(eBook PDF) Nanostructured Materials

for Treating Aquatic Pollution

Go to download the full and correct content document:
https://ebooksecure.com/product/ebook-pdf-nanostructured-materials-for-treating-aqu
atic-pollution/
More products digital (pdf, epub, mobi) instant
download maybe you interests ...

Nanohybrid and Nanoporous Materials for Aquatic

Pollution Control (Micro and Nano Technologies) 1st
Edition Lin Tang (Editor) - eBook PDF

https://ebooksecure.com/download/nanohybrid-and-nanoporous-
materials-for-aquatic-pollution-control-micro-and-nano-
technologies-ebook-pdf/

Advanced Materials for Sustainable Environmental

Remediation: Terrestrial and Aquatic Environments 1st
Edition- eBook PDF

https://ebooksecure.com/download/advanced-materials-for-
sustainable-environmental-remediation-terrestrial-and-aquatic-
environments-ebook-pdf/

Non-Thermal Plasma Technology for Polymeric Materials:

Applications in Composites, Nanostructured Materials,
and Biomedical Fields 1st edition - eBook PDF

https://ebooksecure.com/download/non-thermal-plasma-technology-
for-polymeric-materials-applications-in-composites-
nanostructured-materials-and-biomedical-fields-ebook-pdf/

Magnetism and Spintronics in Carbon and Carbon

Nanostructured Materials - eBook PDF

https://ebooksecure.com/download/magnetism-and-spintronics-in-
carbon-and-carbon-nanostructured-materials-ebook-pdf/
Nanostructured, Functional, and Flexible Materials for
Energy Conversion and Storage Systems 1st Edition
Alagarsamy Pandikumar - eBook PDF

https://ebooksecure.com/download/nanostructured-functional-and-
flexible-materials-for-energy-conversion-and-storage-systems-
ebook-pdf/

Nanostructured Materials for Visible Light

Photocatalysis (Micro and Nano Technologies) 1st
Edition Arpan Kumar Nayak (Editor) - eBook PDF

https://ebooksecure.com/download/nanostructured-materials-for-
visible-light-photocatalysis-micro-and-nano-technologies-ebook-
pdf/

Nanostructured Nonlinear Optical Materials: Formation

and Characterization (Micro and Nano Technologies) -
eBook PDF

https://ebooksecure.com/download/nanostructured-nonlinear-
optical-materials-formation-and-characterization-micro-and-nano-
technologies-ebook-pdf/

Wetlands for Water Pollution Control, Second Edition

Scholz - eBook PDF

https://ebooksecure.com/download/wetlands-for-water-pollution-
control-second-edition-ebook-pdf/

(eBook PDF) Neurolinguistic Approach to Reading: A

Guide for Speech-Language Pathologists Treating
Dyslexia

http://ebooksecure.com/product/ebook-pdf-neurolinguistic-
approach-to-reading-a-guide-for-speech-language-pathologists-
treating-dyslexia/
Engineering Materials

Gil Alberto Batista Gonçalves

Paula Marques Editors

Nanostructured
Materials
for Treating
Aquatic Pollution
viii Contents

Nanostructured Membranes for Water Purification . . . . . . . . . . . . . . . . 243

Xin Li, Gomotsegang Fred Molelekwa, Meryem Khellouf
and Bart Van der Bruggen
Nanostructured Polymer Composites for Water Remediation . . . . . . . . 275
Michael Ovbare Akharame, Ogheneochuko Utieyin Oputu,
Omoniyi Pereao, Bamidele Oladapo Fagbayigbo,
Lovasoa Christine Razanamahandry, Beatrice Olutoyin Opeolu
and Olalekan Siyanbola Fatoki
Removal of Metal Ions Using Graphene
Based Adsorbents

Imran Ali, Zeid A. ALOthman and Abdulrahman Alwarthan

Abstract The pollution of water sources with toxic metal ions is a thoughtful
subject. Numerous aquatic systems are polluted with dissimilar toxic metal ions from
various industrial effluents and anthropogenic activities. Water treatment seems to
the chief environmental test. The sorption is the best effective method for metal ions
elimination in water. Currently, graphene and its composite materials are attaining
significance as new generation nano-sorbents. Graphene is a two dimensional nano-
material with single layer of graphite. These have achieved a great reputation in water
treatment because of their distinctive physico-chemical features. The present chapter
describes the elimination of metal ions using graphene and its composite materials.
The emphasis has been made on syntheses, applications, regeneration and recycling
and future perspectives. Definitely, this chapter will be valuable tool for researchers,
government authorities and academicians.

Keywords Water treatment · Graphene and composite substances · Toxic and rare
earth metals · Adsorption

1 Introduction

Water is the most significant commodity for the existence of all the individuals on
the earth. Everything in this life need water. Because of that, people must not only
take care for water sources but also to keep water sources clean. The international
water community continues to explore safe water for securing the future of human

I. Ali (B)
Department of Chemistry, College of Sciences, Taibah University,
Al-Medina al-Munawara 41477, Saudi Arabia
e-mail: drimran_ali@yahoo.com; drimran.chiral@gmail.com
Department of Chemistry, Jamia Millia Islamia (Central University),
New Delhi 110025, India
Z. A. ALOthman · A. Alwarthan
Department of Chemistry, College of Science, King Saud University, Riyadh
11451, Kingdom of Saudi Arabia

© Springer Nature Switzerland AG 2019 1

G. A. B. Gonçalves and P. Marques (eds.), Nanostructured Materials
for Treating Aquatic Pollution, Engineering Materials,
https://doi.org/10.1007/978-3-030-33745-2_1
2 I. Ali et al.

and aquatic ecosystem health. The quality of water is a significant issuer during last
some decades [1]. If water quality will not be controlled, the disease will develop
and increase and the life will be miserable with short span. Among various water
contaminates, toxic trace metal ions are very serious pollutants owing to their severe
toxicity, carcinogenic and non-biodegradable nature [2]. These metal ions incline to
collect in tissues and create numerous diseases and health maladies in humans. It
is due to their tendency to interact with proteins, enzymes and non-biodegradable
nature [3–5]. The contact to the metal ions, even at bit level, is supposed to be a
risk for the human [6–9]. Thus, this problem is of major concern for the scientists,
academicians and Government authorities. Therefore, their removal is essential for
the health point of views.

