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Heavy Metals Characterization of Sludge from a Philippine Recycling Paper Mill

Article in ASEAN Journal of Chemical Engineering · December 2004

DOI: 10.22146/ajche.50839

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Lorraine Carrillo Susan Gallardo

Technological Institute of the Philippines De La Salle University
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Heavy Metals Characterization of Sludge from a Recycling Paper Mill in the
Philippines

Lorraine A. Carrillo
Asian Regional Research Program on Environmental Technology
De La Salle University, 2401 Taft Avenue, 1004 Manila, Philippines
Email: lorraine_carrillo@yahoo.com

Dr. Susan M. Gallardo

Asian Regional Research Program on Environmental Technology
De La Salle University, 2401 Taft Avenue, 1004 Manila, Philippines
Email: gallardos@dlsu.edu.ph

Wastewater treatment sludge is the largest volume residual waste stream generated by the
pulp and paper industry and generally disposed of in a dedicated landfill. Composting the sludge is
an alternative method proposed by the ARRPET-DLSU Minor Issue Group. The Department of
Agriculture’s (DA) standards for organic fertilizer’s maximum allowable content of heavy metals
provided the legislative regulation for the conversion of sludge to compost.
The research is designed to characterize the sludge of a specific paper-recycling mill in the
Philippines and establish whether the sludge might contain the heavy metals Cadmium, Chromium,
Lead, Mercury, Nickel and Zinc using Atomic Absorption Spectrophotometer (AAS). The analysis is
used to assess the possibility of sludge conversion as soil amendments or as compost.
In the research presented, three discharge points are established as the sampling points.
Analysis shows that the metal content of the sludge vary from point to point but is highest during the
production of white paper. The metals chromium, mercury, and nickel are non-detectable in all
samples at all three-discharge points for the four weeks of sampling. Cadmium is detectable in very
few samples. Lead and zinc are present in all three points and is highest at the deinking sludge.
These results are compared to the US EPA Part 503 and the DA’s guidelines for organic
fertilizers and composts. The sludge results are significantly low compared to these standards leading
us to conclude that composting of the sludge is a feasible option for recycling paper mill sludge.

