A simple sediment color meter to target low-arsenic aquifers in Bangladesh

Ken Kostel

Abstract

A cost-effective design for a simple color meter that measures spectral reflectance of

sediment samples at two pre-selected wavelengths is presented. Differences in the reflectance

spectra of Fe2+ and Fe3+ iron oxyhydroxides permits the meter to provide rapid evaluation of the

redox conditions of an aquifer and therefore offers a possible way to estimate groundwater

arsenic concentration. Tests on two prototype meters indicate that a design using light emitting

diodes (LEDs) with peak wavelengths at 500nm and 590nm provides results comparable to a

more expensive spectrophotometer.

The cost of materials and labor in constructing a prototype meter was just under

$360—almost 1/17 the cost of a Minolta CM-2500d Spectrophotometer, but more than seven

times the target cost of $50. However, mass production and some design changes could reduce

this cost to the point that it might feasibly be deployed by well-drilling teams throughout the

arsenic-affected regions of Bangladesh. This would potentially reduce the number of new wells

later found to have high-arsenic concentration and also reduce the cost of a new well.

Submitted as partial fulfillment of requirements for Earth & Environmental Science Journalism
Department of Earth & Environmental Sciences
Columbia University
September 16, 2002
Re-submitted January 17, 2003

Kostel 1
A simple sediment color meter to target low-arsenic aquifers in Bangladesh

Introduction

Background. Arsenic contamination of groundwater in Bangladesh has been described as the worst

case of mass poisoning in history (UNF, 1999). An estimated 36 million people are at risk of

chronic exposure to arsenic levels that exceed the Bangladeshi standard of 50µg/L; those exposed to

levels that exceed the World Health Organization (WHO) standard of 10µg/L are estimated at 56

million (BGS/DPHE, 2001).

The crisis arose as a result of an initiative led by the United Nations Children’s Fund

(UNICEF) to reduce the country’s infant mortality rate (largely driven by deaths due to diarrheal

diseases) by tapping pathogen-free groundwater with inexpensive, shallow tubewells. As a result of

these and other hygienic initiatives, the infant mortality rate in Bangladesh dropped from 151 per

thousand in 1960 to 83 per thousand in 1996 (UNF, 1999).

However, arsenic was not until recently on the list of elements routinely tested for and, as a

result, was not recognized as a serious problem in the groundwater of Bangladesh until the mid-1990s.

Current estimates of the number of shallow tubewells (< 150m deep) in the country range from 6 to

11 million, with approximately 27% exceeding 50µg/L arsenic and 46% exceeding 10µg/L

(BGS/DPHE, 2001). In addition, the installation of new tubewells in Bangladesh is increasing at a

rate of 15% per year—nearly ten times the growth rate of the population (van Geen et al, 2002A;

CIA, 2002).

Most of the high-arsenic-concentration groundwater occurs in the south and southwest of

Bangladesh, a region dominated by the delta formed by the Ganges, Brahmaputra and Meghna Rivers

(Figure 1). The geology of the region is extremely heterogeneous as a result of seasonal flooding,

channel migration, sea-level changes and tectonic activity (Goodbred and Kuehl, 2000; Smedley and

Kinniburgh, 2002). As a result, arsenic levels in wells are widely variable even on the local level

(Figure 2).

Kostel 2
Mechanism. Most aquifers with high concentrations of naturally occurring arsenic fall into one of

two broad categories: arid-oxidizing and humid-reducing (Smedley and Kinnburgh, 2002). Shallow

aquifers and sediments in Bangladesh fall into the latter category.

Plants convert carbon dioxide from the atmosphere into organic carbon and oxygen through

photosynthesis:

Sunlight

CO2 → COrganic + O2 (1)

When a plant dies or when plant material falls and becomes detritus, microbes in the soil reverse the

process of photosynthesis, oxidizing organic carbon to obtain energy and consuming oxygen in the

process to produce carbon dioxide. As long as free oxygen exists, usually in the form of oxygenated

water, detrital decay is essentially the reverse of photosynthesis:

Metabolism

COrganic + 2H2O → CO2 + 4H+ + 4e- (2)

When molecular oxygen is no longer available as a sink for the free electrons generated

above, decomposition continues via a series of reactions with increasingly lower pe levels that

involve compounds in the plant matter itself or in the surrounding environment. One of these, iron,

can act as either an electron sink or as a source of energy for some soil microbes (Fischer, 1988):

