METALS in Urine 8310

TABLE 1 MW: Table 1 CAS: Table 1 RTECS: Table 1

METHOD: 8310, Issue 2 EVALUATION: PARTIAL Issue 1: 15 February 1984

Issue 2: 15 August 1994

BIOLOGICAL INDICATOR OF: exposure to the following metals or their compounds: aluminum, barium, cadmium, chromium,
copper, iron, lead, manganese, molybdenum, nickel, platinum, silver, strontium, tin, titanium, and zinc.

SYNONYMS: vary according to the compound

SAMPLING MEASUREMENT

SPECIMEN: urine TECHNIQUE: INDUCTIVELY-COUPLED ARGON

PLASMA, ATOMIC EMISSION
VOLUME: 50 to 200 mL in polyethylene bottle SPECTROSCOPY (ICP-AES)

PRESERVATIVE: 5.0 mL conc. HNO 3 added after ANALYTE: elements above

collection
EXTRACTION
SHIPMENT: frozen in dry ice MEDIA: polydithiocarbamate resin

STABILITY: not established FINAL

SOLUTION: 4% HNO 3, 1% HClO 4; 5 mL
CONTROLS: collect at least 3 urine specimens from
unexposed workers WAVELENGTH: depends upon element; Table 2

BACKGROUND
CORRECTION: spectral wavelength shift

CALIBRATION: elements in 4% HNO 3, 1% HClO 4

QUALITY
CONTROL: spiked urines; corrected for creatinine

RANGE: 0.25 to 200 µg per sample [1]

ESTIMATED LOD: 0.1 µg per sample

PRECISION (Sr): Table 2

ACCURACY: Table 2

APPLICABILITY: This method measures urine concentrations of metals. It is particularly useful for workers exposed to several
metals simultaneously. This is a simultaneous, multielemental analysis, but is not compound specific.

INTERFERENCES: Spectral interferences are the primary interferences encountered in ICP-AES analysis. These are minimized
by judicious wavelength selection and interelement correction factors. Background corrections are also made [1,2].

OTHER METHODS: This method uses a measurement technique similar to that of Method 7300 (Elements by ICP) for air
samples.

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94

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REAGENTS: EQUIPMENT:

1. Polydithiocarbamate resin, prepared as 1. Bottles, polyethylene, 125- or 250-mL,

described in the APPENDIX. plastic-lined screw-cap.**
2. Nitric acid, conc.* 2. Inductively-coupled plasma-atomic emission
3. Perchloric acid, conc.* spectrometer equipped for determination of
4. Dissolution acid, 4:1 (v/v) HNO 3:HClO 4. Mix elements of interest.
4 volumes conc. HNO 3 with 1 volume 3. Regulator, two-stage, for argon.
conc. HClO 4.* 4. Filtering apparatus for 50 mL liquid with
5. Metals standards, 1000 µg/mL. 47-mm cellulose ester, 0.8-µm pore size
Commercially available or prepared per filters.
instrument manufacturer's recommendations. 5. Beakers, Griffin, 50-mL, with watchglass
6. Argon. covers.**
7. Deionized water. 6. pH meter and electrodes.
8. Sodium hydroxide, 5 M. Dissolve 20 g 7. Volumetric flasks, 5- and 100-mL.**
NaOH in 50 mL boiled, deionized 8. Assorted volumetric pipets as needed.**
water; dilute to 100 mL. Store in a 9. Hotplate, suitable for use at 100 °C.
polyethylene bottle. 10. Mechanical shaker.
11. Low temperature oxygen plasma asher (acid
* See Special Precautions. ashing may be substituted; see Step 9).

** Clean all labware with detergent, soak

12 h in 10% (v/v) HNO 3, and soak 12 h in
deionized water.

SPECIAL PRECAUTIONS: Concentrated acids are extremely corrosive. Work with concentrated acids
only in fume hoods and wear appropriate safety equipment (safety glasses or face shield, gloves, and
labcoat). Samples of urine collected from humans pose a real health risk to laboratory workers who
collect and handle these samples. These risks are primarily due to personal contact with infective
biological samples and can have serious health consequences, such as infectious hepatitis, and other
diseases. There is also some risk from the chemical content of these samples, but this is much less.
Those who handle urine specimens should wear protective gloves, and avoid aerosolization of the
samples. Mouth pipetting, of course, must be avoided.

