COMPARISON OF HEAVY METAL PATTERN

BETWEEN WATER AND SEDIMENTS

IN PASIG RIVER SYSTEM, PHILIPPINES

Teodinis P. Garcia*, Assistant Professor, Technological University of the Philippines

Taro Urase, Associate Professor, Tokyo Institute of Technology
Yosuke Suzuki, Master Course Student, Tokyo Institute of Technology

*: Stay in Japan from 27 February 2003 to 27 May 2003 funded by the JSPS core
university program

ABSTRACT

Water samples from Pasig river and from its branches were collected and chemically
analyzed using the inductively coupled plasma mass spectrometry (ICP-MS) and the inductively
coupled plasma atomic emission spectrometry (ICP-AES) to quantify heavy metal concentrations.
The study aimed to clarify the heavy metal pollution of this region focusing on the effect of urban
water discharge on sediment quality of Pasig River. The survey was conducted during the dry
season and slight salt intrusion from Manila Bay to the river system was observed. The
concentrations of copper, zinc, lead, titanium and iron were quantified. Furthermore, the results
showed that higher particulate lead concentration of water is observed from the sample taken at San
Juan River. These results suggest that there is a route of lead discharged from urban area and
transported via San Juan River to Pasig River then to Manila Bay.

INTRODUCTION

Pasig River in the Philippines is the main waterway flowing through Metro Manila
between Laguna de Bay and Manila Bay. The Pasig river system includes the Pasig, San Juan and
Marikina rivers in greater Manila. The Pasig river system is heavily polluted with industrial,
municipal and domestic wastes. Rehabilitation works for the Pasig River is on going. The long term
goal of the Philippine Government is to upgrade the water quality of Pasig River to sustain aquatic
life, spur tourism growth and establish new transportation routes.

A comprehensive study into the pollution of the Pasig River, Marikina River and San Juan
River by metals and organic pollutants as a result of polluting industrial practices urban run-off is
deemed necessary. Most of the pollution studies which assessed the health of the river mainly
focuse on organic pollution which can be evaluated by the index of biological oxygen demand
(BOD) and dissolved oxygen (DO). Because BOD only accounts for decaying organic matter, it
tells us little about the presence and effects of persistent toxins including metals (metals do not
degrade in the environment) and long-lived organic poisons.

This study focuses on the determination of the concentration of heavy metals in Pasig
River system. The result of this study will provide baseline data on heavy metal concentration in
water samples of the aforementioned river system and thus aid in the effectiveness of pollution
control strategies.

MATERIALS and METHOD

Study site and sampling

Raw water samples were taken from the Laguna Lake, Pasig River, Marikina River and
San Juan River of the Philippines. Sampling locations are indicated as shown in Table 1. Sampling
point LL refers to Laguna Lake; location 1 is middle stream of Pasig River, between the mouth of
Laguna Lake and the merging point with Marikina River. Location 2 refers to Marikina River, while
sampling point 3 is the San Juan River, which is heavily polluted by domestic and industrial
wastewater. Sampling site 4 is the down stream of Pasig River, near Manila bay. Water sample from
Laguna Lake was collected by Prof. Nadaoka’s laboratory members and water samples from the
four locations were collected in February, 2003 by Prof. Urase and Mr. Suzuki.

The data used for the concentration of bottom sediments were obtained from a previous
study of T. Urase, et al (2002). The sampling sites considered for the sediment samples are those
that roughly coincide with the points of sampling for water samples.

Table 1 Description of sampling locations

Water Description
LL Laguna Lake
1 Pasig River, Bridge of Dr. Sixto Antonio Avenue
2 Marikina River, Bridge of Pasig Boulevard
3 San Juan River, Bridge of Shaw Boulevard
4 Pasig River, Nagtahan Bridge

Analytical Techniques

Preparation of samples for chemical analysis

The raw water samples were divided and fractionated into total fraction and dissolved
fraction. Dissolved fraction samples were prepared by filtration using GFC filters. Nitric acid is
added to the raw samples and dissolved fraction samples in order to preserve the metal and to avoid
precipitation.