Fe3+ + e- ↔ Fe2+ (3)

The development of reducing conditions in an aquifer appears to be a major controlling

factor in the mobilization of arsenic in Bangladesh (BGS/DPHE, 2001; van Geen et al, 2002A). In

addition, arsenic concentration has been found to correlate with iron in aquifer sediments in

Bangladesh (Nickson, 1998)

In general, arsenic will strongly adsorb to oxidized iron oxide and oxyhydroxide coatings on

sediment particles (Farquhar et al, 2002; Nickson et al, 1998). In the presence of oxidized and

insoluble solid phases such as goethite (Fe3+OOH) or hematite (Fe2O3), arsenic will be largely adsorbed

Kostel 3
and immobile. The iron oxides and oxyhydroxides formed in more reducing conditions, however,

release much of the adsorbed arsenic to solution (BGS/DPHE, 2001).

The literature is unclear whether desorption occurs because the reduced solid phases such as

magnetite (Fe3O4) present fewer adsorption sites per unit area (see Bader et al, 1984; Goldberg and

Johnston, 2001); whether differences in electrostatic interaction between the various iron and arsenic

species plays a significant role (see USGS, 1999); or whether reduced iron oxyhydroxides present less

surface area per unit weight than amorphous oxidized phases (see Wang et al, 1997).

Recent Work.

Horneman, et al (in preparation) recently built on the observation that high-arsenic-

concentration groundwater is often associated with gray sediment (BGS/DPHE, 2001; Bull, 2001) to

explore a promising new way of analyzing the redox conditions of sediment in the field and,

therefore, assessing the potential for a well to have high arsenic. This observation is supported by

other first-derivative spectral analysis of iron oxides (Deaton and Balsam, 1991; Arimoto, 2001).

Analysis of the spectral reflectance of gray sediments associated with safe aquifers shows a distinct

peak in the first derivative of the spectral reflectance curve between 510nm and 520nm. This peak

is noticeably absent in sediment associated with high (>50µg/L) arsenic levels (Figure 3a and 3b).

Identification and classification of soil by color was first standardized in 1950 when the

Munsell Company developed a reproducible set of color charts that characterize color by its hue,

value and chroma (Escadafal 1989 and Munsell 2000). Only in the past three decades have portable

spectrophotometers such as those used here made it possible for soil scientists to make accurate,

direct measurements of soil color that do not rely on subjective comparisons. However, these

instruments are expensive, are usually not designed for use in the field and are prohibitively

expensive ($6,000 – $12,000) for widespread deployment in Bangladesh.

For this reason, I designed a simple, cost-effective color meter that could be used to help

determine whether conditions in an aquifer are suitable for low-arsenic-concentration water as a well

is being drilled. This would potentially reduce the need to re-drill wells later found to have high levels

Kostel 4
of arsenic and, because the bulk of the cost of a new well is associated with the materials used

(including PVC pipe), minimize the cost of a new well.

Methods

Instrument design. To create a prototype sediment color meter, I chose to combine two narrow-

band light sources that emit at approximately 510nm and 520nm with a broad-band photo diode in

order to determine the change in reflectance of a sample over the target interval. Light emitting

diodes (LEDs) were first characterized using a hand-held scanning spectrophotometer (ColorTron II)

modified to read emitted rather than reflected light. Based on this, three LEDs (AND

Optoelectronics AND412HG, Stanley DG5306X, and Fairchild Semiconductor MV8315) were chosen

for use in two separate meters. Meter 1 was designed to measure reflectance at wavelengths near the

510-520nm interval (Figure 4a). Meter 2 was designed to minimize spectral overlap between light

sources while staying as close to the target interval as possible (Figure 4b).

The meter head (measuring window, reflecting chamber, light sources and detector) was

designed using the reflector unit from a D-cell flashlight, which provided a rigid, inexpensive base on

which to mount both the light sources and the photoreceptor. The inside of the reflector was

sprayed with a barium sulfate neutral white reflectance coating. LEDs were mounted in the reflector

housing so that they provided an angle of illumination of approximately 45˚ to the sample surface.

