Studies on Polycyclic Aromatic Hydrocarbon Pollution in the Greater Manila Environment

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Research and Analytical Services Laboratory
Natural Sciences Research Institute Research
Thrusts 1. Improvement of the laboratory
protocols and analytical services Development
and validation of procedures for expansion of the
analytical services 2. Environmental
Monitoring of Toxic Trace Metals and Toxic Trace
Organics in the Philippine Environment Endocrine
disrupting compounds (Organochlorine pesticides,
PCBs, phenols, phthalates) in coastal
hydrosphere, river systems and agricultural
areas Arsenic, Mercury, Lead, Cadmium and
Chromium VI in coastal hydrosphere and river
systems Polycyclic aromatic hydrocarbons in the
Greater Manila Area
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Studies on Polycyclic Aromatic Hydrocarbon
Pollution in the Greater Manila Environment

• Evangeline C. Santiago, Ph.D
• Natural Sciences Research Institute
• Dr. Augusto Hermosilla
• Ms. Claudine Ejes
• Department of Mathematics, College of Science

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Background Information

• Polycyclic Aromatic Hydrocarbons (PAHs)
• A group of compounds consisting of carbon and
  hydrogen and having 2 or more condensed benzene
  ring structures.
• Present naturally in petroleum compounds as a
  product of aromatization of saturated compounds
  in diagenesis (low Temperature, high Pressure)
• Naphthalenes, phenanthrenes, and alkyl homologs
• Produced by combustion of fossil fuels or other
  organic matter
• (high Temperature, low Pressure), mechanism is
  believed to be free radical formation
• Different types of PAHs having different numbers
  of condensed rings and isomeric structures
• Flouranthene, pyrene, chrysene, benz-anthracene,
  benzo-k-fluoranthene, benzo-b-fluoranthene,
  benzo-e-pyrene, benzo-a-pyrene, di-benz
  anthracene, indeno-pyrene, etc.

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Why are we concerned with PAHs?

• PAHs are ubiquitous in the environment
• PAHs are aromatic compounds, as hydrophobic
  compounds they can easily cross the cell membrane
  of organisms
• PAHs are potentially carcinogenic substances to
  humans
• Benzo-e-pyrene and high molecular weight PAHs
  have been found to be carcinogens in animal
  studies and in vitro human cell studies
• Mechanism as a mutagen is in-vivo transformation
  to a strong electrophile (carbonium ion) through
  epoxidation and incomplete transformation to
  di-ols
• PAHs are promoters of cancer through the
  activation of Ah receptor site which induces
  among other biological processes the production
  of cytochrome P 450 leading to possible formation
  of free radicals or other more biologically-
  active compounds.

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PAHs Fate in the Environment

• Reactivity of PAHS in the environment depends on
  its molecular weight and condensation of the
  benzene rings.
• Low- molecular weight parental PAHs (2-3 rings)
  have greater solubility in water, more toxic to
  aquatic organisms.
• Low molecular weight (LMW) PAHs partition better
  in air than in particulates.
• High molecular weight (HMW) PAHs have greater
  affinity to natural particulates.
• In natural waters, HMW PAHs sink with the
  sediments.
• In air, LMW PAHs partition in air and HMW PAHs in
  air particulates
• In the atmospheric environment, PAHs can be
  transformed into bioactive compounds by
  photooxidation (e.g. quinones)
• PAHs can be degraded by microorganisms although
  very slowly and only in an oxidized environment.

