United States
                    Environmental Protection
                    Agency
Environmental Monitoring and
Support Laboratory
Cincinnati OH 45268
                    Research and Development
EPA/600/S4-85/011  Mar. 1985
ŁEPA         Project  Summary
                    Evaluation  of Methods for the
                    Determination  of Total Organic
                    Halide in Water and Waste
                    T. F. Cole
                     Various methods were evaluated for
                    determining the total organic halides
                    (TOX) in groundwater and in waste oil
                    samples. From three inorganic halide
                    species generation  approaches and
                    three inorganic halide determinative
                    techniques  evaluated for groundwater
                    analyses, one combined  approach,
                    which used Schoeniger flask oxidation
                    with  colorimetric chloride  determina-
                    tion, was chosen for laboratory valida-
                    tion and method detection limit (MDL)
                    studies. Groundwater samples were
                    also analyzed for TOX using EPA Meth-
                    od 9022, "TOX by Neutron Activation
                    Analysis."
                     The Schoeniger flask/colorimetric
                    chloride and neutron activation analysis
                    methods gave TOX results for spiked
                    groundwaters comparable to those ob-
                    tained using Interim Method 450.1 at
                    halide levels above O.2 mg/L.
                     Oil  sample analysis using  the sodium
                    biphenyl reagent and  a colorimetric
                    chloride method was found to be unsat-
                    isfactory for the analysis of various oils
                    spiked with PCBs due to interferences
                    in the colorimetric determinative step
                    which resulted  in recoveries greater
                    than 100 percent.
                     This Project Summary was developed
                    by EPA's Environmental Monitoring
                    and Support Laboratory. Cincinnati.
                    OH, to  announce key findings of the
                    research project that is fully document-
                    ed in a separate report of the same title
                    (see Project Report ordering informa-
                    tion at back).

                    Introduction
                     This program is a continuation of EPA
                    Contract No. 68-03-2984,  "Surrogate
Methods for Priority Pollutants in Waste-
water." The objective of the work con-
ducted under this research program was
to evaluate additional direct and indirect
methods for TOX analysis.
 Indirect  methods  evaluated included
Parr bomb oxidation, Schoeniger flask
oxidation, and sodium biphenyl dehydro-
halogenation as species-generation ap-
proaches for conversion of organic halide
to  inorganic halide. The determinative
techniques evaluated for the inorganic
halide produced included ion chromatog-
raphy, chloride ion  selective electrode,
and a colorimetric halide procedure. In all
cases, the sample preparation procedure
used was  the charcoal adsorption tech-
nique from Interim  Method 450.1. The
primary thrust of  this  portion of the
program was to select the best species
generation approach and best determi-
native technique, and to combine these
approaches into a TOX method for use as
a less costly alternative to the microcolor-
imetric determinative technique of Inter-
im  Method 450.1.
 Neutron activation analysis using the
sample preparation procedure from Inter-
im  Method 450.1 was the only direct
approach  evaluated. This method was
chosen  for its ability to distinguish be-
tween the various  halogen  species at
parts-per-million levels.
 In addition to these methods for the
determination of TOX in aqueous samp-
les, the sodium biphenyl reagent ap-
proach was evaluated for the analysis of
TOX  in transformer oil  samples. The
determinative technique for these eval-
uations was the colorimetric chloride
method used for the aqueous sample
analyses.

-------
Analytical Methods Evaluation

Evaluation of Oxidation
Approach
  Three oxidation approaches were eval-
uated for the conversion of organic chlo-
rine  to  chloride ion: Schoeniger flask
combustion, Parr bomb combustion, and
sodium  biphenyl  dehydrohalogenation.
The  reference determinative technique
for the  first two comparisons was  ion
chromatography (1C).  For  the sodium
biphenyl approach, ion chromatography
was  not suitable because of interferences
caused  by  high  nitrate concentrations,
and the ASTM D-512 colorimetric chlor-
ide procedure was used.

Schoeniger Flask Procedure
  The Schoeniger flask procedure was
evaluated for halide blank levels due to
glassware,  absorbing  solution, sample
wrapping papers, and glassware cleaning
methods
  Recovery of halide spiked onto gran-
ulated activated charcoal (GAC) and ad-
sorbed from aqueous solutions onto GAC
was  also evaluated.  In all spiking exper-
iments a three component spiking solu-
tion  containing  tetrachloroethylene,
2,4,6-trichlorophenol and bromoform was
used.
  The Schoeniger flask procedure was
found to be superior to both the Parr bomb
and  the sodium biphenyl reagent proce-
dures (described below) in terms of halide
recovery and halide blank levels, and was
used in conjunction with the ASTM  D-
512  colorimetric method for chloride ion
for method  validation.

