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Handout:

BIOREMEDIASI
SENYAWA PENCEMAR

Bahan Kuliah

Sudrajat
FMIPA Unmul
Samarinda
APA SAJA SENYAWA-SENYAWA
PENCEMAR LINGKUNGAN?
 Pencemar  Senyawa xenobiotik
 Senyawa-senyawa yang  Senyawa kimia hasil
secara alami ditemukan rekayasa manusia
di alam tetapi jumlahnya yang sebelumnya
(konsentrasinya) sangat tidak pernah
tinggi tidak alami. ditemukan di alam.
 Contoh:  Contoh:
 Minyak mentah,  Pestisida
minyak hasil  Herbisida
penyulingan  Plastik
 Fosfat  Serat sintetis
 Logam berat
REMEDIASI LINGKUNGAN

• Remediasi: Proses perbaikan.


• Proses perbaikan lingkungan yang
tercemar.
• Pendekatan-pendekatan yang
dilakukan untuk menghilangkan
pencemar dari lingkungan.
TEKNOLOGI YANG UMUM DIGUNAKAN
UNTUK MENGHILANGKAN SENYAWA
PENCEMAR

 Ekstraksi uap tanah


 Tekanan udara
 Serapan panas
 Pencucian tanah
 Dehalogenasi kimiawi
 Ekstraksi tanah
 Penggelontoran tanah in situ
 Bioremediasi
BIOREMEDIASI SENYAWA
ORGANIK:
 Proses mengubah senyawa pencemar organik
yang berbahaya menjadi senyawa lain yang
lebih aman dengan memanfaatkan organisme.
 Melibatkan proses degradasi molekular melalui
aktifitas biologis.
 Campur tangan manusia untuk mempercepat
degradasi senyawa pencemar yang berbahaya
agar turun konsentrasinya atau menjadi
senyawa lain yang lebih tidak berbahaya
melalui rekayasa proses alami atau proses
mikrobiologis dalam tanah, air dan udara.
KEUNGGULAN BIOREMEDIASI
SENYAWA ORGANIK
 Proses alami.
 Mengubah molekul senyawa pencemar
organik, bukan hanya memindahkan.
 Beaya paling murah dibandingkan cara
yang lain.
 Hasil akhir degradasi adalah gas karbon
dioksida, air, dan senyawa-senyawa
sederhana yang ramah lingkungan.
ALASAN PENGGUNAAN
PERLAKUAN BIOLOGIS
Murah, karena:
 Dapat digunakan in-situ sehingga
mengurangi beaya pengangkutan dan
gangguan lingkungan.
 Mikroba alami dapat digunakan.
PELAKU UTAMA:
• Mikroorganisme :
Bakteria, Sianobakteria, dan fungi >
Remediasi oleh mikrobia

• Tanaman > Fitoremediasi

• Mikroorganisme dan tanaman


PENERAPAN BIOREMEDIASI

 Situs-situs yang sulit dijangkau


 Lingkungan di bawah permukaan
tanah
 Air berminyak
 Limbah Nuklir
BIDANG ILMU YANG DIBUTUHKAN
UNTUK KEBERHASILAN
BIOREMEDIASI

 Ilmu tanah  Rekayasa


 Geokimia organik bioproses
dan anorganik  Modeling komputer
 Geofisika
 Mikrobiologi
 Hidrologi dan/atau botani
KEUNTUNGAN MENGGUNAKAN
MIKROBIA UNTUK MENDEGRADASI
SENYAWA PENCEMAR ORGANIK:

 Jumlahnya banyak dan ada dimana-mana


 Jalur metabolisme dalam aktivitas
hidupnya dapat dimanfaatkan untuk
mendegradasi senyawa pencemar organik
dan mengubahnya menjadi senyawa yang
lebih tidak berbahaya
PERTIMBANGAN KIMIA DAN
MIKROBIOLOGIS YANG PERLU
DIPERTIMBANGKAN:

• Apakah kontaminannya dapat


terdegradasi secara biologis?
– hidrokarbon minyak bumi sederhana
– hidrokarbon aromatik (hingga 3 cincin)
– amina sederhana
– ester
– keton
– eter
SENYAWA PENCEMAR ORGANIK YANG
SECARA POTENSIAL DAPAT
DIBIOREMEDIASI
Mudah Sedikit Sulit Umumnya tidak
didegradasi terdegradasi terdegradasi terdegradasi
____________ _____________ _____________ _____________
BBM, kreosot, tars Pelarut terkorinasi Dioxins
Minyak tanah batubara (TCE)

keton dan Pentakoro- Beberapa Bifenil


alkohol fenol (PCP) pestisida dan terpoliklorinasi
herbisida (PCB)
Aromatik
monosiklik

Aromatik
bisiklik
(naftalena)
BIOREMEDIASI SENYAWA
ORGANIK PADA SKALA
MIKROSKOPIS

Nutrien pembatas

Sumber
karbon/energi
bagi bakteria
PENGOLAHAN BIOLOGIS LAHAN
TERCEMAR SENYAWA ORGANIK
Pengolahan lahan tercemar senyawa
organik dapat dikelompokkan ke dalam:
 Ex situ – pengolahan dilakukan di tempat lain
sehingga perlu pemindahan.
 In situ – pengolahan dilakukan di tempat
pencemaran tanpa pemindahan.
BIOREMEDIASI EX-SITU
Tanah terkontaminasi diangkat ke dan diperlakukan di permukaan
CONTOH PENGOLAHAN TANAH
TERCEMAR SENYAWA ORGANIK
SECARA EX SITU (1)
 1.Slurry
Phase : Bejana besar
digunakan sebagai “bio-reactor” yang
mengandung tanah, air, nutrisi dan
udara untuk membuat mikroba aktif
mendegradasi senyawa pencemar.
BIOREAKTOR
Uap keluar
Tanah Pengaduk
terkontaminasi

Pengatur suhu
Cairan
terkontaminasi
Nutrien

Saluran keluar cairan

Saluran keluar tanah

Udara
masuk
CONTOH PENGOLAHAN TANAH
TERCEMAR SENYAWA ORGANIK
SECARA EX SITU (2)
2.Composting:
Limbah dicampur dengan jerami atau bahan
lain untuk mempermudah masuknya air,
udara, dan nutrisi.
Tiga tipe pengomposan:
* Dalam Lubang
* Mechanically agitated in-vessel
* Tumpukan
CONTOH PENGOLAHAN TANAH
TERCEMAR SENYAWA ORGANIK
SECARA EX SITU (3)
 3.Biopile: tanah tercemar tidak dipindahkan
namun diangkat ke permukaan, ditumpuk,
dan diberi perlakuan penambahan air,
udara, dan nutrien.
BIOFILES

Nutrien/
Lapisan air
Gravel

Tanah terkontaminasi

Lapisan Kedap Air Penampungan


Leachate
CONTOH PENGOLAHAN TANAH
TERCEMAR SENYAWA ORGANIK
SECARA EX SITU (4)
 4.Landfarming: Tanah terkontaminasi
dipindahkan dan disebar di permukaan
lapangan kemudian diperlakukan dengan
penambahan bakteri, air, udara, dan
nutrisi. Cara ini yang paling sering
digunakan.
LANDFARMING
Tanah
Saringan/ terkontaminasi
Pompa
Udara Tangki

Lapisan Gravel
2.INSITU BIOREMEDIATION
CONTOH PENGOLAHAN TANAH
TERCEMAR SENYAWA ORGANIK IN
SITU (1)

 Bio-venting:
 pemompaan udara dan nutrisi melalui
sumur injeksi.