2 Water Pollution in Different Ecosystems

The quality of our water springs is worsening rapidly because of rapid growing
of the world people, civilization and industrialization. Our fixed fraction of fresh
water is being polluting continuously by point and non-point sources. These sources
can be categorized based on their targeted water resources i.e. ground and surface
water (Table 1); classified on their maximum probability of water contamination.
The main causes of water contaminations are domestic, industrial and agricultural
happenings [10, 11]. Some other ecological activities and geological variations are
also accountable for polluting water; especially ground water.
More than one thousand pollutants are present in water and these include organic,
inorganic and biological contaminants. The major uses of water are for agriculture,
industrial process, and domestic (household) supply. It is quite obvious that the qual-
ity of water determines its potential uses. The domestic supply must be free from
constituents harmful to health, such as organic, inorganic and biological contam-
inations, and it should taste and smell good. Similarly, quality of water required
for industrial purposes varies widely depending on the process involved. Some pro-
cesses may require distilled water, whereas, other simply needs normal water. Water
for agriculture should be free from boron and possesses 2–10 sodium adsorption
ratio (SAR) value. The various international agencies have devised permissible lim-
its for several constituents in water for different purposes like drinking, bathing,
recreation, agricultural etc. [12, 13]. The wastewater contaminated with metals is
serious aspect in hydrological science. Metals are presented in water systems due
to enduring of rocks and soils, from volcanic outbreaks, and from a diversity of
man actions with the processing, mining, utilization of metals and other substances
that comprise metal contaminants [14, 15]. The most notorious toxic metal contam-
inants are cadmium, arsenic, copper, chromium, lead, mercury, selenium and nickel.
There are dissimilar causes of metal contaminants, that are given in Table 2. The
common restricted metal contamination in water comes via industrial effluents of
battery, tanning, ceramics, glassware, mining, electroplating, photographic, paints
etc. In addition to these industries, acid mine drain typically issues toxic metals from
Removal of Metal Ions Using Graphene Based Adsorbents 3

Table 1 Sources of water pollution

Surface water
• Urban runoff (oil, chemicals, organic
matter, etc.) (U, I, M)
• Agricultural runoff (oil, metals fertilizers,
pesticides, etc.) (A)
• Accidental spills of chemicals including oil
(U, R, I, A, M)
• Radioactive materials (often involving
trucks or train accidents) (I, M)
• Runoff (solvents, chemicals, etc.) from
industrial sites (factories, refineries, mines
etc.) (I, M)
• Leak from surface storage tanks and
pipelines (gasoline, oil etc.) (I, A, M)
• Sediments from a variety of sources,
including agricultural lands and
construction sites (U, R, I, A, M)
• Air fallout (particles, pesticides, metals
etc.) intro river, lake, ocean (U, R, I, A, M)
Key: U urban; R rural; I industrial; A agricultural; M military
Groundwater
• Leaks from waste disposal sites (chemical,
radioactive materials etc.) (I, M)
• Leaks from buried tanks and pipes
(gasoline, oil, etc.) (I, A, M)
• Seepage from agricultural activates
(nitrates, heavy metals, pesticides,
herbicides etc.) (A)
• Saltwater intrusion into coastal aquifers (U,
R, I, M)
• Seepage from cesspools and septic systems
(R)
• Seepage from acid rich water from mines (I)
• Seepage from mine waste pipes (I)
• Seepage of pesticides, herbicides nutrients,
and so on from urban areas (U)
• Seepage from accidental spills (train or
truck accidents, for example) (I, M)
• Inadvertent Seepage of solvent and other
chemicals including radioactive materials
from industrial sites or small business (I, M)

ores, as metals are soluble in an acid. After the drain procedure, these arrangements
scatter acid solutions on the ground, comprising high points of metals, which may
leach into the groundwater. Besides, the concentrations of toxic metals are much
greater than the harmless allowable limits [16].

3 Metal Ions Toxic Effects

The metal ions are important for living systems; but these may have toxicity or car-
cinogenicity at elevated concentrations. Nowadays, the pollution of our atmosphere
owing to toxic metals is very stern and puzzling problem. The toxic metals found into
the atmosphere in dissimilar physico-chemical forms. The organometallic molecules
are more poisonous than the their inorganic forms; with the exemption of arsenic. The
heavy metals inhabit a chiefly significant position as these are maximum poisonous.
Some toxic metals are of vivacious position for flora and fauna progress. However,
these may be toxicant at high concentrations. The most hazardous features of heavy
 4

Table 2 Heavy metal, present in raw materials/processes in major industries

Industry Cd Cr Cu Fe Hg Mn Pb Ni Sn Zn
Pulp & Paper, board mills x x x x x x
Organic chemicals x x x x x x x
Inorganic chemicals x x x x x x x
Fertilizers x x x x x x x x x
Petroleum Refining x x x x x x x
Basic steel works x x x x x x x x x
Basic non-ferrous metal works x x x x x x
Motor vehicle Aircraft plating x x x x x
Glass, Cement x
Textile mill x
Leather tanning x
Steam generation power plant x
I. Ali et al.
Removal of Metal Ions Using Graphene Based Adsorbents 5

metals is their accumulation in living systems even in the neighboring situation. Out
of natural occurring elements, fifty three are heavy metals, while seventeen (Ag, As,
Co, Cd, Cu, Cr, Hg, Mn, Fe, Mo, Pb, Ni, U, Sb, W, V and Zn) are obtainable to the
alive cells and make solvable cations; showing living properties. The men are pre-
dictably bared to carcinogens from ecological, medicinal and occupational sources
[2]. Generally, the noxiousness of metals is defined by calculating LD50 or LC50 .
Nevertheless, some workers described toxicities in terms of EC50 and IC50 termi-
nologies. The metal ions defined in the periodic table are not-toxic and, consequently,
only poisonous metal ions are deliberated here. Amongst numerous metal ions the
maximum shared toxic metals concerned in severe and/or lingering circumstances
comprise arsenic, antimony, lead, chromium, selenium, mercury, etc. Nevertheless,
high amount of other metal ions like rhodium, aluminum, zinc, copper, vanadium,
platinum, etc. may be poisonous [2]. The poisonousness of some notorious metal
ions is discussed below.

