KAJIAN PHYCOREMIDIASI

PADA LOGAM BERAT

oleh:
Rina Sunia Setya
(24020116410006)

Disusun dan disampaikan pada mata kuliah Bioremidiasi

yang diampu oleh
Dr. Tri Retnaningsih Soeprobowati,Mappsc
 DAFTAR ISI
1. DEFINISI FIKOREMIDIASI
2. ALGA
3. LOGAM BERAT
4. PEMBERSIHAN LOGAM BERAT OLEH ALGA
5. MEKANISME PEMBERSIHAN LOGAM BERAT
6. ABSOBSI DAN ADSORBSI LOGAM BERAT
OLEH ALGA
7. BIOPRODUK DAN BIOFUELS DALAM
BIOEKONOMI
 DEFINISI
Phycoremediation may be defined in a broad sense
as the use of macroalgae or microalgae for the
removal or biotransformation of pollutants,
including nutrients and xenobiotics from
wastewater and CO2 from waste air (Olguin,2003;
Dixit and Singh, 2015).
Phycoremediation is defined as the use of algae to
remove pollutants from the environment or to
render them harmless (Sivasubramanian,2016).
Phycoremediation is the process of using algal
species to sequester, remove, break down, or
metabolize pollutants from soil and water (Collins
et al, 2014).
 Phycoremediation,is a remediation
technology based primarily on algae
(Dixit and Singh, 2013,2014; de-Bashan et
al., 2012; Dresback et al., 2001; Fathi et
al., 2013; Fouilland, 2012; Gomes and
Asaeda, 2009; Hanumantha Rao et al.,
2010, 2011a,b; Kamaleswari et al., 2007;
Kong et al., 2010; Kushwaha et al., 2014;
Malla et al.,
The term 2015; Murugesanwas
phycoremediation et al.,
2007).
introduced by John (2000) to refer to the
remediation carried out by algae (Ahmad,
2013).
Phycoremediation dapat didefinisikan
dalam arti luas sebagai penggunaan
makroalga atau mikroalga untuk
menghilangkan atau biotransformasi
polutan, termasuk nutrisi dan
xenobiotik dari air limbah dan CO2 dari
udara limbah
 Phycoremediation is the utilization of
specifically micro or macro algae
species for the removal, or
biodegradation, of extra
environmental compounds (Collins,
2014).
Phycoremediation is comprised of several applications:
(i) nutrient removal from municipal wastewater and
effluents rich in organic matter;
(ii)nutrient and xenobiotic compounds removal with the
aid of algae-based biosorbents;
(iii)treatment of acidic and metal wastewaters;
(iv)CO2 sequestration;
(v)transformation and degradation of xenobiotics; and
(vi)detection of toxic compounds with the aid of algae-
based biosensors.
(Ahmad et al, 2013; Collins et al, 2014)
Phycoremediation terdiri dari beberapa aplikasi:
penghapusan nutrisi dari air limbah kota dan
limbah kaya bahan organik;
nutrisi dan senyawa xenobiotik penghapusan
dengan bantuan biosorbents berbasis alga;
pengobatan asam dan logam air limbah;
penyerapan CO2;
transformasi dan degradasi xenobiotik; dan
deteksi senyawa beracun dengan bantuan
biosensor berbasis alga.
 ALGAE
Microalgae and cyanobacteria respond positively to a
wide range of organic and inorganic pollutants. These
organisms are able to remove compounds from solution
through bioaccumulation of compounds into the cell body
as well as onto the cell surface, in addition to
mineralization activity related to cell metabolism. Algae
and cyanobacteria are able to grow in water with low or
high nutrient value as well as in harsher ecosystems like
high to hyper-salinity or extreme pH. In addition to the
highly versatile survival mechanisms of each organism,
some microalgae species have the ability to utilize both
autotrophy and heterotrophy, making them mixotrophic
in the right conditions.
