mill in a Near-Shore Freshwater
Environment
Brownlee and Strachan (1976), Ref. No. 4
SURVEY DESIGN
Sampling sites : The majority of the sites near the northern shore of
Lake Superior were selected to be outside the area influenced by the effluent
plume.
Sampling plan : Each of the 15 stations were sampled at least once for
water and seston. A limited number of sediment samples were collected (ap-
parently four).
Problems : Not reported.
Goal(s) : Determine if any organic compounds present in the mill effluent
could be detected at significant distances (up to 5 km) from the effluent out-
fall.
Comments : The location of sites for the collection of grab samples was
influenced by the effluent plume movement. Other sampling criteria, e.g.,
temporal or replicate sampling, was not discussed.
Summary : The dispersion of organics from the mill effluent was monitored
by sampling at various distances from the outfall.
SAMPLING
Container preparation : Not reported.
Collection procedure : Water aspirated using Teflon and s.s. apparatus.
Pressure filtered through precombusted (450°C) Nucleopore glass fiber filters
in a Teflon ad s.s. apparatus using N 2 purified through molecular sieves. A
portion extracted the same day. Seston retained on Nucleopore glass fiber
filters from water collection. Sediment collected by Shipek sampler.
Storage conditions : Water extracted same day as collected. Seston placed
in “clean” containers and stored frozen. Sediment stored frozen.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : With the exception of field blanks or spikes and a procedure
for cleaning equipment, the sampling seems quite adequate.
Summary : Water was collected using Teflon and s.s. apparatus and ex-
tracted on day of collection. Seston retained on a Nucleopore filter while
sediment was collected with a Shipek sampler; both sample types stored frozen.
228
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Brownlee and Strachan (1976)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Water made saline with precombusted (450°C)
sodium chloride and extracted with glass-distilled CC1 3 for 22 hr. Reduced to
small volume and stored in a “clean, sealed ampoule.” Taken to dryness at
60°C, methylated with diazomethane in ether-methanol. Solvent removed at 60°C.
Methylated extracts stored at 4°C in sealed ampoules until analysis. Seston
thawed and homogenized with glass-distilled CHC1 3 :CH 3 OH (2:1 v/v). Refluxed
1 hr and filtered. Made acidic with HC1, taken to dryness, methylated, and
stored under same conditions as water samples. Sediment was freeze-dried and
extracted 24 hr with glass-distilled CC1 3 . Extracts treated same as water
extracts.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Presence of ethyl esters of fatty and resin acids in
derivatized extracts. Artifacts of extraction procedure. Dioctylphthalate
and methyl ketodehydroabietate nearly coelute.
Limit of detection : 0.1 pg/liter in H 2 0, 10 pg/g dry weight of
seston, 0.1 pg/g dry weight of sediment.
Problems : Not reported.
Instrument : GC/FID, GC/MS.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : In view of the lack of reported recoveries and the mentioned
interferences this section is of questionable value.
Summary : Due to the nature of the study no attempt was made to optimize
for phthalates. Instrument response linearity was not reported. No attempt
appears to have been made to determine the recoveries of the compounds re-
ported.
229
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Phthalic Acid Esters in the Marine Environment
Corcoran and Curry (1978), Ref. No. 10
SURVEY DESIGN
Sampling sites : Lower Mississippi River (11 sites) and northeast Gulf
of Mexico (6 sites).
Sampling plan : Fall of 1975.
Problems : Not reported.
Goal(s) : Determining the distribution and concentration of various com-
mon phthalic acid esters.
Comments : The design involved collection of grab samples from river
and near-shore waters. Criteria not delineated for selection of sampling
sites.
Summary : Samples of water, particulate matter, and sediment were col-
lected in 1975 from the lower Mississippi River and northeast Gulf of Mexico
to determine the distribution and concentration of various phthalic acid
esters.
SAMPLING
Container preparation : Cleaned with detergent and water, rinsed with
distilled water, and heated to 600°C. Extracted and checked by GC.
Collection procedure : Water collected with all-metal Niskin type sampler.
Samples taken of surface, mid-depth, and close to the bottom.
Storage conditions : Not reported for water. Glass fiber filters stored
frozen.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : The sampling method seems quite adequate and thus the samples
should be representative of the environment.
Summary : After cleanup, glassware and aluminum foil were extracted and
checked by GC for phthalate levels. Water samples were taken at the surface,
mid-depth, and close to the bottom using an all-metal Niskin type sampler.
230
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Corcoran and Curry (1978)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Water was filtered through glass fiber filters,
passed through XAD-2 resin. Eluted from XAD-2 with diethyl ether, dried, and
extracted with hexane. Filters extracted with hexane and cleaned up on Florisil.
Recovery : 98% for extraction from XAD-2 resin “with respect to
the various simple diesters of phthalic acid.”
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/EC.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : The extraction method is good based on high recoveries but
additional validation results should have been reported so that the entire
analytical method could be assessed.
Summary : Water samples were filtered through glass fiber filters, passed
through XAD-2 resin. Eluted from XAD-2 with diethyl ether, dried, and ex-
tracted with hexane. Glass fiber filters were extracted with hexane and
cleaned up on Florisil. Analysis was by GC/EC. Recovery was 98%.
QUALITY ASSURANCE
Method blank : All glassware was precleaned; “no detectable levels were
observed.”
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
231
-------
Corcoran and Curry (1978)
Problems : Not reported.
Comments : The method blanks are indicative of minimal contamination, but
the accuracy and verification of the data are unknown.
Summary : Glassware and aluminum foil was extracted after cleaning. No
detectable levels were observed.
232
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H. SOIL
One article was reviewed for this matrix.
SURVEY DESIGN
The overall design was not clear because of a lack of defining where
sample collection took place.
SMIPL ING
No information given.
ANALYSIS
In principle, the method reported was adequate although the low recovery
at an unknown level points to a deficiency of the method.
QUALTIY ASSURANCE
The limited information presented is not enough to establish the valid-
ity of the data.
233
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DEHP in the Vicinity of an Industrial Area in Finland
Persson (1978), Ref. No. 55
SURVEY DESIGN
Sampling sites : Sites near DEHP factory.
Sampling plan : Unspecified number “of fish, net plankton, freshwater
arthropods, soil arthropods, and soil were obtained. . .“
Problems : Not reported.
Goal(s) : Determination of DEHP levels in the vicinity of a DEHP manu-
facturing plant.
Comments : Sites selected and grab samples collected in the vicinity of
a DEHP plant. “Vicinity” not delineated. The impact of the factory has not
been determined by this preliminary investigation.
Summary : Samples of fish, plankton, freshwater and soil arthropods, and
soil obtained in the vicinity of a DEHP plant were analyzed for DEHP.
SAMPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Fish caught at spawning time; normal whereabouts unknown.
Summary : Sampling methods were not discussed.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Alumina.
Recovery : 40% at unknown level.
Linear recovery : Not reported.
Interferences : Not reported.
234
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Persson (1978)
Limit of detection : 0.1 ppm for unknown sample size.
Problems : Not reported.
Instrument : Varian 2800 GC/FID on two columns: 3% SE-30 and 1% DC-560.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Results corrected for background but not for recovery. Author
calls identification of DEHP by GC “tentative.”
Summary : Samples were dried with sodium sulfate and Soxhiet extracted
with hexane. Extracts cleaned up with alumina and analyzed by GC/FID on two
columns.
QUALITY ASSURANCE
Nethod blank : Background level from chemicals and apparatus reported to
be 0.2 ppm.
Control sample : 40% recovery obtained from somewhere but not discussed.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
? lethod verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Results should be viewed as qualitative at best.
Summary : Quality assurance measures not described but background level
defined at 0.2 ppm and recovery at 40%.
235
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I. TISSUE (HUMAN, EXPERIMENTAL ORGANISMS )
This section presents the reviews on five articles designated for inclu-
sion under this matrix.
SURVEY DESIGN
In three articles (36, 38, and 44) the samples appear to have been col-
lected on an opportunistic basis from tissue available or used in laboratory
experiments. One article (48) states that the samples were collected from
available autopsy accident victims. No information was provided in article
17. Random or replicate sampling, distribution or relationship of sample
population was uncertian in all articles.
SAMPLING
Equipment preparation and collection procedures ranged from insufficient
or no information in three articles (17, 36, and 38) to brief information in
two articles (44 and 48). In all articles the validity of the results cannot
be established based on sample collection techniques.
ANALYSIS
The analytical methods when reported appear to be adequate. Some infor-
mation was provided in three articles (36, 38, and 44). No information was
given in one article (17). The remaining article (48) was the most informa-
tive of the articles for this matrix. However, the recovery data indicates
that the method has not been optimized for low levels. All of the methods
could be further assessed on their merit with additional information.
QUALITY ASSURANCE
In three articles (17, 36, and 44) no information was presented. The
use of method blanks was reported (38 and 48) as was the use of control sam-
ples (48) and method verification (48). In article 48 the validity of the re-
sults would therefore appear to be valid while the results in article 38 might
be questioned.
236
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The Detection and Identification of Unknown Halogenated Compounds in
Environmental Samples
Freudenthal (1978), Ref. No. 17
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : Identification of halogenated compounds in environmental
samples by element specific mass spectrometer.
Comments : The specified number of grab samples collected.
Summary : This paper reports the finding of three phthalates in Rhine
River water by element specific GC/MS.
SAMPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : None.
Summary : No information given.
237
-------
Freudenthal (1978)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/MS operated as a halogen detector by atomizing the column
effluent and tuning the MS to the m/e of a particular element.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Not enough information given to evaluate analytical method.
Summary : GC/MS operated as a halogen—specific detector.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : None.
Summary : None.
238
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Plasticizers from Plastic Devices: Extraction, Metabolism, and Accumulation
by Biological Systems
Jaeger and Rubin (1970), Ref. No. 36
SURVEY DESIGN
Sampling sites : Based on exposure to plastic tubing and storage devices.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : To determine the extent of extraction, metabolism, and accumu-
lation of plasticizers from plastic devices by biological systems.
Comments : Grab samples collected from tubing and other plastic apparatus
used in perfused liver experiment, then from other plastic products used in
medicine, e.g., blood bags.
Summary : Limited survey of plasticizers extracted from plastic devices
by biological systems. Accumulation and metabolism of the plasticizers was
also examined.
SAt 1PL ING
Container preparation : Not reported.
Collection procedure : Not applicable.
Storage conditions : Not applicable.
Stability demonstrated : Not applicable.
Field blanks : Not applicable.
Spiked blanks : Not applicable.
Problems : Not reported.
Comments : Procedures used to control/eliminate contamination not stated.
Summary : No sampling was done se. Outdated whole blood was pur-
chased from a nearby blood bank. Human tissue was obtained from patients at
Johns Hopkins Hospital. White rat tissue and blood were obtained from Johns
Hopkins Hospital.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Dowex-1 for blood extract; also used TLC.
Recovery : Not reported.
Linear recovery : Not reported.
239
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Jaeger and Rubin (1970)
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : Gilford spectrophotometer at 260 rim or 280 run.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Analytical procedures not well-defined. No procedures were
given for any kind of tissue. Lack of method description for tissue and gen-
eral mode of detection used for blood analysis leaves ample room for criticism
of results.
Summary : Chloroform extracts of neutral and acidified blood were applied
to TLC plates or Dowex-1. The eluent was spectrophotometrically examined for
phthalates.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Credibility of the data is in doubt because of the minimal QA
measures reported.
Summary : Minimal quality assurance measures were reported; i.e., no
blanks or spiked samples were mentioned.
240
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Extraction, Localization, and Metabolism of Di-2-ethylhexyl Phthalate from
PVC Medical Devices
Jaeger and Rubin (1973a), Ref. No. 38
SURVEY DESIGN
Sampling sites : Based on possible exposure to DEHP.
Sampling plan : Not applicable.
Problems : Not reported.
Goal(s) : Determination of phthalate levels in various types of fluids
and tissues subjected to DEHP and other plasticizers.
Comments : Logical progress of studies. Each study based on results of a
previous study. Grab samples taken in each case.
Summary : Original experiments designed to determine levels of DEHP in
blood in a liver perfusion system. Additional experiments performed to deter-
mine levels in blood and various tissues exposed to DEHP by virtue of blood
transfusions, operations, or hemodialysis. Attempts were also made to deter-
mine metabolites.
SANPL ING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : In one part of the study different temperatures were
used to determine effect of temperature on migration rate of DEHP from tubing.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : None.
Summary : Sampling methods not discussed.
ANALYSIS
Measurement procedure
Cleanup/fractionation : TLC.
Recovery : Not reported.
241
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Jaeger and Rubin (1973a)
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : TLC.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Analytical methods not explained. Purity of solvents and
reagents used (if any) not reported. Lack of reporting recoveries and ana-
lytical methods indicates that any results reported should be viewed as unsub-
stantiated.
Summary : Analysis method for liquids reported as TLC of an unknown or-
ganic extract. Tissue analyzed by unknown method.
QUALITY ASSURANCE
Method blank : Used for liquid analysis of perfusion system and in tissue
analysis (20 to 60 pg DEHP).
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : ±10% for tissue analysis.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Quality assurance measures skimpy at best.
Summary : Method blanks used in the analysis of the liquids in the liquid
perfusion system and in the tissue analysis. No discussion of use of spiked
samples to determine recoveries.
242
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Studies on Absorption, Distribution & Excretion of Phthalates
Kitanaka et al. (1977), Ref. No. 44
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Samples collected from mice and rats given radiolabeled
phthalates. Unspecified number of urine, feces, blood, kidney, liver, fat,
and spleen samples were collected from the test animals.
Problems : Not reported.
Goal(s) : Determine the distribution and levels over time of radioactive
phthalates and the effects of the phthalates on the body.
Comments : This study is of significance in determining the possible fate
of phthalates ingested orally. The author cautions one to use care in inter-
preting the data since ester hydrolysis of the 14 C-labeled carbonyl group of
the phthalat.es may affect the emission patterns observed.
Summary : This project was designed to determine the effects of phthalic
acid esters on the body. Rats and mice were administered radioactive
phthalates.
SAMPLING
Container preparation : Not reported.
Collection procedure : Test animals were anesthetized, exsanguinated, and
eviscerated. Metabolic cages used to collect urine and feces.
Storage conditions : Processing began immediately after collection.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Unknown whether one group of animals went through all collec-
tion phases or a separate group of animals used for each specific phase.
