



Paparan, perilaku, dan transport
Bio-akumulasi
Toksisitas
Bioakumulasi: uptake - ekskresi
The Wildlife Research Strategy at the intersection of the disciplines of ecotoxicology, population biology, and landscape ecology.
Diunduh dari: http://www.ecologyandsociety.or
g/vol11/iss1/art23/figure1.html




Akumulasi dari semua sumber
Air, Udara. Padatan
Biokonsentrasi: hanya dari air
Lake Ontario Biomagnification of PCBs
Bioaccumulation is the sum of two processes: bioconcentration and biomagnification.
Read more:
Bioaccumulation - water, environmental, pollutants, EPA, chemicals, toxic, life http://www.pollutionissues.com/A-
Bo/Bioaccumulation.html#ixzz3npXNLA gG

 Minamata Bay, Japan. 1956. Hg pollution.
Landmark for environmental studies.
 DDT pesticides. egg shell thinning
 TBT, oyster shell thickness, imposex in snails
 Tanpa lingkungan yang baik, kita tidak dapat bertahan hidup!

 Linking the two is challenging
 Predicting them is also difficult
Bioaccumulation Toxicity
Prediction???



Bioavailability: fraction available
Bioconcentration: uptake from water
 Bioaccumulation: uptake from water and food
Methylmercury accumulates as you move up the food chain:
1. Methylmercury in the water and sediment is taken up by tiny animals and plants known as plankton.
2. Small fishes eat large quantities of plankton over time.
3. Large predatory fish consume many smaller fish, accumulating methylmercury in their tissues. The older and larger the fish, the greater the potential for high mercury levels in their bodies.
Diunduh dari: http://www.mercury.utah.gov/bioaccumulat ion.htm
Bioaccumulation of Mercury
When mercury falls in rain or snow, or when it falls out of the air as dry deposition, it may eventually be washed into waterbodies by rain.

 Biomagnification: increase in conc at higher levels
 Body burden, concentration
 Equilibrium: between compartments
 Steady-state: within one compartment, in and out equal

 Koefisien Partisi (Kd) / Kow
 Laju Eliminasi
 Laju Depuration
 Asimilasi
 Absorption / Penyerapan
 Adsorption / Penjerapan
 Toxicokinetics





Water
Food
Sediments
Bioaccumulation: uptake - excretion
Diunduh dari : http://www.atsdr.cdc.gov/sites/springvalley/images/exposure_pathways.gif

Uptake senyawa / bahan kimia



Lipophilic: lipid biolayer, untuk molekul polar yang tidak bermuatan
Aqueous: difasilitasi, aktif
Endositosis: untuk nanopartikel dan makro-molekul
Basic Mechanism of
Phytoextraction of Heavy
Metals http://bio349.biota.utoronto.ca/2
0079/20079bio349sasha/phytoex traction.html



Proses difusi pasif:

Dari konsentrasi tinggi menuju ke konsentrasi yang lebih rendah

Tidak memerlukan ligand
Transport yang difasilitasi:

Dari konsentrasi tinggi ke konsentrasi yang lebih rendah

Memerlukan Ligand

Transport senyawa Kimia

Transport Aktif


Dari konsentrasi rendah ke konsentrasi tinggi
Diperlukan energi
 Adsorption /Penjerapan: Fisiko-kimia
Source Identification of Florida Bay's Methylmercury Problem: Mainland Runoff versus Atmospheric Deposition and In Situ Production.
By Darren Rumbold 1 , Larry Fink 1 , Nicole Niemeyer 1 , Angela Drummond 1 , David Evans 2 , David Krabbenhoft 3 , and Mark Olson 3
1 South Florida Water Management District, West Palm Beach, Fl., USA
2 National Oceanic and Atmospheric Administration, Beaufort, NC., USA
3 US Geological Survey, Middleton, WI., USA
THg and MeHg in sediments collected semi-annually from the bay and upstream canals ranged from 5.8 to 145.6 ng/g dry weight (median was 19.9 ng THg/g) and from 0.05 to 5.4 ng/g dry weight (median was 0.26 ng MeHg/g), respectively. Although the highest median THg concentration occurred in sediment from the C111 Canal (115 ng/g), sediments from the mangrove transition zone along both flowpaths also contained relatively high levels of THg.
The highest median sediment-MeHg (1.76 ng/g) occurred at the mouth of Taylor River. While these data must be normalized based on total organic carbon (measured in later cores) before any definitive conclusions can be reached, it was clear that sediments both from upstream marshes and from the bay often contained elevated concentrations of MeHg. Sediments collected from near Nest Key, for example, contained up to 1.8 ng MeHg/g, which constituted almost 8 percent of the THg present.