Mikroalga dan cyanobacteria menanggapi positif berbagai
polutan organik dan anorganik. Organisme ini mampu
menghilangkan senyawa dari solusi melalui bioakumulasi
senyawa ke dalam sel tubuh serta ke permukaan sel,
selain aktivitas mineralisasi yang berhubungan dengan
metabolisme sel. Alga dan cyanobacteria mampu tumbuh
di air dengan nilai rendah atau tinggi nutrisi serta
ekosistem yang lebih keras seperti tinggi untuk hiper-
salinitas atau pH yang ekstrim. Selain mekanisme survival
yang sangat serbaguna setiap organisme, beberapa
spesies mikroalga memiliki kemampuan untuk
memanfaatkan kedua autotrophy dan heterotrophy,
membuat mereka mixotrophic di kondisi yang tepat.
 Algae represent a large group of aquatic, most primitive photoautotrophic
organisms that include around 30,000 species, ranging from unicellular
(microalgae) to more complex multicellular organisms (macroalgae).
Cyanobacteria (blue- green algae) were also included under the
microalgae by some authors (Priyadarshani et al. 2011). Algae possess
chlorophyll and are able to transform light energy into chemical energy in
a similar way to higher plants but lack true roots, stems and leaves.
They grow comparatively faster, which results in fixation of CO 2 being
1050 times faster than in plants (Subashchandrabose et al. 2013 ).
Algae are taxonomically divided based on their pigments, storage
compounds and the main compounds present in their cell wall. The major
classes are Chlorophyta (green algae), Rhodophyta (red algae),
Phaeophyta (brown algae), Euglenophyta, Pyrrophyta, Chrysophyta and
Cyanophyta (blue-green algae).
(Dixit and Singh, 2015)
Alga merupakan kelompok besar dari air, organisme fotoautotropik paling
primitif yang mencakup sekitar 30.000 spesies, mulai dari uniseluler
(mikroalga) untuk organisme multisel yang lebih kompleks (makroalga).
Cyanobacteria (alga hijau biru) juga disertakan di bawah mikroalga oleh
beberapa penulis (Priyadarshani et al. 2011). Alga memiliki klorofil dan
mampu mengubah energi cahaya menjadi energi kimia dalam cara yang
mirip dengan tanaman yang lebih tinggi namun kurang akar sejati,
batang dan daun.
Mereka tumbuh relatif lebih cepat, yang menghasilkan fiksasi CO 2
menjadi 10-50 kali lebih cepat dari pada tanaman (Subashchandrabose et
al. 2013).
Ganggang taksonomi dibagi berdasarkan pigmen mereka, senyawa
penyimpanan dan senyawa utama hadir dalam dinding sel mereka. Kelas-
kelas utama Chlorophyta (alga hijau), Rhodophyta (alga merah),
Phaeophyta (ganggang coklat), Euglenophyta, Pyrrophyta, Chrysophyta
dan Cyanophyta (biru-hijau ganggang).
Various groups of algae was used as biosorbents of heavy metals and classifications
of algae are based on pigments, cell walls chemistry, stored food materials, reproductive
structures, life history patterns, etc. Seven major algae groups are classified: Chrysophyta,
Euglenophyta, Pyrrhophyta,Charophyta, Chlorophyta, Phaeophyta and Rhodophyta [3].
The Phaeophyta or brown algae have been proved to be most effective biosobent for metal
removal, based on statistical review among those algae tested in bio sorption [14]. All the
brown algae are almost exclusively marine. They produce a variety of reserve substances,
some polymeric and some as free monomers. This group contains many large, complex
sea-weeds such as kelp. The Chlorophyta or green algae is also been widely used in heavy
metsorption [15,16]. This group of algae produces starch in a form very similar to that of
higher plants to reserve carbon. There are more than seventeen thousand species of green
11
algae abounded in both freshwater and marine. Some species of green algae live in snow,
or in symbiotic associations as lichens, or with sponges or other aquatic animals[17]. There
are also examples of using the Rhodophyta or red algae to treat heavy metal contaminated
wastewater [18]. Like the brown algae, almost all the red algae are marine. [2] Algae could
be simply classified into two categories i.e. microalgae and macroalgae. Microalgae are
unicellular species which exist individually, or in chains or groups. Depending on the species,
their sizes can range from a few micrometers (m) to a few hundreds of micrometers. Unlike
macroalgae, microalgae do not have roots, stems and leaves. Some groups of algae are all
microalgae such as Chrysophyta, while other groups have both microalgae and microalgae
such as Rhodophyta.