Summary : Phthalates with a carbon-14 tag were administered to rats and
mice. Urine, feces, and tissues were collected at specific times after admin-
istration of the ‘ 4 C-phthalates.
243
-------
Kitanaka et al. (1977)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : Liquid scintillation counter.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Recovery and quenching data should have been reported. Other-
wise the results are considered qualitative.
Summary : The various excrements, body fluids, tissues, and organs were
measured for radioactivity to determine which organs contained phthalates and
their relative concentrations with respect to time.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
244
-------
Kitanaka et al. (1977)
Comments : An unspecified comparison with control groups was made to
account for t slight” radioactivity after 12 to 24 hr. It is uncertain as to
what this statement refers or its relevance.
Summary : QA provisions were not reported.
245
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Di-n-butyl- and Di-2-ethylhexyl in Phthalate in Human Adipose Tissue
Mes et al. (1974), Ref. No. 48
SURVEY DESIGN
Sampling sites : Fatty tissue of the abdominal region obtained during
autopsies on accident victims.
Sampling plan : “Except for two samples from the Vancouver and one from
Montreal, all samples came from the Toronto area.”
Problems : Not reported.
Goal(s) : To perform a limited survey of human adipose tissue for di-n-
butylphthalate and DEHP.
Comments : Background of autopsy subjects, randomness or distribution of
this sample population were not given. Appears that the samples are grab
specimens.
Summary : Samples from available accident victims from three Canadian
cities were taken for analysis of DBP and DEHP.
SAMPLING
Container preparation : Glass jars, acid washed and rinsed with residue-
free acetone and hexane; aluminum foil liners.
Collection procedure : Not reported.
Storage conditions : Frozen.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : No indication of what kind of instruments were used to take
the tissue samples or how they were prepared for taking the samples leaves
room for possible contamination.
Summary : Human adipose tissue was collected during autopsies on accident
victims, placed in glass jars, and frozen until analysis. The sample jars
were carefully cleaned, but no mention was made of how the actual tissue sam-
ples were taken.
246
-------
Mes et al. (1974)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Low temperature precipitation and 2% deac-
tivated Florisil.
Recovery : At 1 ppm recovery was 38% for DEHP, 85 to 100% at 5 ppm
for spiked samples.
Linear recovery : Not reported.
Interferences : Lipids, etc.
Limit of detection : 0.1 ppm for 5 g sample.
Problems : Not reported.
Instrument : Varian 1200 GC with EC (tritium foil) on 6 ft x 1/4 in. glass
with 6% OV-210 and 4% SE-30.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Typical tissue procedure. Also applicable to PCBs and other
organochiorine pesticides. Recoveries show that method worked best at 5-ppm
level and was only semiquantitative at the 1-ppm level (40% recovery).
Summary : Tissue samples (5 g) were blended, the extract filtered, con-
centrated to dryness, redissolved, and applied to a Florisil column. The re-
sulting extract was analyzed by GC/EC.
QUALITY ASSURANCE
Method blank : Used, but no indication of how often; no DEHP found.
Control sample : Samples spiked at 1- and 5-ppm levels.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Three samples pooled and subjected to TLC separa-
tion, then GC/MS verification.
247
-------
Mes et al. (1974)
Interlab verification : Not reported.
Problems : Not reported.
Comments : Quality assurance measures apparently taken but could use ex-
pansion. Use of blanks and spikes at two levels indicates the data generated
were meaningful.
Summary : Quality assurance measures employed consisted of an unknown
number of solvent blanks and sample spikes at 1 and 5 ppm. No DEHP was found
in the solvent blanks, but DBP was found at a constant but unspecified level.
Further cleanup of these pooled samples by TLC was done with verification by
GC/MS.
248
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J. URINE
Three articles were reviewed for this matrix and are included in this
section.
SURVEY DESIGN
In the three articles (37, 38, and 44) the samples appear to have been
collected on an opportunistic basis from patients in a hospital or laboratory
animals used in experiments. Random or replicate sampling, distribution or
relationship of sample population was uncertain.
SANPLING
No information was given on equipment preparation and collection pro-
cedures in two of the articles (37 and 38). Article 44 mentioned the use of
metabolic cages but did not give any details on minimizing sample contamina-
tion.
ANALYS IS
The analytical method provided in article 37 appears to be somewhat ade-
quate in view of range of recovery values. The methods were not explained in
the other two articles (38 and 44) and should be considered as unsubstantiated.
QUALITY ASSURANCE
tn two articles (37 and 38) the use of method blanks and precision and
accuracy data were reported. Control samples were also mentioned (37). No
information was given for the remaining article (44).
249
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Nigration of Phthalate Ester Plasticizer from Polyvinyl Chloride Blood Bags
into Stored Human Blood and Its Localization in Human Tissues
Jaeger and Rubin (1972), Ref. No. 37
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Not defined but samples were collected from six units
of stored blood, unspecified number of fresh blood and urine samples, 13
autopsy subjects who had received blood and 7 autopsy subjects who had not.
Problems : Not reported.
Goal(s) : Determination of DEIIP in blood stored in PVC bags.
Comments : Grab samples taken from transfused and nontransfused subjects.
Although not stated, the samples appear to have been collected on an oppor-
tunistic basis.
Summary : DEHP found in stored blood, and patient’s blood who had received
transfusions. DEHP metabolites also found.
SANPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : The problem of contamination is not mentioned. Since no col-
lection procedures were mentioned addressing this problem, the results should
be considered qualitative.
Summary : Blood sampled from patients, and after storage and/or transfu-
sion to determine source of phthalates in patient’s blood.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Blood lyophilized, chloroform extract washed
with saline. Extract dried, reconstituted with methanol, centrifuged, dried,
reconstituted with hexane.
250
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Jaeger and Rubin (1972)
Recovery : 60 to 90%.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : Not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Phthalic acid and other DEHP metabolites also analyzed.
Summary : GC column: 3% SE-30 on Gas Chrom Q. No instrument or detector
mentioned.
QUALITY ASSURANCE
Method blank : Ranged from 20 to 60 Jg.
Control sample : Fresh blood in glass.
Reference material : Not reported.
Precision and accuracy : Reproducibility ±10%.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Blood values were subtracted from tissue values.
Summary : Assay of samples included blood not in contact with. PVC, blood
in contact with PVC for increasing time spans, metabolites found in urine,
fat, and other tissues.
251
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Extraction, Localization, and Metabolism of Di-2-ethylhexyl Phthalate from
PVC Plastic Medical Devices
Jaeger and Rubin (1973a), Ref. No. 38
SURVEY DESIGN
Sampling sites : Based on possible exposure to DEHP.
Sampling plan : Stepwise investigation after DEHP found in a liver per-
fusion system. Grab samples of tubing, blood bags, rat whole-body homogenate,
rat lung, and liver were collected and analyzed.
Problems : Not reported.
Goal(s) : Determination of phthalate levels in various types of fluids
and tissues subjected to DEHP and other plasticizers.
Comments : Logical progress of studies. Each study based on results of a
previous study. Grab samples taken in each case.
Summary : Original experiments designed to determine levels of DEHP in
blood in a liver perfusion system. Additional experiments performed to deter-
mine levels in blood and various tissues exposed to DEHP by virtue of blood
transfusions, operations, or hemodialysis. Attempts were also made to deter-
mine metabolites.
SAMPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : In one part of the study different temperatures were
used to determine effect of temperature on migration rate of DEHP from tubing.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : None.
Summary : Sampling methods not discussed.
ANALYSIS
Measurement procedure
Cleanup/fractionation : TLC.
Recovery : Not reported.
252
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Jaeger and Rubin (1973a)
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : TLC.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Analytical methods not explained. Purity of solvents and
reagents used (if any) not reported. Lack of reporting recoveries and ana-
lytical methods indicates that any results reported should be viewed as unsub-
stantiated.
Summary : Analysis method for liquids reported as TLC of an unknown or-
ganic extract. Tissue analyzed by unknown method.
QUALITY ASSURANCE
Method blank : Used for liquid analysis of perfusion system and in tissue
analysis (20 to 60 pg DEBP).
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : ±10% for tissue analysis.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Quality assurance measures skimpy at best.
Summary : Method blanks used in the analysis of the liquids in the liquid
perfusion system and in the tissue analysis. No discussion of use of spiked
samples to determine recoveries.
253
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Studies on Absorption, Distribution & Excretion of Phthalates
Kitanaka et al. (1977), Ref. No. 44
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Samples collected from mic and rats given radiolabeled
phthalates. Unspecified number of urine, feces, blood, kidney, liver, fat,
and spleen samples were collected from test animals.
Problems : Not reported.
Goal(s) : Determine the distribution and levels over time of radioactive
phthalates and the effects of the phthalates on the body.
Comments : This study is of significance in determining the possible fate
of phthalates ingested orally. The author cautions one to use care in inter-
preting the data since ester hydrolysis of the ‘ 4 C-labeled carbonyl group of
the phthalates may affect the emission patterns observed.
Summary : This project was designed to determine the effects of phthalic
acid esters on the body. Rats and mice were administered radioactive
phthalates.
SAMPLING
Container preparation : Not reported.
Collection procedure : Test animals were anesthetized, exsanguinated, and
eviscerated. Metabolic cages used to collect urine and feces.
Storage conditions : Processing began immediately after collection.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Unknown whether one group of animals went through all collec-
tion phases or a separate group of animals used for each specific phase.
Summary : Phthalates with a carbon-14 tag were administered to rats and
mice. Urine, feces, and tissues were collected at specific times after admin-
istration of the ‘ 4 C-phthalates.
254
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Kitanaka et al. (1977)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : Liquid scintillation counter.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Recovery and quenching data should have been reported. Other-
wise the results are considered qualitative.
Summary : The various excrements, body fluids, tissues, and organs were
measured for radioactivity to determine which organs contained phthalates and
their relative concentrations with respect to time.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
255
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Kitanaka et al. (1977)
Comments : An unspecified comparison with control groups was made to
account for “slight” radioactivity after 12 to 24 hr. It is uncertain as to
what this statement refers or its relevance.
Summary : QA provisions were not reported.
256
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K. WATER (DRINICING, WASTE, GROUND, PROCESS EFFLUENT )
This section presents the reviews on 37 articles designated for inclu-
sion under this matrix.
SURVEY DESIGN
The overall design for most articles could not be determined based on
the information presented. Four articles (46, 69, 72, and 73) however did
contain sufficient details to determine the survey design. Each of the four
articles stated the representativeness of its sample population but only
article 46 states that the sample population was random. Article 73 did men-
tion the use of replicate sampling but the other three articles did not.
Other articles (4, 15, 16, 31, 34, 43, 52, 58, 60, 63, and 67) used monitor-
ing surveys to establish and determine organic pollutants in effluents. Each
of three articles (18, 42, and 61) studied a treatment plant to determine the
degree of effectiveness of the treatment process. Three other articles (12,
13, and 40) used test wells to determine whether leaching occurred at dump
sites. Four articles (10, 20, 25, and 27) reported on samples collected from
the ocean and a tributary and one article (25) suggested a mass balance model
for DEHP but no validation of the model was presented. Two articles (64 and
71) gave results of lake studies while two other articles (68 and 70) dealt
with drinking water surveys. However, randomness or replication of sampling
points were not brought out in any of the above articles except as stated for
the first four articles.
Four articles (17, 21, 24, and 51) reported methods that were developed
and used to analyze selected samples from an unknown source. One article
(32) was a positive paper on the merits of GC/MS analysis for environmental
samples and the results of a single grab sample were given in another article
(30). Use of a laboratory simulated ecosystem using radiolabeled DEHP was
mentioned in one article (49).
SANPLING
The procedures used to collect the samples were described in 27 articles
(4, 10, 11, 12, 13, 15, 16, 18, 21, 24, 25, 27, 30, 31, 34, 40, 42, 43, 46,
58, 60, 61, 63, 64, 67, 70, and 72). Most of the articles described the pro-
cedures in adequate detail. Certain articles, however, only gave the briefest
of details (18, 25, 27, 34, 46, 64, and 70) which was not enough information
to evaluate the sampling procedures. Four articles (31, 32, 43, and 72) re-
fered the reader to other sources for sampling details. The preparation of
the sampling equipment appeared to be adequate in nine of these articles (10,
11, 15, 16, 21, 24, 40, 58, and 70), however two articles (42 and 67) used
plastic bottles or PVC media holders which probably contaminated the samples
in the field. Storage conditions for the samples were given in 16 of these
27 articles (4, 10, 11, 12, 13, 15, 18, 21, 30, 34, 40, 42, 60, 61, 67, and
70) and three of these (30, 34, and 60) “preserved” the samples immediately
after collection with the addition of extraction solvents. Two of these 27
articles reported the use of field spikes. The prime DEHP sampling evalua-
tion criteria was the use of method blanks which were reported in only four
(13, 63, 67, and 70) of the 27 articles. The remaining nine articles (17,
20, 49, 51, 52, 68, 69, 71, and 73) did not give any information.
257
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ANALYS IS
The analytical methods were, in principle, adequate in 21 articles (4,
10, 12, 13, 15, 16, 18, 24, 34, 40, 42, 43, 46, 49, 51, 52, 58, 60, 61, 64,
and 70). Minimal or no information about methods was given in 11 articles
(11, 20, 21, 25, 27, 30, 31, 32, 63, 67, and 73). A judgement about the
validity of the methods in these articles cannot be made. Method validation
data such as recoveries were given in 14 articles. Seven of these articles
(10, 24, 27, 49, 51, 58, and 61) were judged as valid based on good recoveries
(70% or better). The remaining seven (12, 13, 15, 16, 46, 70, and 73) were
judged as weak because of the wide range or high (< 200%) recovery data re-
ported. No information was given in five articles (17, 68, 69, 71, and 72).
QUALITY ASSURANCE
The information provided in 26 articles (4, 10, 11, 12, 13, 15, 16, 21,
24, 25, 27, 30, 34, 40, 43, 46, 49, 51, 52, 58, 60, 61, 63, 64, 67, 70) was
considered minimal. A prime QA element for phthalate analysis is the use of
method blanks. However, only 11 (10, 13, 16, 21, 30, 40, 43, 60, 63, 67, and
70) of the 26 articles mentioned the use of method blanks. One article (49)
through the use of radiolabeled compounds avoided the problems of method blanks.
Verification of results through the use of other columns or detectors was re-
ported in seven articles (4, 15, 16, 24, 34, 52, and 58) and interlab verifi-
cation reported in three articles (63, 64, and 67).
