ASSESSMENT OF HEAVY METAL USING COMBINED X-RAY FLUORESCENCE

AND SPECTRAL CHARACTERISTICS IN KALINAWAN RIVER IN

PROXIMITY TO AGATA MINING VENTURES INC.

John Paul A. Hegina, Mark Shaydrick C. Serrano

BS Mining Engineering Program, College of Engineering and Geosciences, Caraga State

University, Ampayon, Butuan City, Philippines

Abstract: The acquired water samples were analyzed, and Iron (Fe) was detected, and its
concentration for each sampling point portrayed a bell-like trend (13.3 ppm, 26. 4 ppm, 30.57 ppm,
27. 3 ppm, 22.47 ppm, 9.87 ppm, respectively) which revealed that stations closer to the mine site
have a higher concentration of Fe than upstream and downstream stations. Spectral characteristics
were used to detect the presence of Iron (Fe) in the Kalinawan River. Assessing the changes in
reflectance in 6 stations in proximity to AMVI suggested the amount of Iron (Fe) present in the
water. Each sample for the study was infused with 0.5 mol of nitric acid as preservatives. A simple
distribution map was constructed using the Fe concentrations. The identified element was focal to
the study because it’s a heavy metal that can be related to the active mine operations among the
results acquired in the X-Ray Fluorescence (XRF) Analysis. This study employed HEC-RAS
simulation to support the trend of concentration of the determined heavy metal in the area in order
to depict the heavy metal transport using the direction flow. The study demonstrated the
applicability of spectral characteristics in evaluating XRF analysis results and correlating data
obtained via Linear Regression.

Keywords: X-ray Fluorescence, Spectral Characteristics

1. INTRODUCTION
An increasing concentration of heavy metals in any body of water in the vicinity of a mining
operation remained one of the significant problems in the industry. Mining cannot progress without
water use, and without proper implementation of water treatment, it can disrupt the natural setting.
A high level of heavy metal with its transportation and settling projects a state of unbalance in
nature and the living organisms that rely on that body of water. Industrial and untreated domestic
water waste has been increasing due to global population growth, household activities, and the
expansion of industrial production, such as the mining industry [1].
In Agusan del Norte, the Kalinawan River resides as the major outlet of the Lake Mainit. Hence,
various communities from two different municipalities depend on the life that springs from the
river. The river is an integral part of the mining operation of AGATA Mining Venture Inc.
(AMVI). Although there are precautions made by every mining operation addressing the possible
problems of sedimentary setting, particularly on heavy metals, we cannot disprove that as mining
practices continue to progress throughout the decades, it has also become fast-paced, which in
return allowed miners to increase their production, adding to the increased discharge where
concentrations of heavy metals can be traced.
Suitable solutions need to be generated and are usually done by undergoing a physical laboratory
[2]. The introduction of a non-destructive method for water analysis has drawn considerable
attention, but little research has been conducted. The study laid out the application of XRF
Analysis to quantify the heavy metal present in the water samples. These will allow the research
to attain its objectives of using spectral characteristics to support the presence of heavy metal
attained in XRF Analysis, and create a simulation of their transport.

Figure 1. Map of Kalinawan River, in the proximity of AGATA Mining Ventures

2. METHODOLOGY

2.1 Sample Collection

In station 1, the upstream samples were collected in Colorado, a barangay located north of the
river. A 750 ml cleaned polypropylene bottle was filled with water from 30 cm depth. In station 2,
the Nangka Creek was the location for the 2nd station. The 750 ml cleaned polypropylene bottle
was filled with water from 30 cm depth and near the discharge mouth of the creek to the river. In
station 3, the Paiton Creek was the 3rd station for collection. The 750 ml cleaned polypropylene
bottle was filled with water from 30 cm depth and near the discharge mouth of the creek to the
river. In station 4, the Coboy Creek, the 4th station for water sample collection and housed one of
the settlements close to both the mine site and the Kalinawan River. The 750 ml cleaned
polypropylene bottle was filled with water from 30 cm depth and near the discharge mouth of the
creek to the river. In station 5, the Agata Creek, also one of the discharge close to human
settlements was the 5th station and the 750 m cleaned polypropylene bottle was filled with water
from 30 cm depth and near the discharge mouth of the creek to the river. In station 6, in this study,
the Guinaringan Creek discharge is described as the downstream. A 750 ml cleaned polypropylene
bottle was filled with river water from a depth of 30 cm and was collected near the discharge mouth
of the creek.
The distance from each of the sampling points varied depending on the location of the creek
discharge. This was beneficial for our study since this body of water is directly connected to the
production activities and water treatment facilities into the Kalinawan River and the various
settlements around it. The unfiltered water samples collected near the mouth of the discharge
creeks were added with a 5 ml of 0.5 mol nitric acid to each of the collected samples to act as
preservatives and limit the sticking of heavy metals and sediments to the walls of the bottle. Once
nitric acid is added it is indicated that it can be stored and used for at least 6 months according to
the "Methods for Chemical Analysis of Water and Wastes," Environmental Protection Agency,
Water Quality Office, Analytical Control Laboratory, Cincinnati, Ohio. [3] [4]

