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3/13/2008

Processes in the environment : fate of chemicals

ENVIRONMENTAL FATE AND Air BURUNG


BIOACCUMULATION
Sorption to suspended particles
Aerobic degradation and dissolved organic carbon

Water
Xfree Xbound
IKAN
Resuspension
sedimentation
Uptake (accumulation)

Sorption to sediment particles


Sediment Anaerobic degradation

Transport between media : example sediment-water Partitioning between sediment (or soil) and water
Assumption of Equilibrium partition :
Assumption of equilibrium : air Medium 1 Medium 2
Equilibrium partition : e. g. water e. g. sediment
water Cw Cs
Medium 1 Medium 2 Kp : partition coefficient sediment-water
e. g. water e. g. sediment Kp = Cw/Cs
Cw Cs
sediment Koc : organic carbon normalized partition coefficient
Kp : partition coefisient sediment-water/ Koc = Kp/foc
sorption coefficient
Cs = concentration in soil or sediment
Kp = Cs/Cw Cw = concentration in water
foc = fraction organic carbon in sediment or soil

Partitioning between sediment (or soil) and water Soil sorption coefficient of a new chemicals

Sediment particle Kp : partition coefficient sediment-water Chemical log Kow log Koc
Kp = Cs/Cw
Koc : organic carbon normalized partition coefficient
Benzene 2,19 1,96
Koc = Kp/foc Toluene 2,79 2.39
Organic carbon Koc is a property independent of the type of sediment or Naphthalene 3,30 3,11
foc = 0,01 soil Anthracene 4,45 4,27
PCB245245 7,16 5,65
ppDDT 6,91 5,31
Kp ppDDE 6,96 4,82
foc = 0,05
Koc

foc

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Hydrophobicity as important parameter : the octanol-


water partition coefficient : Kow Soil sorption in relation to hydrophobicity

log Koc versus log Kow


Hydrophobicity is tendency of a chemical to “escape” water,
and it depend on :
8
- Size Hydrophobic phases :
lipid phase (biota) organic 6
- Presence of polar groups H2O

log Koc
carbon (sediment)
4

2
Kow
Methanol 0,17 0
Chemical x
Acetanol 0,58 0 2 4 6 8
Benzene 134
DDT 1,0 107 log Kow

Bioaccumulation Uptake and elimination processes

Topics : Growth γ Elimination

‰ models for accumulation ke


Uptake Fish
Biotransformation
‰ different sources of uptake Cf
km
‰ influence of properties on accumulation, including
Reproduction kr
biotransformation

From van Leeuwen and Henmens, 1995 : Risk Assessment of Chemicals


Chapter 3 (van den Berg et al.)

Three uptake routes : water, food and sediment

kw
Water (Cw)

kf ke Surrounding
Food (Cfood) Organism (Co)
medium
ks
Sediment (Cs)

From van Leeuwen and Henmens, 1995 : Risk Assessment of Chemicals


Chapter 3 (van den Berg et al.)

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Partitioning between sediment (or soil) and water :


bioavailability Uptake for water, food or soil

Assumption of Equilibrium partition : Bioconcentration BCF Co/Cw uptake from water


factor
Medium 1 Medium 2
e. g. water e. g. sediment Bioaccumulation BAF Co/Cw uptake from water and
Cw Cs factor food, or sediment

Kp : partition coefficient sediment-water Biomagnification BMF Co/Cf uptake from food


Kp = Cs/Cw factor
Biota to sediment BSAF Co/Cs uptake from water and
Koc : organic carbon normalized partition coefficient accumulation factor food, or sediment
Koc = Kp/foc
Co = consentration in organism
Cs = concentration in soil or sediment Cf = consentration in food
Cw = concentration in water Cs = consentration in sediment
foc = fraction organic carbon in sediment or soil

Influence of properties on accumulation

Growth γ Elimination
ke
Uptake Fish
Biotransformation
Cf
km

Reproduction kr
Accumulation depends on :
• Hydrophobicity
• Size
• Ionization
• Stability of the parent compound (biotransformation)

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Ecotoxicity evaluation
Contaminated Environmental Medium
Soil
Direct Plant Benthic Fish
Invertebrate
Toxicity Community Community Community
Community