Keywords: heavy metals, sludge, deinking, paper recycling mill

INTRODUCTION

One of the most pressing problems today
worldwide is safe disposal of large quantities of
industrial wastes including pulp and paper mill
waste.
The re-use of waste paper in papermaking
inevitably results in the generation of process
residues that cannot be used in paper production
(Webb, 1996). Paper sludge obtained directly
from a mill wastewater treatment plant is
composed generally of 50-75% organics (cellulose
fibers and tissues) and 30-50% kaolinite clay
(Medvitz, 1998). The amount of sludge generated
by a recycled paper mill is greatly dependent on
the furnish being used and the end product being
manufactured.
Land filling is still the most predominant
practice of sludge disposal today. Commercial
establishments disposed off their solid wastes by
dumping it in their own land (McKinney, 1995).
Potential environmental hazards from wastewater
sludge are associated with trace constituents that
partition from the effluent into the sludge
(MacGuire, 1997). The major source of paper
sludge contamination comes from the dyes added
to the paper by manufacturers and inks added by
printers, as well as organochlorine contaminants
added in the bleaching process by paper producers
(http://www.conservatree.Com/learn/essential_Iss
ues/EIPaperContents/shtml).
The Philippines has 1 integrated pulp and
paper mill, 4 abaca pulp mills, and 37 recycling
mills (Rios, 2001). Waste paper is the major
source of raw material in the Philippines
amounting too as much as 90% for printing and
writing paper production (UP Business Research,
1990). A survey of the pulp and paper industry
discharges of the Philippines by ARRPET-DLSU
had eleven (11) respondents out of the 42 mills in
the country (Gallo and Gallardo, 2002). Of the
respondents, ten (10) mills are operational, all
recycled paper mills running twenty-four (24)
hours a day. These mills utilize both local and
imported raw materials as furnish. The volume of
the sludge generated by the mills ranges from 1.5
to 100 metric tons (MT) per day. Solid wastes
which included generated mill garbage were either
landfilled, recycled and/or burned (Bantayan and
Razal, 2001).
The treatment of sludge in developed
countries also includes composting paper mill
sludge. Composted materials of various kinds are
becoming more available as municipality seeks
more economical waste management alternatives
than land filling, since land is a valuable property.
Pulp and paper mill sludge are amenable to well-
controlled composting techniques. Soil
contaminations may also result from heavy
metals, pathogens or persistent toxic organics,
some or all of which can occur in composted
materials (Barry et al, 2000). In the Philippines,
compost products intended for distribution
commercially needs to conform to the standards
for organic fertilizers set by the Department of
Agriculture (DA). Possible existing metals in the
sludge is evaluated against the maximum
allowable level of heavy metals in organic
fertilizers or compost prescribed by the
Department of Agriculture (DA) as shown in
Table 1.
This research study was conducted to
assess the sludge from a Philippine recycling
paper mill. This is to ascertain whether the sludge
might contain possible contaminants like heavy
metals and to establish the carbon to nitrogen ratio
of the sludge. The problem of sludge discharges
from a recycled pulp and paper mill is a minor
issue of ARRPET. The study is conducted by
using the sludge provided by a chosen research
partner, a recycling paper mill. Positive results of
the characterization are rewarding to both
government and the company to verify that the
composition of sludge is benign enough to land
spread or compost. The results of the study are
relevant only to the specific mill, which supplies
the samples.
Table 1. Allowable Level of Heavy Metals in
Organic Fertilizers (Obcemea, 2001)
Heavy Metal Maximum
Allowable Level in
Compost (ppm)
Zn 1000
Pb 750
Cu 300
Cr 150
Ni 50
Hg 5
Cd 5
OBJECTIVES
In general, the study was undertaken to
characterize the sludge from a recycling paper
mill. The specific objectives were to:
1) To determine the presence, concentration
and variation of its concentration of the
metals cadmium, chromium, nickel, lead,
mercury, and zinc present in the primary,
secondary and the de- inking treatment of a
recycling paper mill plant.
2) To determine whether variation in the
input raw materials causes variation in the
composition of the sludge.
MATERIALS AND METHODS
Three sites within the manufacturing plant
were selected in collecting the samples. A total of
fifty-one (51) samples were collected from the
mixed primary outlet of sludge, the deinking tank
and the blended sludge in the wastewater
treatment plant. Sample collection was done
during three weeks of newsprint runs and a week
of white run operation. The samples weighing less
than 200 grams were collected using plastic scoop
samplers for sludge. 150-ml wide-mouthed
polyethylene bottles with Teflon-lined cap were
used to contain the samples. Hold times for each
analyte is at six months except mercury, which
should be tested within 28 days.
Collection was done twice a day, three
samples per round for the three discharge points
or a total of six (6) samples per day, two each per
sludge treatment. Samples were stored first in an
air-conditioned room inside the company site. It
was then brought to DLSU and stored at 9˚C if
analysis is not done immediately. Samples were
digested and analyzed for the metals Cd, Cr, Ni, present in the sludge at higher amounts and trace
Pb, and Zn using AAS Buck Model Scientific the source of these metals.
200. An accredited laboratory, CRL The chemicals used in the recycling
Environmental laboratory, determined the operations of the plant are not major sources of
mercury content of the blended sludge. The the chemicals lead, cadmium, and zinc. The
collection of the samples entailed three to four chemicals sodium hydroxide, sodium silicate,
weeks covering the month of September. The hydrogen peroxide, sodium hydrosulfite are
analytical procedures adopted for digestion, and in common deinking chemicals. The company also
the analysis of cadmium, chromium, nickel, lead, utilizes a variety of surfactants, defoamers,
mercury and zinc were based on US EPA biocides, but the heavy metals found in the sludge
Standard Methods for examination of sludge. analysis are not major nor minor components of
Table 2 presents the US EPA Standard these chemicals. Dyes are also used in paper
methods of analysis using an atomic absorption making. They serve as optical brighteners to attain
spectrophotometer. the required brightness of most white papers. The
company employs a variety of dyes classified as
Table 2. Analytical Methods FWA or Fluorescent Whitening Agents like the
(source: SW-846, 1994) Irgalite blue and the Irgalite violet. The main
types of FWAs used in the paper industry are
derivatives of diaminostilbene di-sulphonic acid.
Parameter Method Analytical They are applied mainly in the wet end, at the size
Description Method press and in coating. Again, these are not point
Cadmium Flame Atomic 7130 sources of the heavy metals found in the sludge
Absorption 3050- analysis.Zinc and lead are the most prevalent
Spectrophotometry Digestion metals in the sludge analysis. The chemicals used
(FLAA) at TIPCO are possible sources of these metals if
7190 they exist in the chemical deinking compounds as
Chromium FLAA 3050- impurities. Another hypothesis is that these heavy
Digestion metals are the results of the deinking and the pre-
7420 treatment done on the recycling papers. The inks
Lead FLAA 3050- from the used paper are possible sources of these
Digestion contaminants. Some inks still utilized lead
Mercury Analysis 7471A compounds, and zinc can find their way since they
Mercury of Soils, Sludges 3050- serve as fillers for some paper.
and Wastes by Digestion
Manual Cold Comparison of Metal Concentrations Per
vapor technique Sampling Point
7520
Nickel FLAA 3050- Figure 1 compares the concentrations of
Digestion cadmium per sampling day per discharge point.
7951 The graph is a comparison of the average
Zinc FLAA 3050- cadmium concentrations resulting from the AAS
Digestion analysis of the sludge samples in the primary
sludge, de-inking sludge and the blended sludge.
The presence of cadmium in the sampling
RESULTS AND DISCUSSION is quite irregular. The primary sludge posted the
highest reading of cadmium concentration and the
Characterization of Primary Sludge, Deinking de-inking sludge posted the most number of days
Sludge and Blended Sludge that the metal has been detected. Most of the time,
cadmium is undetectable or below the detection
The values of the metals concentrations in limit. This can be attributed to the non-use of
all sludge samples were compared against each cadmium compounds in most printing inks. The
other to determine whether which metals are blended sludge has the lowest reading compared
to the primary sludge and the blended sludge.
 8.00 newsprint white newsprint
newsprint white paper newsprint
CONCENTRATION (PPM) 7.00 180
AVWERAGE CADMIUM