SAMPLING:

1. Collect a 50-mL urine sample in a polyethylene bottle.

2. Add 5 mL conc. HNO 3 as a preservative.
3. Pack samples in an insulated shipping container under refrigeration (e.g., styrofoam with dry ice)
for transportation to laboratory.

SAMPLE PREPARATION:

4. Perform a creatinine determination on an aliquot of the sample (e.g., [3]).

5. Adjust the sample pH to 2.0 ± 0.1 with 5 M NaOH and then add 60 ± 10 mg
polydithiocarbamate resin.
NOTE: Start reagent blanks, in triplicate, at this step. Include resin and filters (step 7).
6. Agitate samples (on the shaker) for at least 12 h.
7. Filter samples through a 0.8-µm cellulose ester membrane filter, saving the filtrate and resin.
Place the collected resin and filter in a clean 50-mL beaker.
8. Adjust filtrate pH to 8.0 ± 0.1 with 5 M NaOH, add more resin, then repeat steps 5 and 6,
combining the filters and resins from the two extractions.
9. Ash filters and resins in a low temperature oxygen plasma asher for 6 h or until ashing is

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94

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complete (200 watts at 1 to 2 torr, or manufacturer's recommendations).

NOTE: Steps 5 to 10 of Method 7300 (Elements by ICP), an HNO 3/HClO 4 digestion, may be
substituted for the low temperature oxygen plasma ashing. Use a final solution volume
of 5.0 mL (step 11).
10. Add 0.5 mL dissolution acid and warm on a hotplate (15 min at 50 °C).
11. Transfer solutions quantitatively to 5-mL volumetric flasks and dilute to volume with distilled
deionized water.

CALIBRATION AND QUALITY CONTROL:

12. Calibrate the spectrometer according to manufacturer's recommendations.

NOTE: Typically, an acid blank and 10 µg/mL multi-element solutions are used.
13. Analyze a standard for every 10 samples.
14. Check measurement recoveries with at least three spiked unexposed urine samples per 10
samples.
NOTE: For urine spikes, split a 100-mL control urine sample and analyze 50 mL without
spiking. Subtract the metal quantity found in the unspiked portion from the metal
quantity found in the spiked portion in order to determine measurement recovery.

MEASUREMENT:

15. Set the spectrometer to conditions specified by the manufacturer.

16. Analyze standards and samples.
NOTE: If the values for the samples are above the range of the standards, dilute the sample
solutions with 1 volume dissolution acid plus 9 volumes deionized water, reanalyze, and
apply the appropriate dilution factor in the calculations.

CALCULATIONS:

17. Obtain the solution concentration for the sample, C s (µg/mL), and the average blank, C b
(µg/mL), from the analyses data.
18. Using the solution volumes of sample, V s (mL), and blank, V b (mL), calculate the concentration,
C (µg/mL), of each element in the volume of urine collected, V (L):

19. Report the results as µg metal/g creatinine.

GUIDELINES TO INTERPRETATION:

Acceptable and unacceptable levels for metals have not been determined by this method. Lauwerys [4]
discusses metals and can be consulted for guidance and interpretation.

EVALUATION OF METHOD:

Recovery of these 16 metals from spiked urine samples are shown in Table 2 (recoveries ranged from
77 to 100%). The precisions determined for the various elements are also given in Table 2 [1].

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94

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REFERENCES:

[1] Hull, R. D. Analysis of Trace Metals for Occupationally Exposed Workers, Morbidity and
Mortality Weekly Report, 33, (1984).
[2] Hull, R. D. ICP-AESMulti-element Analysis of Industrial Hygiene Samples, NTIS Publication No.
PB85-221414, 1985.
[3] Tietz, N. W. Fundamentals of Clinical Chemistry , 2nd ed., pp. 994-997, W. B. Saunders Co.,
Philadelphia, PA (1976).
[4] Lauwerys, R. R. Industrial Chemical Exposure : Guidelines for Biological Monitoring , Biomedical
Publications, Davis, CA (1983).
[5] Hackett, D. S. and S. Siggia. Selective Concentration and Determination of Trace Metals Using
Polydithiocarbamate Chelating Ion-Exchange Resins, Environmental Analysis , p. 253,
(G. W. Ewing, ed.), Academic Press, NY (1977).
[6] Bray, J. T. and F. J. Reilly. Extraction of Fourteen Elements from a Sea Water Matrix by a
Polydithiocarbamate Resin, Jarrell-Ash Plasma Newsletter , 4, 4 (1981).