Parr Bomb Oxidation
Procedure
  The  Parr bomb oxidation  procedure
was  evaluated for  halide  blank  levels
from apparatus and reagents, recovery of
halide spiked  onto  GAC,  and effect of
absorption time after sample ignition. The
Parr bomb procedure was unsuitable for
halide analysis because of incomplete
combustion of the GAC and  associated
poor halide recovery.

Sodium Biphenyl Reagent
Procedure
  The sodium biphenyl reagent procedure
was  evaluated for  halide  recovery for
standards in methanol and for standards
spiked onto GAC and in reagent water.
Blank halide levels  associated with the
reagents and glassware were also invest-
igated.
  The sodium  biphenyl procedure was
found to be unsuitable because of high
halide blank levels associated with the
reagent; also, the extraction  procedure
was found to be too difficult for routine
use due to the presence of the GAC at the
interface between the  organic and
aqueous phases in the separatory funnel.

Evaluation of Determinative
Technique
  Three determinative techniques were
evaluated: ion chromatography, chloride
ion specific electrode (ISE), andthe ASTM
D-512 colorimetric chloride procedure.

Ion Chromatography
  1C  was evaluated using  a  Dionex  S2
column over two chloride concentration
ranges: 0.1 to 0.35/ug/mL and 2.0 to 10.0
/ug/mL In addition, the linearity  of re-
sponse for chloride and bromide over the
range of 2 to 10 A/g/mL and the separation
of six common anions was evaluated with
an Si column.
  The chloride response on both columns
and the  bromide  response on the  Si
column  were  linear over the ranges
tested. Due to peak  broadening, the
detection limit for  bromide, estimated at
0.5 fjQ/mL, was much higher than that
for chloride (approximately 0.05 //g/L). In
the evaluation  of anion separation, bro-
mide and nitrate ions were only partially
resolved. The high nitrate level associated
with the GAC was found to obscure small
amounts of  bromide and to render  1C
ineffective for halide speciation in GAC
digests from the Schoeniger flask oxida-
tion procedure.

Ion Specific Electrode
  The ISE determinative technique was
initially evaluated for linearity of response
over a range of 1 to 100 /yg/mL, and the
detection  limit for  both  chloride and
bromide was found to be approximately 1
/ug/mL.  ISE  evaluations  were stopped
when it was determined that extremely
high recoveries (>240 percent), presum-
ably due to some interference in the GAC
digest, were  observed  in  spiked  GAC
samples prepared using the Schoeniger
flask oxidation procedure.

ASTM D-512 Colorimetric
Chloride Procedure
  The ASTM colorimetric procedure was
evaluated for reagent blank levels, chlo-
ride and bromide response, and the effect
of nitrate interference. The response for
both chloride and  bromide was  linear
from 1 to 4 /ug/mL. The estimated detec-
tion limit for both halideswasfoundtobe
approximately  0.5  /vg/mL,  and nitrate
appeared to have no effect on response
  Blank and  spiked  charcoal  samples
were prepared by the Schoeniger flask
oxidation technique and analyzed by the
colorimetric  procedure. Comparison of
the results of these samples with similar
results obtained with ISE and 1C showed
that  ISE was least effective for halide
determination, while  1C and the  color-
imetric method were essentially similar.
The colorimetric procedure was chosen
for the determinative technique for vali-
dation  since the  1C  method was  not
capable of halide speciation with the GAC
matrix  and also due to the less sophfs-
ticated  and  less costly  nature of  the
colorimetric method.

Method Validation
  The MDL of the Schoeniger flask/color-
imetric halide procedure was determined
by the  analyses of  spiked and unspiked
replicates of reagent water according to
the standard EPA protocol.  A detection
limit of 0.1 5 mg/L was calculated with an
average recovery of 57 percent.
  For method validation, three identical
sets of samples were prepared and ana-
lyzed by the Schoeniger flask/colorimet-
ric procedure, EPA Method 9022 (neutron
activation analysis), and Interim Method
450.1.  A summary of recovery results
obtained in these analyses is provided in
Table 1. Agreement between the methods
was good for samples  which contain
halide concentrations above approximate-
ly 0.2 mg/L. Below this value, the halide
blank of the Schoeniger flask/colorimet-
ric halide procedure prevents the deter-
mination of TOX in  the samples

Evaluation of EPA Method 9022
  A  series  of spiked charcoal samples
were prepared and analyzed to evaluate
the neutron activation analysis procedure
(EPA Method 9022) as a direct method for
TOX determination. Chloride recoveries
obtained ranged from 91 percent for low-
level spiked samples to 87 percent for
high-level spiked samples. Bromide recov-
eries ranged from  90 percent for low-
level spiked samples to 88 percent for
high-level spiked samples.