3.1 Arsenic (As)

Arsenic is a well-known poisons for log time. The poisonousness of water soluble
arsenic species is arsenite) > arsenate > monomethylarsonate; > dimethylarsinate.
Arsenic in water sows harming all the phases of arsenic appearance [2]. In human
body about 50% arsenic is expelled through faeces, urine, skin, nails, hair, lungs etc.
[2]. The people consuming arsenic polluted water indicates arsenical skin lesions.
Long use of arsenic polluted water can result into hyperkeratosis, conjunctivitis,
hyperpigmentation, disorder in the periphral nervous and vascular systems, cardio-
vascular diseases, skin cancer and non-pitting swelling, gangrene, leucomelanosis,
splenomegaly, and hepatomegaly [2, 17–19]. The effects on the lungs, uterus, gen-
itourinary tract etc. are noticed in the progressive phase of arsenic poisonousness.
Moreover, high amount of arsenic can also create escalation of spontaneous and still-
births abortions [2, 20]. The additional side effects of arsenic pollution are visual dis-
orders, sensory disorders, energy loss, coma, fatigue, convulsions, shock, paralyses,
atrophy, blindness, kidney damage, etc.

3.2 Cadmium (Cd)

Cadmium has severe toxicities including nausea, diarrhea, cramp muscle and harm
of bone marrow. Besides, it is supposed accountable to kidney stones formation [2,
21, 22]. The studies indicated cadmium as responsible for human cancer of prostatic,
pulmonary and liver, renal, hematopoietic system, stomach and urinary bladder [23–
28]. USA International Agency for Research on Cancer and the National Toxicology
Program recognized cadmium as group 1 carcinogenic metal ion [24, 25]. Cadmium
is considered to be lethal with vomiting and nausea at 15.0 mg/L concentartion. It is
6 I. Ali et al.

acute poisonous metal but not deadly. The cadmium effects are hypertension renal
dysfunction, chest pain, anemia, headache, augmented salivation, diarrhea„ throat
dryness, pneumonitis, cough, tenesmus, etc. The diverse molecules carcinogenic in
nature are Cd, CdO, CdS, CdCl2 and CdSO4 .

3.3 Chromium (Cr)

Cr(III)] is crucial for living beings growth and health (at low level) with a nontoxic
concentration of 0.20 mg/day while Cr(VI) is a strong carcinogenic and very deadly
to human and animals. Thus, the collected Cr in plants parts (food) may characterize
possible health threats to human and animals when it is collected in Cr(VI) form at
elevated concentration. The chief noxious effects of chromium(VI) related to respi-
ratory organs, kidney, liver, with hemorrhagic possessions, ulceration and dermatitis
of skin. Chromium is categorized as group I carcinogenic by International Agency
for research on Cancer; for animals and humans. Chromium is found in ground water
of industrial area of steel works, plating, corrosion tanning, etc. industries. Besides
the anthropogenic actions are also responsible for its contamination; the weathering
of rocks [29, 30]. It is carcinogenic with tendency of forming of respiratory cancers.
It was found that Cr(VI) exposure led to danger of emerging lung cancers [31, 32].

3.4 Lead (Pb)

Lead is very substantial toxin among heavy metals with neurotoxical and toxicolog-
ical effects like damage of brain. Lead is a present in inorganic and organic forms.
Inorganic lead damage peripheral and central nervous systems, renal, hematopoietic,
reproductive, cardiovascular and gastrointestinal systems. Organic lead is poisonous
for central nervous system. These sorts of properties are seen at 100.0–200.0 μg/L
blood concentration. The tumor development in rats is owing to lead toxicity. Other
dangerous effects include loss of cognitive abilities, convulsions, anti-social consti-
pation, anemia, visual disturbances, severe abdominal pain, tenderness nausea, ane-
mia, paralysis, vomiting, etc. The different lead substances carcinogenic in nature are
PbAc2 , PbO, Pb3 (PO4 )2 and PbCrO4 [2]. Inorganic lead are absorbed via inhalation,
ingestion while organic lead salts are engrossed via skin.

3.5 Mercury (Hg)

Mercury is found in inorganic and organic forms. Water contamination due to mer-
cury is because of use of mercury based pesticides [2, 33, 34]. Inorganic mercury
substances are poisonous to nervous and nephrological systems. Organic mercury
Removal of Metal Ions Using Graphene Based Adsorbents 7

substances are acute poisonous to central nervous system. Also, irritability, learning
disabilities, discouragement, behavior changes, jerky gait, tremors, gums and mouth
inflammations, swelling of salivary glands, spasms of extremities, teeth loosening
and saliva disorder are other menace of mercury toxicity. However, the toxicity issue
of mercury is not clear and still in discussion. Mercury also effect DNA activities
and is considered as carcinogen.

4 Water Treatment Methods Available

Many water treatment methods are used for removing toxic contaminants in water.
These are grouped as chemical, physical, thermal, biological and electrical nature.
The most important are filtration, centrifugation, crystallization, screening, gravity
and flotation, sedimentation oxidation, separation, precipitation, solvent extraction,
coagulation, evaporation, ion exchange, distillation, electrodialysis, reverse osmosis,
adsorption electrolysis, etc. Amongst these techniques, sorption is considered as the
finest one owing to ease of operation, eco-friendly, inexpensive and capable to remove
all types of the pollutants [35, 36].
Adsorption is an exterior process and is described as an augment for species
on the edge or surface among two phases. The species (pollutant), which stick to
the solid interface is termed as adsorbate and solid material is called as adsorbent.
The sorption is controlled by features of the adsorbate and adsorbent, contact time,
pH, dose, temperature, adsorbent particle size, other species, etc. The occurrence
of suspended materials, greases and oils decreases the efficacy of the phenomenon.
Therefore, sometimes filtration is needed. The pollutants get adhered to the solid
surface of adsorbent when contaminated water is shacked with adsorbent. After
some times, the amounts of the contaminants sorbed gets constant. The relation-
ship pollutant amounts sorbed at fixed time and equilibrium is termed as adsorption
isotherm (Fig. 1). Freundlich, Langmuir, Dubnin, Tempkins and other isotherms are
well-known and may describe sorption data efficiently [37]. The adsorption process
is determined by batch experiments in the laboratory followed by pilot scale and
column operations.

Fig. 1 A typical batch

adsorption isotherm
8 I. Ali et al.

5 Graphene

Graphite is a crystalline material made of carbon in a sequence of fixed parallel sheets.