No QA information was given in nine articles (17, 20, 31, 42, 68, 69,
71, 72, and 73).
258
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Persistant Organic Compounds from a Pulp Mill in a Near-Shore Freshwater
Environment
Brownlee and Strachan (1976), Ref. No. 4
SURVEY DESIGN
Sampling sites : The majority of the sites near the northern shore of
Lake Superior were selected to be outside the area influenced by the effluent
plume.
Sampling plan : Each of the 15 stations were sampled at least once for
water and seston. A limited number of sediment samples were collected (ap-
parently four).
Problems : Not reported.
Goal(s) : Determine if any organic compounds present in the mill effluent
could be detected at significant distances (up to 5 km) from the effluent out-
fall.
Comments : The location of the sites for the grab samples was influenced
by the effluent plume movement. Other sampling criteria, e.g., temporal or
replicate sampling was apparently not considered.
Summary : The dispersion of organics from the mill effluent was monitored
by sampling at various distances from the outfall.
SANPLING
Container preparation : Not reported.
Collection procedure : Water aspirated using Teflon and s.s. apparatus.
Pressure filtered through precombusted (450°C) Nucleopore glass fiber filters
in a Teflon ad s.s. apparatus using N2 purified through molecular sieves. A
portion extracted the same day. Seston retained on Nucleopore glass fiber
filters from water collection. Sediment collected by Shipek sampler.
Storage conditions : Water extracted same day as collected. Seston placed
in “clean” containers and stored frozen. Sediment stored frozen.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : With the exception of field blanks or spikes and a procedure
for cleaning equipment, the sampling seems quite adequate.
Summary : Water was collected using Teflon and s.s. apparatus and ex-
tracted on day of collection. Seston retained on a Nucleopore filter while
sediment was collected with a Shipek sampler; both sample types stored frozen.
259
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Brownlee and Strachan (1976)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Water made saline with precombusted (450°C)
sodium chloride and extracted with glass-distilled Cd 3 for 22 hr. Reduced to
small volume and stored in a “clean, sealed ampoule.” Taken to dryness at
60°C, methylated with diazomethane in ether-methanol. Solvent removed at 60°C.
Methylated extracts stored at 4°C in sealed ampoules until analysis. Seston
thawed and homogenized with glass-distilled CHC1 3 :CH 3 OH (2:1 v/v). Refluxed
1 hr and filtered. Made acidic with HC1, taken to dryness, methylated, and
stored under same conditions as water samples. Sediment was freeze-dried and
extracted 24 hr with glass-distilled CC1 3 . Extracts treated same as water
extracts.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Presence of ethyl esters of fatty and resin acids in
derivatized extracts. Artifacts of extraction procedure. Dioctylphthalate
and methyl ketodehydroabietate nearly coelute.
Limit of detection : 0.1 pg/liter in H 2 0, 10 pg/g dry weight of
seston, 0.1 pg/g dry weight of sediment.
Problems : Not reported.
Instrument : GC/FID, GC/MS.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : In view of the lack of reported recoveries and the mentioned
interferences this section is of questionable value.
Summary : Due to the nature of the study no attempt was made to optimize
for phthalates. Instrument response linearity was not reported. No attempt
appears to have been made to determine the recoveries of the compounds re-
ported.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
260
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Brownlee and Strachan (1976)
Reference material : Apparently not used for phthalates.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Verification was by GC/MS.
Interlab verification : Not reported.
Problems : Not reported.
Comments : QA section was of no value.
Summary : No quality assurance provisions, blanks, spikes, or replicates
were reported.
261
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Phthalic Acid Esters in the Marine Environment
Corcoran and Curry (1978), Ref. No. 10
SURVEY DESIGN
Sampling sites : Lower Mississippi River (11 sites) and northeast Gulf
of Mexico (6 sites).
Sampling plan : Fall of 1975.
Problems : Not reported.
Goal(s) : Determining the distribution and concentration of various com-
mon phthalic acid esters.
Comments : The design involved collection of grab samples from river
and near-shore waters. Criteria not delineated for selection of sampling
sites.
Summary : Samples of water, particulate matter, and sediment were col-
lected in 1975 from the lower Mississippi River and northeast Gulf of Mexico
to determine the distribution and concentration of various phthalic acid
esters.
SAMPLING
Container preparation : Cleaned with detergent and water, rinsed with
distilled water, and heated to 600°C. Extracted and checked by GC.
Collection procedure : Water collected with all-metal Niskin type sampler.
Samples taken of surface, mid-depth, and close to the bottom.
Storage conditions : Not reported for water. Glass fiber filters stored
frozen.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : The sampling method seems quite adequate and thus the samples
should be representative of the environment.
Summary : After cleanup, glassware and aluminum foil were extracted and
checked by GC for phthalate levels. Water samples were taken at the surface,
mid-depth, and close to the bottom using an all-metal Niskin type sampler.
262
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Corcoran and Curry (1978)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Water was filtered through glass fiber filters,
passed through XAD-2 resin. Eluted from XAD-2 with diethyl ether, dried, and
extracted with hexane. Filters extracted with hexane and cleaned up on Florisil.
Recovery : 98% for extraction from XAD-2 resin “with respect to
the various simple diesters of phthalic acid.”
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/EC.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : The extraction method is good based on high recoveries but
additional validation results should have been reported so that the entire
analytical method could be assessed.
Summary : Water samples were filtered through glass fiber filters, passed
through XAD-2 resin. Eluted from XAD-2 with diethyl ether, dried, and ex-
tracted with hexane. Glass fiber filters were extracted with hexane and
cleaned up on Florisil. Analysis was by GC/EC. Recovery was 98%.
QUALITY ASSURANCE
Method blank : All glassware was precleaned; “no detectable levels were
observed.”
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
263
-------
Corcoran and Curry (1978)
Problems : Not reported.
Comments : The method blanks are indicative of minimal contamination, but
the accuracy and verification of the data are unknown.
Summary : Glassware and aluminum foil was extracted after cleaning. No
detectable levels were observed.
264
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Final Report on Potential Health Hazards Associated with the Use of Plastic
Pipe in Potable Water Systems
Departments of Health Services and Industrial Relations, California (1980),
Ref. No. 11
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Unspecified number of samples collected at different dwell
times and flowing versus nonflowing water.
Problems : Not reported.
Goal(s) : To determine the extent of health risks, if any, posed by the
use of plastic pipe systems in homes.
Comments : A static lab setup was used to simulate pipe exposure.
Summary : Potable water from PVC pipe was sampled for a variety of organic
pollutants.
SAMPLING
Container preparation : Washed in detergent followed by rinses in tap
water, deionized water, and pesticide grade hexane. Baked > 1 hr at 400°C.
Collection procedure : Collected 1.65 liters of water in an “organic-
free” graduated cylinder by opening a valve spout.
Storage conditions : Amber glass bottles stored at 4°C.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Spiked “samples” were used.
Problems : Not reported.
Comments : The sampling plan did not cover field blanks and therefore
does not permit assessment of contamination but only indicates changes in the
phthalate level.
Summary : Samples were collected in amber bottles washed in detergent
followed by rinses in tap and deionized water, then in pesticide grade hexane
and baked ? 1 hr at 400°C.
265
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Departments of Health Services and Industrial Relations, California (1980)
ANALYSIS
Measurement procedure
Cleanup/fraction : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : DMP - 10 pg/liter; DBP - 10 pg/liter; butybenzyl
phthalate (BBP) - 10 pg/liter; DEli? - 10 pg/liter; DOP - 10 pg/liter.
Problems : Not reported.
Instrument : Not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Detection limits were reported to be 10 pg/liter, but the ana-
lytical instrument used is not specified. The analytical method was not re-
ported and therefore cannot be assessed.
Summary : No cleanup was reported, nor was sample preparation reported.
Detection limit was 10 pg/liter.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Hot and cold tap water was collected prior to use.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
266
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Departments of
Comments:
Summary :
spiked samples
not reported.
Health Services and Industrial Relations, California (1980)
The QA information provided is of little value.
Little information reported on QA provisions. The use of
was mentioned, but the specific compounds or levels used were
267
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Isolation and Identification of Organic Contaminants in Groundwater
Dunlap et al. (1976a), Ref. No. 12
SURVEY DESIGN
Sampling sites : Land disposal site near Norman, Oklahoma. Moderately
to highly permeable soil with normally shallow water table, in use as a dump
u 50 years.
Sampling plan : No schedule reported. Control well up-gradient of land-
fill. Continuous water sampling for 126 hr at the two wells yielded two com-
posite samples.
Problems : Not reported.
Goal(s) : Identify organic pollutants contributed to groundwater by mu-
nicipal solid waste and septic tank effluents.
Comments : The only part of the article dealing with phthalates is the
landfill study. The experiment was not designed for specific compounds, but
was limited to determining dump-site leachables from one test well.
Summary : Project designed to identify organic pollutants contributed to
groundwater by municipal solid waste near Norman, Oklahoma.
SA 1PLING
Container preparation : Not reported.
Collection procedure : Adsorbed on activated carbon columns.
Storage conditions : Drained, sealed with “solvent washed t ’ aluminum foil.
Solvent not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : The collection method is not designed specifically for phthal-
ates. No field blanks were reported. The value of the sampling method could
be significantly improved by the use of field blanks and spiked blanks.
Summary : Collection was on activated carbon columns which were then
drained and sealed with solvent-washed aluminum foil.
268
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Dunlap et al. (1976a)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Carbon was dried at 40°C for 48 hr. Ex-
tracted 48 hr with CHC1 3 in Soxhlet. Extracts were filtered and vacuum con-
centrated to 3 ml. The carbon was then extracted with pure ethanol and evap-
orated to 2.0 ml (control well) and 4.0 ml (other wells).
Recovery : Less than 10% of organic matter present in groundwater
was recovered.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Chromatograms were very complex, requiring further frac-
tionation of both samples.
Instrument : GC/MS, 3% OV-1 on 100/120 mesh Gas Chrom Q, 3% Carbowax 20M
on 80/100 mesh Gas Chrom Q, or 10% SP-1200/1% H 3 P0 4 on 80/100 mesh Chromosorb
W(AW).
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : The analytical method leaves much to be desired. No method
blanks or limits of detection were reported. Recovery of organic matter was
reported to be less than 10%.
Summary : The activated carbon columns were extracted with CIIC1 3 and
C 2 H 5 OH. The extracts were reduced and further separated. The fractions were
analyzed by GC/NS. Quantitation was estimated.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Only control was a control well up-gradient of landfill.
Reference material : Used but not specified.
Precision and accuracy : Not reported.
Replicates : Not reported.
269
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Dunlap et al. (1976a)
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Quantitation was estimated.
Comments : This section appears to be of minimal value.
Summary : A control well up-gradient of the landfill was used to provide
background levels. No other standard QA procedures were used.
270
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Organic Pollutants Contributed to Groundwater by a Landfill
Dunlap et al. (1976b), Ref. No. 13
SURVEY DESIGN
Sampling sites : Land disposal site “ 1 mile south of Norman, Oklahoma.
Samples collected from three wells.
Sampling plan : 200 gal. water at each location. A control well was lo-
cated up-gradient from the landfill and two wells down-gradient.
Problems : Not reported.
Goal(s) : To investigate organic compounds contributed to groundwater by
a landfill containing refuse deposited below or near the water table.
Comments : This article is essentially the same as the other by Dunlap
(No. 12). The experimental design was limited to determining dump-site
leachables from one test well. A control site was utilized.
Summary : The study was to investigate organic pollutants contributed to
groundwater by a landfill near Norman, Oklahoma.
SANPLING
Container preparation : Not reported.
Collection procedure : Collected by pumping through activated carbon col-
umns. Pump was downstream of the activated carbon columns.
Storage conditions : Drained, sealed with solvent-washed aluminum foil
and transported to lab.
Stability demonstrated : Not reported.
Field blanks : An activated carbon column prepared identically and at
same time as the other two.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Collection method not optimized for phthalates, but the sam-
pling procedure was sound and used a field blank.
Summary : Samples were collected on activated carbon columns. A third
column was prepared and treated the same as the other two. This column served
as a blank.
271
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Dunlap et al. (1976b)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Activated carbon columns extracted with
CHC1 3 and C 2 H 5 OH. Extracts were reduced and later were further fractionated.
Recovery : Less than 10% of the organic matter present in the ground-
water was recovered.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/MS, 3% OV-1 on 100/120 mesh Gas Chrom Q, 3% Carbowax 20M
on 80/ 100 mesh Gas Chrom Q, or 10% SP-2100/1% H 3 P0 4 on 80/100 Chromosorb W(AW).
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Analytical method was not optimized for phthalates. Extrac-
tion efficiences were not reported and overall recoveries were low. The
method is of questionable value.
Summary : Samples were extracted from activated carbon with CHC1 3 and
C 2 H 5 OH, and reduced. The reduced extracts were run by GC/MS and then further
fractionated and rerun by GC/MS. Author states that results should be viewed
as “estimates” of probable groundwater contamination.
QUALITY ASSURANCE
Method blank : A third carbon column used as a blank gave chromatograms
similar to those from the control site.
Control sample : A control well up-gradient of the landfill.
Reference material : Used but not specified.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
272
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Dunlap et al. (1976b)
Interlab verification : Not reported.
Problems : Not reported.
Comments : No replicates used. A field blank gave results similar to
those of the control sample. The QA reported should have included other val-
idations such as precision and accuracy. Results should be viewed as qual-
itative.
Summary : Quality assurance provisions were in the form of a control well
up-gradient and a method blank (third activated carbon column).
273
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Monitoring to Detect Previously Unrecognized Pollutants in Surface Water
Ewing et al. (1977), Ref. No. 15
SURVEY DESIGN
Sampling sites : 204 sites; waterways near major industrial areas. Sites
selected so that “all principal types of industries would be represented.”
Sampling plan : Grab samples collected from August 1975 to October 1976.
Control sites upstream from discharges. One sample set from each site.
Problems : Not reported.
Goal(s) : Sampling and analytical survey to determine identities and
semiquantitative concentrations of organic compounds and inorganic elements
present in the waterways around industrial centers in the United States.
Comments : The design was applicable to monitoring studies used to de-
termine, in general, pollutants in a water system. Replicates or random sam-
pling would have added significantly to the design.
Summary : The purpose of the survey was to determine the identities and
semiquantitative concentrations of organic compounds and inorganic elements
present in waterways around industrial centers. Two hundred four sites were
sampled. Control sites upstream from discharge points were utilized.