(Li et al, 2016)
Berbagai kelompok alga digunakan sebagai biosorbents logam berat dan
klasifikasi
ganggang didasarkan pada pigmen, dinding sel kimia, bahan makanan
yang disimpan, reproduksi
struktur, pola sejarah hidup, dll Tujuh kelompok alga utama
diklasifikasikan: Chrysophyta,
Euglenophyta, Pyrrhophyta, charophyta, Chlorophyta, Phaeophyta dan
Rhodophyta [3].
The Phaeophyta atau ganggang coklat telah terbukti biosobent paling
efektif untuk logam
removal, berdasarkan tinjauan statistik di antara mereka ganggang diuji
dalam penyerapan bio [14]. Semua
ganggang coklat hampir secara eksklusif laut. Mereka menghasilkan
berbagai zat cadangan,
beberapa polimer dan beberapa monomer bebas. Kelompok ini
mengandung banyak besar, kompleks
laut-gulma seperti rumput laut. Chlorophyta atau ganggang hijau juga
telah banyak digunakan dalam berat
metsorption [15,16]. Kelompok ini alga menghasilkan pati dalam bentuk
yang sangat mirip dengan
tumbuhan tingkat tinggi untuk cadangan karbon. Ada lebih dari tujuh
belas ribu spesies hijau
Components of cell wall of various groups of algae will be described since it is closely
related to the metal binding capacity of algae. Structure and chemistry of cell walls of
different groups of algae varied. In many cases the cell wall is a network of polysaccharides
such as pectin, xylans, mannans, alginic acids or fucinic acid. In some algae, calcium
carbonate is deposited in the wall to strengthen the structure. Sometimes chitin, a polymer
of N-acetylglucosamine, is also present in the cell wall [3]. There is no cell wall present in the
group Euglenophyta . Diatom contains a special kind of siliceous component responsible
for the rigidity of the cell. All of the three major groups of algae (green, brown, and red
algae) of research interest contain cellulose; however, the structure of the cell wall of the
three groups differed. The cell walls of brown algae (Phaeophyta) generally contain three
components: cellulose, alginic acid, and sulphated polysaccharides (fucoidan matrix). Red
algae (Rhodophyta) also contain cellulose, but their interest in connection with biosorption
lies in the presence of sulphated polysaccharides made of galactanes (agar and carragenates).
Green algae (Chlorophyta) are mainly cellulose, and a high percentage of the cell wall is
proteins bonded to polysaccharides to form glycoproteins (Li et al, 2016).
Komponen dinding sel berbagai kelompok alga akan dijelaskan
karena merupakan erat
terkait dengan logam kapasitas ganggang mengikat. Struktur dan
kimia dinding sel
berbagai kelompok alga bervariasi. Dalam banyak kasus dinding sel
adalah jaringan dari polisakarida seperti pektin, xylans, mannans,
asam alginat atau asam fucinic. Dalam beberapa alga, kalsium
karbonat diendapkan pada dinding untuk memperkuat struktur.
Kadang-kadang kitin, polimer N-asetilglukosamin, juga hadir dalam
dinding sel [3]. Tidak ada dinding sel hadir dalam kelompok
Euglenophyta. Diatom mengandung jenis khusus dari komponen
mengandung silika yang bertanggung jawab untuk kekakuan sel.