The carbon atoms in every sheet are fixed in even hexagons in a fashion that every
carbon atom is linked via three other carbon atoms. The 3.35 Å is a space between
two adjacent graphite sheets. The carbon—carbon space in hexagonal collection is
1.42 Å. The intra-planar bonding attractions in every sheet are owing to metallic and
covalent bondings, that are greater in comparison to forces of van der Waal. Graphite
can react with dissimilar reagents forming intercalation substances; resulting into
surface substitution and alteration. The graphite intercalation substances are much
essential in water management as showing quite good sorption dimensions for differ-
ent contaminants. Graphene is one of the most amazing carbon materials in nano size.
The widespread graphene use is in numerous areas industrial purposes. A graphene
only sheet (classically showing graphene) was achieved over compounds by trans-
feral from only crystal graphite utilizing a glue tape. Much progressive techniques
for graphene distinct layer on substrates are described. The even graphene distinct
layers are steady on the substrates, while free may be unstable and tending to form
a roll. Graphene distinct layer can be made constant due to their contacts with the
setting. The surface sorption is utilized to make stable diffusions in water and other
organic solvents [38, 39]. Normally, graphene dispersion and powder structures are
rarely perfect. Graphene particles are bent to a definite degree with raggedy ends.
The basic flaws and outside atoms and elemental groups are committed to graphene
frame. Classically graphene is defined as a distinct carbon layer [40]. Nevertheless,
recent definition is graphene comprises 10 or less sheets. It is also called as exfoliated
graphite nano-sheet or graphite nano-platelet [41]. Graphite nano-platelets fluctuate
in the structures dependent on the width. Graphite nano-platelet of lesser than 50.0 nm
width does not indicate a cellular construction while graphite nano-platelet more than
50.0 nm thick can or cannot show cellular frame-work.
Graphene distinct layer shows sp2 carbon hybridization (organized in honeycomb
hexagonal lattice) with ~5000 W/mK thermal conductivity (at ambient temp.) in dif-
fusion and hypothetical surface area of 2630 m2 g−1 [42, 43]. The side interactions
contain an extreme reduction of 60% in conductivity, which is about 2000 W/mK;
at 100 nm graphene sheet thickness. The size of graphene may range 10 to 100 nm
(thickness) owing to the reasonable thermal conductivity (κ ≈ 1500 W/mK) at ambi-
ent temp [44]. Graphene is examined owing to its tunable and stretchy carbon sup-
port; leading into easy integration and functionalization in a range of utilities [45].
Newly, graphene astonished scientists to discover the prospective in water man-
agement owing to the unique properties like typical structural properties [46], good
mechanical power [47], and small thickness [48]. Elevated tensile power and impene-
trability of graphene are well recognized [49]. Sub-nanometer holes may be generated
in graphene by electron ion beam, oxidation, doping, cluster/ion bombardment, etc.
[50]. These holes are meant to discover the transference of gases and ionic molecules
[51]. Graphene and its compounds are few sheets of graphene, monolayer graphene,
Removal of Metal Ions Using Graphene Based Adsorbents 9

Fig. 2 Crystal structure of graphene

reduced and normal graphene oxides, graphene nano-ribbons, graphene nano-sheets

etc.
The dissimilar methods utilized for graphene and nanocomposites preparations
are electrochemical, reduction, decomposition exfoliation etc. (thermal, microwave,
photochemical) [52, 53]. The laboratory and engineering graphene nano-platelets
can be categorized into two categories i.e. multi-layered (10–60 sheets) and few
coated (1–10 sheets). The graphene crystal assembly described in Fig. 2. The supra-
molecular surface altered graphene structure is represented in Fig. 3. The figure
of graphene interpolating compounds is described in Fig. 4. The supra-molecular
graphene oxide features are given in Fig. 5. The features of this exceptional material
(graphene) is revealed in Table 3. Many methods are described and used to prepare
graphene i.e. motorized utility of extremely inclined chemical vapour deposition,
pyrolytic graphite, epitaxial growth on SiC, bottom-up preparation from organic
moieties, liquid phase utilization carbon nanotubes unzipping, natural reduction of
exfoliated graphite oxide [54]. Table 4 shows the profits and disadvantages of some
commonly utilized syntheses procedures.
10 I. Ali et al.

Fig. 3 Surface modified graphene

6 Wastewater Treatment by Exploring Graphene Sorbents

The adsorption is a process where a pollutant sorbed on the sorbent solid surface [55,
56]. It is controlled by a number of factors like pore volume, surface area and func-
tional groups. It is frequently happened with the opposite desorption, which indicates
transference of sorbates from sorbent superficial to the solution. The renewal of adsor-
bent may be tried depending on the sorbate quantity desorbed from sorbent; renewal
and desorption processes increase [57]. The sorption can be of physico-chemical
type. This being controlled by the types of interactions among the adsorbate and
sorbent. For physical sorption, the increase in sorbate quantity at the boundary is
because of non-specific van der Waal’s interactions. The chemisorptions is devel-
oped via chemical reactions between sorbate and the sorbent, that produce covalent
or ionic bonds. The latter is specific, weak, reversible with small thermal effect,
whereas former irreversible, specific, typically with tens to hundreds of kJ/mol as
heat of sorption [58].
The sorption controlling factors are pH, dose, concentration, ionic strength, tem-
perature, the presence of organic moieties, interaction time and shacking stirring
speed. The adsorption may be demarcated by normally used Freundlich, Langmuir,
Tempkin etc. models [58]. Graphene and its composites are attaining reputation in
water treatment through sorption process because of their remarkable features such
as high surface area, great quantity of handy groups and outstanding movement of
charge species. The graphene and its related materials have been widely explored as
adsorbents for water treatment process.
Removal of Metal Ions Using Graphene Based Adsorbents 11

Fig. 4 Schematic diagram

of intercalating compounds
of graphene
12 I. Ali et al.