AVERAGE ZINC CONCENTRATION

6.00
160
5.00
140
4.00
120
3.00

(PPM)
100
2.00
80
1.00
60
0.00
I-1 I-2 II-1 II-2 II-3 III-1 III-2 III-3 IV-1 IV-2 IV-3 40
SAMPLING DAY
20

PRIMARY DEINKING BLENDED 0

I-1 I-2 II-1 II-2 II-3 III-1 III-2 III-3 IV-1 IV-2 IV-3
SLUDGE SAMPLING DAY

Figure 1. Average Cadmium Concentration PRIMARY DEINKING BLENDED

120 newsprint white paper newsprint

AVERAFE LEAD CONCENTRATION

Figure 3. Average Zinc Concentration in the Sludge

100

80
Figure 3 is a comparison of the average
concentration of zinc at the three discharge points.
(PPM)

60 The figure represents the average concentration of

40
20
0
I-1
Figure 2. Average Lead Concentration
Figure 2 compares the average
concentrations of lead per sampling day per
discharge point. The graph is a representation of
the average concentration of lead in the primary
sludge, deinking sludge, and blended sludge. As
can be seen from the graph, the deinking sludge
posted a higher reading per day compared to the
primary sludge and the blended sludge. It also
posted the highest concentration of lead in the
whole period of sampling. The results are
expected because of
the cleaning processes, chemicals added and
removed during deinking. Although most of these
contaminants end up in the wastewater, still some
ends up in the sludge.
zinc in the primary sludge, deinking sludge, and
blended sludge. The deinking sludge posted the
highest concentration of zinc occurring at the third
week of sampling, while the lowest zinc
I-2 II-1 II-2 II-3 III-1 III-2 III-3 IV-1 IV-2
concentration is present at the first and second
SLUDGE SAMPLING DAY week of sampling.
PRIMARY DEINKING BLENDED
Comparison of Metal Concentrations Per
Week
In the Sludge Figure 4 shows the concentration of the
metal cadmium in the sludge discharge points for
the four weeks of sampling. The primary sludge
has the highest concentration of cadmium at the
first week of sampling, while at the second week
of sampling, the blended sludge posted the highest
cadmium concentration. The third week of
sampling has the deinking sludge posting the
highest concentration of cadmium.
The fourth week of sampling posted the
lowest cadmium concentration at all discharge
points with the primary sludge having the
maximum concentration within that week.
Figure 5 is a representation of the
concentration of the metal lead at the different
discharge points for the four weeks of sampling,
Lead has the highest concentration on the third
week of sampling at the deinking sludge.
 The lowest concentration of lead was
posted on the first two weeks of sampling at the newsprint white paper newsprint
primary sludge. The third week of production 140.00
posted the highest lead concentration for the
deinking sludge and the blended sludge. Again 120.00

CONCENTRATION (PPM)
this is the week of producing white paper.
100.00

AVERAGE ZINC
. 80.00

4.50 newsprint white paper newsprint 60.00

4.00
40.00
CONCENTRATION (PPM)