 Model penjerapan menurut Freundlich :
Model Empirik

X/M = kC 1/n
X adalah jumlah yang dijerap, M adalah masa penjerap (adsorbent), k adalah konstante, C adalah konsentrasi “solute” setelah proses penjerapan

Adsorption/ Penjerapan
 Model Penjerapan Langmuir : Model Teoritis

X/M = abC/(1+bC)
“a” adalah jerapan maksimum
“b” adalah afinitas regresi linear
Dose-dependent growth inhibition and bioaccumulation of hexavalent chromium in land snail Helix aspersa aspersa by Michael Coeurdassier, Annette Gomot-de Vaufleury, Pierre-Marie Badot
Environmental Toxicology Chemistry (2000)
Volume: 19, Issue: 10, Pages: 2571-2578
The toxicity of Cr6+ was determined in a laboratory environment in the snail Helix aspersa aspersa. The effects on growth were evaluated on animals reared in controlled conditions at the age of one month that had been exposed for 28 d to increasing doses of Cr6+ mixed in with their food. Two experimental groups were set up with concentrations of chromium in the feed of 250 to 1,250 Mu g/g(test 1) and 100 to 800 Mu g/g (test 2). Growth inhibition was dose dependent, and the mean EC50 calculated at four weeks for tests 1 and2 were, respectively,
354.7 and 298.8 Mu g/g and for the EC10 195.3 and 160.9 Mu g/g.
The levels of Cr6+ bioaccumulated in thefoot and the viscera of the snails were dose dependent in both typesof tissues. The highest concentrations occurred in the viscera, the levels being 0.79 Mu g/g in the controls and reaching 3,067 Mu g/g inthe animals exposed to the maximum contamination (1,250 Mu g/g).
These high levels of bioaccumulation in addition to the lower concentrations of Cr6+ excreted in the feces than those present in the food suggest that chromium is not physiologically regulated by Helix aspersa. The results provide added support for the use of snails as a model to determine the toxicity of substances in laboratory biotests by measuring the effects on growth and by assessing bioaccumulation.

Langmuir

 Pergerakan suatu material kimia menuruni gradien elektron
 Difusi sederhana: Saluran ion, Lapisan lemak
 Difusi difasilitasi: Memerlukan carrier.
 Difusi pertukaran – Pertukaran ion.

 Proses difusi dapat dijelaskan dengan
Hukum Fick:
 dS/dt = -DA dC/dx

S is the movement across the surface, D is the diffusion coefficient, A is the surface area
 dC/dx is the concentration gradient across the boundary of interest.

 Melawan gradien kimiawi elektron
 Memerlukan energi seperti ATPase, pompa ion
 Beberapa jenis logam dapat diangkut dengan transport aktif

Cd-Ca

Cs-K




Pinocytosis
Phagocytosis
Fe-transferrin protein.
Metalloproteins and metalloenzymes
These are metal complexes of proteins. In many cases, the metal ion is coordinated directly to functional groups on amino acid residues. In some cases, the protein contains a bound metallo-cofactor such as heme. In metalloproteins with more than one metalbinding site, the metal ions may be found in clusters. Examples include ferredoxins), and nitrogenase, which contains both Fe a novel MoFe
7
S
8 cluster.
4
S
4 units and
Read more: http://www.answers.com/topic/bioinorganicchemistry#ixzz3nk96spoz
Iron complex of protoporphyrin IX, or heme.







The Liver Detoxification Pathways
Biotransformation: biologically mediated such as enzymes
Elimination
Detoxification
Sequestration
Redistribution
Activation
Inside the liver cells there are sophisticated mechanisms that have evolved over millions of years to break down toxic substances. Every drug, artificial chemical, pesticide and hormone is broken down
(metabolised) by enzyme pathways inside the liver cells.
Many of the toxic chemicals that enter the body are fat-soluble which means they dissolve only in fatty or oily solutions and not in water. Fat-soluble chemicals have a high affinity for fat tissues and cell membranes, which are made of fatty substances. In these fatty parts of the body toxins may be stored for years, being released during times of exercise, stress or fasting. During the release of these toxins, symptoms such as headaches, poor memory, stomach pain, nausea, fatigue, dizziness and palpitations may occur.
The liver is designed to convert fat-soluble chemicals into water-soluble chemicals so that they may then be easily excreted from the body via watery fluids such as the bile and urine.
Sumber: http://www.positivehealth.com/article/weight-loss/ahealthy-liver-and-weight-loss

 Bio-methylation, Methyl-Hg, biotransformasi
 Metallothionein,<7000 Da. 25-30% amino acid as cysteine.
 Phytochelatins (in plants): glutothioneine
/ cysteine
 Bio-mineralisasi / sequestration

 Phase I reaction: add –COOH, -OH, -
NH
2
, -SH to increase hydrophilicity (add
O by MFOs)
 Phase II: form conjugates (glucuronic acid, etc) to inactivate and foster elimination.