Fig. 5 The supramolecular structure of graphene oxide

Table 3 The characteristics

Features Values
features of single layer
graphene [54] C–C bond length thickness 14.2 × 10−2 nm
Optical transparency 97%
Theoretical BET specific surface 2630 m2 g−1
area
Thermal conductivity 5000 W m−1 K−1
Density 0.77 mg m−3
Density carrier 1012 cm−2
Young’s modulus 1100 GPa
Fractural strength 125 GPa
Resistivity 10−6  cm
Electron mobility 200,000 cm2 V−1 s−1

6.1 Toxic Metal Ions Sorption

The contamination of water resources through toxic metal ions like Ag, As, Cd, Cu,
Co, Cr, Hg, Fe, Pb, Mn, Ni, Zn etc. It is being increased progressively in last years
due to unrestrained releases of industrial effluents. The most contaminated industries
are tanneries, mining, metal plating, painting, automobile manufacturing, printing,
petroleum refining, smelting, etc. In view of their perseverance in the atmosphere,
these metal ions incline to gather in living beings, thus, affecting numerous possible
Removal of Metal Ions Using Graphene Based Adsorbents 13

Table 4 The advantages and disadvantages of some graphene synthetic methods [54]
Route
Mechanical uses of
particularly sloping pyrolytic
graphite
CVD
Epitaxial growing on SiC
Reduction of exfoliated
graphite oxide
Liquid phase exfoliation
Carbon nanotubes unzipping
Advantage
Less defects, inexpensive,
excellent charge mobility,
great chemical constancy and
mechanical robustness
Mass manufacture, high
quality, big graphene layers
size
Big graphene layers size and
good quality
Large scale production & low
cost
Large scale production, low
cost
High quality, high yield &
potentially low cost
Disadvantage
Problem of large scale
manufacture & little yield
Expensive
High growth temperature and
costly method
Low purity, numerous
defects, electrical properties
and poor mechanical
Moderate quality, low yield
and many impurities
Moderate scalability

unpleasant effects on human and animals at approval levels. Presently, numerous

studies have been completed to measure metal removal ability of graphene and its
related materials (Table 5).
The graphene ability to pick up Co(II) and Fe(II) from water is described by
Chang and co-workers [59]. Graphene was prepared via ionic liquid assisted electro-
chemical phenomenon as per the procedure described by Liu and co-workers [60].
Co(II) and Fe(II) adsorption was inspected by batch mode. The graphene displayed
great sorption capabilities of 370.0 and 299.30 mg g−1 for Fe(II) and Co(II), corre-
spondingly. Wu and co-workers [61] tested the adsorption ability of graphene oxide
(GO) to remove Cu(II) in water. The finest sets for Cu(II) removal by GO in a batch
mode were 1.0 mg mL−1 dosage, 5.3 pH and 150.0 min interaction time. Copper(II)
equilibrium adsorption information fitted completely to Freundlich isotherm. GO
displayed great adsorption ability (117.5 mg g−1 ) for Copper(II) as per Langmuir
constants. The sorption of Copper(II) on GO was primarily accredited to electrostatic
attraction, outside ion exchange, and complexation as per equations given below:

Cu2+ + GO − COOH → GO − COO − Cu2+ + H+ (1)

 
Cu2+ + (GO − COOH)2 → GO − COO− 2 − Cu2+ + 2H+ (2)

Cu2+ + GO − OH → GO − O − Cu2+ + 2H+ (3)

Cu2+ + (GO − OH)2 → (GO − O−)2 − Cu2+ + 2H+ (4)

Table 5 The adsorption of heavy metal ions in water with graphene-based nanomaterials (data from Ref. 54 with permission)
14

Adsorbents Metal ions Concs. pHs Temp. (K) Contact Adsorption capacity References
times (h)
Graphene Pb(II) 40 mg L−1 4.0 303 15 22.42 mg g−1 [104]
Graphene Sb(III) 1–10 mg L−1 11.0 303 4 10.919 mg g−1 [71]
Graphene Pb(II) 40 mg L−1 4.0 303 15 35.46 mg g−1 [70]
Graphene Pb(II) 40 mg L−1 4.0 303 15 35.21 mg g−1 [104]
Graphene Fe(II) 20 mg L−1 8.0 – 24 299.3 mg g−1 [59]
Graphene Co(II) 20 mg L−1 8.0 – 24 370 mg g − 1 [59]
CTAB modified graphene Cr(VI) 20–100 mg L−1 2.0 293 1 21.57 mg g−1 [67]
Functionalized graphene Cd(II) – 6.2 – 4 73.42 mg g−1 [68]
(GNSPF6)
Functionalized graphene Pb(II) – 5.1 – 4 406.4 mg g−1 [68]
(GNSPF6)
Functionalized graphene Cd(II) – 6.2 – 4 30.05 mg g−1 [68]
(GNSC8P)
Functionalized graphene Pb(II) – 5.1 – 4 74.18 mg g−1 [68]
(GNSC8P)
GO Zn(II) – 5.6 – – 30.1 ± 2.5 mg g−1 [79]
GO Pb(II) 5–300 mg L−1 6.8 298 ± 2 24 367 mg g−1 [72]
(continued)
I. Ali et al.
Table 5 (continued)
Adsorbents Metal ions Concs. pHs Temp. (K) Contact Adsorption capacity References
times (h)
GO Pb(II) – 5.6 – – 35.6 ± 1.3 mg g−1 [79]
GO Cd(II) – 5.6 – – 14.9 ± 1.5 mg g−1 [79]
GO Pb(II) 5–300 mg L−1 7.0 ± 0.5 298 ± 5 24 692.66 mg g−1 [85]
GO Cu(II) 25–250 mg L−1 5.3 – 2.5 117.5 mg g−1 [61]
GO Zn(II) – 5.0 298 2 345 mg g−1 [64, 85]
GO Cu(II) – 5.0 298 2 294 mg g−1 [62]
GO Pb(II) – 5.0 298 2 1119 mg g−1 [62, 85]
GO Cd(II) – 5.0 298 2 530 mg g − 1 [62, 85]
GO Zn(II) 10–100 mg L−1 7.0 ± 0.1 293 – 246 mg g−1 [63]
Poly(amidoamine) modified Pb(II) 0.0193 mmol – Room temp. 24 0.0513 mmol g−1 [69]
GO L−1
Poly(amidoamine) modified Zn(II) 0.0193 mmol – Room temp. 24 0.2024 mmol g−1 [69]
Removal of Metal Ions Using Graphene Based Adsorbents

GO L−1
Poly(amidoamine) modified Cr(III) 0.0193 mmol – Room temp. 24 0.0798 mmol g−1 [69]
GO L−1
(continued)
15
Table 5 (continued)
16