2.2 X-ray Fluorescence Analysis

The samples were prepared and collected in a specified container for XRF analysis. Each of the
six (6) station water samples were analyzed and was filled with enough water (at least 2mm) which
covered the XRF film completely. The container-filled samples were delivered to the chemistry
lab and was analyzed by the Laboratory attendant. The results were given and verified by
competent persons of the Chemistry department.

2.3 Spectral Characteristics Acquisition

The USB4000 spectrometer was utilized in a laboratory at the Caraga State University. The
preparation of the equipment revolves around using direct sunlight as a light source as an
alternative to the Halogen Light Bulb, thus clear weather was required advised by a specialist
residing in CEGS. The calibration of the spectrometer was performed for the light reflectance
using a white standard reflectance, and dark reflectance was performed by cutting off the light
source before directing the cable probe to each of the 6 samples collected from the 6 stations
described in figure 1. Each sample was measured three (3) times to verify its consistency. For
heavy metal analysis, the spectral signatures from the USGS spectral library were used [5].

2.4 Simulation Model

The created simulation required the slope file which consisted of necessary hillslope parameters
such as slope gradient, shape, width, and orientation along its length or a Digital Elevation Model
(DEM). The DEM (prj and tiff) files of the Kalinawan River were acquired from NAMRIA to fill
the terrain and projection file. These parameters were used to configure a simulation. The most
efficient tool to use is a model that can simulate flow, sediment transportation, and deposition;
these sediments supposedly contain heavy metals such as iron and nickel. The HEC-RAS
simulation software was utilized to produce and developed a simulation model of the heavy metal
transport in the Kalinawan River.

3. RESULTS AND DISCUSSION

3.1 X-ray Fluorescence Results and Distribution Mapping

The acquired result from the XRF analysis at Caraga State University – Chemistry Lab identified
four (4) consistent elements, these are Iron (Fe), Silicon (Si), Phosphorous (P), and Calcium (Ca).
The study selected Iron as the focus of the study since it’s the only heavy metal detected.
The XRF results showcased a bell-like trend of the mean of the three (3) replicates for each sample
of the study area in the vicinity of AMVI. The trend is proved by the low concentration in the
upstream (station 1) Fe – 13.3 ppm and downstream (station 6) Fe – 9.87 ppm relative to the
midstream, (station 2) Fe – 26.4 ppm, (station 3) Fe – 23.9 ppm, (station 4) Fe – 34.27 ppm, (station
5) Fe – 22.47 ppm, (station 6) Fe - 9.87 ppm. The data is a representation that the content of
elements increased when it is closer to a discharge coming from a mine site. Therefore, distance
from AMVI, a source, is the most important parameter to these concentrations. [6]
Table 1. Iron (Fe) Concentrations in 6 Stations

IRON (Fe)
Location Min (ppm) Max (ppm) Avg. (ppm)
Station 1 7.4 23.3 13.3
Station 2 23.1 30.9 26.4
Station 3 25.4 34.1 30.57
Station 4 27.3 43.3 34.27
Station 5 18.5 24.9 22.47
Station 6 9.1 11.0 9.87

Figure 2. Simple Distribution Map of Iron in the 6 Stations (using their mean values)
3.2 Spectral Characteristics Acquired from the Samples
The spectral images of the samples showed that the most sensitive bands are identified in the
ranges’ 350 nm – 400 nm and 900 nm – 1050 nm for all samples acquired from the 6 different
stations This demonstrated that the present heavy metal is consistent all throughout the sample
stations. The wavelengths above 1050 nm were not investigated due to the high noise to signal
ratio. Only the wavelengths from 350 nm to 1050 nm portion of the spectrum were collected due
to the observed low noise-to-signal ratio at both ultraviolet and near-infrared wavelengths [8].
The analysis of the spectral characteristics indicates a highly significant wavelengths of 900 nm,
950 nm, and 1000 nm. No other heavy metal was identified due to lack of similarities in terms of
peaks and reflectance. In analyzing it is important to look at the wavelengths of peaks or troughs,
rather than reflectance curves. The focus was on the process of evaluating the data and justifying
the selection [9].
The spectral characteristics from the six (6) stations showed significant differences in reflectance.
Station 1 and 6 specifically the upstream and downstream of the study area depicts a below 20%
reflectance in the overall assessment of each of the 350 nm -1050 nm wavelengths. In contrast to
the remaining sampling points (station’s 2, 3, 4, and 5) where above 20% reflectance is observed.
The considerable increasing then decreasing trend of reflectance between the samples is due to the
absorption capacity of water which is influenced by the concentration of sediment (heavy metal
bearing sediments) particles, the backscattering from visible to the near infrared range increases,
intensifying with shorter wavelength [10]. Suspended sediments (heavy metal indicator) increase
the radiance emergent from the surface water in the visible and near infrared (NIR) proportion of
the electromagnetic spectrum, so it is a promising and feasible to detect water pollutants using
spectral signatures, [11].

