Watersheds Laboratory Suspended Metals Digestion Procedures

VU Stormwater Partnership SOP VUSP -E Rev. No.. 1

Villanova University Date Oct 2011 Page 1 of 7

Villanova University
Villanova Urban Stormwater Partnership
Watersheds Laboratory

Standard Operating Procedure VUSP E

Suspended Metals Digestion Procedure

Author: _____________________________________________________
Water Resources Laboratory Technician Sonali Joshi

Approved: __________________________________________________
VUSP Director Robert G. Traver

SOP-E-1
Watersheds Laboratory Suspended Metals Digestion Procedures
VU Stormwater Partnership SOP VUSP -E Rev. No.. 1
Villanova University Date Oct 2011 Page 2 of 7

Distribution

Sonali Joshi
Laboratory Copy, maintained by Quality Assurance Officer

Revision Date Responsible Person Description of Change

0 March 2008 Mary Ellen Dukart Initial
1 Oct 2011 Sonali Joshi Update
2
The following laboratory staff have read and been trained on this Manual. A copy of
this page will be maintained in the Laboratory. Training is good for one year.

Signature Name / Position Date Trainer

Robert G. Traver Director

Bridget Wadzuk PI

John Komlos
Quality Assurance Officer

SOP-E-2
Watersheds Laboratory Suspended Metals Digestion Procedures
VU Stormwater Partnership SOP VUSP -E Rev. No.. 1
Villanova University Date Oct 2011 Page 3 of 7

TABLE OF CONTENTS

1.0 SCOPE AND APPLICATION 4

2.0. METHOD SUMMARY 4

3.0. DEFINITIONS 4

4.0 HEALTH AND SAFETY WARNINGS SEE LAB SAFETY PLAN 4

5.0. INTERFERENCES 4

6.0. HANDLING AND PRESERVATION 5

7.0. EQUIPMENT AND SUPPLIES 5

8.0. QUALITY CONTROL 5

9.0. PROCEDURES 5

10.0. CALCULATIONS 6

11.0. WASTE MANAGEMENT 6

12.0. REFERENCES 6

SOP-E-3
Watersheds Laboratory Suspended Metals Digestion Procedures
VU Stormwater Partnership SOP VUSP -E Rev. No.. 1
Villanova University Date Oct 2011 Page 4 of 7

1.0 Scope and Application

1.1 This standard operating procedure (SOP) delineates the total suspended metals
digestion and preservation methods.
1.2 Membrane digestion for the determination of suspended metals is useful in
quantifying the concentration of metals that do not pass through a 0.45-m
membrane filter. Following digestion, the total suspended metal concentration is
measured via AA spectrophotometry (see SOP-VUSP-G, SOP-VUSP-F).
1.3 This method has been proven to be sensitive and reliable for preparing samples
for the determination of trace level concentrations of Cadmium, Chromium,
Copper, Lead, and Zinc metals suspended in stormwater run off.

2.0. Method Summary

2.1 Approximately 300 mL of all collected samples is passed through a pre-washed
0.45-m membrane filter (see SOP D). The dried membrane containing the
insoluble material is transferred to a 250-mL beaker, and digested using
concentrated Nitric Acid (TM Grade). Digested filtrate is analyzed using AA
spectroscopy.

3.0. Definitions
3.1 Suspended Metals: Those metals of an unacidified sample that are retained by a
0.45-m membrane filter.

4.0 Health and Safety Warnings See Lab Safety Plan

4.1 Digestion must be performed in a regulation fume hood.
4.2 All concentrated acid waste must be placed in its appropriate waste disposal
container.
4.5 Always add acid to water.

5.0. Interferences
5.1 Contamination from sampling device and possibly from filters.
5.2 Loss of metals from adsorption on and/or precipitation in sample container by failure
to acidify the sample properly where required.

SOP-E-4
Watersheds Laboratory Suspended Metals Digestion Procedures
VU Stormwater Partnership SOP VUSP -E Rev. No.. 1
Villanova University Date Oct 2011 Page 5 of 7

6.0. Handling and Preservation

All glassware and plastic ware used for collection, transportation, and laboratory analysis
of the samples are acid-washed using 10% Nitric Acid Wash (TM Grade). The glassware
and plastic ware is first cleaned with a laboratory detergent and rinsed with tap water.
Next, the container is rinsed in 1:10 Nitric Acid Solution. The container is then rinsed
with MilliQ water three times and allowed to air dry.

The samples are digested immediately upon collection. In case these cannot be digested
immediately, the filters that are oven dried at app. 105 degrees Celsius are stored in
desiccators until digestion. Once digestion is done, the digested samples are analyzed
promptly. However, in the event that the samples cannot be analyzed promptly, the
samples are preserved in the refrigerator and analysis is done within six months. .

