American Industrial Hygiene Association Journal

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A rapid method for the determination of arsenic

concentrations in urine at field locations

J. G. LAMBERTON , B. L. ARBOGAST , M. L. DEINZER & L A. NORRIS

To cite this article: J. G. LAMBERTON , B. L. ARBOGAST , M. L. DEINZER & L A. NORRIS

(1976) A rapid method for the determination of arsenic concentrations in urine at field locations,
American Industrial Hygiene Association Journal, 37:7, 418-422, DOI: 10.1080/0002889768507485

To link to this article: https://doi.org/10.1080/0002889768507485

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 A colorimetric method for arsenic in urine utiliaing a portable hood and
requiring minimal laborafory facilities is described. Urine samples are
cornbusted in a hot plate-oven with MgO and M ~ ( N O Arsine
~ ) ~ . is generafed
from the ashed product and passed into silver diethyldithio-carbamate in
pyridine. Inorganic and organic arsenicals in urine at 0.03 ppm with 6%
variation is def ectable.

A rapid method for the determination of

arsenic concentrations in urine at
field locations
J. G. LAMBERTON, B. L. ARBOGAST, M. L. DEINZER, and L. A. NORRIS'k
Department of Agricultural Chemistry, Oregon State University, Corvallis, Oregon
97331; "Pacific Northwest Forest and Range Experiment Station, USDA Forest
Service, Corvallis, Oregon 97330

Introduction chemicals that would be acceptable for use at

The increasing use of organic arsenicals such as
monosodium methanearsenate (MSMA) and
dimethyl arsenic acid (cacodylic acid) as silvi-
cides in forestry has raised questions concern-
ing the health and safety of exposed workers.lJ
Silvicide applicators may either accidentally or
carelessly expose themselves to levels of arsenic
greater than recommended by one of the arseni-
cal formulators.3 Recent studies by the U.S.
Forest Service4 have shown that careful han-
dling and application of MSMA and cacodylic
acid can be easily accomplished and applicator
exposure minimized; but a program of moni-
toring urine for arsenic is necessary to insure
against excessive exposure and to maintain a
high degree of applicator awareness when ar-
senicals are used.
A rapid, simple method is needed that can
be used by personnel with little training in
chemistry for monitoring arsenic in the urine of
applicators at field locations. Reduction in
costs and timely results are needed since urine
sample handling and shipping is often difficult
and costs of laboratory analyses are high. Due
to present analytical methods, considerable
"lag time" is experienced between exposure
and analysis, thus preventing the immediate
removal of an overexposed individual from
I further exposure to arsenic and correction of
practices resulting in the increased exposure.
At the beginning of this study, criteria
were established regarding the instruments and
For more infomation abmut authors, see pages 445 & 446
418
field locations. Colorimeters, propane labora-
tory burners, hot plates, small furnaces, and
special glassware such as arsine generators,
were considered acceptable. Additior~ally, the
chemicals must present minimum halzards to
the relatively untrained personnel using the sys-
tem. Strong oxidizing acids which are normally
used, very toxic chemicals and explosive mix-
tures were not considered acceptable.
Apparatus
Portable hood
This hood device (Figure 1) is constructed of
24 gauge stainless steel in such a manner that
the removal of the top, bottom, and a pin from
each corner will allow the hood to be readily
disassembled and moved to another location or
stored. The top readily slips from the four walls
and ths divider slides into two 1/16" I.D.
tracks. This partition is a means of separating
the drying-combustion area from the generator
area. A 148 cfm fan is connected externally by
4" diameter aluminum and plastic vent tubing.
It can then be vented outside or to an appro-
priate vent stack. The front door is .hinged to
allow raising it to a near vertical position, thus
allowing ready access to the apparatus within
the hood. A 3/16" x 18" x 8" plexiglass win-
dow was later installed in the door and found
to be helpful in observing the arsine generators.
The bottom consists of a 1/2 thick piece of
.. .
July, 1976
 u
., DETAIL
nF
-,
TOP

Figure 1-Hood design for sample combustion and arsine generation. Overall
dimensions: 48" x 23" x 18" ( L x H x I));Door, 48" x 14"; Window, 8" x 18";
Divider, 21" x 18"; Bottom, 48" x 24"; 24 gauge stainless steel was used
throughout. The hinge material was also stainless steel.