Semua dari tiga kelompok utama alga (hijau, coklat, dan merah
ganggang) tujuan penelitian mengandung selulosa; Namun, struktur
dinding sel dari tiga kelompok berbeda. Dinding sel ganggang coklat
(Phaeophyta) umumnya mengandung tiga komponen: selulosa, asam
alginat, dan polisakarida sulfat (fucoidan matrix). Merah ganggang
(Rhodophyta) juga mengandung selulosa, tapi kepentingan mereka
PRIYADARSHINI ET AL
 HEAVY METALS
Heavy metals are conventionally defined as elements with
metallic properties and an atomic number >20 (Tangahu et
al,2011).
The heavy metals, commonly defined as metals having a
specific density of more than 5 g/cm 3 (Hawkes 1997 ).
Include Fe, Mn, Cu, Mo, Zn and Co, which are required in traces
as nutrients by the living organisms, but they become toxic at
higher concentrations.
The other group of metals like Cd, Hg and Pb exert their
potential toxic effects even at extremely lower concentrations.
More than 40 heavy metals have been widely found in
wastewater and the most common ones include Cu, Zn, Mn,
Ni, Al, Hg, Cd, Pb, Cr, As, Mo, Co and Sn etc (Li et al, 2016).
logam berat secara konvensional didefinisikan sebagai elemen
dengan sifat logam dan nomor atom> 20 (Tangahu et al, 2011).
Logam berat, biasanya didefinisikan sebagai logam memiliki
kerapatan tertentu lebih dari 5 g / cm -3 (Hawkes 1997).
Sertakan Fe, Mn, Cu, Mo, Zn dan Co, yang dibutuhkan dalam
jejak sebagai nutrisi oleh organisme hidup, tetapi mereka
menjadi beracun pada konsentrasi yang lebih tinggi.
Kelompok lain dari logam seperti Cd, Hg dan Pb mengerahkan
potensi efek beracun mereka bahkan pada konsentrasi yang
sangat rendah.
Lebih dari 40 logam berat telah banyak ditemukan dalam air
limbah dan yang paling umum termasuk Cu, Zn, Mn, Ni, Al, Hg,
Cd, Pb, Cr, As, Mo, Co dan Sn dll (Li et al, 2016) .
 Zinc is a trace element that is essential for human health. It is important for the
physiological functions of living tissue and regulates many biochemical processes.
However, too much zinc can cause eminent health problems, such as stomach
cramps, skin irritations, vomiting, nausea and anemia (Oyaro et al., 2007).
Copper does essential work in animal metabolism. But the excessive ingestion of
copper brings about serious toxicological concerns, such as vomiting, cramps,
convulsions, or even death (Paulino et al., 2006).
Nickel exceeding its critical level might bring about serious lung and kidney problems
aside from gastrointestinal distress, pulmonary fibrosis and skin dermatitis (Borba et
al., 2006). And it is known that nickel is human carcinogen.
Mercury is a neurotoxin that can cause damage to the central nervous system. High
concentrations of mercury cause impairment of pulmonary and kidney function, chest
pain and dyspnoea (Namasivayam and Kadirvelu, 1999). The classic example of
mercury poisoning is Minamata Bay.
Cadmium has been classified by U.S. Environmental Protection Agency as a probable
human carcinogen. Cadmium exposes human health to severe risks. Chronic
exposure of cadmium results in kidney dysfunction and high levels of exposure will
result in death.
Lead can cause central nervous system damage. Lead can also damage the kidney,
liver and reproductive system, basic cellular processes and brain functions. The toxic
symptoms are anemia, insomnia, headache, dizziness, irritability, weakness of
muscles, hallucination and renal damages (Naseem and Tahir, 2001).
Chromium exits in the aquatic environment mainly in two states: Cr(III) and Cr(VI). In
Zinc merupakan unsur jejak yang sangat penting bagi kesehatan manusia. Hal ini
penting untuk fungsi fisiologis jaringan hidup dan mengatur banyak proses biokimia.
Namun, terlalu banyak zinc dapat menyebabkan masalah kesehatan terkemuka, seperti
kram perut, iritasi kulit, muntah, mual dan anemia (Oyaro et al., 2007).
Tembaga tidak bekerja penting dalam metabolisme hewan. Namun konsumsi yang
berlebihan dari tembaga membawa keprihatinan serius toksikologi, seperti muntah,
kram, kejang, bahkan kematian (Paulino et al., 2006).