SAflPLING
Container preparation : Glass bottles, 350°C overnight, then fitted with
Teflon-lined caps. Polyethylene containers rinsed with H:N0 3 , then water.
Collection procedure : Depth-integrated samples in 1-gal. glass bottles.
Some samples in polyethylene containers and some in 120-mi vials. All sealed
with Teflon-lined caps after being rinsed three times with sample.
Storage conditions : liNO 3 added to samples for inorganic analysis. All
samples refrigerated immediately.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Sampling method was adequate; however, a more stringent clean-
ing procedure and the use of field blanks would provide significant improvement.
Summary : Samples were collected in glass and polyethylene containers.
Glass bottles were heated to 350°C overnight. Polyethylene containers were
rinsed with nitric acid, then distilled water. All containers were rinsed
three times with sample. Samples were refrigerated pending analysis.
274
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Ewing et al. (1977)
ANALYSIS
Measurement procedure
Cleanup/fractionation : VOA samples purged. Others extracted with
CHC1 3 in liquid-liquid extractors after adjusting pH.
Recovery : Extraction efficiencies (amines) 100 ppm: 48 to 100%;
1 ppm: 47 to 100%; 50 ppb: 47 to 100%.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/FID and GC/MS, 12 ft x 1/4 in. glass column with 3% OV-17
on Gas Chrom Q, 60/80 mesh, 35°C for 5 mm, then 10°C/mm to 350°C. Spark-
Source Mass Spectral Analysis (SSNS), Instrumental Neutron Activation analysis
(INAA), and Energy Dispersive X-ray Fluorescence analysis (EDXRF) for inorganics.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Analytical protocol is widely accepted, although some of the
recoveries were low.
Summary : VOA samples were purged and trapped on Tenax before flashing
into GC. Other samples were extracted into chloroform and separated into acid
and base/neutral fractions. Extraction efficiencies for amines was 47 to 100%.
Analysis of organics was by GC/IIS. Techniques used were state of the art at
the time of the surveys.
QUALITY ASSURANCE
Method blank : Reported used.
Control sample : Internal standard.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : GC/MS.
275
-------
Ewing et al. (1977)
Interlab verification : Not reported.
Problems : Not reported.
Comments : Not enough information was provided to adequately assess QA
procedures. However, overall design of study would suggest that the data were
highly relevant.
Summary : Method blanks were used, but it was not reported how often.
Internal standards were used. Evaluation of different sorptive materials,
optimization of extraction solvents, and conditions are indicative of a well-
planned study.
276
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Fate of Selected Organic Compounds in the Discharge of Kraft Paper Mills into
Lake Superior
Fox (1976), Ref. No. 16
SURVEY DESIGN
Sampling sites : Red Rock, Ontario chosen because the effluent plume
could be identified and tracked.
Sampling plan : Grab samples taken four to six times per day on eight
occasions at 2-day intervals in July 1974. Background sample 20 km from mill.
Problems : Not reported.
Goal(s) : Determine the fate and effective zone of persistence of dis-
solved organic compounds in the effluent plume of a kraft paper mill.
Comments : Survey not designed specifically for phthalates; however, the
experiment was limited to grab sampling.
Summary : Sampling was conducted on eight occasions in the effluent plume
of a kraft paper mill near Red Rock, Ontario, to determine the effective zone
of persistence of dissolved organic compounds.
SAMPLING
Container preparation : Clean amber glass bottles with Teflon-lined caps.
Collection procedure : Water samples collected at 0.5 m below the surface
and then acidified. Samples collected from center of dye plume.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : The sampling method was not optimized for phthalates and did
not provide blanks. Sampling method would require further validation.
Summary : Samples were collected from the center of a dye-marked plume
and acidified.
277
-------
Fox (1976)
ANALYSIS
Measurement procedure
Cleanup/fractionation : XAD-2 resin columns eluted with residue-free
diethyl ether and evaporated down to 1 ml.
Recovery : Using pure compounds to represent classes, 80 to 100%.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Precipitation of low solubility free acids upon acidifi-
cation.
Instrument : GC/FID and GC/MS. 1.8 m S.S. column with 3% OV-1 on
Chromosorb W-HP.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Concentrating diethyl ether extracts by evaporation may be
hazardous. The data are of limited value since recoveries were based on the
use of pure compounds to represent classes.
Summary : Loaded XAD-2 columns were eluted with diethyl ether and concen-
trated to 1 ml. Extracts were analyzed by GC/FID and GC/MS. Recoveries re-
ported to be 80 to 100%.
QUALITY ASSURANCE
Method blank : Reported used; no dioctylphthalate found.
Control sample : Not reported.
Reference material : Used but not identified.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : GC/MS.
Interlab verification : Not reported.
278
-------
Fox (1976)
Problems : Not reported.
Comments : Could not account for presence of dioctylphthalate. Produced
blank free of DOP although the method for preparing blanks was not adequately
reported. No quantitation of plume values. Background levels of 10 to 15
Jg/liter, which may invalidate findings.
Summary : QA was primarily method blanks which reportedly showed no di-
octylphthalate.
279
-------
The Detection and Identification of Unknown Halogenated Compounds in
Environmental Samples
Freudenthal (1978), Ref. No. 17
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : Identification of halogenated compounds in environmental
samples by element specific mass spectrometer.
Comments : Unspecified number of grab samples collected.
Summary : This paper reports the finding of three phthalates in Rhine
River water by element specific GC/MS.
SANPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : None.
Summary : No information given.
280
-------
Freudenthal (1978)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/MS operated as a halogen detector by atomizing the column
effluent and tuning the MS to the m/e of a particular element.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Not enough information given to evaluate analytical method.
Summary : GC/MS operated as a halogen—specific detector.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : None.
Summary : None.
281
-------
GC/MS Analysis of Organic Compounds in Domestic Wastewaters
Garrison et al. (1976), Ref. No. 18
SURVEY DESIGN
Sampling sites : EPA’s Advanced Waste Treatment Research Laboratory -
Cincinnati and Blue Plains sewage treatment plant - Washington, D.C.
Sampling plan : August 1972 and December 1973. Unspecified number of
grab and composite samples collected “at intervals corresponding to the re-
tention time of each treatment system.”
Problems : Not reported.
Goal(s) : Develop analytical techniques to identify extractable, volatile
organic compounds in domestic wastewaters and provide specific compound data
to help determine wastewater treatment effectiveness.
Comments : Sample collection was adequate to define the effectiveness
of the treatment systems studied, but the results probably do not apply to
all wastewater treatment systems.
Summary : The goals were to develop analytical techniques, identify com-
pounds, and provide specific compound data to help determine wastewater treat-
ment effectiveness for extractable, volatile compounds in domestic wastewaters.
SAMPLING
Container preparation : Not reported.
Collection procedure : Collected in glass containers but aliquots were
placed into polyethylene containers.
Storage conditions : Stored in glass containers at 4°C. Polyethylene
containers were frozen.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : The sampling procedure was considered inadequate. The un-
certainty of using the aliquots stored in polyethylene cast doubt on source
of the phthalates reported.
Summary : Samples were collected in glass containers and stored at 4°C.
Aliquots also stored frozen in polyethylene containers. No field blanks or
field spikes reported used.
282
-------
Garrison et al. (1976)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Extracted using liquid-liquid extraction
scheme to separate components into acid and base/neutral fractions. Pesticide
grade CH 2 C1 2 was used for extraction. Water was distilled and pre-extracted.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/FID and GC/MS. 6 ft x 1/8 in. ID glass, 3% SE-30 on
Gas Chrom Q (80/100).
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : No method validation results such as recoveries were reported.
The validity of the analytical procedure is therefore questionable.
Summary : Samples were extracted into pesticide grade methylene chloride
using liquid-liquid extraction. Separated into acid and base/neutral frac-
tions. Analyzed by GC/FID and GC/MS.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : One for each sample. Appropriate amounts of solvents
and reagents taken through extraction scheme.
Reference material : Organic acid standards from Applied Science Labora-
tories, Inc., or Supelco, Inc.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : GC/MS.
283
-------
Garrision et al. (1976)
Interlab verification : Not reported.
Problems : Not reported.
Comments : No quantitation was done on phthalates identified. Not enough
information was provided to assess the quality assurance provisions.
Summary : QA was primarily in the form of control samples. Identifica-
tion was by GC/NS with spectra matched against standard spectra in the EPA-
Battelle computer files and the NIH mass spectral search system.
284
-------
Concentration and Fluxes of Phthalates, DDTs, and PCBs to the Gulf of Mexico
Giam et al. (1976a), Ref. No. 20
SURVEY DESIGN
Sampling sites : Thirty-five stations in the Mississippi River Delta and
the Gulf of Mexico.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : To analyze selected samples from the Gulf of Mexico for
phthalates.
Comments : This report is concerned mainly with the analytical results
and their significance. Criteria used to select sampling sites are unknown.
Apparently grab samples were collected to assess phthalate loading in the
Gulf.
Summary : The goal of this project was to analyze selected samples from
the Gulf of Mexico for phthalates and to assess the significance of the data.
The Mississippi River accounts for only one-fourth of the total DE}IP loading.
“The origins of the remaining inputs have not yet been determined.”
SAMPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : See other Giam articles for procedures.
Summary : No information was provided on sampling methods.
285
-------
Giam et al. (1976a)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : 0.1 ng/g phthalates.
Problems : Not reported.
Instrument : Not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : See other Giam articles for procedures.
Summary : No information was given concerning the analytical procedures.
The detection limit for phthalates was reported as 0.1 ng/g.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : None.
Summary : No QA information was reported as this was a discussion of
published data.
286
-------
Problems in Analysis of Organic Pollutants in Open-Ocean Samples
Giam et al. (1976b), Ref. No. 21
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : To propose methods for very low background sampling and analy-
sis, as well as for evaluation of procedures.
Comments : Design not part of report. Selected results of 10 biota,
9 water, and 6 sediment samples were reported.
Summary : Paper proposed methods for very low background sampling and
analysis, as well as for evaluation of procedures for biota, sediment, and
water.
SANPL ING
Container preparation : Glass and metal cleaned with detergent, water,
solvent, and heat. Aluminum foil heated to 320°C. XAD-2 resin extracted.
Collection procedure : Biota collected by hook and line or diving.
Plankton collected with nets. Sediment collected with corers. Water with
XAD-2 column.
Storage conditions : Biota, frozen. Plankton and sediment, precleaned
Mason jars with aluminum foil-lined caps.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Recommended use of spiked samples.
Problems : Not reported.
Comments : The sampling procedures recommended are very good. Emphasis
is on reducing possible sample contamination.
Summary : Recommends cleaning glass and metal with detergent, water, sol-
vent, and then heating. Recommends heating aluminum foil to 320°C overnight
and solvent extraction with XAD-2 resin. Also recommends use of spiked
samples.
287
-------
Giam et al. (1976b)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Proposes thorough cleaning of equipment but
does not report method for sample cleanup.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : 25 ng DBP and 50 ng DEJIP.
Problems : Not reported.
Instrument : Not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Analytical method not reported.
Summary : Analytical procedure covers only cleaning of glassware and
equipment.
QUALITY ASSURANCE
Method blank : Recommends use of method blanks.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Mentioned ‘ t satisfying” results.
Comments : The discussion of QA procedures is somewhat minimal. The rec-
ommended procedure for minimizing contamination in blanks is quite good.
Summary : Paper recommends procedures for minimizing contamination.
288
-------
Trace Analyses of Phthalates (and Chlorinated Hydrocarbons) in Marine Samples
Giam et al. (1976e), Ref. No. 24
SURVEY DESIGN
Sampling sites : Gulf of Mexico.
Sampling plan : Selected results reported on 10 biota, 9 water, 6 sedi-
ment samples, and some laboratory materials (e.g., Teflon®, Na 2 SO 4 , etc.).
Problems : Not reported.
Goal(s) : To analyze marine samples for phthalates and chlorinated hydro-
carbons.
Comments : Origin of samples given as the Gulf of Mexico. Grab samples
inferred to have been collected.
Summary : The purpose of this paper was to report a procedure for the
analysis of marine biota, water, and sediment. No design was reported.
SAMPLING
Container preparation : Equipment cleaned with detergent, rinsed with water
and acetone, heated to 320°C for 10 hr.
Collection procedure : Water aspirated through precleaned copper tubing
into a glass carboy, then passed through Amberlite XAD-2 resin.
Storage conditions : Biota at or below 0°C. Others not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : The sampling procedure should have yielded samples with a mm-
imum of phthalate contamination.
Summary : Samples were collected in containers cleaned with detergent,
rinsed with water and acetone, and heated to 320°C. Water samples were passed
through XAD-2 resin column. Biota samples were stored at or below 0°C.
289
-------
Giam et al. (1976e)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Biota macerated, extracted with acetonitrile,
methylene chloride-petroleum ether. Water eluted with acetonitrile and ex-
tracted with methylene chloride-petroleum ether. Sediment extracted with ace-
tonitrile, methylene chloride-petroleum ether. All through Florisil.
Recovery : From XAD-2 - DMP (abbreviation not specified): 79.8 to
85.7%; DBP: 94.1 to “ 100%; DEEP: 88.5 to 97.3%.
Linear recovery : Not reported.
Interferences : By GC: DBP and Aroclor 1254 interfere with each
other, and DEEP and Aroclor 1260 interfere with each other.
Limit of detection : 5 ng DEEP = 50% full-scale deflection.
Problems : Coelution with Aroclors.
Instrument : GC/EC. Biota: 1.8 in x 0.64 cm OD glass, 3% SE-30 on Gas
Chrom Q (100/120); water and sediment: 1.8 m x 0.64 cm OD, 3% SE-30 on
Chromosorb WHP (100/120); confirmation: 1.8 m x 0.64 cm OD, 1.5 % SP-2250
and 1.95% SP-2401 on Supelcon AW-DMCS (100/120).
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : The analytical procedure seems quite acceptable based on the
recovery values reported.
Summary : Samples were extracted with acetonitrile, methylene chloride-
petroleum ether, and cleaned up on a Florisil column. Recoveries of phthal-
ates were in the range 79 to 100%. Analysis was by GC/EC with 5 ng DEEP
yielding 50% full-scale deflection.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
290
-------
Giam et al. (1976e)
Replicates : Not reported.
Method verification : GC/EC using a different column.
Interlab verification : Not reported.