Food chain

Indirect
Toxicity
Amphibian
Bird Mammal or
Reptile

Ecotoxicity evaluation Ecotoxicity evaluation


Mammalian Pathway Fish eating Birds
Contaminated Environmental Medium Contaminated Environmental Medium
Soil Soil
Direct Plant Benthic Fish Direct Plant Benthic Fish
Invertebrate Invertebrate
Toxicity Community Community Community Toxicity Community Community Community
Community Community

Food chain Food chain

Indirect Indirect
Toxicity Toxicity
Amphibian Amphibian
Bird Mammal or Bird Mammal or
Reptile Reptile

Environmental Fate of Nitrobenzene:


Physico-chemical properties Environmental Release:

Depending on its purity: pale yellow-brown oily liquid


at room temperature; odor: bitter almonds and shoe
polish (vapor pressure 0.27 mmHg @ 25°C)
Released into environment from: primarily industrial
uses (production of aniline, rubber chemicals,
pesticides, dyes, pharmaceuticals); formed in the
atmosphere by nitration of benzene

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Transport
In air levels: from industrial areas 0.09 ppb up to 3.5 – 5.7 ppb.
Atmospheric samples were higher during summer, and lower Nitrobenzene will volatile slowly from soil to
during heavy rain or snow. Air sample over landfill max. 14.48
ppb surface water and is subjected to
In surface water: only 0.4% of 836 stations and 1.8% of 1245 biodegradation
reporting industrial wastewaters
In soil: 8 ppm along Buffalo River in New York, but not in
Adsorption and bioconcentration are not
sediment samples thought to be significant fate processes in
In 1992 USA: total released 917 thousand pounds water
- to atmosphere: 52 thousand pounds (5.6%)
- to surface water:442 thousand pounds
Nitrobenzene may leach through soil and is
To underground injection sites: 865 thousand pounds (94.32%) considered to have intermediate mobility
No nitrobenzene was released to land

Transformation/Persistence - AIR Transformation/Persistence - SOIL

undergoes photolysis Subjected to biodegradation in soil


photoproducts: ortho- and para- nitophenols and
nitrosobenzene However results from screening test was
lab test: 35% nitrobenzene photochemically degraded in 5 conflicting: with activate sludge inoculum from
hours by irradiation of xenon lamp 98% in 5 days to no degradation in 10 days
chemical reacts slowly with hydroxil radicals and ozone
half-life for reaction of nitrobenzene and hydroxyl radicals
and ozone in moderately polluted air: 90 days and 2 years
removal by wet deposition is not significant

Transformation/Persistence - WATER Transformation/Persistence - BIOTA

Subjected to biodegradation and photodegradation Bioconcentration factors in two species of fish


Small amount also adsorb to sediment or volatile L.idus and P. promelas estimated at 15 and
from the surface less than 10, and in P. reticulata: 3
Half-life in model waste stabilization ponds: 3.8 Nitrobenzene is not expected to accumulate
days; 89.5% of the added chemical was degraded;
significantly in aquatic organisms, however, it
4.9% volatilized, 2.3% adsorbed to sediment; 2.4%
lost in effluent; and 1% remained has been shown to be taken and may
Half-life in aquatic environments estimated: 0.3 days bioconcentrate in terrestrial plants

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SOAL EKOKINETIKA Pertanyaan:


a. Berapa prediksi konsentrasi lindan di air danau?
(Dikumpulkan minggu depan di TU TL, ditulis tangan b. Berapa prediksi konsentrasi lindan di ikan?
pada HVS A4) c. Berapa nilai BCF lindan terhadap ikan?
d. Apakah dengan konsentrasi yang ditemukan akan
Pada area pertanian terdapat danau yang menyebabkan keracunan lindan pada Common tern dan
otter?
selama 20 tahun menerima limbah kimia.
e. Bila Max. Permissible Concentration (MPC) lindan di air
Analisis terhadap sedimen menunjukkan pada Common tern 0,015 μg/L dan pada otter: 0,21 μg/L,
berapa konsentrasi lindan yang boleh/harus ada di sedimen
kandungan lindan 0,38 mg/kg. Terdapat hewan sehingga tidak membahayakan Common tern & otter.
common tern dan otter yang makan ikan dari f. Apa yang Saudara rekomendasikan dalam pengelolaan
lingkungan untuk permasalahan ini? Uraikan!
danau tersebut. Ada juga sapi, diambil
dagingnya, yang minum dari danau. Data: log Kow = 3,78, kw fish= 175 L/kg/d; log Kd= 2,4,
BCFwet weight untuk lindan= 302 L/kg