Figure 2-Photograph of complete system with ovens and generatqrs i n place.

Reagent dispensers and calorimeter are also shown.

Marinite 36" (Johns-Manville) which is an in-
;dating type board.
jot plate oven
Special boxes constructed of 95 " thick Marin-
te 36 foirm the 10" x 5" x 10" (L x H x D)
wen for the top of a lo1' x 10" ceramic top
lot plate (Corning). The oven lid is constructed
rom two thicknesses of the Marinite 36 board
(Figure 2). The lower layer of the lid is cut to
fit just inside the sides and the upper layer is
extended to cover the sides. The box is fast-
ened to the hot plate by means of sheet metal
brackets to existing screw holes and the lid is
provided with a handle to facilitate its removal.
Arsine generators
The arsine generator (Figure 3) shown is con-

meriaan Industrial Hygiene Association Journal , 419

 a funnel with 40 ml of 2.3 N HCI and '2-20 ml
2.3 N HC1 rinses. An additional 40 ml of 2.3
N HC1 is added by rinsing through the fun-
nel.
After most of the residue is dissolved, 2
ml of 15% K1 is added and after 5 min, 1 ml
of 40% SnC12 is also added. The receivers are
then filled with 5 ml of 0.5% silver diethyl-
dithiocarbamate in pyridine while the sample
solution is allowed to stand for at least 15 min.
The top of the flask is wet with a little distilled
water and 4 g of zinc is added through a fun-
Figure 3-Arsine generator system. A, 15 ml centri-
nel. Since the evolution of gas start!; almost
fuge tube; 6. #8 soft rubber stopper; C. 4 m m O.D. immediately, the receiver is rapidly placed in
glass tube; D. 250 m l wide mouth, Pyrex Erlen- the flask tight enough to prevent gas from
meyer flask; E. 5 m m glass beads. leaking around the stopper. The generators are
run for 1 hour and the resultant colored solu-
structed from a 250 ml wide-mouth Pyrex flask tion is compared to the reagent blank at the
and 15 ml centrifuge tube. A water lubricated 530 nm filter range using a Chemtrix model
resilient rubber stopper carefully slipped over 20 colorimeter. Since some colored residue will
the lip of the centrifuge tube is used to seal form in the small tube at the bottorn of the
the flask. The receiver tube is 'filled with 5 mrn receiver, a rubber bulb is used to draw the so-
glass beads to provide a longer contact time, lution out of the small tube several times, thus
A small drop of silicone cement is used to mixing the solutions before reading them in the
anchor the glass tube (C) to the side of tube colorimeter, Acetone or methanol is useful in
(A) thus making the receivers less fragile. rinsing the receivers, but will interfere with
Automatic pipettes and dispensers are color development if it is not completely re-
used to add the various reagents used in the moved from the receivers before reuse. Dis-
procedure. For dry measures, plastic or glass posal of used chemicals should follow guide-
beakers and vials were cut to contain the prop- lines outlined by the Manufacturing Chemists
er amount of reagent used in the procedure, Assn.6 or local agencies.
thus eliminating the need for weighing. A 3-point curve using 0, 5, and 10 pg of
arsenic is constructed and the samples are
compared to it. These 3 points are usually suf-
Method ficient for this screening procedure. When only
A 20 ml aliquot of urine is added to 3 g of 20 ml samples are used, it is convenient to plot
magnesium oxide (U.S.P. light powder) in a the graph directly in ppm using 0.25 and 0.5
100 ml porcelain crucible. Standards and blanks ppm points.
are prepared by adding to the magnesium
oxide 0 to 101pg of As using a 301 ppm AS203
solutioi5 The contents of the crucible are mixed Results and discussion
by gentle swirling and placed in the oven to Urine samples were digested using concen-
dry. It is convenient to dry the samples over- trated hydrochloric acid.7 Tests of this system
night on low heat (without lid), but 21/2 hours with inorganic arsenicals were promising, but
are usually sufficient. After drying, 2 ml of a organic arsenicals such as MSMA or cacodylic
saturated Mg (No& solution are added to each acid could not be detected. Dry ash procedures
crucible. The crucibles are then placed in the which involved charring the tissue samples with
oven, the lid placed over them and the hot MgO, MG(NO&, and celluose powder over a
plate thermostat set at "6" (-550°C) for 1% burner and then combusting at 500 O C in a
hours. The contents of the cooled crucibles are muffle furnace,Qroduced detectable arsine
then transferred to the 250 ml flasks through from both organic and inorganic arsenicals with
good recoveries.
*Mention of a proprietary product in this paper does not In order to decrease the amount of equip-
consistute a recommendation or an endorsement of this prod- ment and length of time necessary to compIete
uct by the U.S. Department of Agriculture or Oregon State
University. an analysis, the cellulose and charring steps
 TABLE I molybdenum blue method,g and the silver di-
Determination of Arsenic in Cacodylic ethyldithiocarbamate (Ag-DDC) method.1° The
Acid Spiked Urine Samples
Gutzeit method was not sufficiently precise
SAMPLE # fig AS ADDED pg AS FOUND
(<30% variation) and the molybdenum blue
method was not as convenient to use as' the Ag-
DDC method. The use of the Ag-DDC method
allowed 0.5 y g of arsenic to be detected or
less than 0.03 pprn when it was used with the
MgO-combustion system.
The generator system that was used by
Elliott and Loperlo initially was used in our
work, but it was found to be quite fragile. In
order to avoid ground glass joints and frequent
TABLE I I breakage, a new generator was devised using
Cornparison of Wet Digestion and Dry Ash
Methods for the Analysis of Urine Samples
the internal, low-profile design in Figure 3.
Field and laboratory use of these generators
-- IJsing the Ag-DDC Detection Method
ACID DIGEST DRY ASH has shown them to be durable and convenient.
SAMPLE N o . (WSDH) ppm IOSU) ppm When the combined method of MgO-com-
p-