7.0. Equipment and Supplies

7.1 Hot plate: A 20 x 17-in heating surface is adequate.
7.2 250-mL graduated beakers
7.3 TenSette Pipettes
7.4 Concentrated Nitric Acid (TM Grade)
7.5 4 in. diameter watchglasses
7.6 50ml graduated cylinders
7.7 50 mL plastic bottles with screw caps
7.8 0.45 m micro-fiber filters
7.9 Solution of 1:1 Nitric Acid (TM Grade) in MQ water

8.0. Quality Control

8.1 An unused, but pre-washed, filter will be digested with every filter batch/case to
accommodate for any trace metals inherent in the membrane fibers.

9.0 Procedures
Prior to starting the operations make sure that you wear gloves. All glassware, plastic
ware and filters handled for these operations should be done only after wearing
gloves. This is important as otherwise moisture from hands can cause a significant
change in the weights.

9.1 Filter app. 300 mL sample through a pre-washed 0.45 m micro-fiber filter,
according to SOP-VUSP-D.
9.2 Dry and weigh the filter according to SOP-VUSP-D.
9.3 Place the dried filter in a 250 mL beaker.
9.4 Using a HACH Tensette pipette, add 3 mL concentrated nitric acid (TM Grade) to
each sample filter/beaker. Swirl to cover the entire filter with the acid.
9.5 Place a pre-washed watch glass over the beaker and slowly heat under reflux
(250-300).

SOP-E-5
Watersheds Laboratory Suspended Metals Digestion Procedures
VU Stormwater Partnership SOP VUSP -E Rev. No.. 1
Villanova University Date Oct 2011 Page 6 of 7

9.6 After the filter dissolves, which takes around 4 to 6 minutes, remove the watch
glass and increase the heat to app. 350.
9.7 Allow the acid to evaporate until the beaker reaches near dryness. Do not bake!
9.8 Remove the beaker from the heat and add 3 mL more of the Nitric Acid (TM
Grade). Heat under reflux until the solution is a bright yellow color.
9.9 Remove the cover and allow acid to evaporate. Do not boil!
9.10 Remove beaker from heat and add 0.5 mL of 1:1 HN O3 . Warm the beaker
gently. Swirl to be sure all residue is coated with the acid.
9.11 While heating, rinse the sides of the beaker with MQ water taken in the
50ml graduated cylinder. Remove beaker from heat.
9.12 Transfer the 50ml filtrate in pre-washed 50 mL container for analysis.
Filter any samples that may still contain considerable particulates.

10 Data Analysis and Calculations

The concentration of the metals calculated using AA spectroscopy is populated into the
excel sheet Metals Testing in the WREE folder. Care is taken to include only those
concentrations that lie between the lowest and highest calibrant. Concentrations below
the lowest calibrant are given a designation ND (See SOPs F and G).

11.0. Waste Management

11.1 All acid waste, including the 1:1 Nitric Acid solution, and all preserved sample
waste, is directed into an enclosed, properly labeled container.

11.2 Concentrated Nitric Acid is placed in a tightly sealed, labeled glass bottle.

11.3 Unused filters are thrown in the trash.

12.0. References
Standard Methods (1999). Standard Methods for the Examination for Water and
Wastewater 20th Edtion, American Public Health Association (APHA),
American Water Works Association (AWWA), Water Environment Federation
(WEF).

U.S. Environmental Protection Agency (USEPA). Urban Stormwater BMP Performance

Monitoring U.S. Environmental Protection Agency, 2002a.

U.S. Environmental Protection Agency (USEPA). Methods for Chemical Analysis of

Water and Wastes, U.S. Environmental Protection Agency, 1983.

SOP-E-6
Watersheds Laboratory Suspended Metals Digestion Procedures
VU Stormwater Partnership SOP VUSP -E Rev. No.. 1
Villanova University Date Oct 2011 Page 7 of 7

Working Notes:
1) The lysimeter samples are assumed filtered and are directly tested for metals.
We need to compare filtered vs. non Filtered lysimeter sample to see if it
yields different metal concentrations.
2) There is a validity concern about the digestion of filters and the final
extractant. As per the method, the output of digesting the filter with HNO3
isnt yielding 2% HNO3. But all the other samples and standards are made in
2% HNO3. Hence, it is advisable to check if 12% HNO3 matrix and the 2%
matrix yield different results.
3) After digestion of filters, TIFFO2 sample still has some particulates. It was
discussed that a second cycle of digestion can be performed to check if the
particulates can dissolve. Even if they do not dissolve, it will be helpful to
compare the one-time digested sample with a two-time digested sample and
see if there is any difference in the metal concentration.

SOP-E-7