 Air Sparging:
 pemompaan udara untuk meningkatkan
aktifitas degradasi oleh mikroba.
2.1.Biostimulation

Biosparging
AIR SPARGING
CONTOH PENGOLAHAN TANAH
TERCEMAR SENYAWA ORGANIK IN
SITU (2)
 InjeksiHidrogen Peroksida :
menggunakan sprinkler atau
pemipaan.
 Sumur Ekstraksi : Untuk
mengeluarkan air tanah yang
kemudian ditambah nutrisi dan oksigen
dan dimasukkan kembali ke dalam
tanah melalui sumur injeksi.
Sumur Penambahan Sumur
Injeksi Nutrien/ Pengolahan Recovery
Oksigen Air

Permukaan air
tanah yang
baru

Zona terkontaminasi

Permukaan
air tanah
yang lama
3.KOMBINASI BIOREMEDIASI EX-SITU DAN
IN-SITU

Unsaturated
zone

Aquifer

Dalam cara ini aktifitas mikrobia penghuni tanah ditingkatkan


OPTIMASI BIOREMEDIASI LAHAN
TERCEMAR SENYAWA ORGANIK (1)
 Untuk mengoptimalkan dan
mempercepat biodegradasi senyawa
pencemar yang ada di dalam air dan
tanah dapat digunakan mikroba yang
telah beradaptasi dan digabungkan
dengan:
 Menjamin ketersediaan air (kadar air
antara 30-80%).
 Menambahkan nutrisi (nitrogen, fosfor,
sulfur).
OPTIMASI BIOREMEDIASI LAHAN
TERCEMAR SENYAWA ORGANIK (2)

 Menjamin ketersediaan oksigen.


(jika tipe degradasi aerobik) 2-3 kg oksigen
per kg hidrokarbon yang didegradasi.
 Menjamin pH moderat – Tidak terlalu
masam maupun basa, antara 6-9.
 Menjamin suhu yang moderat - 10o to
40oC.
OPTIMASI BIOREMEDIASI LAHAN
TERCEMAR SENYAWA ORGANIK (3)

 Penambahan enzim, katalis


kimia untuk mendegradasi
senyawa-senyawa limbah.
 Penambahan surfaktan
(detergen).
KELEMAHAN PERLAKUAN
BIOLOGIS

 Kadang-kadang tidak efektif di


beberapa lokasi karena
toksisitas pencemar:
 Logam
 Senyawa organik berkhlor
 Garam-garam anorganik
WAKTU YANG DIPERLUKAN