1 0.21 0.17 bustion: Ag-DDC was used in our laboratory

2' 0.21 0.21
38 0.23 0.24 to analyze for inorganic and organic arsenic
4 0.23 0.27 compounds, average recoveries of 100% were

TABLE Ill
-- Comparison of Arsenic Analysis at th~eColville Ranger Station and OSU Lab
SAMPLE CO'LVILLE TRAINEE, ppm AS TRAINER, pprrl AS OSU LAB, pprn AS

*Range of three determinations

were eliminated since they were found to be obtained. Urine samples spiked with only
unnecessary for urine analysis. As a means of cacocylic acid showed a 6% variation from the
reducing reagent costs, U.S .P. grade magnesium mean when several determinations were made
oxide (light powder) was tried and found to (Table I). Further laboratory tests were made
contain no inter£erences or detectable amounts using urine samples which previously had been
of arsenic with this procedure. Calcium oxide8 analyzed by a perchloric acid digestion method
was also tried, but high blanks and variable at the Wenatchee laboratory of the Washington
results were obtained. When magnesium nitrate State Department of Health (WSDH). As can
was added as a covering layer or as a saturated be seen in Table 11, the mean values obtained
solution after drying, higher and more consist- using the dry ash procedures were within
ent recoveries occurred than when it was added 20.04 pprn of those obtained by the WSDH.
before the urine sample had been dried. The
magnesium nitrate also eliminated the need TABLE IV
for the lead acetate scrubbers used by oth- Comparison of Arsenic Analysis of Samples
The use of either Fisher burners or a Analyzed at Colville Ranger Station and WSDH
muffle furnace was adequate, but due to the SAMPLE COLVILLE, pprn AS WSDH*, pprn AS

amount of heat generated with the burner,

and power requirements for most muffle fur-
naces, tlhese were undesirable. Tests using the
hot plate-oven showed consistent results with
minimum power requirements and losses of
heat.
The detection of arsine was accomplished
by various methods including the use of mer- mean variation between analysis = 0.01 pprn
cury bromide paper (Gutzeit m e t h ~ d ) ,the
~ *Wenatchee, Washington, Laboratory