Nikel melebihi tingkat kritis mungkin membawa masalah paru-paru dan ginjal yang serius
selain dari gangguan pencernaan, fibrosis paru dan dermatitis kulit (Borba et al., 2006).
Dan diketahui bahwa nikel karsinogen manusia.
Merkuri merupakan racun saraf yang dapat menyebabkan kerusakan pada sistem saraf
pusat. Konsentrasi merkuri yang tinggi menyebabkan penurunan fungsi paru dan ginjal,
nyeri dada dan sesak (Namasivayam dan Kadirvelu, 1999). Contoh klasik dari keracunan
merkuri Teluk Minamata.
Kadmium telah diklasifikasikan oleh AS Environmental Protection Agency sebagai
karsinogen manusia kemungkinan. Kadmium menghadapkan kesehatan manusia risiko
berat. paparan kronis dari hasil kadmium dalam disfungsi ginjal dan tingginya tingkat
paparan akan mengakibatkan kematian.
Timbal bisa menyebabkan kerusakan sistem saraf pusat. Timbal juga dapat merusak
ginjal, hati dan sistem reproduksi, proses seluler dasar dan fungsi otak. Gejala toksik
adalah anemia, insomnia, sakit kepala, pusing, mudah marah, kelemahan otot, halusinasi
dan kerusakan ginjal (Naseem dan Tahir, 2001).
keluar kromium dalam lingkungan air terutama di dua negara: Cr (III) dan Cr (VI). Secara
Methods for removal of heavy metals
from aqueous environment including
chemical
precipitation, ion exchange,
adsorption, membrane filtration,
coagulation, flocculation,
flotation, and electrochemical
treatment have been widely studied
by researchers ()
 Mechanisme of Metal
Uptake
1. Binding site on alga
2. Mechanisms of adsorption and
Absorption n algae
 Binding site on alga
Cell wall of algae contains a variety of functional groups (amino, carboxyl, sulphate
and hydroxyl etc.), which works as the binding site of metals [4,5] . Table 2 listed
some
major functional groups and classes of organic compounds in algae possibly
involved in the
biosorption process. The cell wall component difference in different species of
algae resulted
in different functional groups. Carboxyl is proved to be the most abundant acidic
functional
group in the cell wall of brown algae [6]. The carboxyl, hydroxyl, and amino and
sulphonate
groups on cell walls of marine brown macro algae Cystoseira barbata are
responsible for the
binding of metal ions [7] . The presence of amino, carboxylic and sulfonate groups
on the
cell wall of green microalgae Chlamydomonas reinhardtii are responsible for
adsorption of
the metal ions [8].
dinding sel ganggang berisi berbagai kelompok fungsional (amino, karboksil, sulfat
dan hidroksil dll), yang bekerja sebagai situs pengikatan logam [4,5]. Tabel 2
tercantum beberapa
kelompok fungsional utama dan kelas senyawa organik dalam alga mungkin terlibat
dalam
Proses biosorpsi. Perbedaan komponen dinding sel pada spesies yang berbeda dari
alga menghasilkan
dalam kelompok-kelompok fungsional yang berbeda. Karboksil terbukti menjadi
asam fungsional yang paling melimpah
kelompok di dinding sel ganggang coklat [6]. The karboksil, hidroksil, dan amino dan
sulfonat
kelompok pada dinding sel dari laut coklat makro alga Cystoseira barbata
bertanggung jawab atas
pengikatan ion logam [7]. Kehadiran amino, karboksilat dan sulfonat kelompok pada
dinding sel mikroalga hijau Chlamydomonas reinhardtii bertanggung jawab untuk
adsorpsi
ion logam [8].
 Mechanisms of adsorption and
Absorption n algae

Adsorption is the adhesion of atoms, ions or molecules

from a gas, liquid, or dissolved solid to a surface.
Adsorption is carried out by extracellular cell-
associated materials. It is a non-metabolic and rapid
process, which occurs in both living and non-living
cells.