 Elimination: metabolism/excretion
 Depuration: untuk mencuci lingkungan
 Clearance: untuk kontaminan organik
 Growth dilution
 Efflux
 There are subtle differences among these terms






Ekskresi (melalui ginjal)
Molting
Produksi telur
Hilang dalam bentuk bulu/rambut, kulit, insang
Exhalation
Urine is produced in the glomeruli and renal tubules and carried to the renal pelvis by collecting tubules. The glomeruli act as simple filters, through which water, salts, and waste products from the blood pass into the spaces of Bowman's capsules and from there down into the renal tubules. Most of the water and salt is reabsorbed from these tubules; the remainder is excreted as urine. The renal tubules also secrete other salts and waste products from the blood into the urine.
The average amount of urine excreted in
24 hours is about 1.4 litres (2.4 pt), but the quantity varies considerably, depending on intake of fluid and loss from such sources as the skin in perspiration, or from vomiting.
Diunduh dari: http://dspace.dial.pipex.com/town/plaza/j c75/inf_2.htm

 Model berbasis laju-konstan
 Sederhana , fungsi kehilangan orde pertama
 dC/dt = -kC

Ct = Co*exp(-kt) t
1/2 adalah waktu paruh biologis
(retention life) = ln2/k

Fungsi kehilangan dua kompartemen:
 C t
= C
1
*exp(-k
1 t) + C
2
*exp(-k
2 t)
Back stripping technique (C2 first, then C1)

 Model yang lebih rumit:

 dC
1
/dt = k
21
XC
2
-(k
10
+k
12
)xC
1 dC
2
/dt = k
12 xC
1
– k
21 xC
2




Kualitas Senyawa/Bahan Kimia

Species

Bentuk senyawa kimia
Biologis


Physiologis dan biokimia
Genetik


Ecologis
Perilaku
Kondisi Lingkungan

Temperatur, Salinitas
 pH, Unsur Hara



Bebas untuk penyerapan
Bebas untuk diambil dan menyebabkan efek pada tempat berlangsungnya proses

 Spesies-spesies Ion bebas
 Free ion + inorganic complex ion + organic complex ion

Free ion is the most important species bioavailable to the organisms and causing toxicity (the so called free ion activity model—FIAM)




Anion: Cl, HCO
3
, CO
3
, F, PO
4
, NH
3
,
SO
4
, SiO
4
, OH
Kation: H, K, Na, Ca, Mg
Logam:



Cd: CdCl
2
Ag: AgCl
2
-
Zn: Zn 2+ , ZnOH + , ZnCO
3
, ZnCl +





Implikasi dari Model
Contoh-contoh
Perkecualian : HgCl
2
, AgCl
Mekanisme transport logam
Metal Uptake by Phytoplankton.
(Adapted from Kustka et al, Journal of Phycology, 2007)
Diunduh dari: http://www.princeton.edu/morel/research/metal-uptake/

Campbell dan Tessier (1996):
Aktivitas logam-bebas sangat menentukan serapan, nutrisi dan toksisitas semua kation logam-logam mikro
Journal of Environmental Science and Management, Vol 14, No 2 (2011)
Bioaccumulation in Nile Tilapia (Oreochromis niloticus) from Laguna de Bay, Philippines
Victorio B. Molina, Ma. Victoria O. Espaldon, Maxima E. Flavier, Enrique P. Pacardo, Carmelita M. Rebancos
This study provides an assessment of the risks to human health associated with the exposure to heavy metals bioaccumulation in Nile tilapia (Oreochromis niloticus) from Laguna de Bay. Samples of the fish were collected in eight sampling stations in three major areas of the lake during the dry and wet seasons. Dry season samples were collected from May to June 2010 and wet season samples from September to
November 2010. Coordinates of sampling site locations were recorded using Global Positioning System
(GPS) and plotted in Geographic Information System (GIS) digital maps. Heavy metals analyses for cadmium (Cd), lead (Pb), mercury (Hg), arsenic (As), and chromium (Cr) were conducted using am Atomic
Absorption Spectrophotometer (AAS) and a Mercury Analyzer (Mercur-Duo).
Estimates of health risks associated with fish consumption were summarized according to non-carcinogenic and carcinogenic health effects. Non-carcinogenic Health Quotient (NHQ) values of the five heavy metals showed that lead is the most urgent pollutant of concern in terms of adverse health effects from risks associated with fish consumption from all sampling locations in the lake. Among the five heavy metals only arsenic is a confirmed human carcinogen (Class A) through the oral route of exposure.
The highest life time cancer risk for arsenic was computed from sampling station 2B (west bay) during the dry season with risk value of 8.5x10-4 or an excess of 85 cancer cases per 100,000 population. From the point of view of human health protection and disease prevention, the Nile tilapia from Laguna de Bay is not fit for human consumption due to arsenic and lead contamination.