A photoreceptor (Perkin-Elmer VTB-1113) was mounted at the top of the reflector. The plastic

window of the flashlight was replaced with a piece of hardened optical plastic and attached with a

waterproof sealant.

Each LED was given its own adjustable voltage regulator so that illumination would remain

stable over as wide a range of battery voltage as possible and to permit the meter to be calibrated by

adjusting the brightness of each LED individually. Two 9V batteries connected in parallel provide

power (Figure 5).

Kostel 5
 All components are housed in a 12-inch piece of 2-inch diameter PVC pipe. Voltage output

from the photodiode as well as battery voltage are read directly on a digital multi-meter (DMM) set

to display DC voltage (Figure 6).

All voltage regulator circuits were initially set to provide a voltage output equal to their

individual LED’s typical operating voltage as defined in manufacturer specifications. Both

instruments were then calibrated by measuring the reflectance of a photographic gray card (Kodak)

and adjusting the voltage of the LEDs until the DMM read the same output voltage when either pair

of lights was activated. The gray card is spectrally neutral and reflects roughly the same amount of

light (18%) at any wavelength in the visible spectrum.

Prototype evaluation. Both instruments were first tested on a set of four sediment cuttings that

were collected from separate well installations in Araihazar in January 2002. The wells were drilled

using a hydraulic method common in Bangladesh in which the members of a well-drilling team

repeatedly raise and lower a PVC pipe with a cutter bit attached, forcing it into the ground while one

member of a drill team uses his hand as a check valve on the top of the drill string to permit

sediment slurry forced up through the pipe to overflow. Samples of the coarser material in the slurry

were taken every ten feet by allowing them to settle out before the water was poured off.

Seven months had passed between collection and measurement of the samples and, as a result,

the sediments were drier and had oxidized. As a result of oxidizing, they were noticeably more orange

than when first collected (Figure 7). This was not judged to be a problem because new measurements

of the same, aged sediment using Meter 1, Meter 2, and a spectrophotometer would be compared in

order to determine the performance of the two prototypes relative to the more sophisticated and

accurate instrument.

In the lab, a sediment sample was removed from its box and gently crushed to separate the

grains. The surface of a two-inch diameter piece of gray card was then covered with sediment. The

sediment was then placed against the meter window and pressed firmly to ensure complete contact.

Kostel 6
 Each set of LEDs was activated in turn and the resulting voltage output from the silicon

photo diode read on the DMM. The difference between the voltages produced for each sample (∆V)

was then compared to the difference between reflectance values (∆R) at the same wavelengths (λ)

obtained using a spectrophotometer (Minolta CM-2500d):

∆V = Vλ2 – Vλ1 (4)

∆R = %Rλ2 – %Rλ1 (5)

The spectrophotometer was set according to manufacturer directions to the following

measuring parameters (Minolta Co., Ltd.; 2001) and calibrated:

• Spectral component excluded (SCE)

• 10˚ standard observer

• D 65 illumination

• Three-measurement auto average

To measure a sample with the spectrophotometer, the cap of a scintillation vial was filled to

overflowing and covered with plastic wrap. The spectrophotometer measuring port was pressed

firmly over the sample and five measurements made, with the spectrophotometer repositioned after

each. Calculated values for ∆R and ∆V were plotted to evaluate the performance of each prototype

relative to the spectrophotometer (Figures 8a and 8b).

The samples were also evaluated with a Munsell Soil Color Chart (2000) (Table 1).

Colorimetric data from the spectrophotometer were then compared to determine the quantitative

color difference between sediment samples (Table 2a and 2b, Figure 9). This was done by calculating

color difference values (∆E) in L*a*b* color space with and without lightness values:

∆E Lab = [(L*2-L* 1)2+(a*2-a*1)2+(b* 2-b*1)2]1/2 (6)

∆E ab = [(a*2-a*1)2+(b* 2-b*1)2]1/2 (7)

where subscripts denote L*, a*, and b* for samples being compared. Values for ∆E provide a measure

of the spatial separation of colors plotted in L*a*b* color space, which describes a color by its

location along lightness (L*), red-green (a*), and yellow-blue (b*) axes. The smallest difference that

Kostel 7
is considered perceptible by a trained observer in a side-by-side comparison under ideal conditions is

∆E=1 (Judd and Wysecki, 1975).

