Harvey LaRocque, student intern

A. LaVallie, faculty P.I., Turtle Mountain Community College

2010 Research Project for TCU REU

- I am testing high risk areas across the reservation where heavy metals contaminates maybe found. - I expect to find moderately high levels of heavy metal containments across the reservation.

Objectives of the study:

-Evaluation of effectiveness of chosen methodology in use of microwave digestion and atomic absorption spectrometry in measurement of various metal concentrations: Pb, Cd, Ni, Ag.
-Evaluation of random field samples from waste locations on the Turtle Mountain Reservation to tentatively identify potential areas of high metal concentrations.

DH (destroyed housing) HS (new high school) ID (illegal dump) LF (landfill proper) MC (manufacturing plant) NLF (North landfill slope) OD (old dump) SLF (South landfill slope)

Illegal dump site

Scale: Reservation outline is in purple, 6 mi x 12 mi.

- DH: Destroyed housing site of 30 public housing units which were destroyed due to flooding and mold growth. -HS: The new high school site, where elders report that a dump once existed. -ID: An illegal dump located near the destroyed housing site. The dump is fairly large and contains unknown substances. -LF: The main landfill on the reservation, located on clay soil on a hill. Limitation of types of waste disposed there in years past is somewhat doubtful. -MC: A manufacturing site where metal fabrication of military trailers took place. Various solvents and metal wastes were reported by tribal EPA. - NLF: The north slope of the landfill hill. - SLF: The south slope of the landfill hill. - OD: An old dump located in the Northeast area of the reservation, which, according to older residents, was filled in. The surface shows no waste.

Destroyed housing site

Part of illegal dump

Upper left and right: landfill

Bottom left: industrial waste near manufacturing plant

Our Selected Procedure for Metal Evaluation:

1. Digestion of soil samples by acid. 2. Continued soil chemical digestion by microwave. 3. Extraction of solution containing metals. 4. Dilution to standard volume. 5. Preparation of metal standards for use in AA. 6. Evaluation of metal samples by AA and comparison to standards.

- Field samples were crushed mildly with mortar and pestle, and then baked at 180 C for 30 minutes.

- Then 0.50-gram samples were digested overnight with 9.0 ml of redistilled nitric acid, 3.0 ml hydrochloric acid and 2.0 ml 30% hydrogen peroxide and 2 ml water.

- Samples were microwaved at 180 C for 5.5 minutes and then maintained at 180 C for 4.4 minutes in a Milestone Ethos model.

- Samples were filtered and solution was diluted with deionized water to produce 100 ml of sample with a 5% HNO3 background.

Atomic Absorption Protocol

Buck 200A model: an old reliable, manual AA (emphasis on the manual). Settings controlled by hand include: -Current (must not exceed lamp current maximum)

- Continuous zeroing of absorbance (during drift). -Slit and wavelength settings -Level of voltage to maximize absorption readings -Fuel and oxygen levels (reducing or oxidizing flame) -lighting of the flame

Analyte Pb Cd Ni Cr Ag

detection limit(ppm) (nm) 0.6 217.0 0.01 228.8 0.02 232.0 0.01 357.9 0.02 328.1

flame type oxidizing oxidizing oxidizing reducing oxidizing

- AA Theory: Electricity in metal gas lamps produces specific UV radiation which is absorbed in turn by the same metal present in the flame. - Standards preparation: Stock solution is diluted to specific concentrations to produce an absorbance vs concentration curve. - Detection limit: 3X the standard deviation of variances in blank readings. - Sensitivity: The concentration which corresponds to one absorbance unit (out of 1000).

1) Evaluation of methodology:
a. Production of standards easy and accurateespecially with commercial stocks (1000 ppm). b. AA easy to operate with experience- need to be able to feed solution, adjust wavelength and zero absorbance at the same time.

2. Evaluation of concentrations of metal in field samples

a. Results are reliable within limit of detectionwhich is amplified for soil ppm. b. Results should be checked with another lab(Gary Halvorson at SBC?)

AA: Standards Curves

- 1000-ppm stock solutions (Buck Scientific) were diluted to produce at least five standards within recommended range for each metal. - Standards graphs (concentration vs absorbance) were fit with trendlines for later calculation of sample concentrations. - Solution concentrations were converted to soil concentrations by factoring in dilution factors and soil mass.

Concentration (y axis) vs absorbance (x axis) graphs.