Problems : Not reported.
Comments : The only quality assurance provisions reported were procedures
to minimize background in blanks. With the addition of replicate samples and
spiked blanks the method could be better evaluated.
Summary : Procedures given to minimize background in sample blanks.
Verification by GC/EC using a different column. DEHP levels of laboratory
items reported.
291
-------
Estimation of Fluxes of Organic Pollutants to the Marine Environment -
Phthalate Plasticizer Concentration and Fluxes
Giam (1977), Ref. No. 25
SURVEY DESIGN
Sampling sites : Not applicable.
Sampling plan : Mean concentration of water (31), sediment (34), air
(6), and biota (20) samples were reported.
Problems : Not applicable.
Goal(s) : Develop a mass balance model for fluxes of DEHP.
Comments : The mass balance model was developed using a combination of
data and assumptions. Author states that atmospheric input to the Gulf was
the most important route but cautions that “direct field measurements are
important.”
Summary : This paper deals primarily with a mass balance model for es-
timation of fluxes of DEHP in the Gulf of Mexico. Sampling and analysis as
in reference 27.
SAMPLING
Container preparation : Not reported.
Collection procedure : Water was solvent extracted or passed through XAD-2
resin. Sediment with metal coring device; biota by hook and line or trawl.
Air through columns of Florisil or polyurethane foam.
Storage conditions : Biota and sediment frozen.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : This section only briefly outlines the sampling method and
is of limited value.
Summary : Water samples were solvent extracted on site or adsorbed on
XAD—2 resin. Biota samples were collected by hook and line or trawl. Sedi-
ment samples were collected with a metal coring device. Air was adsorbed on
Florisil or polyurethane.
292
-------
Giam (1977)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Extraction with organic solvents, separation
by column chromatography.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/EC; column not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : This section lacks enough information to assess its value.
Summary : Samples were extracted with organic solvents, cleaned up by
column chromatography, and analyzed by GC/EC.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Chemical derivatization.
Interlab verification : Not reported.
Problems : Not reported.
Comments : None.
Summary : No QA data of significance reported.
293
-------
Phthalate Ester Plasticizers: A New Class of Marine Pollutant
Giam et al. (1978a), Ref. No. 27
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Resutls were reported on samples collected from the
Mississippi Delta (36), Gulf Coast (19), Open Gulf (10), Gulf of Mexico (28),
and North Atlantic (15).
Problems : Not reported.
Goal(s) : To analyze for phthalate esters and chlorinated hydrocarbons in
air, water, sediment, and biota samples predominately from the Gulf of Mexico.
Comments : Basically same information as other articles by Giam. Grab
samples apparently collected.
Summary : The purpose of the project was to analyze for phthalate esters
and chlorinated hydrocarbons in air, water, sediment, and biota samples pre-
dominately from the Gulf of Mexico.
SAMPLING
Container preparation : Not reported.
Collection procedure : Sediment collected with metal coring devices.
Water extracted directly or adsorbed on XAD-2. Biota collected with hook and
line or trawl. Air adsorbed on Florisil or polyurethane foam.
Storage conditions : Sediment and biota frozen.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : This section is too brief to be of value.
Summary : Sampling methods are brief. Sediment collected by metal coring
device. Biota collected by hook and line or trawl. Water extracted directly
or adsorbed on XAD-2. Air adsorbed on Florisil or polyurethane foam. Sedi-
ment and biota samples frozen.
294
-------
Giam et al. (1978a)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Extraction with organic solvents. Cleanup
by column chromatography.
Recovery : “90% or better.”
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Instrument : GC/EC, column not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Too little information provided to properly assess this section.
Summary : Samples were extracted with organic solvents and cleaned up by
column chromatography. Analysis was by GC/EC. Recoveries of “90% or better”
were mentioned as well as “background values of 50 ng.”
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Chemical derivatization.
Interlab verification : Not reported.
Problems : Not reported.
Comments : None.
Summary : Appropriate QA information was not provided.
295
-------
Water Pollution: Organic Compounds in the Charles River, Boston
Hites and Biemann (1972), Ref. No. 30
SURVEY DESIGN
Sampling sites : One site in Charles River. Basis unknown.
Sampling plan : Grab sampels collected weekly for 2 months; one site only.
Problems : Not reported.
Goal(s) : Characterization of major organic pollutants in river system.
Comments : Grab samples of river water were collected to show that GC/MS
is a powerful survey technique to identify the general nature of organic pol-
lutants.
Summary : The characterization of the major organic pollutants was
achieved by GC/MS identification and HPLC quantitation.
SAMPL ING
Container preparation : Not reported.
Collection procedure : Brown jug lowered to a depth of 0.9 to 1.5 m from
Havard Bridge.
Storage conditions : Sample was immediately acidified and extracted with
methylene chloride.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Sampling consisted of collection of grab samples.
Summary : Other than the procedure for collecting the sample, no comments
were made about stability, blanks, container preparation, etc.
296
-------
Hites and Biemann (1972)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/NS, 0.1% OV-1 on glass beads, 70 to 260°C at 8°C/mm.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Minimal method validation information given.
Summary : Analysis was performed by GC/MS with 0.1 OV-1 column.
QUALITY ASSURANCE
Method blank : Procedural blank consisted of 3.5 liters of doubly dis-
tilled water.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Information given was minimal and results should be termed
“tentative.”
Summary : Use of distilled water as a procedure blank was the only QA
mentioned.
297
-------
Analysis of Trace Organic Compounds in New England Rivers
Hites (1973a), Ref. No. 31
SURVEY DESIGN
Sampling sites : Two river systems were sampled. Monatiquot River was
used to determine the influence of a factory on the receiving waters. Merrimack
River was sampled downstream from five cities which should reflect the sum of
pollutants from these urban sources.
Sampling plan : Upstream and downstream samples from the Monatiquot col-
lected during March 1973. Merrimack — samples collected from mid-river at 2
to 5 ft during 1 day in April and 1 day in January. Total number of grab sam-
ples collected was not specified.
Problems : Not reported.
Goal(s) : Monitor the environment to permit early detection of potential
organic pollutants.
Comments : Survey design limited to grab sampling and did not address
seasonal or spatial variation in the rivers.
Summary : Two rivers were sampled to determine the influences of a fac-
tory and five urban areas.
SAMPLING
Container preparation : Not reported.
Collection procedure : Referred to Hites, Ref. No. 30.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Number of samples collected is unknown, as is the preparation
and subsequent storage conditions, all of which add an unknown to the data.
Summary : Four-liter water samples were collected.
298
-------
Hites (1973a)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/MS (referred to Hites, Ref. 30); “other” column listed as
150 ft x 0.02 in. stainless steel capillary coated with OV-101.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Lack of method validation.
Summary : Only information given was that samples were analyzed by GC/MS.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : The source and validity of the DEHP data are open to question.
Summary : No information reported.
299
-------
Phthalates in the Charles and the Merrimack Rivers
Hites (1973b), Ref. No. 32
SURVEY DESIGN
Sampling sites : Four sites in Charles River.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : See Hites (1972), Ref. No. 30.
Comments : This is a position paper to describe the merits of GC/MS
analysis.
Summary : Author presented evidence to demonstrate “the power of modern
analytical methods for the identification and determination of organic pol-
lutants at the fractional parts per billion level in water.”
SANPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
piked blanks : Not reported.
Problems : Not reported.
Comments : Information is minimal. Reader is referred to Ref. No. 30.
Summary : The analytical results of duplicates collected at two depths
from three sites were reported, but whether other samples were collected is
unknown.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
300
-------
Hites (1973b)
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GCIMS: 150 x 0.32 cm, 0.1% OV-1 on glass beads, temperature
program 70 to 260°C at 8°C/mm. HPLC: 120 x 0.32 cm, Porasil T operated at
400 psi, 23°C with methylene chloride as the liquid phase; detection at 254 nm.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Extraction scheme was reported in Ref. No. 30.
Summary : Samples were analyzed by GC/MS, and phthalates quantitated by
HPLC.
QUALITY ASSURANCE
Method blank : A procedural blank used.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Four sets of duplicates were reported.
Method verification : Identification by GC/MS and quantitation.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Duplicate results reported at a given depth agreed within 0.1
ppb. Lack of information other than “procedural blank showed only very small
amounts of material” means that data should be considered qualitative.
Summary : A procedural blank was analyzed by GC/IIS. Quantitation of the
phthalates was by HPLC compared to an internal standard.
301
-------
Potentially Toxic Organic Compounds in Industrial Wastewaters and River
Systems
Hites et al. (1979), Ref. No. 34
SURVEY DESIGN
Sampling sites : Study 1 - Upstream and downstream from specialty chem-
ical plant. Study 2 - Industrialized area of river and also source of
drinking water supply for several cities.
Sampling plan : Study 1 - Grab samples of water collected at clarifier
(1), upstream (2) and downstream (13); sediment (19) downstream only. Study
2 - Water collected near point sources and at two different seasons (13 in
August/October and 5 in Ilarch).
Problems : Not reported.
Goal(s) : To identify compounds discharged into receiving waters, those
already present, and those formed through in situ transformation.
Comments : Grab samples collectd to assess influence of chemical point
sources on a given system. Study 1 appears to have been a single sampling
of multiple points along a river system. Temporal differences investigated
in Study 2 with 5 of the 13 sites resampled.
Summary : Survey designed to provide samples for detailed organic analy-
sis by various sample concentration techniques and GC/MS.
SAMPLING
Container preparation : Not reported.
Collection procedure : Water samples - amber bottles with Teflon-lined
caps; sediment - “dredge-type” sampler to collect and then stored in glass
jars with aluminum foil-lined caps.
Storage conditions : Water samples stored in refrigerator; samples for
solvent extraction were acidified to pH 2 and MeCl 2 added; sediments were
packed in dry ice.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Samples preserved immediately after collection--an effective
procedure for minimizing artifacts. Without mention of container preparation,
the validity of the samples is questionable because of the unknown possibility
of contamination from the sampling equipment.
302
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Hites et al. (1979)
ANALYSIS
Summary : Water samples were cooled to refrigerator temperature, and
those for solvent extraction were acidified and solvent added; sediments were
frozen after collection.
Measurement procedure
Cleanup/fractionation : Study 2 - 5% deactivated silica gel and base
extraction. Study 1 - not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Fatty acids.
Limit of detection : “ 1 ppb.
Problems : Not reported.
Instrument : GC using EC, FID, and MS; columns: 180 cm x 2 mm glass with
3% SP-2100 and 25 m x 0.25 mm glass capillary with SE-52.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Blanks were run through cleanup procedure and showed no con-
tamination. Solvents used were nanograde but were not concentrated and
checked by GC for contamination; thus there would still be some room for
phthalate contamination.
Summary : Grab water samples were extracted in the collection bottle by
stirring overnight. Some extracts were cleaned up using silica gel followed
by basic extraction cleanup. Analysis of the extracts was carried out by GC
using EC, FID, or MS and authentic standards.
•QUALITY ASSURANCE
Method blank : Used in cleanup procedure of Delaware River (Study 2)
extracts. Study 1 - not reported.
Control sample : Not reported.
Reference material : Not reported.
303
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Hites et al. (1979)
Precision and accuracy : 20%.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Low levels of DEHP reported could conceivably be due to con-
tamination plus its presence in the wastewater. Quantitative identification
good, however, because of the use of MS. Lack of method recoveries indicates
results are semiquantitative in nature.
Summary : Minimal quality assurance procedures were reported.
304
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PCBs, Phthalates and Other Organic Compounds in Groundwater
Jorque (1973), Ref. No. 40
SURVEY DESIGN
Sampling sites : Landfill near Norman, Oklahoma. Five wells were used.
Sampling plan : Two wells located up-gradient, two in the landfill, and
one down-gradient.
Problems : Not reported.
Goal(s) : To find evidence of groundwater contamination with polychiorin-
ated biphenyls and other chlorinated hydrocarbons and to determine the major
organic compounds polluting the groundwater.
Comments : The design is adequate for identification of groundwater
contamination, but should have included randomization or replication to have
a complete experimental design.
Summary : The goal of finding evidence of groundwater contamination and
identifying major organic pollutants contributed by a landfill near Norman,
Oklahoma, was reached by sampling groundwater from five wells drilled at the
site, up-gradient, and down-gradient.
SAMPLING
Container preparation : Glassware washed with detergent and chromic acid,
rinsed with water and acetone.
Collection procedure : Water was pumped through columns using a Carbon
Absorption Method (CAN) sampler containing activated charcoal and one sample
through XAD-2 resin.
Storage conditions : Drained and dried with nitrogen at 65°C.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Filtering the water prior to the gravity flow of water through
the XAD-2 resin column was required.
Comments : The quality of the sampling portion of this project could have
been improved by using spiked blanks and field blanks.
Summary : Groundwater was pumped through an all-glass and Teflon system
containing an activated carbon trap. Glassware was washed with detergent and
chromic acid and rinsed with water and acetone.
305
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Jorque (1973)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Carbon extracted with CHC1 3 for 36 hr in
Soxhlet. Extract dried with Na 2 SO 4 and concentrated. XAD-2 flushed with hot
ethanol and distilled water. Aqueous solution extracted with hexane and con-
centrated. The extract fractionated on “silicar” column with hexane, benzene,
chloroform, and 1:1 CHC1 3 -NeOH.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/MS. 1% OV-1; 10% QF—1, and 5.3% DC-200 columns.
Linear response : Reported as linear for phthalates.
Stability of response : Not reported.
Problems : Not reported.
Comments : Adequate extraction/cleanup technique but validation results
are needed to determine the effectiveness and limits of the method.
Summary : Carbon was extracted with chloroform for 36 hr in a Soxhlet
extractor. The extract was dried with Na 2 SO 4 , fractionated, and analyzed by
GC/MS.
QUALITY ASSURANCE
Method blank : Apparently used once. Extracted with CHC1 3 , dried with
Na 2 SO 4 , and evaporated. Not reported if the samples were corrected for the
blank values.
Control sample : Not reported.
Reference material : Reported standard phthalates. Source not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
306
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Jorque (1973)
Interlab verification : Not reported.
Problems : Not reported.
Comments : Quality assurance as reported was minimal, although a compar-
ison of the blank and sample results was made.
Summary : A method blank was done on activated carbon.
307
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GC/MS Analysis of Organic Compounds in Treated Kraft Paper Mill Wastewaters
Keith et al. (1976a), Ref. No. 42
SURVEY DESIGN
Sampling sites : Two paper mills with different treatment systems.