Site F profile. After it was determined that Meter 1 did not provide adequate performance, its use

was discontinued and Meter 2 alone was used to test cuttings from a single well that were collected

from Site F of Araihazar study area (see Figure 2). Cuttings were collected in January 2002 as

described above. This site was chosen because arsenic concentration increases with depth to 120 feet,

while ∆R steadily decreases indicating a gradual graying of the sediment.

The samples were measured with a spectrophotometer (Minolta CM-2500d) and Meter 2

using the method described above. Samples from the clay layers between 120 and 150 ft. were too

hard to be measured accurately with either the spectrophotometer or Meter 2. Data from

measurements made with the spectrophotometer and Meter 2 were compared graphically to each

other and to the ratio of Fe2+ to total iron (an indication of redox state) in sediment from the well

and arsenic concentration in nearby wells (Figures 10a – 10e).

Results

Prototype evaluation. From the initial tests on the four sediment samples, it was determined that

Meter 1 was not a good candidate to continue with further testing. Figure 8a shows that variability

between measurements (depicted as +/- 1 standard deviation) was unacceptably high. Moreover, ∆V

for three of the four sediment samples was very near the DMM’s limit of detection and two of the

four indicate a negative trend in spectral reflectance between 510nm and 520nm. Meter 2, however,

not only provided a greater magnitude difference and displayed a generally increasing ∆R and ∆V

from sample to sample (Figure 8b), but it also exhibited less variability in its measurements.

The Munsell method was determined to be ineffective in evaluating sediment color here, a

conclusion borne out by colorimetric data obtained from the spectrophotometer. Two of the three

gray sediments had the same Munsell color name; a third differed by only one brightness unit. In

addition, ∆ELab ranged from 2.1 to 1.6, values that could be considered perceptible, but only under

Kostel 8
ideal conditions not likely to be encountered in the field. When the lightness values are removed and

the difference in color alone is compared, ∆E ab ranged from 2.0 to 0.9, again making it unlikely that

even a side-by-side comparison would provide an accurate assessment of a sample with the naked eye.

The difference between the gray and orange sediments, however, is easily identifiable and, in fact,

drillers use the presence of orange sediments as an indicator that they have reached a safe depth.

Site F profile. Meter 2 test results on sediments from Site F show that the instrument very closely

approximates the performance of the spectrophotometer. The general gradient displayed in the ∆R

profile is also seen in data obtained using Meter 2 (Figure 10c). Many of the smaller features in the

gradient are also retained in the ∆V profile. This is supported by the strong correlation between ∆R

and ∆V (Figure 11), as well as the relationship between ∆V and the ratio of reduced iron to total iron

(Figure 12). Arsenic concentration from nearby wells also shows a similar gradient as ∆R, ∆V and

iron ratio (Figure 10e). However, because of the limited number of nearby wells and because it is

difficult to sample groundwater in an aquifer while drilling, the strength of this connection for Site F

is inconclusive and should be examined further before the instrument is deployed.

Discussion

Given the potential for cost reduction and the level of the meter’s performance, this

instrument or one like it shows great promise for further testing. While Meter 2 appears to perform

sufficiently to make it a useful tool to evaluate the redox conditions of an aquifer in the field, it may

benefit from the addition of an operational amplifier to the signal output circuit. This would boost

the overall signal strength and provide greater separation between reflectance measurements without

increasing variability.

The material and labor cost of constructing a prototype meter was calculated to be

approximately $360—approximately one-seventeenth the cost of a new Minolta

spectrophotometer. If the digital multi-meter is replaced with a simple voltage comparator, then the

projected budget for building a meter would still fall outside the target of $50 (Appendix 1). The

Kostel 9
greatest additional reduction in unit cost would likely be realized by building more than one. Labor

costs, especially the specialized labor needed to machine brackets for the LEDs and photo diode,

would decrease dramatically if total production is increased, as will component costs. In addition,

further testing should be conducted on the need for the barium sulfate white reflective coating in the

meter head.

Acknowledgements

This project was supported by a grant from NSF. I am extremely grateful to Lex van Geen for his
guidance and optimism throughout the course of this work and to the other members of my advisory
committee (Kim Kastens, George Flynn and Sidney Hemming) for their encouragement. Thanks are
also due to Allan Horneman for his unlimited generosity, to Dale Chayes and Richard Perry at the
Lamont-Doherty Earth Observatory’s Instrument Lab for their invaluable help early on, to Michael
McNamara at Popular Photography for his donation of equipment, and to my mentor Kristina
Rodriguez-Czuchlewski. Finally, this project would not have been possible without the loving support
of Anne-Marie Runfola.