3.3 Spectral Characteristics and XRF Correlation Analysis

A correlation analysis between two variables [12]: the acquired metal content from XRF analysis
and spectral reflectance was conducted. The First graph shows the highest correlation of the
significant wavelengths of iron (Fe) to be found at 900 nm (R2 = 0.6947) followed by wavelengths
at 950 nm (R2 = 0.6253) both are considered to be highly significant. Lastly, at 1000 nm (R2 =
0.3356) which was determined the lowest among the distinguished wavelengths but still
considered as highly significant. [13]
All the linear regression results indicate a positive linear trend. This means that it can proved that
as concentration of the heavy metal (the independent variable) increases the reflectance also
increase. This can be attributed to the capacity of the water to absorb light. Thus, indirectly
revealing the heavy metal content of the Kalinawan River. Further research are suggested to
improve the significance and additional variables is also suggested to attain this. [13]
Figure 3. Correlation of Reflectance and XRF Results of Iron (900)

Figure 4. Correlation of Reflectance and XRF Results of Iron (950)

Figure 5. Correlation of Reflectance and XRF Results of Iron (1000)

3.4 Simulation on the transport of Iron in the Kalinawan River

Figure 6. Flow Simulation in Kalinawan River using Hec Ras

4. CONCLUSIONS AND RECOMMENDATIONS
The Kalinawan River in proximity to the mine site was evaluated by using combined X-Ray
Fluorescence and Spectral Characteristics. The findings revealed that samples near the 6
designated discharges showed relative differences from each other. Forming a bell – like trend,
samples closer to the mine operations and human settlements (station 2, 3, 4, 5) were higher
compared to the further ones (station 1 and 6). Distance was an important parameter that supported
this trend. The river was classified as Class C and the finding of iron exceeds its permissible limit.
[15]. Significant correlations were found in the present study, depicting that reflectance increased
as concentration of Iron increased at wavelength’s 900 nm, 950 nm, and 1000 nm. A Hec-Ras
simulation was created to support the concentration trend of iron in the area. The visualization
identifies locations where accumulation is likely to occur and discharged from the AMVI.
The study laid out the groundwork for further implementation of the methods used. Utilizing a
spectrometer provides researchers with an alternative approach when identifying heavy metals.
Thus, this study is a gateway for creating a prediction model from the reflectance – concentration
relationship. Constructing numerical models that will determine the presence of heavy metals and
quantify results in much fewer steps. Exploring other means of utilizing spectral characteristics
such as the spectral images such as hyperspectral, Landsat, and other satellite-based sources is an
improvement. Extend the scope of study area to accurately determine the possible causes and
which contributed most to the exceeding of the permissible iron limit.

5. ACKNOWLEDGMENTS
We want to express our sincere gratitude to our advisor Engr. Gerome L. Amper for the continuous
support of our thesis study and research and his patience, motivation, enthusiasm, and immense
knowledge. His guidance helped us in all the time of research and writing of this thesis could not
have imagined having a better adviser and mentor for our undergraduate thesis study.
We would like to express my heartfelt gratitude to Agata Mining Ventures Incorporated, based in
Jabonga, Santiago, Tubay, Agusan Del Norte, for collaborating with us on our research and
allowing us to conduct and collect samples at their mine.
We would also like to express our gratitude to NAMRIA for providing us with a Digital Elevation
Model file for our study simulation. We'd like to thank CCGEO for always lending us the
equipment and materials we needed for our research and MinRes for allowing us to use their XRF
to examine our sample.
We are incredibly grateful to our parents, family, and friends for their love, prayers, care, and
sacrifices in educating and preparing us for our future. We want to extend our special thanks to
those who assisted us and showed a keen interest in completing this study successfully.
Lastly, we want to express our gratitude to God, the Almighty, for showering us with blessings
throughout our research and allowing us to complete our work thoroughly.
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