Absorption is a physical or chemical phenomenon or a
process in which atoms, molecules, or ions enter some
bulk phase-gas, liquid, or solid material . It is an
intracellular accumulation process. This is a different
process from adsorption, since molecules undergoing
absorption are taken up by the volume, not by the
surface (as in the case for adsorption).
Adsorpsi adalah adhesi atom, ion atau molekul dari
gas, cairan, atau padatan terlarut ke permukaan.
Adsorpsi dilakukan oleh sel bahan terkait ekstraseluler.
Ini adalah proses non-metabolik dan cepat, yang terjadi
pada sel non-hidup hidup dan.
Penyerapan adalah fenomena fisik atau kimia atau
proses di mana atom, molekul, atau ion memasukkan
beberapa fase-gas, cair, atau bahan padat massal. Ini
adalah proses akumulasi intraselular. Ini adalah proses
yang berbeda dari adsorpsi, karena molekul menjalani
penyerapan yang diambil oleh volume, bukan oleh
permukaan (seperti dalam kasus untuk adsorpsi).
 In the case of algae, the biosorption
process took place in two stages: a
very rapid surface adsorption and a
slow intracellular diffusion or
absorption [5].
The mechanism of metal biosorption is a complicated process. The status of
biomass (living or nonliving), types of biomaterials, properties of metal
solution chemistry and environmental conditions such as pH infl uence the
mechanism of metal biosorption. The uptake of heavy metal ions by algae
was found to occur in two principal ways: passive uptake due to surface
adsorption (metabolism independent) followed by cellular uptake
(metabolism dependent) via intracellular transport and chelation
(absorption) (Khummongkol et al. 1982 ; Cho et al. 1994 ; Yee et al. 2004 ).
Some metals such as Pb and Sr may be passively adsorbed by charged
polysaccharides in cell wall and intracellular matrix (El-Sheekh et al. 2003 ;
Osman et al. 2004 ; Fathi et al. 2000 ; 2005 ); other metals (e.g. Zn, Cd) are
taken up actively against large intracellular concentration gradients. As
passive biosorption mainly depends on the binding to functional surface
ligands, the cell wall structure is the most important for rapid metal ion
uptake. The probable sites of an algal cell for the binding of metal ions are
shown in Fig. 2.2 . Adsorption occurs directly into the cell wall in some algae,
but the presence of various amounts of mucilage or extracellular polymeric
substances (EPS) (Leppard 1995 ; Lee 1997 ) in others (e.g. Cyanophyta)
may play a key role in metal binding (Weckesser et al. 1988 ). The algal cell
wall contains many functional groups, such as hydroxyl (OH), phosphoryl,
amino (NH 2 ), carboxyl ( COOH), sulphydryl (SH), etc., which confer a
negative charge on the cell surface. Since metal ions in water are generally
in the cationic forms, they are adsorbed onto the cell surface. The functional
group involved in the metal sorption by algae have been identifi ed by FTIR
spectroscopy, pH titration, potentiometric and conductimetric titration
techniques and also after blocking of functional groups by certain chemicals.
Each functional group has a specific dissociation constant (pKa), and it
l.J.L. 2002. Celluler Mechanisms for heavy metal detoxification and tolerance.
rnal of experimental Botani. 53(366):1-11.
 Bioeconomy of
Phycoremediation
Biofertilizer
Compost
Aquaculture feed
Waste water treatment
 Indias largest phytoremediation plant is in
operation at SNAP Natural and Alginate Products,
Ranipet, India from September 2006 (Figure 1).
The industry generates 30-40 kL of highly acidic
effluent every day which is being pH corrected and
evaporated using an algae based treatment
technology developed by Sivasubramanian and his
team from Phycospectrum Environmental Research
Centre (PERC), Chennai, India (Sivasubramanian et
al., 2009). The physico-chemical characteristics of
effluent are provided in Table 1. There is 100%
reduction in sludge by phycoremediation.
DAFTAR PUSTAKA