References

Acharyya, S. K., S. Lahiri, B. C. Raymahaashay, and A. Bhowmik, Arsenic toxicity of groundwater in

parts of the Benhal basin in India and Bangladesh: the role of Quaternary stratigraphy and Holocene
sea-level fluctuation, Environmental Geology, 39(10):1127-1137, 2000.

Bader, R. F. W., MacDougall, P. J., and Lau, C. D. H., “Bonded and non-bonded charge
concentrations and their relation to molecular geometry and reactivity,” Journal of the American
Chemical Society, 106: 1594-1604, 1984.

British Geological Survey and Department of Public Health Engineering (Bangladesh) (BGS/DPHE),
Arsenic Contamination of Groundwater in Bangladesh, Eds., D. G. Kinniburgh and P. L. Smedley,
BGS Technical Report WC/00/19, October, 2001.

Bull, D. C. and R. B. Williamson, Prediction of principal metal binding solid phases in estuarine
sediments from color image analysis, Environmental Science and Technology, 35:1658-1662, 2001.

Central Intelligence Agency (CIA), The World Factbook 2001, 6/24/02, accessed 9/15/02
<http://www.cia.gov/cia/publications/factbook/index.html>.

Deaton, B. C. and W. L. Balsam, Visible spectroscopy—a rapid method for determining hematite and
goethite concentration in geological materials, Journal of Sedimentary Petrology, 61: 628-632,
1991.

Drever, J. I., The Geochemistry of Natural Waters, Upper Saddle River, New Jersey: Prentice Hall,
1997.

Escadafal, R. and M-C. G. D. Couralt, Munsell soil color and soil reflectance in the visible spectral
bands of Landsat MSS and TM data, Remote Sensing of Environment, 27(1): 37-46, 1989.

Kostel 10
Farquhar, M. L., J. M. Charnock, F. R. Livens, and K. J. Vaughan, Mechanisms of arsenic uptake
from aqueous solution by interaction with goethite, lepidocrocite, mackinawite, and pyrite: An X-ray
absorption spectroscopy study, Environmental Science and Technology, 36(8): 1757-1762, 2002.

Fischer, W. R., “Microbiological reactions of iron soils,” Iron in Soils and Clay Minerals, Eds., J. W.
Stucki, B. A. Goodman, and U. Schwertmann, Boston: D. Reidel Publishing, 1988.

Goldberg, S., and Johnston, C. T., “Mechanisms of arsenic adsorption on amorphous oxides evaluated
using macroscopic measurements, vibrational spectroscopy, and surface complexation modeling,
Journal of Colloidal and Interface Science, 234: 204-216, 2001

Goodbred Jr., S. L. and S. A. Kuehl, The significance of large sediment supply, active tectonism, and
eustasy on margin sequence development: Late Quaternary stratigraphy and evolution of the Ganges-
Brahmaputra delta, Sedimentary Geology, 133:227-248, 2000.

Horneman, A., A. van Geen, S. O’Connell, P. E. Mathe, D. Kent, Y. Zheng, R. K. Dhar and K. M.
Ahmed, Release of arsenic to Bangladesh groundwater by reduction of iron oxyhydroxides without
dissolution. Part 1: Evidence from borehole cuttings (in preparation).

Judd, D. B. and G. Wyszecki, Color in business, science and industry, 3rd ed., New York: Wiley and
Sons, 1975.

Minolta Co., Ltd., Spectrophotometer CM-2600d/2500d Instruction Manual, Osaka, Japan: 2001.

Munsell Color, Munsell soil color charts, GretagMacbeth: 2000.

Nickson, R. T., McArthur, J., Burgess, W., Ahmed, K. M., Ravenscroft, P., and Rahman, M.,
“Arsenic poisoning of Bangladesh groundwater,” Nature, 365: 338, 1998.

Nickson, R. T., P. Ravenscroft, W. G. Burgess, and K. M. Ahmed, Mechanism of arsenic release to

groundwater, Bangladesh and West Bengal, Applied Geochemistry, 15(4), 403-413, 2000.