Evaluation of Waste Oil
Methodology
  Ten  PCB-spiked  oil samples obtaineo
from the Quality Assurance Branch of th€
Environmental  Monitoring and Support

-------
Table 1     Summary of Recovery Results lor Validation Samples Obtained Using the Schoeniger
           Flask TOX Method, Interim Method 450 1, and Neutron Activation Analysis Method
           9022
Average Halide Amount Found
for Given Method, mg/L
Sample
Identification
Reagent water
Reagent water
Groundwater #/
Groundwater #1
Groundwater # /
Groundwater #2
Groundwater #2
Groundwater #2
Spike
Level,
mg/L
Unspiked
0.51
Unspiked
0.51
1.0
Unspiked
5 1
10.2
Schoeniger
Flask TOX
0.19
048
0.23
059
13
1.3
4.2
7.9
Interim
Method
450.1
0.020
0.43
0.044
0.56
1.3
1 7
4.0
82
Neutron
Activation
Analysis
0087
0.049
0.12
0.59
15
2.7
7.2
10.1
Average Percent Recovery
for Given Method
Schoeniger
Flask TOX
a
56
--
70
105

58
65
Interim
Method
450.1

81
-
94
120
-
45
64
Neutron
Activation
Analysis
..
78
-
92
135
--
88
72
"Not applicable.
Laboratory at  Cincinnati,  Ohio,  were
analyzed for organic chloride  content
using the sodium biphenyl reagent spec-
ies generation  method  and the ASTM
colorimetric chloride determinative. High
recoveries ranging from 145 percent to
268 percent were obtained for these oil
samples. To evaluate these high recov-
eries, an analytical curve study was per-
formed by spiking a PCB-f ree transformer
oil with Arochlor 1254. Results showed a
high positive bias for  all samples, al-
though this bias was reduced consider-
ably with increased sample dilution.

Conclusions and
Recommendations
  Based on the results of spiked reagent
water and groundwater samples ana-
lyzed, the Schoeniger flask oxidation and
colorimetric halide  TOX procedure is
recommended as an alter native to Interim
Method 450.1 for use as a TOX screening
method for aqueous  matrices,  with  the
caveat that this procedure is applicable
only to levels of TOX at or above 0.2 mg/L
in aqueous matrices. This method pro-
vides a significantly less costly alternative
for the analysis of samples which contain
low parts-per-million levels of organic
halogen and gives results comparable to
those obtained with Interim   Method
450.1.
  The results of the  evaluation of EPA
Method 9022,  Total Organic Halides by
Neutron  Activation  Analysis,  indicate
that this direct method also is an  ap-
propriate technique for TOX analysis and
offers the additional  advantage of pro-
viding  individual chlorine and bromine
values for the sample at levels equal to
TOX detection limits achievable with the
rnicrocoulometric  determinative  tech-
nique of Interim Method 450.1.
  The sodium biphenyl reagent and color-
imetric halide determinative  technique
for analysis of total organic chloride from
oil matrices is not suitable as a screening
procedure in its present form.  Further
evaluation of the sodium biphenyl reagent
with some alternative determinative tech-
nique, such as microcoulometrictitration,
is recommended. Perhaps an additional
cleanup step for the extract prior to the
colorimetric determinative step would
establish the usefulness of this technique
at those halide levels in the range of from
20 to350jug/g.

-------
      T F. Cole, A. M. Berry, andR. L. Wilson are withBattelle Columbus Laboratories,
      Columbus, OH 43201.
      Thomas A, Pressley is the EPA Protect Officer (see below).
      The complete report, entitled "Evaluation of Methods for the Determination of
      Total Organic Halide in Water and Waste." (Order No. PB 85-166 304/AS; Cost:
      $13.00, subject to change) will be available only from:
              National Technical Information Service
              5285 Port Royal Road
              Springfield, VA22161
              Telephone: 703-487-4650
      The EPA Project Officer can be contacted at:
              Environmental Monitoring and Support Laboratory
              U.S. Environmental Protection Agency
              Cincinnati, OH 45268
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
Official Business
Penalty for Private Use $300
         0000329    PS
         U  S ENVIR PROTECTIOfc  SGENCY
         REGION  5  LIBRARY
         118 S OIARBCRN  STREET
         CHICAGO              !»-

-------