 K ow secara langsung mempengaruhi akumulasi kontaminan organik dalam organisme akuatik.
 QSAR: Quantitative Structural Activity
Relationship.
 BCF: Faktor Biokonsentrasi

0.01
1

 Cytoplasm hypothesis: assimilation is related to the metal distribution in algal cytoplasm
 Does it work? Some
 Why? Easy digestion
 Significance? Increase our predictability

Copepods: Hipotesis Sitoplasma
(Reinfelder & Fisher 1991, Science)

Pencernakan Zooplankton
Copepod’s gut
Desorption
Cell breakage and cytosolic discharge
M
Diatoms
Speed to pass the gut
Assimilation

100
80
60
Cd
40
20 r2=0.981
0
0 20 40 60 80 100
% Cd in diatom's cytoplasm

80
60
40
20
0
0
Calanus -Tp
Calanus -Tw
Acartia -Tp
Acartia -Tw
20 40 60
% in diatom's cytoplasm
80

Aliran Makanan melalui Saluran Pencernaan Copepoda
100
75
50
25
Cd
0
0.0
0.2
0.4
0.6
Food Passage (h)

Pencernaan Bivalve
Desorption bivalve’s gut
Cell breakage and cytosolic discharge
M
Speed to pass the gut
Diatoms
Digestive gland
Assimilation

Assimilation in the mussel M. edulis (Wang
& Fisher 1996)



Teori tentang AVS (acid volatile sulfide):
Cd 2+ + FeS Fe 2+ + CdS
 Definisi AVS: Konsentrasi sulfida yang terekstraks oleh HCl
 Kontrol AVS terhadap ketersediaanbiologis logam




Ekstraksi partial (1 N HCl)
Ekstraksi Sequential (Tessier et al. 1979).
Different geochemical phases (easily exchangeable, Fe oxide)
Akar tanaman menyerap hara tersedia (kation) melalui proses pertukaran ion.
http://bcs.whfreeman.com/thelif ewire8e/pages/bcsmain_body.asp?v=chapter&s=36
000&n=00010&i=36010.01&o=|
00010|&ns=0

 Temperatur sangat mempengaruhi metabolisme binatang
 Serapan meningkat kalau suhu T meningkat, tetapi juga ada pengecualiannya
 Tergantung pada mana yang lebih terpengaruh: uptake atau efflux.



Hubungan Alometrik
Y = a W b (fungsi pangkat)

Y is the metal burden (without weight unit), W is the weight
 Weight specific function: y = a W b-1
 y is the metal concentration (with weight unit)

ug/g konsentrasi
g (bobot) b >1 b = 1 b < 1

 dC/dt = k
C t

C


 dC/dt = kC
C = C o x exp(kt)
Most typical t


 dC/dt = kC 2 not very common
C t


V = dC/dt = V max
C/(k m
+C)
V max
V km
C



Sederhana dan langsung
Appealing to environmental policy makers
 Used in Water Quality Criteria and Sediment
Quality Criteria
 BCF = C/Cw

BCF: Faktor biokonsentrasi

C : Konsentrasi dalam organisme

C w
: Konsentrasi dalam fase larutan




Assumptions:

Equilibrium

One phase of uptake
Examples of WQC failing in protecting environments:
Se in San Francisco Bay, USA
??
Food




 dC/dt = k
1 xC w
Ct = C w
(k
1
/k
2
– k
2 xC
) [1-exp(-k
2 t)]
C ss
/C w
= k
1
/k
2
= BCF k
1
: uptake rate constant, C w
: water conc, k
2
: efflux rate, C ss
: conc in organisms under steady state
k1
k2



 dC/dt = k
1 xC w
+ AExIRxC f
– k
2 xC
Ct = (k
1 xC w
+AExIRxC f
)/k
2
(1-e -k2t )
AE: assimilation efficiency, IR: ingestion rate, C f
: conc in food