Smedley, P. L. and D. G. Kinniburgh, A review of the source, behavior and distribution of arsenic in
natural waters, Applied Geochemistry, 17: 517-568, 2002.

United Nations Foundation (UNF), Arsenic poisoning in Bangladesh and West Bengal, 1999.

United States Geological Survey (USGS), 1999 “Geochemistry of arsenic,” Arsenic in Ground Water
of the Willamette Basin, Oregon, <http://Oregon.usgs.gov/pubs_dir/Online/Html/WRIR98-4205/>,
January 3, 2003.

van Geen, A., H. Ahsan, A. H. Horneman, R. K. Dhar, Y. Zheng, I. Hussain, K. M. Ahmed, A.

Gelman, M. Stute, H. J. Simpson, S. Wallace, C. Small, F.. Parvez, V. Slavkovich, N. J. Lolacono, M.
Becker, Z. Cheng, H. Momotaj, M. Shahnewaz, A. A. Seddique, and J. H. Graziano (in press)
“Promotion of well-switching to mitigate the arsenic crisis in Bangladesh,” Bulletin of the World
Health Organization, 2002A.

van Geen, A, Y. Zheng, R. Versteeg, M. Stute, A. Horneman, R. Dhar, M. Steckler, A. Gelman, C.

Small, H. Ahsan, J. Graziano, I. Hussein, and K. M. Ahmed (in press), Spatial variability of arsenic in
6000 contiguous tube wells of Araihazar, Bangladesh, under review, Water Resources Research, 2002B

Wang, F. Y., Chen, J. S., Chen, H. L., and Forsling, W., “Surface properties of natural aquatic
sediments,” Water Research, 31: 7, 1706-1800, 1997.

Kostel 11
Tables

Table 1: Munsell characterization of sediment samples used to test prototype meters. The names are in
the form Hue Value/Chroma. The one Value unit difference between Sample 1 and 2 or 3 indicates that
#1 was judged to be slightly darker than the other two, a fact supported by the spectral reflectance curves
shown in Figure 7.

Sample Munsell color

1 2.5Y 7/2

2 2.5Y 6/2

3 2.5Y 6/2

4 10YR 6/8

Table 2a: Color difference between sediment samples used to test prototype meters in L*a*b* color
space. ∆E=1 is the minimum noticeable difference between two colors under ideal conditions and in a
side-by-side comparison.

∆ELab
Sample 1 2 3 4
1 0
2 2.01 0
3 2.10 1.56 0
4 14.75 13.94 12.79 0

Table 2b: Color difference between sediment samples used to test

prototype meters in a*b* plane of L*a*b* color space.

∆Eab
Sample 1 2 3 4
1 0
2 0.94 0
3 2.01 1.06 0
4 14.75 13.83 12.78 0

Kostel 12
Figures

Figure 1: Percentage of tubewells in upazillas of Bangladesh that tested positive for arsenic (>100µg/L),
also showing the most heavily affected areas in the delta region of the south (prepared by J. W.
Rozenboom for UNICEF). Araihazar study area indicated by black rectangle.

Kostel 13
Figure 2: Distribution of high- and low-arsenic wells in the Araihazar Upazilla (District) 30km east of
Dhaka. The widely variable distribution of good (≤50µg/L As) and bad (>50µg/L As) wells is visible
here. Even in areas that have predominantly high-arsenic wells, there are low-arsenic wells scattered
throughout, and vice-versa.

Kostel 14
 Figure 3a: Spectral reflectance of visually identical gray sediments. Gray sediment is generally
associated with reducing conditions and high arsenic levels in groundwater, but may also be present with
low-arsenic conditions.

20
18
16
14
% Reflectance

12
10
8
6
4
2
0
0

0
40

45

50

55

60

65

70
Wavelength (nm)

Figure 3b: First-derivative plot of spectral curves in 3a showing characteristic peak in difference
between reflectance at 510nm and 520nm. Water from sediment associated with blue line had 13µg/L
arsenic; water from sediment associated with pink line had 229µg/L arsenic (data courtesy A. Horneman).