Adsorbents Metal ions Concs. pHs Temp. (K) Contact Adsorption capacity References
times (h)
Poly(amidoamine) modified Fe(III) 0.0193 mmol – Room temp. 24 0.5312 mmol g−1 [69]
GO L−1
Poly(amidoamine) modified Cu(II) 0.0193 mmol – Room temp. 24 0.1368 mmol g − 1 [69]
GO L−1
FGO Cd(II) – 6.0 ± 0.1 303 – 106.3 mg g−1 [65]
FGO Pb(II) – 6.0 293 24 842 mg g−1 [65]
FGO Co(II) – 6.0 ± 0.1 303 – 68.2 mg g−1 [65]
Graphene/δ-MnO2 Cu(II) – 6.0 298 ± 2 2 1637.9 μmol g − 1 [91]
Graphene/δ-MnO2 Ni(II) 10–100 mg L−1 – 298 3 46.55 mg g−1 [90]
GO aerogel Cu(II) 50–75 mg L−1 6.3 283 0.5 17.73 mg g−1 [64]
EDTA modified GO Pb(II) 5–300 mg L−1 6.8 298 ± 2 24 525 mg g−1 [72]
Graphene/Fe Cr(VI) 25–125 mg L−1 4.25 293 4 162 mg g−1 [73]
Graphene/Mn2+ Fe3+ O2− As(III) 1–8 mg L−1 7.0 ± 0.1 300 ± 1 2.5 14.42 mg g−1 [104]
Graphene/Fe@Fe2O3@Si\S\O Cr(VI) 1g L−1 7.0 – – 1.03 mg g−1 [105]
(continued)
I. Ali et al.
Table 5 (continued)
Adsorbents Metal ions Concs. pHs Temp. (K) Contact Adsorption capacity References
times (h)
SiO2 /graphene Pb(II) 20 mg L − 1 6.0 298 1 113.6 mg g−1 [75]
Graphene/c-MWCNT Pb(II) 50 mg L−1 – Room temp. 120 104.9 mg g−1 [77]
Graphene/c-MWCNT Hg(II) 50 mg L−1 – Room temp. 120 93.3 mg g−1 [77]
Graphene/c-MWCNT Cu(II) 50 mg L−1 – Room temp. 120 33.8 mg g−1 [77]
Graphene/MWCNT Cu(II) 50 mg L−1 – Room temp. 120 9.8 mg g−1 [77]
Graphene/c-MWCNT Ag(II) 50 mg L−1 – Room temp. 120 64.0 mg g−1 [77]
Graphene/MWCNT Ag(II) 50 mg L−1 – Room temp. 120 46.0 mg g−1 [77]
Graphene/MWCNT Pb(II) 50 mg L−1 – Room temp. 120 44.5 mg g−1 [77]
Graphene/MWCNT Hg(II) 50 mg L−1 – Room temp. 120 75.6 mg g−1 [77]
Graphene/MgAl-layered Cr(VI) 50–250 mg L−1 2.0 – 24 183.82 mg g−1 [80]
double hydroxides As(V) 0.5–20 mg L−1 4.0–9.0 Room temp. 24 23.78 mg g−1 [76]
GO/ferric hydroxide
Removal of Metal Ions Using Graphene Based Adsorbents

GO–iron oxide Pb(II) – 6.5 ± 0.1 303 48 588.24 mg g−1 [103]

(continued)
17
Another random document with
no related content on Scribd:
As mentioned above, Ludwig has proved that the paxillae develop in
the life-history of the individual out of ordinary plates, the axis of the
paxilla representing the plate.

Order V. Forcipulata.
This order, which includes the most highly developed members of
the class Asteroidea, is at once distinguished by the possession of
forcipulate pedicellariae which, as we have seen, possess a well-
marked basal piece with which the two plates articulate. The
pedicellariae are consequently sharply marked off from the spinelets,
and no intermediate forms occur. The first conjoined adambulacrals,
which in other orders form the "teeth" or mouth-angles, do not here
project beyond the first pairs of ambulacral plates.

Fam. 1. Asteriidae.—Forcipulata in which the tube-feet are

apparently arranged in four rows. Aboral skeleton a loose reticulum.

The general features of the family Asteriidae have been explained in

the description of Asterias rubens (p. 432). There are five well-
marked species of the genus found on the British coasts. Of these A.
glacialis is found chiefly in the south-western parts of the English
Channel. It is a large Starfish of a purplish-grey colour, with large
spines surrounded by cushions of pedicellariae arranged in one or
two rows down each arm. A. muelleri resembles the foregoing
species, but is of much smaller size, and is further distinguished by
having straight pedicellariae in the neighbourhood of the ambulacral
groove only. It is found on the east coast of Scotland, and carries its
comparatively large eggs about with it until development is
completed. A. rubens is the commonest species, and is found on
both east and west coasts. Its colour is a bright orange, but varies to
almost a straw colour. It is at once distinguished from the foregoing
species by the spines of the dorsal surface, which are small and
numerous, an irregular line of somewhat larger ones being
sometimes seen down the centre of each arm. A. murrayi is a
peculiar species restricted to the west coast of Scotland and Ireland.
It has flattened arms, with vertical sides, and only three rows of small
spines on the dorsal surface. It is of a violet colour. A. hispida is also
a western species. It is a small Starfish with short stout arms; there
are no straight pedicellariae, and only a few sharp spines on the
dorsal surface.

On the eastern coast of North America there are several species of

Asterias, of which the most noteworthy is the 6-rayed A. polaris of
the Gulf of St. Lawrence. This species exhibits a marvellous range of
colour-variation, ranging from bluish-violet through purple to red and
straw-coloured. This variation seems to show that colour, as such, is
of no importance to the animal, but probably depends on some
compound of slightly varying composition which is being carried by
the amoebocytes towards the exterior. On the Pacific coast there is a
rich fauna of Starfish, among which we may mention as members of
this family Asterias ochracea, a large violet species, so strong that it
requires a severe wrench to detach it from the rock, and Pycnopodia
with twenty-two arms.

Fam. 2. Heliasteridae.—Forcipulata allied to the Asteriidae, but with

very numerous arms and double interradial septa. Heliaster.

Fam. 3. Zoroasteridae.—Forcipulata with the tube-feet in four rows

at the base of the arm, in two rows at the tip. Aboral skeleton of
almost contiguous plates bearing small spines or flattened scales.
Zoroaster, Pholidaster.