Digestion of Sample

There is a need for proper preparation of the materials to be used for digestion of samples.
As much as possible eliminate contamination of the sample to be analyzed since it will affect the
result. The laboratory wares were soaked in nitric acid bath and were rinsed thoroughly using pure
water to avoid contamination of metal. The materials used were glass beaker (100ml), glass cover,
mess flask (50 ml & 100 ml), plastic bottles for the sample. Likewise clean the working area to
minimize possible contamination. Digestion of sample is carried out to reduce interference by
organic matter and to convert metals associated with particulates to form (usually the free metal)
that can be determined by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and
Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES).

The total number of samples digested was twelve (12), five water samples for each
category and two blanks (pure water). The blanks were pure water as old as the water samples (may
contain some degree of contamination) and pure water taken from the de-ionized machine during
the performance of the digestion process. One hundred (100) ml of water sample were placed in a
glass beaker, and then 1 ml of nitric acid was added. It was then heated for two hours using a hot
plate. When the digested sample has cooled down, it was filtered using Whatman GF/C 47 mmφ
filter. The filter was pre-rinse with nitric acid to ensure minimization of contamination. After
filtration, the sample was transferred to a mess flask in which 100 µl of internal standard solution
was added. Bismuth (Bi) and Ytrium (Y) were used as internal standards. It was then diluted with
pure water to make up 100 ml and transferred to the plastic bottle for analysis.

ICP Analysis

Chemical analysis of the samples is done using the Inductively Coupled Plasma Atomic
Emission Spectrometry (ICP-AES) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS).
These analytical methods are used for the detection and quantification of desired metal species
present in the sample. For elements with low concentration, ICP-MS is used since it provides
greater sensitivity compared to ICP-AES. Likewise for elements with high concentration, ICP-AES
is more suitable to use because it may not be affected by mass-spectral interference.

Target Elements

There are ten (10) target elements to be quantified using the above mentioned analytical
methods. These are the following elements: copper, nickel, zinc, cadmium, cobalt, lead, chromium,
manganese, titanium, and iron.

General Water Quality

The anion concentration was determined using the Ion Chromatography (HITACHI
G-7000 series). The cations like Na, K, Ca, Mg, Sr, Ba were measured as metal by ICP/AES.
Suspended solid concentrations were measured by using GF/C filters.

DISCUSSION AND ANALYSIS OF RESULTS

General Water Quality

Measurement of Suspended Solids

The result of Table 2. Suspended Solids Measurement

measurement of suspended
solids (SS) is tabulated in
Sample Trial 1 (mg/l) Trial 2 (mg/l) Ave (mg/l)
Table 2. The measurement
was done twice and the 1 78.4 86 82.2
average concentration is 2 32.8 36.4 34.6
computed as shown in the 3 21.2 22.8 22
table. It can be noted that 4 84.4 81.2 82.8
suspended solids (SS) in LL 103.2 109.2 106.2
sample 1 and 4 (Pasig river) Blank -4 -3.2 -3.6
yields almost the same
quantity. The suspended solids in the Laguna Lake are relatively high compared to other sampling
sites. Sample location 3 gives the lowest value. Consequently, the main source of the suspended
solids in the Pasig river is not the urbanized wastewater but the Laguna Lake.
Anion concentration

The summary of results using the ion chromatography machine is shown in Figure 1. The
obtained concentrations were corrected by standard concentration of the ions being considered and
by dilution factor. Figure 1 shows the concentration of the anions Cl-, SO42-, NO3- in each sampling
points. Take note that the unit of the concentration of elements for the sample from Manila bay is in
g/l, while the rest is in mg/l.
19.9 g/l

2.50 g/l raw MB

rawLL
Concentration(mg/l) raw 1
200.00 raw 2
raw 3
150.00 raw 4

100.00

50.00

0.00
Cl- SO4-2

Figure 1. Anion concentration

Raw water sample from Manila bay was also analyzed aside from the five samples. The
chloride and sulfate concentrations of Manila bay is very high. There is only a slight difference in
concentration of Cl- and SO42- from the mouth of Laguna Lake to the stretch of Pasig River. The
concentration of Cl- and SO42- in Marikina and San Juan rivers were lower than that of the Pasig
river. The presence of NO3- is observed in sample locations 1, 2, and 3. Concentration of NO3- is
considerably higher in San Juan River (point 3) than in the other sampling locations. Nitrification
from ammonium to nitrate may have taken place during storage or transportation of the samples.

