The document summarizes a study that quantified copper concentrations in sediment samples from harbors and beaches via flame atomic absorption spectroscopy. Sediment samples were collected from Alameda and Santa Cruz harbors and beaches and analyzed for copper content. Results showed that all harbor samples had copper concentrations between the EPA's effects range low and median guidelines, while all beach samples were below the low effects range. There were statistically higher copper levels found in Santa Cruz harbor sediments compared to Alameda harbor, with a potential correlation between higher copper near the inner harbor at Santa Cruz.

1. Quantification of Copper in
Surface Sediment Samples via
Flame Atomic Spectroscopy
Austin Tang and Edward Conley

2. Hypothesis and Objectives
 Objectives:
 Quantify copper concentrations and compare with:
 Established EPA guidelines
 Concentrations known to harm aquatic wild life
 Different harbors and beaches
 Hypothesis:
 Sediment samples in harbors will exceed EPA standards
 The coast will have copper concentrations below EPA standards and
amounts that harm wildlife
 There will be a difference in [Cu] between different harbors

3. Ship Hull Fouling
 Problem:
 Ship fouling decreases fuel
efficiency from friction and
added mass
 Solution:
 Antifouling paint
 Another problem:
 Antifouling paint contains
biocides such as copper

4. Background: ERL and ERM
 EPA Guidelines:
 Copper Effects Range Low (ERL) = 34 μg · g-1
 Copper Effects Range Median (ERM) = 270 μg · g-1
 Below ERL scarce effects
 Above ERM often effects
 Generalized terms
Example of ERL and ERM assay with Arsenic

5. Rationale: Aquatic Wildlife and Copper
 IC50 = 17.4 μg · L-1 for coral fertilisation and
metamorphosis
 Brine Shrimp S/V-LC50 = 24.6 mm2 · mL-1 with
surfaces of Flexgard VI-II antifouling paint
 Atherinops affinis (Topsmelt):
 Adversely affected at [Cu] = 109 μg · L-1
 Lethal at [Cu] = 238 μg · L-1

6. Perkin Elmer AAnalyst 200 Flame Atomic Absorption
Spectrometer
 HCL
 λ = 324.8 nm
 Gaseous Free Atoms
 Nebulizer aerosolizes particles
 Baffles size selectivity
 Flame:
 Desolvates, Vaporizes, Volatilizes
 This instrument cannot account for matrix
 Method of Additions

7. Sampling Technique
 Window Wiper (20ft) with PVC
elbow screwed onto the end
 Plastic Shovel
 Samples were taken from docks,
beaches and shores during low
tide

8. Sample Preparation
 ~ 1 gram of sample dried
 Digested in 5mL of 7.95 M HNO3
 Supernatant extracted after centrifugation (twice)
 Diluted to final concentration of ~ 1M
 Analyzed with the FAAS

9. Experimental Methods
 Standard Curve
 Blanks
 LoD: Ave ± 3(SD)
 LoQ Ave ± 10(SD)
 Method of Additions for both Alameda and Santa Cruz
Harbor

10. Copper Standard Curve via Flame Atomic Spectroscopy
Linear Regression
y = 0.0074x + 0.0121
R = 0.9998
Polynomial Regression
y = -4E-06x2 + 0.0077x + 0.0113
R = 0.9999
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
0 20 40 60 80 100 120 140 160 180
Absorbance(AU)
Copper Concentration (µM)
Instrumentation* Figures of Merit
Limit of Detection 0.527 µM
Limit of Quantification 1.35 µM
Limit of Linearity 167 µM
Dynamic Range 0.527 - 167 µM
Sensitivity 0.0074 AU· µM-1
* Perkin Elmer AAnalyst 220 Flame Atomic
Spectrometer

11. Alameda Surface Sediment Sample Locations and Results
[Cu] in Alameda Samples
A1 114 µg· g-1
A2 50 ± 12 µg· g-1
A3 42.1 µg· g-1
A4 10 ± 2.1 µg· g-1

12. Santa Cruz Surface Sediment Sample Locations and Results
[Cu] in Santa Cruz Samples
S1 261 µg· g-1
S2 220 µg· g-1
S3 112 ± 2 µg· g-1
S4 76 µg· g-1
S5 53 µg· g-1
S6 6 ± 3 µg· g-1
S7 2 µg· g-1

13. S1
S2
S31 S32
S33
S4
S5
S61
S62
S63
S7
A1
A21
A22 A23
A3
A41
A42
A43
0
50
100
150
200
250
300
0 5 10 15 20 25
Concentration(ug/g)
Sample #
Samples compared to EPA Guidelines
Effects Range Median
Effects Range Low
 Santa Cruz Samples
 28.6% < ERL
 ERM > 71.4% > ERL
 0% > ERM
 Alameda Sample
 25.0% < ERL
 ERM > 75.0% > ERL
 0% > ERM

14. Method of Additions
y = 0.0096x + 0.1758
R = 0.9591
0.00
0.05
0.10
0.15
0.20
0.25
-25 -20 -15 -10 -5 0 5
Absorbance(AU)
Amount of Copper Stock Added (µL)
MoA Series for Santa Cruz Harbor (S32)
y = 0.0111x + 0.1221
R = 0.9968
0.00
0.04
0.08
0.12
0.16
-16 -14 -12 -10 -8 -6 -4 -2 0 2 4
Absorbance(AU)
Amount of Copper Stock Added (µL)
MoA Series for Alameda Harbor (A1)
 [Cu] from MoA: 128 µg · g-1  [Cu] from MoA: 104 µg · g-1

15. Accuracy and Precision
 Accuracy
 % Difference between MoA and S.C.
 Alameda: -8.63%
 Santa Cruz: 16.7%
 Precision
 SD varied between 2 - 7 µM
 CV ∝ 1/[Cu], CV varied between 2 - 48%
[(MoA / S.C.) -1]*100%

16. [Cu] vs. Distance from Harbor Mouth (Santa Cruz)
 Point removed because
the sample was taken at a
different depth
 Prob > F
 0.0753 w/ R.P.
 0.0020 w/out R.P.
 Summary of fit
 R = 0.9980

17. [Cu] - Alameda vs. Santa Cruz
 t – Test
 Performed w/o beach
samples
 t = 1.583
 p = 0.167
Alameda Santa Cruz
Mean 70.8 144
Std. Dev. 38.3 91.6

18. Conclusions
 All beach samples below ERL
 All harbor samples between ERL and ERM
 No sample above ERM
 Potential correlation between position in harbor and [Cu]
 Results between Alameda and Santa Cruz are not statistically different

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