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Studies on PAHs in the Environment

• Indicator of pollution due to human activity
• Sources of pollution-policy action in
  environmental management
• Receptor modeling
• Source modeling
• Pollution and adverse effects to human health
• Inhalable air
• Food

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Studies on PAHs in the Greater Manila Environment

• Sediments in Manila Bay (1996-97)
• Types and Levels of PAHs in the sediments in the
  western side (Limay Coast) and eastern side (GMA)
• 16 sampling sites in the east and 19 in the west
• One-time sampling
• Primary sources of PAHs (1998-99)
• PAHs in 7 diesel engine soot, 6 gas engine soot,
  9 used diesel and 5 gas engine lubricating oil, 8
  used cooking oil, 7 unused crude oil
• PM10 Air Particulates (2000-2001)
• PAHs in particulates on glass fiber filter of
  High Volume sampler from air collected at
  selected sites along EDSA and two industrial
  sites and two residential sites
• Nine sampling sites plus one reference site
• Two sampling frequencies

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PAHs in Manila Bay SedimentsSampling Sites
Limay Coast on Western Manila Bay
Manila Bay on Eastern Side
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Sampling points along EDSA and in industrial
sites in Valenzuela and Paranaque
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Studies on PAHs in the Greater Manila Environment

• Sampling
• Sediments in Manila Bay
• Sampling using Eckman Dredge
• Primary sources of PAHs
• Random sampling
• Soot from tailpipes of motor vehicles
• Used lubricating oils from vehicles in gas
  station
• Used cooking oil from restaurants
• Crude oil used in refineries from oil companies
  (Petron and Shell)
• PM10 Air Particulates (2000-2001)
• 24 hour sampling in Andersen Hi volume sampler

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Studies on PAHs in the Greater Manila Environment

• Analysis
• Sediments, soot and air particulates
• Soxhlet extraction, alumina-silica clean-up and
  determination by Gas Chromatography/Mass
  Spectometry (Selected Ion Mode)
• Oil samples
• Liquid-liquid extraction, alumina-silica clean-up
  and determination by Gas Chromatography/Mass
  Spectometry (Selected Ion Mode)

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Studies on PAHs in the Greater Manila Environment

• Analysis
• Establish the validity of data by quality control
  samples or reference materials
• Acceptance Criteria
• At least 80 recovery of PAHs in reference
  material for the method
• At least 50 recovery for surrogate material in
  every sample.

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Andersen PM10 high volume air sampler
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WHO Criteria for PAHs Cancer risk estimate for
lifetime exposure to 1ng. m-3 8.7 x
10-5(ng.m-3)-1 Risk 1 x 10-6 US EPA Standard
for PM10 50 ug. m-3
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Statistical Analysis

• What do we want to show from statistical
  analysis?
• PAHs in Manila Bay
• Overall picture of the distribution of PAH
  contamination in Manila Bay
• Can we actually see the difference in types of
  PAH contamination in the western and eastern side
  of Manila Bay considering possible differences in
  major sources of contamination?

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Statistical Analysis

• PAHs in air particulates
• Overall picture of the PAHs contamination of
  inhalable air particulates along the stretch of
  EDSA and in Valenzuela City and Paranaque and in
  relatively unpolluted sites in residential areas.
• Are there significant differences in the PAHs
  contamination in different sites along EDSA?
• Are there significant differences in the PAHs
  contamination in Valenzuela and Paranaque and in
  sites along EDSA?

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Statistical Analysis

• PAHs in Primary Sources
• Are there significant differences in the PAHs
  from diesel engine and non-catalyst gas engine
  motor vehicle emission?
• Are there significant differences in PAHs from
  motor vehicle soots and oil sources?
• Can we use the data on the PAHs in primary
  sources to apportion the sources of PAHs in the
  sediments?
• Can we use the data on the PAHs in primary
  sources to determine which type of motor vehicle
  emission contribute more to the PAHs in the air
  particulates?

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Statistical Analysis

• Manila Bay Sediments
• Over-all picture done from PCA analysis
• We need to do a PCA on the western and eastern
  sites separately
• We need to do ANOVA between the western and
  eastern sites.
• Inhalable Air Particulates
• Over-all picture done from PCA analysis
• We need to do ANOVA between industrial sites and
  EDSA sites, between two residential sites
• Primary Sources
• GLM on each primary source
• Statistical analysis to help improve the
  experimental design to come up with more definite
  conclusions
• Policy recommendation?