Fam. 4. Stichasteridae.—Forcipulata with the tube-feet in four rows.

Aboral skeleton of almost contiguous plates covered with granules.
Stichaster, Tarsaster.

The Stichasteridae and Zoroasteridae have acquired a superficial

resemblance to some of the long-armed Valvata, from which they are
at once distinguished by their pedicellariae. It would be exceedingly
interesting if more could be found out concerning the normal
environment of these animals; it might then be possible to discover
what is the cause of the assumption of this uniform mail of plates.

Fam. 5. Pedicellasteridae.—Forcipulata with two rows of tube-feet.

The aboral skeleton bears projecting spines surrounded by cushions
of straight pedicellariae. Pedicellaster, Coronaster.

Fam. 6. Brisingidae.—Forcipulata with numerous arms and only

two rows of tube-feet. Aboral skeleton largely rudimentary and
confined to the base of the arms. The small blunt spines are
contained in sacs of skin covered with pedicellariae.

The Brisingidae, including Brisinga and Odinia, are a very

remarkable family, chiefly on account of the smallness of the disc
and of the extraordinary length of the arms. The arms have what we
must consider to have been the primitive arrangement, since there is
no lateral adhesion between them, and interbrachial septa are
consequently entirely absent. The reduction of the skeleton is a very
marked peculiarity and, like the tendency to the reduction of the
skeleton of deep-sea fish, may stand in some relation to the great
pressure under which the animals live.

Fig. 205.—Aboral view of Odinia. × ⅔. (After Perrier.)

 Fossil Asteroidea.
The Asteroidea occur somewhat plentifully as fossils. In the Lower
Jurassic Asterias, Astropecten, Luidia, Solaster, and Goniaster have
already made their appearance. In the Cretaceous Pentaceros
appears. In the older rocks occur a number of forms of different
character from any now existing. Of these Aspidosoma (Fig. 206),
with short lancet-shaped arms sharply distinguished from the disc
and continued along its under surface, seems to be intermediate
between Asteroidea and Ophiuroidea. The skeleton of the arm is
composed of alternating ambulacral ossicles bordered by
adambulacral ossicles, which are at the same time marginals and
sharply distinguished from the marginals forming the edge of the
disc. Palaeaster, on the other hand, is a true Asteroid; there are
marginals distinct from the adambulacrals, but the disc is reduced to
its smallest dimensions, there being only one plate on the ventral
side of each interradius. There are a number of genera
(Palaeocoma, for instance) with a large disc and very short arms and
very shallow ambulacral grooves; all have alternating ambulacral
plates. Some genera appear to have had the madreporite on the
ventral surface of an interradius. On the other hand, in the Devonian
occurs Xenaster, which was a fairly normal Asteroid, with pavement-
like marginals, deep ambulacral grooves, and broad arms.

Fig. 206.—Three views of Aspidosoma, a fossil Asteroid. A, oral view; B, aboral

view of one arm; C, enlarged view of a portion of the ambulacral groove.
adamb, Adambulacral plate; amb, ambulacral plate; marg, marginal plate;
pod, aperture for extension of tube-foot.

Thus it will be seen that already in Jurassic times the three orders,
Forcipulata, Paxillosa, and Spinulosa were differentiated from each
other, but how these are related to the older Palaeozoic forms it is at
present impossible to say.

CHAPTER XVII

ECHINODERMATA (CONTINUED): OPHIUROIDEA = BRITTLE STARS

CLASS II. OPHIUROIDEA

The second class of Eleutherozoa are familiarly known as "Brittle
Stars," on account of their tendency, when seized, to escape by
snapping off an arm, although this habit is by no means confined to
them, but is shared in a marked degree by many Asteroidea, such as
Luidia, for instance. Like the Asteroidea, they are "starfish," that is to
say, they consist of a disc and of arms radiating from it; but the
scientific name Ophiuroidea really expresses the great dominating
feature of their organisation. Literally it signifies "Snake-tail" (ὄφις,
snake; οὐρά, tail), and thus vividly describes the wriggling, writhing
movements of the long thin arms, by means of which the Ophiuroid
climbs in and out of the crevices between the stones and gravel in
which it lives. This feature, viz. the effecting of movement by means
of muscular jerks of the arms, instead of by the slow protrusion and
retraction of the tube-feet, is the key to the understanding of most of
the points wherein the Brittle Stars differ from the true Starfish.

Asteroidea and Ophiuroidea agree in the common ground-plan of

their structure, that is, they both possess arms; but the most obvious
difference in their outer appearance is that whereas in Asteroidea
the arms merge insensibly into the disc, in Ophiuroidea the disc is
circular in outline and is sharply marked off from the arms. Closer
inspection shows that in the Ophiuroid the arms are continued
inwards along grooves, which run on the under surface of the disc,
and that they finally coalesce to form a buccal framework
surrounding the mouth. In the very young Ophiuroid the arms melt
into a small central disc, as in the Starfish, but the disc of the adult is
made up of a series of interradial dorsal outgrowths which meet one
another above the arms.

Fig. 207.—Aboral view of Ophiothrix fragilis. × 1. r, Radial plate.

Fig. 208.—Oral view of the disc of Ophiothrix fragilis. g.b, Opening of the genital
bursa; m.p, madreporite; pod, podia; t.p, tooth-papillae; v.p, ventral plates of
the arms. × 1.

One of the commonest British Ophiuroids is Ophiothrix fragilis (Figs.