0.6

0.5

0.4
∆ R (520-510nm)

0.3

0.2

0.1

0
0

-0.1
40

45

50

55

60

65

70

-0.2
Wavelength (nm)

Kostel 15
Figure 4a: Combined spectral emittance for LED pairs used in Meter 1. LEDs with peak at 490nm
(AND412HG) and those with a peak at 520nm (DG5306X) were used so that reflectance values from
each light would most closely approximate the target interval of the spectral reflectance curve. Graphs
show emittance relative to peak wavelength in each pair of LEDs.

100
90
80
Relative emittance

70
60
50
40
30
20
10
0
0

0
40

42

44

46

48

50

52

54

56

58

60

62

64

66

68

70
Wavelength (nm)

Figure 4b: Combined spectral emittance for LED pairs used in Meter 2. LEDs with peak at 500nm
(AND412HG) were paired with and those with a peak at 590nm (MV8315) in order to minimize overlap
in the spectral emittance curves and, therefore, increase signal separation. Graphs show emittance
relative to peak wavelength in each pair of LEDs.

100
90
80
Relative emittance

70
60
50
40
30
20
10
0
0

0
40

42

44

46

48

50

52

54

56

58

60

62

64

66

68

70

Wavelength (nm)

Kostel 16
Figure 5: Cross-section schematic of reflectance color meter and circuit diagram of adjustable voltage
regulator. Each meter has a total of four light emitting diodes (LEDs) arranged around the photodiode.
Two switches (S1 and S2) control each of the matched pairs of LEDs separately. The setting of the
5,000Ω adjustable resistor determines the voltage to the LED, thereby controlling the brightness of the
diode. Both the voltage output from the photodiode and the battery voltage are read on a digital multi-
meter (DMM) connected to leads from the top of the meter housing.

Battery voltage

Photo diode voltage

S1 S2

AVR

Adjustable Voltage Regulator (AVR)

9V

AVR LM-317
VIN
330Ω 100Ω
9V

0.1µF LED
5,000Ω
AVR

AVR To LED
2 and 4

Photodiode

LED 1 LED 3

Kostel 17
Figure 6: Completed meter prototypes with digital multi-meter (lower left). The arrangement of LEDs
around the central photodiode is visible inside the measuring head of the meter at lower right.

Kostel 18
Figure 7: Spectral reflectance curves for sediment samples used to evaluate the performance of Meter 1
and 2. Sediments were drier and had aged (were visibly more orange) than when first collected in
January 2002. Photo below shows the color of each of the sediments when measured in July. Samples 1
and 2 have roughly parallel reflectance curves, differing only in overall lightness. Sample 3, while judged
to be the same Munsell color as 2, is spectrally different. Sample 4 displays the spectral reflectance of
oxidized sediment that is easily recognizable in the field. Measurements were made on a Minolta CM
2500d spectrophotometer.

45

40

35

30
% Reflectance

25
1
20 2

15 3
4
10

0
0

0
40

42

44

46

48

50

52

54

56

58

60

62

64

66

68

70

Wavelength (nm)

1 2 3 4

Kostel 19
Figure 8a: Performance comparison between spectrophotometer Meter 1 (above) and spectrophotometer
(below) measuring sediment samples shown in Figure 7. Wide variability (denoted by error bars showing
one standard deviation) and the small difference between ∆V for samples 1, 2, and 3 disqualified Meter 1
from further testing.

Meter 1

4
∆ V [520-490nm]

-1

-2 3
1 2 4

Minolta CM-2500d

5
4.5
4
∆ %R [520-490nm]

3.5
3
2.5
2
1.5
1
0.5
0 2
1 3 4

Kostel 20
Figure 8b: Performance comparison between Meter 2 (above) and spectrophotometer (below) measuring
sediment samples shown in Figure 7. Less variability and better discrimination between gray sediments
than Meter 1 made it a good candidate for further testing.

Meter 2

25

20
∆ V [590-500nm]

15

10

0 1 2 3 4

Minolta CM-2500d

20
18
16
∆ %R [590-500nm]

14
12
10
8
6
4
2
0
1 2 3 4

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Figure 9: Colorimetric representation of sediment color. Values for a*>0 correspond to increasing
redness and values for b*>0 correspond to increasing yellow. Samples 1-3 are clustered together, an
indication of the similarity in their appearance, while sample 4 displays a marked difference, again, as
observed in side-by-side comparisons and in calculations of ∆Eab (see Figure 7 and Table 2b). Color
space has been optimized to show uniformity across the a* b* dimensions.