3.50
AVERAGE CADMIUM

20.00
3.00
0.00
2.50 I II III IV
2.00 WEEKS OF SAMPLING

1.50 Primary
primary deinking blended
1.00
0.50
Figure 6. Average Zinc Concentration for the four
0.00 weeks of Sampling
I II III IV
WEEKS OF SAMPLING
Figure 6 is a representation of the average
primary deinking blended zinc concentration in the four weeks of sampling
at the different discharge points The third week of
sampling posted the highest concentration of zinc
Figure 4. Average Cadmium Concentration for the in the four weeks of sampling. The fourth week of
Four Weeks of Sampling sampling also posted higher concentrations of
zinc. The first two weeks of sampling has the
lowest concentrations.
The highest concentration is at the deinking
sludge, while the blended sludge posted its highest
newsprint white paper newsprint
reading at the second week of sampling.
60.00
AVERAGE LEAD CONCENTRATION

Evaluation of Average Results with Regulatory

50.00
Standards
40.00
Figure 7 represents the average
(PPM)

concentration of the metals cadmium, lead, and

30.00
zinc present in the primary sludge, deinking
sludge and blended sludge against US EPA Part
20.00
503. From the graph, the AAS results from the
10.00
three discharge points are very low compared to
the US EPA sludge standards. The comparison is
0.00
necessary to evaluate the sludge results against the
I II III IV US EPA Standards. The metal zinc has the highest
WEEKS OF SAMPLING concentration in the sludge results at 68.90 ppm
compared to the sludge standard at 2800 ppm.
primary deinking blended Figure 8 is a graph of the sludge results
against the Department of Agriculture’s standards
Figure 5. Average Lead Concentration in the Four
Weeks of Sampling
for organic fertilizers. The sludge results are
 considerably lower than the DA’s standards. The
graph is a comparison of the average sludge 3000
results at the different sampling points versus the
Department of Agiculture (DA) Standards. Zinc

METAL CONCENTRATION (PPM)

2500
posted the highest metal concentration present in
the deinking section at a value of 68.90 ppm
2000
against the DA’s standards for organic fertilizers
at 1000 ppm. The maximum lead concentration
1500
also occurs at the deinking sludge at 40.72 ppm
against the DA’s standard of 750 ppm.
1000

500
3000
0
2500 CADMIUM LEAD ZINC
CONCENTRATIONS (PPM)

METALS
AVERAGE METAL

2000
US-EPA PART 503 DA ORGANIC FERTILIZERSTANDARD PRIMARY DEINKING BLENDED

1500

1000 Figure 9. Comparison of the Sludge Results against

US EPA Part 503 and the DA’s Organic Fertilizer
500 Standards
0
CADMIUM LEAD ZINC Figure 9 compares the average results of
METAL ANALYTES the primary, deinking, and blended sludge against
the DA Standard and the US EPA Part 503. The
US-EPA PART 503 PRIMARY DEINKING BLENDED results of the analysis clearly shows that the
metals are very low compared to the two
standards. Both the local and the international
Figure 7. Comparison of Sludge Results against
standards are very high compared to the sludge
US EPA Part 503
results so that even if there is a 50 to 100 %
reduction in the weight of the sludge after
composting, the results will still be very low. This
only points out the fact that the sludge at TIPCO
1000
does not contain the heavy metals at levels, which
AVERAGE METAL CONCNETRATION

900 are deemed hazardous. The sludge without

800 composting can be landspread and still not exceed
700 the levels set for heavy metal presence by both
600 standards.
(PPM)