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Statistical Analysis

• Results of Statistical Analysis
• Manila Bay Sediments
• Over-all picture done from PCA analysis

Part 1- Locations PCA-one principal component can
describe the variability of the data 2 factors
accounting for 97 variability of the data
set Factor 1 E2 site- Las Pinas, Paranaque and
E14 site- Malabon most polluted due to
proximity to the outfalls of the rivers which
unload the pollution from Paranaque and Malabon
rivers. Factor 2 L16, L22, L15, L24, L1 and L2--
probably related to the deposition sites, silt
and PAH/TOC and direction of current E2, E13,
E14- deposition site of sediments from the
outflows of polluted rivers.
More generalized factor procedure L2, L24, L27,
L1, L20, L26, L15similarities in loading could
be due to the distance from the deposition sites
of the sediments in relation to source and the
current flow.
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• Clustering
• Least to Biggest loads
• N0, F
• soluble in water
• DBA, Anthracene,Benzo-a-anthracene,Indenopyrene,Be
  nzo-a-pyrene
• not soluble but less loading could be because of
  they come only from combustion sources
• Phenanthrene
• maybe present in significant amount coming from
  petroleum sources but have substantial solubility
  in water
• Fluoranthene, chrysene, benzofluoranthene,Methylph
  enanthrene, Pyrene, benzo(ghi)perylene-
  Benzo-e-pyrene,
• Above PAHs could come from both petrogenic
  sources and combustion materials and they are
  relatively less soluble in water
• dimethylnaphthalene, trimethylnaphthalene,dimethyl
  phenanthrene,methylnaphthalene trimethylphenanthre
  ne
• higher loading could be due to greater
  contributions from both petrogenic and combustion
  sources.

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Part 2- PAHs PCA1 Trimethylphenanthrene,
dimethylphenanthrene, methylnaphthalene- explain
88 of the variability PCA2 Methylnaphthalene,
dimethylnaphthalene, trimethylnaphthalene and
trimethylphenanthrene explain 1 of the
variability Factor 1- 65 Anthracene,
flouranthene, Pyrene, Chrysene, Phenanthrene,
dimethylphenanthrene, indenopyrene,
benzo(ghi)perylene, trimethylnaphthalene similar
loadings Factor 2- 11 Benzo-a-pyrene and
Benzo-e-pyrene Similar loadings Varimax
Factor Anthracene, fluoranthene, pyrene,
chrysene, phenanthrene, dimethylphenanthrene,
Benzo(ghi)perylene, trimethylnaphthalene Benzo-a-
pyrene and Benzo-e-pyrene Clustering Anthracene,
Chrysene, Fluoranthene, Pyrene Indenopyrene,
Benzo(ghi)perylene, Dibenzanthracene Flourene,
Trimethylnaphthalene, Dimethylnaphthalene Methylna
phthalene, methylphenanthrene Naphthalene Benzo-e-
pyrene, Benzo-a pyrene
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The analysis shows that across all the locations
or sediments, methylated phenanthrenes and
methylated naphthalenes are present in biggest
concentrations. Benzo-e-pyrene,
benzo-flouranthenes, benzo(ghi)perylene,
chrysene and pyrene are present in comparable
amounts. The methylated phenanthrenes,
methylated naphthalenes and the parent al PAH
phenanthrene, fluorine and fluoranthene ,
pyrene, chrysene can be contributed by direct
spillage of petroleum compounds . However, the
methylated phenanthrenes and methylated
naphthalenes and the parental PAHs chrysene,
benzofluoranthenes, benzopyrenes and
benzo(ghi)perylene and indenopyrenes can come
from deposition of air particulates and soot
from combustion sources.
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Statistical Analysis

• Primary sources of PAHs

The study employed a generalized linear model
(GLM) approach constructed from mixed-effects
models of a two (2)-way analysis of variance
(ANOVA).
Statistical analyses of the data sets were
performed using the GLM procedure (PROC GLM) of
the Statistical Analysis System (SAS) Version
8e. The analysis of the data set of ech of the
primary sources was done.
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