American lrldustrial Hygiene Association Journal

 Although extensive testing had been con-
ducted in the laboratory, it was necessary to
determine the reliability of the system using
non-chemists who had been given only a mini-
mum amount of training. The field testing pro-
gram involved taking the complete system to
the Colville Ranger District Station, setting it
up, training one of the regular employees there,
and outlining the series of comparison tests
that were to be made. A brief manual explain-
ing the procedure, safety precautions, and use
of the system was prepared and used to assist
in the training procedure. After 1-1/2 days of
orientation by a chemist, a designated Forest
Service employee was usually able to perform
the analysis satisfactorily. A comparison of
results from the trainee and the on-site trainer,
and an additional analysis at Oregon State
University are shown in Table 111. Analysis of
variance showed no significant difference
among analysts (P > 0.05).
Additional samples were compared after
the Colville Forest Service employee had ob-
tained several weeks experience with the sys-
tem. These results (Table IV) showed only a
0.01 ppm mean variation between the field
analyses and laboratory analyses. Collaborative
studies utilizing several Forest Service units
will be reported later.
Acknowledgement
The investigators thank Ken Carter and per-
some1 from the Colville Ranger Station for
their assistance and cooperation. The work was
fuxled in part by supplement number 96 to
the master memorandum of understanding be-
tween the Forest Service and Oregon State Uni-
versity. Finally, we are grateful to the National
Institute of E n v i r o nrn en t a1 Health Sciences
Foundation Grant No. ES 00210 for the sup-
port of Jack Lamberton, Brian Arbogast, and
Max Deinzer. This is Oregon Agricultural Ex-
periment Station Technical P a p e r 'Number
4129.
References
1. TARRANT, R. F. and J . ALLARD:Arsenic Levels
in Urine of Forest Workers Applying Silvicides.
Arch. Erzviuon. Health 24:277 (19'72).
2. WAGNER,S. L. and P. H. WESWIG:Arsenic in
Blood and Urine of Forest Workers. Arch. En-
viron. Health 28:77 (1974).
3. ANON: Bulletin on Arsenical Safety. Ansul Co.,
Marinette, Wis. 54143. (1969).
4. NORRIS, L. A., Coordinator: Final RLeport of
Cooperative Arsenic Studies: Pacific Northwest
Regional Office, U.S. Forest Service, Portland,
Oregon (1972).
5. GEORGE,G. M., L. J. FRAHMand .I. P. MCDON-
NEL: Dry Ashing Method for the Determination
of Total Arsenic in Animal Tissues: Collaborative
Study, J . Assoc. Off. Anal. Clzem. .56:793 (1973).
6. ANON: Guide for Safety in the Chemical Lab-
oratory. 2nd Ed. p. 323. Van Nostrand Reinhold,
New York (1972).
7. KINGSLEY, G. R. and R. R. SCHAP'FERT: Micro-
determination of Arsenic and Its Application to
Biological Material. Anal. Chenz. .B:9 1 4 (195 1).
8. FEIGL,F.: Spot Tests in Organic Analysis, 5th
Ed. p. 98, Elsevier Pub. Co., New York (1966).
9. HORWITZ, W., Ed.: Official Methods of Analysis
of the Association of Official Analytical Chem-
ists. 12th Ed. p. 428, Assn. of Official Analytical
Chemists, Washington (1975).
LO. ELLIOTT,S. C. and B. R. LOPER:Improved Ab-
sorption Tube for Arsenic Deterrninatiolns. Anal.
Clzem. 46:2256 (1974).
11. VASAK,V. and V. SEDIVEK:Colorimetric Deter-
mination of Arsenic. Clzem. Listy (Czechoslovak-
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Accepted March 16, 1976

errata The author has requested that an error which

notice occurred in the original manuscript of his arti-
cle, "Safety Studies on a Series of Fatty Acids",
Am. Ind. Hyg. Assoc. J. 37:251 (1976), be
corrected.
On p. 253, under 'LLD50ingestion", the
sfiatement: ". . . the acute oral LDjo for male
albino rats is greater than 10 mg/kg of body
weight . . ." should read: ". . . acute oral LD50
for male albino rats is greater than 10 g/kg of
body weight . . .".

July, 1976