500
400
CONCLUSIONS
300
The results of the AAS analysis revealed
200 that the metals cadmium, lead and zinc are
100 detected in all three sampling points namely the
0 primary sludge, deinking sludge, and the blended
CADMIUM LEAD ZINC
sludge. The metals chromium, nickel, and
METAL ANALYTES
mercury are non-detectable in all samples. The
DA ORGANIC FERTILIZERSTANDARD PRIMARY DEINKING BLENDED deinking sludge shows a higher concentration for
the lead and zinc, while cadmium is slightly
Figure 8. Comparison of Sludge Results
higher in the primary sludge than in the deinking
against DA Organic Standards sludge. The blended sludge, which is the sludge
for final disposal, shows lower concentrations of Bantayan, Rosario and Dr. Ramon A. Razal.
the metals zinc and cadmium, except for lead “Status of Environmental Protection and
where it is slightly higher in the primary sludge. Control in Philippine Pulp and Paper
The metals lead and zinc posted the mills.” Inpaper International. October
highest concentration during the white run 2001
production, while cadmium is highest in the first
week of production. The production of white Barry, G.A, E.A. Gardner, G.E. Rayment and
paper requires old magazines and coated book P.M. Bloesch. Recycling Organic
papers and a more thorough removal of inks and Materials On Agricultural Lands. 1998.
fillers from these old magazines. The major source Department of Natural Resources, and
of paper sludge contamination comes from the CRC for Sustainable Sugar Production.
dyes added to the paper by manufacturers and inks
added by printers. Conservatree.
The results of the study showed a higher E n v i r o n m
lead and zinc content at the deinking treatment. e n t a l l y
Most of the heavy metals detected can be traced S o u n d
from this sludge as a result of deinking P a p e r
newspapers and magazines. It is therefore O v e r v i e
recommended that the sludge from the deinking w :
treatment be segregated from the rest of the sludge E s s e n t i
before composting of the blended sludge. a l
After positive results from the analysis I s s u e s .
and comparison of the metal concentrations with P a r t
regulatory standards, composting the sludge for I I I -
final disposal is the next step towards proving that M a k i n g
composting is indeed an alternative sludge P a p e r : C
management. o n t e n t .
. S a n
ACKNOWLEDGEMENT F r a n c i s
c o ,
The authors would like to extend sincerest thanks C a l i f o r
to the following: n i a .
Swedish International Development ( http://www.conservatree.Com/learn/
Cooperation Agency (SIDA) the funding agency E s s e n t i
of the Asian Regional Research Programme on a l I s s u e
Environmental Technology (ARRPET) through s / E I P a p
the Asian Institute of Technology (AI), Thailand. e r C o n t e
Trust International Paper Corporation n t s / s h t
(TIPCO) through Engr. Roland Peñ̃ a, Head of the m l )
Environmental Management Department. Document dated: 1988. Document
Engr. Jurex Gallo, MEP graduate of DLSU and accessed: 12 January 2003.
member of the ARRPET minor issue group.
Gallo, Jurex and Dr. Susan M. Gallardo.
REFERENCES “ Assessment of Pulp and Paper Industry
Discharges in the Philippines.” Chemical
Bajpai, P., P.K. Bajpai, R. Kondo. 1999. Engineering Congress. Manila, October
Management of Wastewater Treatment 2002.
Sludges.Biotechnology for Environmental
protection in the Pulp and Paper Industry. Kidder, G. 2001. Using Waste Products in Forage
Springer- Verlag Berlin Heidelberg. Production. Fact Sheet. A Fact Sheet of
Germany. the Soil and Water Science Department,
Florida Cooperative Extension Service.
 Institute of Food and Agricultural
Sciences, University of Florida.
MacGuire, Frances. November 1997. Paper
Recycling-Exposing the Myths. (Briefing
Paper), Friends of the Earth Ltd. London,
England
McKinney, R. W. J., Technology of Paper
Recycling. Blackie Academic and
Professional. January 1995.
Medvitz, Albert. “Sludge, Sludge on the Range:
Unresolved Science in the 503
Regulations.” The 1998 California Plant
and Soil Conference: Agricultural
Challenges in an Urbanizing State,
January 21-22, 1998. California Chapter
of American Society of Agronomy and
California Fertilizer Association.
Obcemea, Wilma N. “ Technical Requirements
and Potential Markets of Compost.”
Seminar on Ecological Solid Waste
Management. Pasig City, August 31,
2001.National Solid Waste Commission.
Rios, Amando T. “Overview of the Paper
Industry.” 5th International Workshop on the Use
of Paper Industry Sludges in Environmental Geo-
View publication stats
Technology and Construction. Makati City, may
23-25, 2001. Pulp and Paper Manufacturers
Association.
Starbuck, Christopher J. 2001. Making and
UsingCompost. Agricultural Publications.
University of Missouri-Columbia.
SW-846 Test Methods for Evaluating Solid
waste, Physical/ Chemical Methods (1994). 3rd
Edition. 2 Volume. Washington DC,
U.S.A.
(http://www.greatescapesmotors.com/me
mbers/sosan/Sops/SW846SOPS.html)
Document dated. 20 November 1998.
Document accessed. 20 February 2002.
UP Business Research Foundation Inc.
February 1990. Executive Summary.
Study on Waste Paper Recovery.
US EPA Part 503
(http://www.users.erols.com/taylew/503.
html)
Webb, L .1996. “A host of options available for
sludge.” Pulp and paper International,
November, pp 44-48.