It can be observed that water sample from Manila Bay has almost 20,000 mg/l of chloride;
this means that the sample is seawater. Judging from the measurement in September, 2002,
complete freshwater in this Pasig river area is around 30 mg/l for chloride concentration. Actually,
the February, 2003 survey shows that chloride concentration for sampling points 2 and 3 is about 30
mg/l. This value indicates that water sample in points 2 and 3 are complete freshwater. Whereas the
chloride concentration in samples 1, 4, and LL is about 200 mg/l, this means that there is a slight
intrusion of seawater in these sampling points. Further observation denotes that in the Philippines,
September is wet season and February is part of the dry season. Based on the two measurements, it
can be deduced that there is a slight seawater intrusion in Pasig River in the dry season.

Cation and Metal Concentration using ICP-AES

Table 3 shows the summary of cation and metal concentration present in the water samples.
For comparison, measurement conducted in 2002 September for the Pasig river sample was added
as reference P2. The cations analyzed were Na, Mg, K, Ca, Sr, and Ba. It is observed that the
concentration of Na is higher than that in the previous survey due to salt intrusion in the dry season.
Table 3. The concentration of cations. Dissolved fractions were subjected to analysis for
ICP/AES (All units are mg/l).
Sample ID Na Mg K Ca Sr Ba
LL 82 21 1.9 14 0.19 0.07
1 75 21 1.9 14 0.20 0.08
2 33 12 1.1 33 0.27 0.06
3 35 7.7 1.2 32 0.20 0.09
4 67 19 1.8 17 0.20 0.06
Ref. P2 28 8.4 5.4 14 0.12 0.02

Heavy Metal Concentration

There are ten (10) elements analyzed in the water samples from Pasig River, Marikina River,
San Juan River, and Laguna Lake. These elements are Cu, Ni, Zn, Cd, Co, Pb, Cr, Mn, Ti, and Fe.
All the samples including total fractions and dissolved fractions were analyzed both by ICP-AES
and ICP/MS. The repeated measurements were conducted for Mn, Ti, and Fe with increased
maximum quantified concentration because their concentrations were too high to be quantified.
Table 4 shows the detection methods for target elements and reason for the selection of the method.

Table 4. Selection of detection methods for target elements.

Element Method Reason of the selection of the method

Cu ICP/MS Concentration was too low for ICP/AES
(m/z)=65 Slight interference by NaAr on 63Cu. 65Cu was selected.
Ni not Concentration was too low for ICP/AES.
determined Due to interference neither 60Ni nor 62Ni can be used.
Zn ICP/MS Slight difference between 66Zn nor 68Zn was observed. ICP/AES can also
(m/z)=68 be used but sometimes higher sensitivity was required. The use of 68Zn is
recommended by Japan sewer works association.
Cd not Concentration was too low both for ICP/AES and ICP/MS.
determined
Co not Concentration was too low both for ICP/AES and ICP/MS.
determined
Pb ICP/MS Concentration was too low for ICP/AES
(m/z)=208 Larger counts can be obtained for 208Pb than for 206Pb.
Cr not Concentration was too low both for ICP/AES. Severe interference on
determined 53
Cr. There is inconsistency between ICP/AES and ICP/MS (m/z=52)
Mn ICP/AES ICP/AES and ICP/MS(m/z=55) gives consistent results. ICP/AES was
used due to its linearity in the higher concentration measurement.
Ti ICP/AES ICP/MS did not give appropriate results.
Fe ICP/AES ICP/MS did not give appropriate results.