Sampling plan : If possible, a slug of waste was sampled before it en-
tered the waste treatment system and, according to the retention time in the
system, sampled the same slug after it had been treated.
Problems : Not reported.
Goal(s) : To characterize a wastewater chemically, trace the dissolved
volatile organics through a treatment system, and correlate this information
with the traditional pollution parameters (BOD, TOC).
Comments : In one case (Interstate Mill) the stabilization pond had a
retention time of at least 3 months, and no attempt was made to take a sam-
ple of that “slug” after treatment.
Summary : Study was designed to follow a given slug of wastewater through
the treatment system used at that facility.
SANPL ING
Container preparation : Not reported.
Collection procedure : In March 1972, plastic containers used for grab
samples; in January 1974, composite samplers used with carbon filters.
Storage conditions : -10°C.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Inability to collect the same slug of wastewater after treat-
ment due to long residence time in system.
Comments : Use of plastic bottles casts doubt on validity of any phthal-
ate data reported.
Summary : Grab and composite samples were collected at two paper mills
before and after treatment if possible. Each plant was sampled twice, 2 years
apart.
308
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Keith et al. (1976a)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/FID and GC/MS on 50 ft SCOT capillary coated with
Carbowax 20M/TPA.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Data table for compounds identified in paper mill effluents
lists only “a dioctyl phthalate,” - listed as unconfirmed with no levels
specified.
Summary : Grab samples were extracted with pesticide grade chloroform as
were the carbon filters. After concentration the extracts were analyzed by
GC/FID and GC/MS. Some samples were methylated.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
309
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Keith et al. (1976a)
Comment : Data reported are unconfirmed and tentative at best.
Summary : Ninimal quality assurance measures reported.
310
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Identification of Organic Compounds in Drinking Water from Thirteen U.S.
Cities
Keith et al. (1976), Ref. No. 43
SURVEY DESIGN
Sampling sites : Results of analyzing 13 water plants in 11 cities
across U.S. are reported.
Sampling plan : Grab samples and carbon adsorption were used at New Orleans
while carbon adsorption used for the remaining 10 cities.
Problems : Not reported.
Goal(s) : Determination of the identity, concentration, and potential ef-
fects of organic chemicals in water supplies of representative cities across
the nation.
Comments : Survey design for National Organics Reconnaissance Survey
(NORS). Inferred that a single sampling period was used to characterize the
organic content of drinking water from various cities.
Summary : Survey design for NORS not discussed, but data presented are
monitoring data for several cities.
SAMPLING
Container preparation : Not reported.
Collection procedure : Used XAD-2 columns and CAM samplers.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Activity and cleanliness of carbon used for concentrating or-
ganics in water.
Comments : Detailed sampling procedures given in EPA reports. Activity
and cleanliness of carbon used in CAM samples could be a source of erratic ex-
traction efficiencies and contamination.
Summary : Samples of various drinking water supplies were concentrated
using CAM samplers with carbon and XAD-2 resin cartridges.
311
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Keith et al. (1976)
ANALYS IS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Lowest reported value 0.04 ppb.
Problems : Not reported.
Instrument : GC/FID with 3% SP-2100 and GC/MS with SP-2100 capillary.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : New Orleans samples quantitated using GC/FID peak areas; re-
suits for 10 cities in NORS quantitated using RGC/tIS peak areas. Lack of
recovery data for extraction efficiency of DEHP from carbon adds a degree of
error to the analytical method.
Summary : Carbon chloroform extracts from CAN samplers analyzed by GC/FID
and GC/MS. Soxhiet extractions were carried out in a special room designed to
minimize contamination.
QUALITY ASSURANCE
Method blank : Used for every method of sample concentration, including
separate adsorbent/solvent blanks for each carbon and resin extract.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
312
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Keith et al. (1976)
Comments : Method blanks examined for interfering background components
by FID and MS but values not reported. Actual recoveries for effectiveness of
carbon filters not given. Data reported can be considered only as semiquanti-
tative.
Summary : Solvent blanks and carbon blanks generated, but data not pre-
sented on whether blanks were subtracted from values in tables.
313
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Sources of Toxic Pollutants Found in Influents to Sewage Treatment Plants
Levins et al. (1979), Ref. No. 46
SURVEY DESIGN
Sampling sites : Cincinnati, St. Louis, Atlanta, and Hartford. Selection
of plants based on geographic location, plant and drainage basin size, and
having secondary or better treatment technology.
Samp 4ng plan : Six days at each site “resulting in 30 to 60 24-hr or
48-hr composite samples per city.”
Problems : Not reported.
Goal(s) : To determine the relative significance of the major source type
(residential, commercial, industrial) and their contributions of priority pol-
lutants to POTW influents.
Comments : The survey design appears adequate for an indication of the
level of pollutants in the systems studied.
Summary : Influents to POTWs were sampled in Hartford, Connecticut,
St. Louis, Missouri, Atlanta, Georgia, and Cincinnati, Ohio, to determine the
relative significance of the major source type--residential, commercial,
industrial--contributions of priority pollutants.
SA 1PLING
Container preparation : Not reported.
Collection procedure : Manual collection using a 2—liter stainless steel
bucket.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : The description of sampling methods is inadequate.
Summary : Samples were collected manually using 2-liter stainless steel
buckets.
ANALYSIS
Measurement procedure
Cleanup/fractionation : EPA Screening Protocol - Priority Pollutants.
Recovery : 42 to 74% for phthalates.
314
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Levins et al. (1979)
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : 10 pg/liter for phthalates.
Problems : Not reported.
Instrument : EPA Screening Protocol - Priority Pollutants.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : The analytical procedure was quite adequate. The emphasis of
the paper is not, however, on the chemical analysis.
Summary : Samples were analyzed by the EPA screening protocol for prior-
ity pollutants. The detection limit for phthalates was 10 pg/liter, and the
recoveries were 42 to 74%.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : 29 to 84 RSD.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Not enough data reported to comment.
Summary : The EPA “QA Program for the Analysis of Chemical Constituents”
(1978) was used.
315
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Uptake and Fate of D-2-ethylhexyl Phthalate in Aquatic Organisms and in a
Model Ecosystem
Metcalf (1973), Ref. No. 49
SURVEY DESIGN
Sampling sites : Not applicable.
Sampling plan : Unknown number of fish, snail, clam, Daphnia, and Elodea
were used in DEHP uptake experiments.
Problems : Not reported.
Goal(s) : To study the metabolism and possible bio-magnification of DEHP
in a variety of aquatic organisms and its ecological behavior in food chains
of a laboratory model ecosystem.
Comments : No actual field survey conducted.
Summary : Controlled laboratory studies of the uptake and metabolism of
DEHP in aquatic organisms in a model ecosystem were performed. No monitoring
data presented.
SAMPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : None.
Summary : Sampling of the model ecosystem was not discussed.
ANALYSIS
Measurement procedure
Cleanup/fractionation : TLC.
Recovery : 14 C-labeled DEHP used in study. Scintillation counting
used to detemine amount of DEHP left and any evidence of metabolism.
Linear recovery : Not reported.
316
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Metcalf et al. (1973)
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : Not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Total recovery for method not discussed but broken down into
recoveries for DEJIP and each metabolite. Major degradative pathways inferred
to be through hydrolysis of the ester groups to produce the monoester, then
phthalic acid, and finally phthalic anhydride.
Summary : Aquatic organism exposed to ‘ 4 C-labeled DEMP spiked water and
analyzed by homogenization and extraction with ether, TLC separation, and sub-
sequent scintillation counting. Identities of metabolites determined by chro-
matography (TLC) with known standards. Actual method recoveries not generated
for DEHP but rather results expressed in percent of metabolites found versus
percent DEHP remaining.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Use of 14 C-labeled DEHP virtually eliminates the need for ex-
tensive quality assurance measures in terms of method blanks.
Summary : No method blanks, control samples, or other standard quality
assurance measures were taken because of the nature of the radioactive metab-
olism experiments performed.
317
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Identification of Phthalate Esters in River Water by High Performance Liquid
Chromatography
Mon (1976), Ref. No. 51
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : To show applicability of the discussed HPLC method to river water.
Comments : No survey design discussed.
Summary : RPLC method applied to analysis of river water of unknown origin.
No actual survey design implied.
SAMPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Sampling of river(s) not discussed.
Summary : Unknown river sampled in an unknown manner.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Extraction efficiency for di-n-butylphthalate reported:
5 mm shaking time, 88%; 10 mm, 99%; 20 mm, 100%.
Linear recovery : Not reported.
Interferences : Not reported since UV system did not detect chlorin-
ated hydrocarbons and other pesticides.
Limit of detection : 2 ppb in river water.
318
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Mon (1976)
Problems : Not reported.
Instrument : HPLC system: syringe pump and a variable wavelength detector.
Column - 50 cm x 2 mm packed with Shodex Polymer Beads ffP-255. Eluent: methanol
(System B), hexane (System A).
Linear response : System A: 0.02 to 6 ppm, extract concentration.
System B: Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Use of these separation modes with a UV detector provides the
basis for a very sensitive method for the determination of phthalate esters in
river water. The method is a viable one for samples which do not require
cleanup. Recovery for extraction of DEHP from water not reported so final re-
suits may be questionable.
Summary : System A (normal hexane phase) eluted phthalates in order of
decreasing chain length or increasing polarity. System B (reversed phase,
methanol) eluted phthalates in order of increasing chain length or decreasing
polarity; System C (GPC, chloroform) governed by steric exclusion effects and
eluted phthalates in order of decreasing chain length.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : Method blanks were not reported nor were results from any
spiked samples. River water results (“i 10 ppb) may reflect some contamination
and unknown extraction efficiency.
Summary : Filters used to filter samples were preextracted with hexane.
Other solvents used for extraction or for the LC eluent system were re-
distilled before use.
319
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Phthalic Acid Esters in Water
Morita et al. (1974), Ref. No. 52
SURVEY DESIGN
Sampling sites : Based on suspected levels of contamination.
Sampling plan : River water sampled at 12 stations, well water (5) and
city water (not reported). Grab samples apparently collected.
Problems : Not reported.
Goal(s) : Determination of DEHP and DBP contamination in various water
sources in Japan.
Comments : Survey designed to assess phthalate contamination in river,
well, and treated city water of Tokyo. Data generated can be considered as
monitoring data for areas involved.
Summary : Sample sites ranged from upper tributary streams, to raw water,
to the city treatment system. City and suburban wells were also sampled.
SANPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Bottle preparation, sample storage, etc., not reported. Since
bottle preparation and sampling methods were not reported, contamination could
have occurred before sampling.
Summary : No actual sampling methods were reported, only locations.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
320
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Morita et al. (1974)
Interferences : Not reported.
Limit of detection : 0.5 ppb for 500-mi sample.
Problems : Not reported.
Instrument : GC/FID - dual columns: (1) OV-17 and (2) SE-30.
Linear response : Not reported.
Stability of response : Repeated injections had RSD of 10%.
Problems : Not reported.
Comments : Ether distilled twice before use; acid also distilled; Na 2 SO 4
rinsed with distilled ether and dried at 200°C. Caution taken to avoid con-
tamination of reagents adds credibility to the analysis. However, lack of
recoveries indicates results reported may only be semiquantitative.
Summary : Water samples were adjusted to pH of 2 with HC1 and extracted
three times with ether. Extractwas dried, concentrated to 0.5 ml, and ex-
tracted by dual column GC/FID.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Peaks in GC/FID chromatogram verified by IR and
GC/MS.
Interlab verification : Not reported.
Problems : Not reported.
Comments : No mention of sample collection procedures, bottle preparation
procedures, or method blanks casts doubt on validity of these findings.
Summary : Although the existence of DEHP and BlIP was verified in the sam-
ples, no mention was made of method blanks or control samples.
321
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Pesticides in the Illinois Waters of Lake Michigan
Schacht (1974), Ref. No. 58
SURVEY DESIGN
Sampling sites : Lake Michigan; streams feeding into the lake; sources
of contamination (sewage, etc.) being dumped into feed stream.
Sampling plan : Samples of sediment (50) and water (45) were collected
from tributaries, streams, near-shore, and off-shore stations in and around
sewage treatment plants and associated waters. Fish samples (255) were col-
lected from the lake.
Problems : Not reported.
Goal(s) : Determination of levels of pesticides discharged as well as
levels then found in Lake Michigan water, sediment, and fish. Phthalates were
secondary to the major goal.
Comments : Design inferred to be a monitoring of the open lake and tribu-
taries near sewage treatment plants.
Summary : Survey design ostensibly formed to determine levels of various
pesticides in Lake Michigan and their source, but no information given as to
actual design formulation. Grabs of sediment, fish, and 24-hr water composites
were collected over a 3-year period.
SANPLING
Container preparation : Glass bottles with aluminum foil liners, rinsed
with Nanograde hexane.
Collection procedure : Fish from commercial fishermen; water by grab sam-
pling and composite samplers; sediments collected directly in glass bottles or
by use of a Ponar dredge.
Storage conditions : Fish frozen; sediment stored at ambient; water not
reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Composite sampler rubber tubing replaced with glass tubing to
prevent contamination. Water and sediment sampling procedure appeared to elim-
inate source of contamination. Fish samples may have been contaminated while
taking a filet or when stored in aluminum foil if the foil was not rinsed with
solvent.
322
-------
Schacht (1974)
Summary : Water samples collected in glass bottles. Both grab samples
and composite (24 hr) samples taken. Fish obtained from local fishermen and
stored frozen in aluminum foil. Sediment samples taken in glass jars by hand
or with a Ponar dredge.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Florisil standard column; sodium sulfate
heated overnight at 450°C.
Recovery : Fish, 85 to 95%; sediments, 90%; water, 90%. Spike
levels not reported, however.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Fish, 10 ppb; sediment, 1 ppb; water, 100 ppt
(all DE}IP data).
Problems : Not reported.
Instrument : Varian 204; 63 Ni 255°; column 200-210°, inj. 225°. Pesticide
analysis: 1/8 in. x 8 m column, 2.0% QF-1 and 1.25% OV-17 on 100/200 mesh
Supelcoport. For DEHP: 1/8 in. x 1 in column, 4% QF-1 and 2.0% OV-17.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : A well-defined analytical scheme was used to separate the ana-
lytes from the matrix. Although not specifically stated except for sodium
sulfate, mention of the decontamination procedures used, if any, would remove
any doubt about the validity of the data.