Pb Standards Curve (AA)
16 14 12 10 8 6 4 2 0
0 0.1 Pb conc ppm Cd conc. ppm

Cd Standards Curve (AA)

2.5 2 1.5 1 0.5 0 y = 4.6777x + 0.0275

y = 43.868x - 0.4616

0.2 absorbance AA

0.3

0.4

0.1

0.2

0.3

0.4

0.5

absorbance AA

Ni Standards Curve (AA)

6 5 Ni conc in ppm Cr conc ppm 4 3 2 1 y = 42.22x - 0.6975 6 5 4 3 2 1 0.15 0 0

Cr Standards Curve (AA)

y = 30.321x - 0.135

0
-1 0 0.05 0.1 absorbance AA

0.05

0.1 absorbance AA

0.15

0.2

Soil ppm
Site Pb soil ppm Cd soil ppm Ni soil ppm Cr soil ppm Ag soil ppm DH#2 D-S DH#2 D-12 HS#4 D-S HS#4 D-12 ID# 1 D-S ID# 1 D-12 LF#1 D-S LF#1 D-12 LF#2 D-S LF#2 D-12 0 59.07 72.23 6.44 0 0 203.81 0 85.39 0 23.53 31.95 29.15 50.19 43.18 30.55 27.74 26.34 27.74 24.94 4.42 0 0 3.16 0 0 0.62 0 0 4.42 4.98 50.46 0 23.17 41.36 50.46 32.27 41.36 23.17 77.75 27.70 20.57 27.70 32.45 22.94 27.70 25.32 22.94 34.83 27.70

MC#4 D-S
MC#4 D-12 MC#9 D-S MC#9 D-12 NLF#1 D-S NLF#1 D-12 OD#3 D-S OD#3 D-12 SLF#1 D-S SLF#1 D-12 SLF#2 D-S SLF#2 D-12

98.54
0 59.07 72.23 45.91 0 59.07 59.07 85.39 85.39 124.86 6.44

38.97
26.34 26.34 30.55 33.36 31.95 26.34 27.74 36.16 36.16 24.94 36.16

0
0 0 0 4.42 0 0 0.62 NA 0 0 0

68.65
77.78 0 4.98 68.65 50.46 59.56 32.27 23.17 68.65 0 77.75

27.70
34.83 25.32 25.32 30.08 37.21 30.08 32.45 25.32 22.94 22.94 25.32

Sample Pb Cd Ni Cr Ag

Soln. conc. (ppm) Soil conc. (ppm) range range . 0 - 0.42 0 - 204 0.08 0.17 23.53 50.19 0 0.15 0 4.42 0.- .26 43 - 77.75 0.08 0.12 20.57 - 34.83

- Microwave digestion and atomic absorption spectrometer methodology gave good results - (standards read well).

- Preparation time (crushing, drying, digesting) was time-consuming, but AA evaluation was rapid. - Water samples had also been collected, but time was limited and samples were not evaluated.

- Metal levels were not above EPA soil screening levels (ingestion), but may have been problems in terms of EPA soil screening levels (groundwater) in some cases.* - All Cd levels over 8 ppm (SSL groundwater) - Nine Cr levels over 38 ppm (SSL gw) - Three Ag levels over 34 ppm (SSL gw)

* (Caution: generic soil screening levels give an average value;

actual limits must be based on soil conditions like permeability, pH, texture. Sloughs tend to have high clay and actual limits may be above the SSL.)

Metal Pb Cd Ni Cr Ag Fe

ingestion limit (ppm)

groundwater limit (ppm)

400 78 8 1600 130 390 38 390 34 (can occur naturally in soils up to 20%)

* (to be used as guidelines; actual limits must be based on soil conditions)

Soil metal contamination can be a huge problem with land use change; land use maps are essential. This study helped increase the number of samples in an overall metal contaminants study, which was started last year.

- Further summer studies will increase the number of samples and attempt to pinpoint any problem areas.

A&L Eastern Laboratories, Inc. Interpreting Soil Heavy Metals; retrieved July 2009 from http://al_labs_eastern.com/forms/HeavyMetals/ Chasteen, Thomas (2000).Atomic Absorption Spectroscopy, retrieved July 2008 from http://faculty.sdiramar.edu/ Day, Robert W (2000). Soil-Testing Manual (1st Ed.) McGraw-Hill. EPA method 3051: Microwave Assisted Acid Digestion of Sediments, Sludges, Soils and Oils (2009). Retrieved July 2009 from http://www.epa.gov/epawaste/hazard/testmethods/sw846/ EPA method 7000b: Analysis of Metals in Solution by Flame Atomic Absorption Spectrophotometry (2009). Retrieved July 2009 from http://www.epa.gov/epawaste/hazard/testmethods/sw846/

Jury, William and Horton, Robert (2004). Soil Physics (6th Ed.). Wiley.
Liu, David and Liptak, Bela (1999). Groundwater and Surface Water Pollution (1st Ed.). CRC Press.

NIOSH method Lead by FAAS; Retrieved July 2010 from http://www.cdc.gov/niosh/nmam/method-8000.html Soil series maps for Rolette County, N.D. Retrieved July 2010 from: http://websoilsurvey.nrcs.usda.gov/app/WebSoilSurvey.aspx Sumner, M, (editor, 1999). Handbook of Soil Science (1st Ed.). CRC Press. USEPA Generic SSLs (1996); retrieved July 2010 from Table A- 1 http://www.epa.gov/superfund/health/conmedia/soil/ USEPA Regional Screening Levels (2009); retrieved July 2010 from http://www.epa.gov/region09/superfund/prg/files/