 in situ perlu waktu bervariasi


antara 1 - 6 tahun.
 ex situ antara 1-7 bulan.
REMEDIASI LAHAN TERCEMAR
SENYAWA ANORGANIK (LOGAM)
INTERAKSI LOGAM-MIKROBIA
LOGAM BERAT YANG DAPAT
DIPERLAKUKAN
Logam beracun Logam lainnya
• Uranium • Vanadium
• Kromium • Molibdenum
• Tembaga
• Selenium
• Emas
• Timbal (Pb)
• Perak
• Teknetium
• Raksa
BIOLEACHING
 Mekanisme mobilisasi logam
 Produksi asam organik atau asam sulfat yang
dapat membentuk khelat logam
 Mikrobia heterotropik = asam organik
 Thiobacillus spp. = asam sulfat
 Meleaching logam dari padatan limbah kota
 Zn, Cu, Cr, Pb, Ni, Al
 Ada hubungan antara efisiensi penghilangan
dengan pH
BIOSORPSI
 Biosorpsi merupakan salah satu
mekanisme imobilisasi logam
 Logam terserap di permukaan sel oleh
interaksi anion-kation
OVERVIEW FITOREMEDIASI
Phytoremediation can be applied as
long as the concentration of the
pollutant is within an appropriate
concentration range, which shall not be
too high, since it may cause
phytotoxicity to the plant
Phytoremediation can be performed following
different methods:
• Phytoextraction: Uptake and
concentration of pollutants from the
environment into the plant biomass.
• Phytostabilization: Reduction of the
mobility of the contaminants in the
environment.
• Phytotransformation: Chemical
modification of the environmental
substances as a direct result of the plant
metabolism.
FITOEKSTRAKSI
Absorpsi logam berat oleh akar tanaman dan
translokasinya dalam tanaman
FITOSTABILISASI
Imobilisasi logam dalam tanah oleh
penjerapan, pengendapan dan kompleksasi.
• Phytostimulation: Enhancement of
the native soil microbial activity for
the degradation of contaminants.
• Phytovolatilization: Removal of
substances from soil or water with
release into the air.
• Rhizofiltration: Filtering water
through a mass of roots to remove
toxic substances or excess nutrients.
RHIZOFILTRASI
Penghilangan logam dari lingkungan
perairan
• Regarding the rhizosphere, there are other
techniques besides the rhizofiltration.
• The roots can be used as stimulator of the
micro-organisms living there due to the
exudates that plants expulse in this medium.
• This can increase the amount of organisms in
2 or 3 orders of magnitude.
• Within remediation, one of the most important factors to
take into account is the tolerance of the plant.
• The same chemical species may produce different effects
at the same concentration in different plants.
• For this reason, it is important to know about the
background levels in the polluted area:
– Sites with natural high concentration of some pollutant
may lead to an increased presence of tolerant species.
– These species are of big interest for phytoremediation
and hence many are used for remediation purposes.
• These plants are able to accumulate due to different
detoxifying mechanisms such as the chelation of
heavy metals or the storage of the contaminants in
vacuoles or the cellular wall
• Plants which are able to accumulate extremely high
concentrations in their tissues are considered
hiperaccumulator species. Although their ability of
accumulating high concentrations of metals is highly
interesting, these species normally only show low
growth rates and hence are not suitable for
extracting high amounts of pollutants from the soil.
• However there are plants which are able to
accumulate lower concentrations of metal but
present higher growth rates. For this reason, these
species showed to be more suitable for
phytoextraction processes.
• The low accumulation capacity of these species
may be highly improved by the addition of
synthetic chelates, which increase the solubility of
metal in the soil, making them more bioavailable
for the plant and hence increasing the uptake rate
of metals by the plant
• . Examples of chelating agents are EDTA, NTA
or weak organic acids, such as citric acid.
Chelates, however, have to be used with
caution, since they may increase the mobility
of pollutants, posing a risk of contamination of
underlying groundwaters

• They may also provoke negative effects for the


native microbial community of the soil. In
particular, EDTA has recently been banned as a
chelating agent, due to its toxicity for the soil
microbiota and its high persistence.
• These plants are able to accumulate due to different
detoxifying mechanisms such as the chelation of
heavy metals or the storage of the contaminants in
vacuoles or the cellular wall

• Plants which are able to accumulate extremely high


concentrations in their tissues are considered
hiperaccumulator species. Although their ability of
accumulating high concentrations of metals is highly
interesting, these species normally only show low
growth rates and hence are not suitable for
extracting high amounts of pollutants from the soil.
• However there are plants which are able to
accumulate lower concentrations of metal but
present higher growth rates. For this reason,
these species showed to be more suitable for
phytoextraction processes.
• The low accumulation capacity of these species
may be highly improved by the addition of
synthetic chelates, which increase the solubility of
metal in the soil, making them more bioavailable
for the plant and hence increasing the uptake rate
of metals by the plant
• Examples of chelating agents are EDTA, NTA or
weak organic acids, such as citric acid.
Chelates, however, have to be used with
caution, since they may increase the mobility
of pollutants, posing a risk of contamination of
underlying groundwaters

• They may also provoke negative effects for the


native microbial community of the soil. In
particular, EDTA has recently been banned as a
chelating agent, due to its toxicity for the soil
microbiota and its high persistence.
• To improve the effectiveness of these
technologies, genetic manipulation of some
organisms can be used.
• For example, tobacco plant was inoculated
with bacterial genes encoding a
nitroreductase enzyme.
• Genetically engineered tobacco plant showed
a significantly faster degradation of TNT and
an enhanced resistance to the toxic effect of
the explosive.
• Regarding the economical aspects of these
technologies, some studies suggest that when
a phytoremediation process is used instead the
conventional processes,
– the costs may be reduced up to 50-60%.
– However, the effectiveness of the process has to be
taken into account.
– Although the price is significantly lower,
– the time needed for the remediation may be much
longer.
• No specific regulatory standards have been
developed for phytoremediation processes, so that
installations must be approved on a case by case
basis. There are several regulatory issues which will
need to be addressed on most sites
• Several methods exist for the disposal of the
harvested pollutant-rich crop after a phytoextraction
process: Pre-treatment processes aim to reduce the
volume of biomass to be treated, by strongly
reducing its water content. Composting,
compactation and pyrolisis are the most important
ones. After the pre-treatments, the final disposal of
vegetal material takes places.
• Although the only technique used in praxis is the
incineration (in combination with filtering
mechanisms to clean the gas effluent), other
techniques exist, such as the direct disposal in a
deponie.