I w is influx rate from water
I f is influx rate from food k is efflux constant
 I w
= absorption efficiency x filtration rate x concentration in water
 I f
= assimilation efficiency x ingestion rate x concentration in food
 C ss
= (I w
+ I f
)/k



Terlalu banyak parameter
Tidak ada nilai generik untuk setiap parameter
Implikasi Pemodelan:
 Jalur paparan
 Sumber tercemar, implikasi untuk:

Kriteria kualitas air

Kriteria kualitas sedimen
 Prediksi konsentrasi

 Konsentrasi karena serapan makanan harian :

C = I f
/k
Faktor transfer trofik adalah C/C f dan dapat dihitung :
TTF = AE * IR /k
 TTF dalam rantai makanan akuatik

MeHg

Bio-magnifikasi PCB

Konsekwensi Transfer Trofik



Biomagnification (we have to be careful about this term)
Biodiminification
Constancy
Biomagnification , also known as bioamplification , or biological magnification is the increase in concentration of a substance, such as the pesticide DDT, that occurs in a food chain

Bioaccumulation of some heavy metals in tilapia fish relevant to their concentration in water and sediment of
Wadi Hanifah, Saudi Arabia
Abdel-Baki, A. S.1, 2*, Dkhil, M. A.1,3 and Al-Quraishy, S.1
1Zoology Department, College of Science, King Saud University, P.O. Box: 2455, Riyadh- 11451, Saudi Arabia.
2Zoology Department, Faculty of Science, Beni-Suef University, Egypt.
3Department of Zoology and Entomology, Faculty of Science, Helwan University, Egypt.
Accepted 25 February, 2011
Concentrations of some heavy metals (Pb, Cd, Hg, Cu and Cr) were determined in water, sediment and tissues of tilapia fish collected from
Wadi Hanifah during summer 2010.
The concentrations of the heavy metal in water were within the international permissible level. Cu had the highest accumulating level in fish whilst Hg had the lowest.
The transfer factors of all metals in fish from water were greater than those from sediments. This led to the conclusion that fish bioaccumulation with these metals was from water.
Heavy metals under study in the edible parts of tilapia were within the safety permissible level for human use.

100
80
Copepods biomagnified
Possibly biomagnified
60
40
20
0
0.01
Zn(T) Se(T)
Zn(A)
Cd(A) biodiminished
Cd(T)
Se(A)
IR=20%
IR=60%
Co(T)
Ag(T)
0.1
Efflux rate constant (d
-1
)
1

100
80
Fish
CH
3
Hg(L) biomagnified
Cs(L)
Possibly biomagnified
Se(L) 60
40
20
IR=2%
0
IR=10%
0.001
Zn(L)
Se(M)
Zn(M)
Cd(L)
Cd(M)
Ag(M) biodiminished Am(M)
0.01
Efflux rate constant (d
-1
)
0.1

100
Bivalve
80
60
40
20
0
0.001
Zn(S)
Cd(S ) biomagnified
IR=10%
Zn(C )
Cd(C ) Se(M )
Se(S )
Cd(R )
Zn(R )
Se(C )
Co(M )
Zn(M)
Possibly biomagnified
Zn(P)
IR=30%
Se(R)
Cd(M )
Cd(P )
Se(P )
Cr(M )
Am(M )
Ag(M) biodiminished
0.01
Efflux rate constant (d
-1
)
0.1

100
Cd(B)
Cd(N)
80
60
Zn(B) biomagnified
Zn(N)
Possibly biomagnified
Cs(B)
40
Gastropod
20 biodiminished
IR=2%
IR=10%
0
0.001
0.01
Efflux rate constant (d
-1
)
0.1

2
0
300
8
6
4
Rataan Geometrik dalam rantai makanan benthik
Cd
80
60
40
20
0
Cu
Zn
200
100
0
Phy Mus Sna

Sumber:
Kerry BC et al. 2007,
Science
13 July 2007

 Secara sederhana: produsen primer,
Konsumen primer, Konsumen sekunder, dll.
 Typically difficult to assign to a specific level
 Isotopic discrimination (more heavier isotope with increasing trophic position)
 Lebih jelas N daripada Carbon