Summary : “FWPCA Method for Chlorinated Hydrocarbon Pesticides in Water
and Wastewater 1 ’ used with some modifications. Results not corrected for re-
covery.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
323
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Schacht (1974)
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Two columns (not specified); one more, one less
polar than specified, were used.
Interlab verification : Yes, but no other information.
Problems : Not reported.
Comments : Sample fortification and recovery results mentioned in table
of contents but missing from the report. Results can be considered somewhat
quantitative since method blanks not reported.
Sununary: Spike recovery and detection limit data were reported, but use
of method blanks was not.
324
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Organic Compounds in the Delaware River
Sheldon and Hites (1978), Ref. No. 60
SURVEY DESIGN
Sampling sites : Based on industrial effluent, from locations along the
Delaware River.
Sampling plan : Grab samples taken in August (11), October (2), and
March (5).
Problems : Not reported.
Goal(s) : Identify compounds present in the Delaware River between
Wilmington and Trenton.
Comments : March samples taken were more widely spaced than the first two
groups. Eleven sampling points over 80 miles.
Summary : Survey design based on industrial discharge locations along the
Delaware River, and samples taken during different seasons. Designed to iden-
tify organic compounds in Delaware River and trace compounds to their dis-
charge point.
SAMPLING
Container preparation : Not reported; 1-gal. amber glass bottles with
Teflon-lined caps.
Collection procedure : Grab samples taken, from 3.5 to 21 liters in size.
Storage conditions : Preserved in field with CH 2 C1 2 and HC1, stored at
refrigerator temperatures.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Both field and spiked blanks are important in this type of
survey and should have been reported. Any report of phthalates in the samples,
especially low level, should be viewed cautiously in light of the apparent
absence of blanks.
Summary : Grab samples collected in 1-gal. amber glass bottles with
Teflon-lined caps. Samples preserved in the field and returned to lab as soon
as possible for workup. No indication of the use of field blanks.
325
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Sheldon and Hites (1978)
ANALYSIS
Measurement procedure
Cleanup/fractionation : HPLC fractionation and silica gel cleanup;
also base extraction.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Fatty acids and “non chromatographable organic
material”.
Limit of detection : 0.06 ppb (lowest reported value).
Problems : Artifact formation during the course of sampling, concen-
tration, and/or analysis procedures. May not affect phthalate analysis.
Instrument : Ref. No. 30 cited.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Details of analytical procedure cited in Ref. No. 30. Proce-
dure not specifically designed for phthalates.
Summary : General methylene chloride extraction with silica gel cleanup
and identification by GC/MS using authentic standards. Di-(2-ethylhexyl)adi-
pate also found.
QUALITY ASSURANCE
Method blank : Run for all cleanup and concentration steps only. Levels
found reported as “no significant contamination”.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : ±50% to an order of magnitude. Method referred
to as primarily qualitative.
Replicates : Not reported.
Method verification : Not reported.
326
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Sheldon and Hites (1978)
Interlab verification : Not reported.
Problems : Identification of artifacts as such.
Comments : Method blanks only indication of quality assurance measures.
Absence of field blank a significant omission.
Summary : Quality assurance limited to use of method blanks for cleanup
and concentration only. No recovery data given. Method referred to as pri-
marily qualitative.
327
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Sources and Movement of Organic Chemicals in the Delaware River
Sheldon and Hites (1979), Ref. No. 61
SURVEY DESIGN
Sampling sites : Based on location of chemical plants, sewage treatment
plants, and water treatment plants.
Sampling plan : Chemical plant study involved a 24-hr composite at the
plant and grab samples of the effluent to and through the water treatment
plant. A 1-day composite sample per week for 10 weeks was used to determine
influx of sewage treatment effluent through the water treatment plant.
Problems : Not reported.
Goal(s) : To follow a 24-hr slug of industrial wastes through the cycle
from “Plant A t to the finished drinking water and to monitor the water from
the sewage treatment to the drinking water.
Comments : “The sampling scheme was designed to account for retention
times between the various sampling locations, as well as for the tidal move-
ments in the river.” Design was adequate to give an indication of problems,
but continuous rather than once a week sampling would have been better.
Summary : Sampling designed to trace the movement of various industrial
chemicals from their origin, through the river, and into Philadelphia’s drink-
ing water supply.
SANPLING
Container preparation : Not reported; used glass bottles with Teflon-
lined caps.
Collection procedure : One 24-hr composite sample; the rest were compos-
ites of 200-ml grab samples.
Storage conditions : Stored in dark and on ice during transport; stored
in refrigerator at lab.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Used to establish recoveries; used pre-extracted water.
Problems : Not reported.
Comments : Samples preserved on site with CH 2 C1 2 and HC1. No bottle
preparation given. Absence of bottle preparation measures and field and/or
bottle blanks subtracts a degree of credibility from the low level ( 1 ppb)
results.
328
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Sheldon and Hites (1979)
Summary : 24-hr composite sample taken from chemical plant effluent. All
others were composites of individual grab samples collected at a particular
site. Another set collected weekly over a period of 10 weeks.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Liquid chromatographic fractionation.
Recovery : From spiked samples (triplicate): better than 75% in
all cases.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : 0.5 ppb.
Problems : Not reported.
Instrument : Not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Method employed not specifically designed for phthalates but
rather used for a wide range of industrial organic chemicals.
Summary : Analytical techniques used were only summarized. Recoveries
reported for seven target compounds but not for DEHP. High levels of DEHP re-
ported (100 to 200 ppb) may not be quantitative but do indicate that DEHP was
being discharged from industries in the area.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Triplicate spikes on samples from four locations.
Reference material : Not reported.
Precision and accuracy : Estimated errors of ±20% for “Plant A” effluent
and ±50% for river water; order of magnitude for finished drinking water.
Replicates : Not reported.
329
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Sheldon and Hites (1979)
Method verification : Not reported.
Interiab verification : Not reported.
Problems : Not reported.
Comments : Use of field blanks and method blanks not mentioned. DERP was
not one of the seven compounds for which extraction efficiencies were estab-
lished. Contamination of reagents could conceivably account for low level
findings of DEHP.
Summary : Solvent extraction efficiencies (from preextracted water sam-
pies) measured for 7 of the 84 compounds identified in the water samples taken.
Spiked samples from four locations analyzed in triplicate for percent recoveries
(> 75%). Reported concentration values were corrected for solvent extraction
efficiencies (not for DEHP) and had errors of less than ±20%, excluding sampling
errors.
330
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GC/MS Identification of Trace Organics in Philadelphia Drinking Waters During a
2-Year Period
Suffet et al. (1980), Ref. No. 63
SURVEY DESIGN
Sampling sites : Water sampled after treatment and in the water distribu-
tion system.
Sampling plan : Composite sample collected at single stations for 5 to
37 hr during 11 days of a 2-year period.
Problems : Not reported.
Goal(s) : To establish organic levels in Philadelphia drinking water and
to compare results against previous work done by a different method.
Comments : Experimental design can be described as only supplying in-
ferrential data for the water treatment system.
Summary : Survey designed to determine organic contaminant levels in
Philadelphia drinking water after treatment, in storage, and in the water dis-
tribution system. Study presents monitoring data from 2/75 to 1/77.
SANPLING
Container preparation : Not reported.
Collection procedure : Organics concentrated by an XAD-2 macroreticular
resin accumulator ( IRR) and a continuous liquid-liquid extractor (CLLE).
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : XAD-2 cartridges cleaned each time before use; blanks
saved for analysis.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Extensive distillation and reagent cleaning procedures assured
the validity of the samples taken.
Summary : Water from several points in Philadelphia’s drinking water sys-
tem was passed through an XAD-2 MRR or a CLLE for time periods ranging from
5 hr to over 24 hr.
331
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Suffet et al. (1980)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/MS. Columns: 5 ft x 2 mm glass, 6% SE-30; 6 ft x 0.085
in. S.S., 20% SE-30; 30 m x 0.25 mm capillary, SE-30; 45 mx 0.25 capillary,
FlAP; 6 ft x 2 mm glass, 20% SE-30).
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Despite the variety of instrumentation used for identificaton
of the compounds found, the data table indicates that dioctylphthalate was
only a tentative identification. In addition, the author viewed the data pre-
sented as only “qualitative in nature.”
Summary : Ether extracts of XAD-2 resin columns and chloroform extracts
from the continuous liquid-liquid extracts were analyzed by GC and GC/MS on
several different columns.
QUALITY ASSURANCE
Method blank : Used before each analysis.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Results qualitative.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Extracts analyzed on several different GC/MS
systems in different labs.
332
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Suffet et al. (1980)
Problems : Not reported.
Comments : Despite the QA measures taken, the data for dioctylphthalate
are considered a tentative identification based on mass spectrum only; the
compound is not assigned a concentration level in absolute terms.
Summary : Extensive use of solvent and resin blanks assures presence of
only those compounds which were actually extracted from the water. Data not
reported for those compounds also seen in blanks.
333
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Chlorinated Organic Residues in Fish, Water, and Precipitation from the
Vicinity of Isle Royale, Lake Superior
Swain (1978), Ref. No. 64
SURVEY DESIGN
Sampling sites : Lake Superior sites chosen near populated areas and also
in deep lake region. Compared with data from sites on an “untouched” lake on
Isle Royale.
Sampling plan : Eight whitefish and 17 trout obtained from Isle Royale.
Ten whitefish and 30 trout obtained from Lake Superior.
Problems : Not reported.
Goal(s) : Determination of baseline levels of selected contaminants in
sport or commercially valuable fish in the nearshore waters of Lake Superior.
Comments : Survey designed to point out differences in organic contamina-
tion between populated and unpopulated areas. Isle Royale selected because
of remoteness from inhabited or industrial areas, the lake has no direct con-
nection to Lake Superior, and no internal combustion engines have been used
on the island.
Summary : Selected sites in Lake Superior were sampled for fish and water
in order to determine background levels of contaminants. These were compared
with samples taken from a remote area.
SAMPLING
Container preparation : Gallon glass containers for water; fish wrapped
in something but not reported what.
Collection procedure : Deep water trawls or gill nets. Fish eviscerated
immediately or held on ice. No procedure reported for water.
Storage conditions : Fish were frozen. Storage conditions for water were
not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : Chance for contamination in both fish and water sampling could
lead to high results.
Summary : Fish caught using deep water nets and either eviscerated on
site and then stored on ice or simply wrapped and stored on ice until process-
ing.
334
-------
Swain (1978)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Fish: GPC (SX-3), toluene:ethyl acetate,
1:3, then Florisil cleanup. If PCB’s present, further silicic acid column
separation used. Water extracts: Subjected to micro—Florisil cleanup if
necessary.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : 0.1 pg/g.
Problems : Not reported.
Instrument : GC/EC, 6 ft x 4 mm glass with 1.5% OV-17/2% OV-210 on Q.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Sample preparation procedures delineated but analysis by GC
not discussed in detail other than operating parameters. Sample preparation
not specifically designed for phthalates. Lack of recoveries for method, es-
pecially with the indicated cleanup steps, leaves room for considerable ana-
lyte losses as well as further contamination.
Summary : Fish samples homogenized with sodium sulfate, extracted, sub-
jected to GPC and Florisil, and silicic acid if PCBs present, then analyzed
by GC/EC.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Error estimates are indicated as ± two standard
error units.
Replicates : Not reported.
335
-------
Swain (1978)
Method verification : Not reported.
Interlab verification : Four different labs for fish, two for water.
Problems : Not reported.
Comments : Four different labs used in these analyses but results not
compared. Not known if identical samples were analyzed by each lab. These
facts cast considerable doubt on whether the analytical data are unequivocable.
Summary : No mention of blanks or spikes was made. Use of four different
labs was supposed to “minimize analytical error.”
336
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New Orleans Area Water Supply Study
U.S. EPA (1974c), Ref. No. 67
SURVEY DESIGN
Sampling sites : Based on request from State of Louisiana and city of
New Orleans.
Sampling plan : Results were reported for 24 samples collected during
a 2-month period from three water treatment plants.
Problems : Not reported.
Goal(s) : To determine the identities and levels of trace organic com-
pounds which might be present in the finished drinking water of three treat-
ment plants in the New Orleans area.
Comments : Design was not explained in detail, but data would serve as
monitoring data for New Orleans.
Summary : Survey designed to characterize water supplies in the New Orleans
area by sampling water at three water treatment plants in the area.
SANPLING
Container preparation : Not reported.
Collection procedure : Used Mega sampler, CAM sampler, and Mini-sampler;
grab samples were also taken.
Storage conditions : Extracts stored at 4°C.
Stability demonstrated : Not reported.
Field blanks : “Blank samples were taken through all stages of the oper-
ations in parallel with the actual samples.”
Spiked blanks : Not reported.
Problems : Not reported.
Comments : The minisampler consisted of a sample column constructed of
PVC. Samples taken with this sampler were probably contaminated with phthal-
ates in the field.
Summary : Water samples were concentrated by using mega samplers, CAll
samplers, and minisamplers. Additonal samples were concentrated on XAD-2
resin, and triplicate 1-liter grab samples were extracted with tetralin.
337
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U.S. EPA (1974c)
ANALYSI S
Measurement procedure
Cleanup/fractionation : “Further details may be obtained from” the
principal investigator for each type of sample preparation.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Lowest reported value, 0.06 ppb.
Problems : Not reported.
Instrument : Varian 1400 GC/FID with 3% SP-2100, and Finnigan 1015 GC/MS.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Absence of recovery values indicates data only semiquantita—
tive in nature. Values are the “highest concentration values” as measured by
the method and are not absolute concentration values.
Summary : Chloroform extracts of the activated carbon used in the various
samplers were analyzed by GC and GC/MS. Compounds were identified by GC/MS
and quantitated versus authentic standards by GC/FID.
QUALITY ASSURANCE
Method blank : Mentioned but not elaborated upon.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Two different labs involved but each analyzed
extracts from different samplers.
338
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U.S. EPA (1974c)
Problems : Not reported.
Comments : The data are only semiquantitative because of the lack of re-
coveries and incomplete detail on method blanks.
Summary : Nethod blanks were apparently used but were not reported in
detail.
339
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Compilation of the Compounds Identified in the Water Suppy of the City of
Cincinnati
U.S. EPA (1975a), Ref. No. 68
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : Not reported.
Comments : This is only a compilation of the compounds identified in
Cincinnati tap water (1973—1975). Analytical methods are only mentioned in
passing. No judgment of the reliability of the phthalate data can be made.