25

20

15 1
2
b*

3
10
4

0
0 5 10 15 20 25 30 35 40
a*

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Figure 10a-e: Comparison of ∆R520-510, ∆R590-500, ∆V, and the ratio of reduced iron to total iron in sediments taken from Site F (a–d). Also shown
is arsenic concentrations taken from nearby monitoring wells of various depths (e). Both plots of ∆R show a gradually decreasing gradient,
indicating a general graying of the sediment with increasing depth. This trend is also seen in measurements made with Meter 2 and is supported
by a generally increasing ratio of reduced iron to total iron. Below the clay layer (120-150 ft.), sediment turns noticeably orange, indicating more
oxic conditions. Arsenic levels in nearby wells also tend to increase with depth above the clay layer, but fall to <5µg/L in the oxidized sediment.
(Iron and arsenic data courtesy A. Horneman)

a: ∆ R 520-510nm b: ∆ R 590-500nm c: Meter 2 ∆ V d: Fe+ 2/Total Fe Site F Arsenic

∆ R (%) ∆ R (%) ∆ V (mV) FE+2/Total Fe [As] (µg/L)

0 0.5 1 1.5 2 2.5 0 2 4 6 8 10 12 14 16 0 5 10 15 20 250 200 150 100 50 0
1 0.8 0.6 0.4 0.2 0
0 0 0 0
0

20 20 20 20
20

40 40 40 40
40

60 60 60 60
60

80 80 80 80
80

100 100 100 100 100

Depth (ft.)

Depth (ft.)
120 120 120 120 120

140 140 140 140 140

160 160 160 160 160

180 180 180 180 180

200 200 200 200 200

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Figure 11: Comparison of Meter 2 output relative to spectrophotometer data showing good correlation
between the two measuring methods.

20

15
∆ V (mV)

10
R2 = 0.87
5

0
0 5 10 15
∆ R (%)

Figure 12: Comparison of Meter 2 output to ratio of reduced Fe to total Fe, giving an indication that
Meter 2 is providing a measure of the redox state of sediment.

12
10
R2 = 0.71
8
∆ V (mV)

6
4
2
0
0 0.2 0.4 0.6 0.8 1
Fe+2:Total iron

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Appendix

Appendix 1: Cost break-down of Meter 2

Component Cost Unit Amount Sub-total

Digital Multi-Meter 162.75 ea 1 $162.75
Labor (specialized) 60.00 hr 1 $60.00
Labor (non-specialized) 20.00 hr 2 $40.00
White reflectance coating 225.00 bottle 0.08 $18.00
Optical plastic window 11.10 ea 1 $11.10
Flashlight 11.00 ea 1 $11.00
9V batteries 5.00 ea 2 $10.00
Breadboard 7.35 ea 1 $7.35
5K adjustable resistor 1.75 ea 4 $7.00
LED 1 (AND412HG) 2.50 ea 2 $5.00
Photo diode (VTB-1113) 4.40 ea 1 $4.40
LM317 0.63 ea 4 $2.52
glue 20.00 tube 0.125 $2.50
End cap 1.19 ea 2 $2.38
6-pin connector 1.50 ea 1 $1.50
10-pin connector 1.50 ea 1 $1.50
Push buttons 2.99 4-pack 2 $1.50
Banana clips 0.50 ea 2 $1.00
PVC 1.00 ft. 1 $1.00
LED 2 (MV8315) 0.50 ea 2 $1.00
R1 0.20 ea 4 $0.80
R2 0.20 ea 4 $0.80
Battery clips 1.99 5-pack 2 $0.80
Shielded cable 35.00 100 ft. 0.02 $0.70
wire 14.00 100 ft. 0.05 $0.70
Ribbon cable 0.25 ft. 2 $0.50
Threaded cap 0.48 ea 1 $0.48
Silicon sealer 3.27 tube 0.125 $0.41
0.1 uF capacitor 0.40 ea 1 $0.40
LED holder 0.05 ea 4 $0.20
Photo diode holder 0.05 ea 1 $0.05
solder 4.49 roll 0.01 $0.04
teflon tape 1.19 roll 0.01 $0.01
TOTAL $357.39

Kostel 25