Table 5 summarizes the metal concentration of the samples. Figure 2 shows the graphical
representation of the comparison between the total and dissolved metal fraction of lead. Lead is
considered as a good indicator of pollution by urban run-off. Its presence in higher concentration in
sample 3 as shown in the figure 2 suggests that there is a route of lead discharge from San Juan
river and transported via Pasig river then to Manila bay. In sample 3, which is the San Juan river, it
can be seen in the table that there is a higher concentration of Mn in the dissolved form. In the case
of zinc, higher concentration of dissolved fractions compared to those of total fractions was
observed. This might be related to problems in chemical analysis.
Table 5. Summary concentration of elements considered for further analysis. (µg/l)

LL-T 1-T 2-T 3-T 4-T LL-D 1-D 2-D 3-D 4-D
Cu 10 13 4.4 6.6 6.5 2.7 5.1 2.2 3.4 2.8
Zn 11 19 13 33 13 18 29 24 47 16
Pb 2.5 3.9 1.6 6.3 2.4 0.53 1.0 0.39 1.9 0.54
Mn 130 83 490 380 110 5.0 5.8 450 400 35
Ti 210 130 8.8 9.7 91 16 24 0.24 0.43 17
Fe 3100 2800 810 850 2000 230 400 260 320 280

7.0
Pb: Total fraction
Concentration(ug/l)

6.0 Pb: Dissolved fraction

5.0
4.0
3.0
2.0
1.0
0.0
LL 1 2 3 4
Sample location
Figure 2. Concentration of dissolved and total lead in the samples.

Comparison of Particulate Metal Concentration in Unit Weight of Suspended Solids in

Water Sample to Metal Concentration of Bottom Sediments Sample

The result of the analysis of the water samples was compared to the bottom sediments
analysis. The concentration of particulate metal which is the total concentration subtracted by
dissolved concentration was calculated as metal weight based on unit suspended solids and was
compared to the concentration of sediments corresponding to the sampling points of water sample.

The summary of results for the particulate metal concentration in water and sediments are
shown in Tables 6 and 7 respectively. In the case of copper, titanium and iron, it can be observed
that the metal concentration in sediments is higher than in the water sample in all the sampling
points.

Lead concentration is highest in sample location 3 (San Juan river). It can also be noted that
the lead concentration in sample 1 and 3 gives higher value in water than in the sediments. Higher
particulate lead concentration of water in sample 3 indicates that run-off from the vicinity of San
Juan river is a source of lead in water and transported to Manila Bay through the Pasig river.
 Table 6. Summary of particulate metal concentration in
unit weight of suspended solids

Element Cu Pb Mn Ti Fe SS
Sample mg/kg mg/kg g/kg g/kg g/kg mg/l
LL 70.24 18.64 1.135 1.80 27.32 82.20
1 61.50 34.92 0.938 1.31 29.73 34.60
2 65.09 34.393 0.968 0.25 15.85 22.00
3 143.68 199.09 -0.634 0.42 24.20 82.80
4 44.59 22.22 0.74 0.90 20.99 106.20

Table 7. Summary of metal concentration of sediment samples

Element Cu Pb Mn Ti Fe
Sample mg/kg mg/kg g/kg g/kg g/kg
L1 116 21 1.2 3 58
P4 76 18 0.8 3 56
M1 128 23 0.8 3 63
S1 114 88 0.9 3 57
P2 114 51 0.9 2 58

CONCLUSION

Water samples from Pasig river and from its branches were collected and chemically
analyzed using the inductively coupled plasma mass spectrometry (ICP-MS) and the inductively
coupled plasma atomic emission spectrometry (ICP-AES) to quantify heavy metal concentrations.
The study aimed to clarify the heavy metal pollution of this region focusing on the effect of urban
water discharge on sediment quality of Pasig River. The survey was conducted during the dry
season and slight salt intrusion from Manila Bay to the river system was observed. The
concentrations of copper, zinc, lead, titanium and iron were quantified. Furthermore, the results
showed that higher particulate lead concentration of water is observed from the sample taken at San
Juan River. According to Y. Suzuki and F. Siringan’s survey, spatial distribution of concentration of
lead in sediments shows diffusion pattern from the mouth of Pasig river. These results suggest that
there is a route of lead discharged from urban area and transported via San Juan River to Pasig
River then to Manila Bay, though further analysis and discussion is necessary to obtain clearer
conclusion.

Acknowledgement

This research is a subtopic of the Integrated-Manila Bay-Laguna Lake and Surrounding

Watersheds Environmental Study (IMSWES) headed by Prof. Kazuo Nadaoka, who is responsible
for the management of Group 1 of the JSPS core university program on environmental engineering
between Tokyo Institute of Technology and the University of the Philippines.