Summary : None.
SANPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comment : None.
Summary : None.
340
-------
U.S. EPA (1975a)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : Not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : None.
Summary : None.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : None.
Summary : None.
341
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Preliminary Assessment of Suspected Carcinogens in Drinking Water
U.S. EPA (1975b), Ref. No. 69
SURVEY DESIGN
Sampling sites : Chosen to represent five major categories of raw water
sources in use in the United States for the production of finished drinking
water.
Sampling plan : The 80 sites were selected based on their representa-
tiveness of treatment techniques, source of water and geographic locations.
Problems : Not reported.
Goal(s) : NORS: (1) determine extent of four trihalomethanes, (2) deter-
mine effects of various processes on formation of trihalomethanes, and (3)
characterize the organic content of 10 finished drinking water supplies.
Comments : Data only reported; methodology not discussed.
Summary : Survey designed to totally characterize the organic content of
finished water supplies in the United States.
SMPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comment : None.
Summary : None.
342
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U.S. EPA (1975b)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : Not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : None.
Summary : None.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : None.
Summary : None.
343
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Organics and Inorganics in Selected Drinking Water Supplies
U.S. EPA (1975), Ref. No. 70
SURVEY DESIGN
Sampling sites : Selected “...to get a broad representation of Region V
water supply systems.’ t
Sampling plan : Sampled during winter months.
Problems : Concentrations could vary substantially if compared with dif-
ferent times of the year.
Goal(s) : To establish baseline parameters to judge the effects of the
Safe Drinking Water Act.
Comments : Criteria to select sites was not reported. Temporal and
replicate sampling could provide a better study.
Summary : Report contains a comprehensive list of pollutants and their
levels two months after the Safe Drinking Water Act became law.
SAMPLING
Container preparation : No preparation. “. . .bottles (glass) known from
previous work to be clean.”
Collection procedure : Fourteen samples per city. Raw and finished water.
Storage conditions : Samples preserved with chloroform. Stored at wet
ice temperature.
Stability demonstrated : Not reported.
Field blanks : Preservative and distilled water; prepared daily by sam-
pling team.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : No special cleanup was used; however, the authors state that
blanks in the same kinds of containers did not indicate contamination.
Summary : Grab samples of drinking water, just prior to and several hours
after chlorination, as well as carbon filter extracts.
344
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U.S. EPA (1975)
ANALYSIS
Ileasurement procedure
Cleanup/fractionation : No cleanup for nonvolatiles. Straight ethyl
ether extraction.
Recovery : 289% of DEHP spike of 3,200 pg/liter.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Suspected phthalate contamination.
Instrument : FID, 6 ft x 1/4 in. glass with 5% OV-1O1.
Linear response : Not reported.
Stability of response : Not reported.
Problems : High levels found felt indicative of possible lab contam-
ination.
Comments : The extremely high recovery for DEHP indicates a probable con-
tamination problem. This makes the value of these data questionable.
Summary : GC/FID of ethyl ether extracts of water samples preserved with
CHC1 3 (2.5 ml/liter samples), Soxhlet extraction of carbon.
QUALITY ASSURANCE
Nethod blank : Blank with each group. Spike with each group.
Control sample : Standard every tenth sample.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Nethod verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
345
-------
U.S. EPA (1975)
Comments : The authors state that the phthalate results be used “with
appropriate caution.”
Summary : No quality assurance mentioned for DEHP analysis; extensive EPA
QA/QC procedure described for other priority pollutants and pesticides.
346
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Organic Contaminants - Lake Huron
EPA (1977b), Ref. No. 71
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Not reported.
Problems : Environmental analysis is a still developing “state-of-the-
art.”
Goal(s) : Not reported.
Comments : A good synopsis of the persistance that a selected list of or-
ganics have in Lake Huron. A literature and data review of monitoring data
for the lake and its inputs.
Summary : This report relates the sources of organic compounds entering
Lake Huron and describes their potential impact on the environment. The re-
port was used as a means of proposing a total ban on PCB, aidrin, dieldrin,
DDT, and its derivatives.
SAMPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : None.
Summary : Sampling method not described.
347
-------
EPA (1977b)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : Not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : None.
Summary : Analysis methods not mentioned. DEHP found ranging from < 1 to
1.4 pg/liter in water samples.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : None.
Summary : No quality assurance mentioned.
348
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Environmental Assessment for the Pulp, Paper, and Paperboard Industry
EPA (1980), Ref. No. 72
SURVEY DESIGN
Sampling sites : Selection was stated as being representative of sub-
categories in the pulp, paper, and paperboard industry.
Sampling plan : Eleven mills were included in the screening program
while 60 mills were surveyed during the verification program. Selection
based on treatment plant discharges of the mill effluent and the plant’s
representativeness the industry subcategory.
Problems : Not reported.
Goal(s) : To confirm presence and quantify toxics detected during screen-
ing program.
Comments : The selection of the plants to be sampled was based on need
to characterize the waste effluent from this industry.
Summary : Effluent pollutants were identified, quantified, and assigned
to a significance category.
SAMPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : No information given.
Summary : Verification phase sampling method, but not specified.
349
-------
EPA (1980)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Problems : Not reported.
Instrument : Not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : No analytical methods were specified.
Summary : In data tables, DEHP was detected in majority of samples ana-
lyzed; categorized, however, as “pollutant of unknown environmental signifi-
cance . H
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : None.
Summary : No QA reported.
350
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Environmental Assessment for the Timber Products Processing Industry
EPA (1981), Ref. No. 73
SURVEY DESIGN
Sampling sites : Representative subcategories of timber product plants
selected to provide maximum number of pollutants on list.
Sampling plan : Thirteen plants were sampled representing six types of
subcategories of the industry.
Problems : Not reported.
Goal(s) : Assess the environmental significance of Section 307 (a) (1)
toxic pollutants discharged from the wood preserving, hardboard/insulation
board and hydraulic barking segments of the industry.
Comments : Survey design appears adequate based on the selection cri-
teria given and the replicate plants sampled. However, no information given
about how representative the sampled plants were with the entire industry.
Summary : A category of environmental significance was assigned to all
pollutants detected in the 19 samples.
SAMPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : No direct sampling methods given.
Summary : Nineteen effluent water samples taken from representative sub-
categories of the timber processing industry.
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
351
-------
EPA (1981)
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Detection limits were 20 times higher than acceptable
criteria limits.
Instrument : Not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : This section is of minimal value.
Summary : DEHP considered “D” category, or pollutant of unknown environ-
mental significance in one table; in another table DEHP is classified as en-
vironmentally significant. DEHP not detected during verification phase. Spe-
cific methods never mentioned.
QUALITY ASSuRANCE
Nethod blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Nethod verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : The lack of information raises a question about data validity.
Summary : No QA mentioned.
352
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L. MISCELLANEOUS
Four articles (4, 35, 50, and 1) are included in this section. Two of
them (50 and 1) report on a medical survey and on a statement of arguments
for an environmental impact statement, respectively, and are not included in
the following.
SURVEY DESIGN
The representativeness of the incenerators sampled in article 14 is ques-
tioned based on the information given. A limited selection of laboratory
chemicals and solvents was performed in article 35.
SAMPLING
The lack of control over sample collection for two-thirds of the samples
collected is a deficiency of article 14. Samples in article 35 were tested
as received from the manufacturer.
ANALYSIS
The methods used were, in principle, adequate for both articles (14 and
35).
QUALITY ASSURANCE
Method blanks were used in both studies but one article (14) indicated
the presence of a large peak in the blank which raises a concern about data
validity.
353
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Analysis of Fly Ash from Municipal Incinerators for Trace Organic Compounds
Eiceman et al. (1979), Ref. No. 14
SURVEY DESIGN
Sampling sites : Japan, Canada, the Netherlands. The basis for site
selections is not reported.
Sampling plan : Grab samples
Problems : Not reported.
Goal(s) : To identify organic compounds in fly ash from municipal incin-
erators.
Comments : Not designed for phthalates or as a representative sample of
the total plants available.
Summary : The purpose of the project was to identify organic compounds in
fly ash from municipal incinerators in Japan, Canada, and the Netherlands.
SAMPLING
Container preparation : Ultrasonic agitation 30 mm in 2% aqueous Alconox,
rinsed with hot tap water, deionized water, and heated 1 hr at 350°C.
Collection procedure : Grab samples taken and sent to the authors.
Storage conditions : Closed containers at room temperature, protected
from UV and visible light.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comments : The authors had no control over samples collected in Japan and
the Netherlands.
Summary : Grab samples were collected and placed in containers cleaned
with Alconox, rinsed with hot water, deionized water, and heated to 350°C for
1 hr. Samples were stored in closed containers at room temperature and pro-
tected from UV and visible light.
354
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Eiceman et al. (1979)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Extracted 12 to 16 hr with benzene (B&J)
and concentrated to 100 p1.
Recovery : “Not studied although they are believed to be quite high.”
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : GC/FID and GC/MS. 2.6 m x 2 mm ID glass column with 0.2%
Carbowax 20N on 100/120 mesh Chromosorb W(AW).
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Authors did not report recoveries, and the data may be consid-
ered semiquantit.ative.
Summary : Samples were extracted with benzene and concentrated to 100 p1.
Sample extracts were analyzed by GC/FID and GC/MS.
QUALITY ASSURANCE
Method blank : Empty extraction thimble treated same as samples.
Control sample : Not reported.
Reference material : Used but not identified.
Precision and accuracy : Reproducibility of retention times was 5% RSD.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
355
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Eiceman et al. (1979)
Comments : Two large peaks identified as phthalate esters were present in
method blank but not column blank. Study would therefore be of little value
for phthalate data.
Summary : A method blank was used in the QA; however, phthalates were
found in the method blank.
356
-------
Background Contamination by Phthalates Commonly Encountered in the
Chromatographic Analysis of Lipid Samples
Ishida (1980), Ref. No. 35
SURVEY DESIGN
Sampling sites : Not applicable.
Sampling plan : Grab samples taken of water, organic solvents, solid
reagents, aluminum foil, and other material.
Problems : Not reported.
Goal(s) : To examine various sources of phthalate contamination in lab-
oratory chemicals and equipment.
Comments : Scope of survey limited to those chemicals commercially avail-
able to author (Japan). Results cannot be considered monitoring data.
Summary : Commonly used solvents, chemicals, and laboratory equipment
were included in this survey of laboratory sources of phthalate contamination.
SANPLING
Container preparation : All lab glassware washed with water, heated at
250°C for 10 hr, and/or rinsed with acetone four times and hexane twice.
Collection procedure : N t applicable.
Storage conditions : Not applicable.
Stability demonstrated : Not applicable.
Field blanks : Not applicable.
Spiked blanks : Not applicable.
Problems : Not reported.
Comments : No actual sampling done.
Summary : Samples of organic solvents, water, solid reagents, aluminum
foil, and other materials were acquired to test for the extent of DBP and DEHP
contamination.. All were tested as received from manufacturers.
357
-------
Ishida (1980)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : u 5 rig.
Problems : Not reported.
Instrument : GC/FID, 2 m x 3 mm ID, SS, packed with 1.5% SE-52 or 1.5%
OV-17.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : Water and organic solvent phthalate results probably fairly
accurate. Results for solid reagents arid other materials probably much less
accurate due to testing procedure. No recoveries given; this detracts from
the credibility of the results.
Summary : Five liters of each water sample were extracted, the extract
reduced, and then analyzed by GC/FID. Each organic solvent (100 ml) was evap-
orated to dryness, redissolved, and then analyzed by GC/FID. Each powdered
reagent was soaked in 100 to 300 ml of 1:1 CHC1 3 :MeOH, filtered, reduced in
volume, and analyzed by GC/FID. Aluminum foil, rubber stoppers, etc., were
similarly immersed in solvent and the resultant extract analyzed by GC/FID.
QUALITY ASSURANCE
Method blank : Solvents used in the analysis of other materials shown to
be phthalate-free after a 200-fold concentration.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
358
-------
Ishida (1980)
Iethod verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : No recoveries given so actual levels reported may not be accu-
rate. However, use of solvent blanks indicates that phthalates were present.
Summary : Solvents used in the determination of phthalate concentration
of other materials were redistilled and proven to be phthalate-free. Actual
levels of DBP and DEHP in some of the materials like rubber stoppers, aluminum
foil, etc., are probably not quantitative due to lack of procedural recoveries.
359
-------
Health Status of Workers Exposed to Phthalate Plasticizers in the Manufacture
of Artificial Leather and Films Based on PVC Resins
Milkov et al. (1973), Ref. No. 50
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : Not reported.
Comments : Medical and physiological survey--no methods or chemical data
mentioned.
Summary : None.
SAMPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comment : None.
Summary : None.
360
-------
Milkov et al. (1973)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : Not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : None.
Summary : None.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : None.
Summary : None.
361
-------
Leaching of Toxic and Carcinogenic Chemicals into Drinking Water Requires
Preparation of an Environmental Impact Statement
Adams and Broadwell (1980), Ref. No. 1
SURVEY DESIGN
Sampling sites : Not reported.
Sampling plan : Not reported.
Problems : Not reported.
Goal(s) : Not reported.
Comments : None.
Summary : The document is a statement of arguments for the necessity of
an environmental impact report before the use of plastic pipe is approved for
potable water systems by and for the State of California. No applicable in-
formation for the subject task. Note: See also Refs. Nos. 56 and 62.
SANPLING
Container preparation : Not reported.
Collection procedure : Not reported.
Storage conditions : Not reported.
Stability demonstrated : Not reported.
Field blanks : Not reported.
Spiked blanks : Not reported.
Problems : Not reported.
Comment : None.
Summary : None.
362
-------
Adams and Broadwell (1980)
ANALYSIS
Measurement procedure
Cleanup/fractionation : Not reported.
Recovery : Not reported.
Linear recovery : Not reported.
Interferences : Not reported.
Limit of detection : Not reported.
Problems : Not reported.
Instrument : Not reported.
Linear response : Not reported.
Stability of response : Not reported.
Problems : Not reported.
Comments : None.
Summary : None.
QUALITY ASSURANCE
Method blank : Not reported.
Control sample : Not reported.
Reference material : Not reported.
Precision and accuracy : Not reported.
Replicates : Not reported.
Method verification : Not reported.
Interlab verification : Not reported.
Problems : Not reported.
Comments : None.
Summary : None.
363
-------
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