• Other techniques also are being developed at a


laboratory scale, such as the ashing or the liquid
extraction techniques. However they still lack the
required technology for its on-field application
• Phytoremediation is an emerging and promising
technology which permits a low cost alternative to
other remediation processes.
• However, the mechanisms behind the remediation
process still need to be better understood, so that
the best species-pollutant combination can be
chosen.
• Other problems such as contaminant migration
need to be focused in further studies to minimize
the drawback of this new technology.
FITOREMEDIASI

Phyto-
extraction

Rhizo-
filtration

Phyto-
stabilization

Rhizo-
degradation

Phyto-
degradation
FITOREMEDIASI

Phyto-
volatilization

Hydraulic
Control

Vegetative
Cover

Riparian
Corridors
Kelebihan fitoremediasi
• Memanfaatkan cahaya matahari
• Biaya murah
• Mudah diterima masyarakat

• Bioremediasi EXSITU, mahal


• Bioremediasi INSITU, lebih murah
Keterbatasan fitoremediasi
• Terbatas pada air dan tanah
• Cara kerja lambat
• Meracuni tnaman
• Potensi racun masuk makanan
• Racun sulit diketahui jenisnya
• Hanya untuk lingkungan tanah dan air
Jenis tanaman fitoremediasi
• Bunga matahari/ Heliantus anuus :
mendegradasi Uranium
• Populas trichocarpa, P.deltaritas Famili
sacnaceae : mendegradasi TCE
(Trichloroethylene)
• Najar graminae (tumbuhan air) : menyerap
Co, Pb,Ni
• Vetiver grass (Vetiveria zizonaides), akar wangi
: mendegradasi Pb, Zn
Tanaman air fitoremediasi
• Menyerap/mengakumulasi logam berat pada
semua jaringan
• Kangkung air
• Teratai
• Eceng gondok
Bioremediasi dengan mikroba
• Dengan 2 cara
– Oxidasi, bersamaan pertumbuhan mikroba
– Reduksi, elektron akseptor

• Akumulasi logam pada dinding sel


• Akumulasi logam dalam vakuola sel
• Menghasilkan enzim pendegradasi logam,
eksoenzim diluar sel, endoenzim dalam sel
Mikroba bioremediasi logam
• Bakteri mentransformasi Fe : Thiobacillus,
Leptothrix, Crenothrix,Sulfolobus, Gallionela
• Bakteri mentransformasi Mn :
• Arthrobacter, Leptothrix, Sphaerotillus
• Hg : Pseudomonas, Bacillus
Phytoremediation
• ≈350 plant species naturally take up toxic
materials
– Sunflowers used to remove radioactive cesium
and strontium from Chrenobyl site
– Water hyacinths used to remove arsenic from
water supplies in Bangladesh, India
Phytoremediation
• Drawbacks
– Only surface soil (root zone) can be treated
– Cleanup takes several years
Transgenic plants

Royal
Demolition
eXplosive

Gene from
bacterium
moved to
plant genome

Stimulates plant growth!


Careers in Bioremediation

• Outdoor inspection
• Lab testing
• Administration

Government
Employee Company employee
Regulatory oversight
Summary
• Many factors control biodegradability of a
contaminant in the environment
• Before attempting to employ
bioremediation technology, one needs to
conduct a thorough characterization of the
environment where the contaminant exists,
including the microbiology, geochemistry,
mineralogy, geophysics, and hydrology of
the system