METHOD WRITTEN BY:

R. DeLon Hull, Ph.D., NIOSH/DBBS.

TABLE 1. GENERAL INFORMATION

Element Atomic
(Formula) Weight CAS # RTECS

Aluminum (Al) 26.98 7429-90-5 BD0330000

Barium (Ba) 137.34 7440-39-3 CQ8370000
Cadmium (Cd) 112.40 7440-43-9 EU9800000
Chromium (Cr) 52.00 7440-47-3 GB4200000
Copper (Cr) 63.54 7440-50-8 GL5325000
Iron (Fe) 55.85 7439-89-6 NO4565500
Lead (Pb) 207.19 7439-92-1 OF7525000
Manganese (Mn) 54.94 7439-96-5 OO9275000
Molybdenum (Mo) 95.94 7439-98-7 QA4680000
Nickel (Ni) 58.71 7440-02-0 QR5950000
Platinum (Pt) 195.09 7440-06-4 TP2160000
Silver (Ag) 107.87 7440-22-4 VW3500000
Strontium (Sr) 87.62 7440-24-6
Tin (Sn) 118.69 7440-31-5 XP7320000
Titanium (Ti) 47.90 7440-32-6 XR1700000
Zinc (Zn) 65.37 7440-66-6 ZG8600000

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 METALS in urine: METHOD 8310, Issue 2, dated 15 August 1994 - Page 5 of 5

TABLE 2. RECOVERY OF METALS FROM URINE [1,2]

Quantity
Added, Precision, Precision,
Element Wavelength µg/50 mL Sr % Accuracy
(Formula) (nm) sample (n = 4) Recovery ±%

Aluminum (Al) 308.2 20 0.088 100 17.2

Barium (Ba) 455.4 0.4 0.11 80 41.6 a
Cadmium (Cd) 226.5 1.0 0.12 100 23.5
Chromium (Cr) 205.6 1.0 0.078 100 15.3
Copper (Cu) 324.8 10 0.042 100 8.2
Iron (Fe) 259.9 40 0.059 100 11.6
Lead (Pb) 220.4 10 0.040 100 7.8
Manganese (Mn) 257.6 10 0.50 85 113 a
Molybdenum (Mo) 281.6 2.0 0.16 100 31.4 a
Nickel (Ni) 231.6 2.0 0.42 80 102 a
Platinum (Pt) 203.7 0.4 0.29 77 79.8 a
Silver (Ag) 328.3 2.0 0.12 100 23.5
Strontium (Sr) 421.5 4.0 0.25 100 49.0 a
Tin (Sn) 190.0 2.0 0.21 100 41.2 a
Titanium (Ti) 334.9 2.0 0.16 86 45.4 a
Zinc (Zn) 213.9 200 0.089 100 17.4
a
Does not meet the NIOSH criterion of ± 25% accuracy.

APPENDIX: POLYDITHIOCARBAMATE RESIN PREPARATION

The procedure used for preparation of the polydithiocarbamate resin is that of Hackett and Siggia [5] as
modified by Bary and Reilly [6].

1. Dissolve 72 g polyethyleneimine, molecular weight 1800, in 1 L tetrahydrofuran and 28 g

polymethylenepolyphenyl isocyanate in 1 L tetrahydrofuran.
NOTE: Polyethyleneimine stored for one year would not dissolve in the solvent; however, fresh
polyethyleneimine readily dissolved.
2. Pour these two solutions simultaneously into a large flask, allowing the two streams to mix before
entering the flask.
3. Let the mixture stand at least 12 h with occasional mild agitation, then remove the solvent by
filtration.
4. Wash the product twice with methanol and once with deionized water.
5. Add the product to 300 mL carbon disulfide, 100 mL ammonium hydroxide and 500 mL isopropyl
alcohol; let stand 72 h.
6. Filter to remove the resin from the solvent mixture. Wash the resin three times with methanol and
allow it to dry.
7. Grind and sieve the resin, saving the 60/80 mesh size for use.

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94