207, 208), which is found in swarms in shallow water off the west
coast of England and Scotland. We may therefore select it as the
type, and, since the arm is the most characteristic organ of an
Ophiuroid, we may commence by studying it. Speaking generally, an
Ophiuroid either drags itself forward by two arms and pushes itself
by the other three (Fig. 207),[458] or else it drags itself by one and
pushes with the other four (Fig. 217). The arms during this process
are bent into characteristic curves, by the straightening of which in
the posterior arms the animal is pushed onwards, whilst the
intensification of these curves in the anterior arms causes the animal
to be dragged forwards. The grip of the arm on the substratum is
chiefly in the distal portion of the curve. The alteration of the
curvature is due to the contraction of the muscles on one side of the
arms. There is no ambulacral groove such as is found on the under
side of the arms of all Asteroidea, for the arm is completely
ensheathed by four series of plates, an upper row of dorsal plates,
an under row of ventral plates, and two lateral rows of lateral plates.
The last named, which in all probability correspond to the
adambulacral plates of Starfish, bear each a transverse row of seven
spines with roughened surfaces; these enable the animal to get a
grip on the substratum over which it moves. The podia in
Ophiuroidea are termed "tentacles"; they are totally devoid of
suckers, being simple conical papillae used as sense-organs, and
are of little, if any, service in locomotion. They issue from openings
called "tentacle-pores" situated between the edges of the ventral and
lateral plates, guarded each by a valve-like plate called the "tentacle-
scale." In Ophiothrix they are covered with sense-organs, each
consisting of a hillock-like elevation of the ectoderm, in which are
cells carrying long stiff sense-hairs. In most Ophiuroids such organs
are not present, though abundant scattered sense-cells occur, and
the outer surface of the tube-feet and the lining of certain pockets
called "genital bursae" (Fig. 208, g.b) are the only portions of the
surface where the ectoderm persists. Everywhere else, although
present in the young, it disappears, leaving as remnants a few nuclei
here and there attached to the under side of the cuticle.[459]
 Fig. 209.—Diagrammatic transverse section of the arm of an Ophiuroid. coe,
Dorsal coelomic canal; ect, ectoderm covering the tube-foot; ep, epineural
canal; gang.p, pedal ganglion; L, nerve-cord; musc, longitudinal muscles
attaching one vertebra to the next; nerv.rad, radial nerve-cord; perih, radial
perihaemal canal; pod, podium (tube-foot); sp, lateral spines; w.v.r, radial
water-vascular canal.

The greater part of the section of the arm is occupied by a disc-like

ossicle called the "vertebra." Each vertebra articulates with its
predecessor and successor by cup-and-ball joints, and it is
connected to each of them by four powerful longitudinal muscles.
Above, its outline is notched by a groove, in which lies an extension
of the coelom of the disc (Fig. 209, coe), but contains no outgrowth
of the alimentary canal, as is the case in Asteroidea. The vertebra is
also grooved below, and in this lower groove are contained the radial
water-vascular canal (Fig. 209, w.v.r), and below it perihaemal
canals as in Asteroidea; below this again the radial nerve-cord (L),
and beneath this again a canal called the "epineural canal" (ep),
which represents the missing ambulacral groove. This canal in the
very young Brittle Star is an open groove, but becomes closed by the
approximation of its edges. The vertebra, which has a double origin,
represents a pair of fused ambulacral ossicles. In Ophiohelus these
are only slightly adherent to one another (Fig. 216).
 Fig. 210.—Proximal and distal views of the three types of vertebra found
amongst Ophiuroidea. A, Ophioteresis, a type of the Streptophiurae (after
Bell), × 24; B, Astroschema, a type of the Cladophiurae (after Lyman), × 10;
C, Ophiarachna, a type of the Zygophiurae (after Ludwig), × 3. The upper
figure in all cases represents the distal aspect, the lower the proximal
aspect of the vertebra. v.g, Ventral groove.

When the surface of a vertebra is examined it is found that it can be

divided into a thin border, to which are attached the four muscles by
which it is connected to its successor and predecessor, and a central
portion, on which are situated the knobs and pits, by means of which
it articulates with the next vertebra.

The simultaneous contraction of the two upper muscles causes the

arm to bend upwards. The contraction of the two lower bend it
downwards, whilst a sideward movement is effected by the
contraction of the upper and lower muscle of the same side. On the
proximal surface of the central portion of the vertebra there is a
central knob and two ventro-lateral knobs, a median ventral pit and
two dorso-lateral pits, and on the distal surface there are pits
corresponding to the knobs on the proximal side and vice versa (Fig.
210, C). These knobs and pits restrict the movement of one vertebra
on the next, so that although the arms can undergo an unlimited
amount of flexion from side to side, they cannot be rolled up in the
vertical plane. When the under surface of the vertebra is examined
there is seen on each side of the central groove two round holes, a
distal and a proximal. The distal pair are for the passage of the
canals connecting the radial water-vessel with the tentacles, these
canals traversing the substance of the vertebra for a part of their
course; the proximal pair are for nerves going to the longitudinal
muscles, which likewise perforate part of the ventral border of the
vertebra.

In order to understand the anomalous circumstance that the canals

going to the tentacles actually perforate the vertebrae, it must be
clearly borne in mind that the basis of the body-wall in all
Echinoderms is a mass of jelly with amoebocytes in it, to which we
must assign the power of secreting carbonate of lime, and all we
have to assume in the case of Ophiuroids is that calcification spread
outwards from the original ambulacral ossicles into the surrounding
jelly, enclosing any organs that happened to traverse it.

When the ossicles of the arm are followed inwards towards the
mouth, they are seen to undergo a profound modification, so as to
form, by union with the corresponding ossicles of adjacent arms, a
structure called the mouth-frame. The general character of this
modification is similar to that affecting the first ambulacral and
adambulacral ossicles in the arms of an Asteroid, but in the
Ophiuroid the change is much more profound. The first apparent
vertebra consists of two separated halves, and each is fused with the
first adambulacral (lateral) plate, which in turn is firmly united with
the corresponding plate in the adjoining arm. Thus is formed the
"jaw," as the projection is called. The extensions of the mouth-cavity
between adjacent jaws are termed "mouth-angles." To the apex of
each jaw is attached a plate bearing a vertical row of seven short
blunt spines called "teeth" (Fig. 212, p). The plate is called the "torus
angularis" (Fig. 211, T), and on its ventral edge there is a tuft of
spines which are termed "tooth-papillae" (Fig. 208, t.p). On the upper
aspect of the jaw are a pair of plates termed "peristomial plates."
These discs—of which there are two in each radius, one on each jaw
which flanks the radius—possibly represent the separated halves of
the first vertebra, the apparent first vertebra being really the second.
On the flank of the jaw there is dorsally a groove for the water-
vascular ring and nerve-ring (Fig. 212, n.r), and beneath this a
groove for the first tentacle and a pore for the second, both of which
spring directly from the ring-canal; below these, in most Ophiuroidea,
but not in Ophiothrix, there is a row of blunt triangular spines called
"mouth-papillae" (Fig. 212, p1).

Fig. 211.—Diagrams to show the modification of the ambulacral and

adambulacral ossicles to form the armature of the mouth. A, Asteroid; B,
Ophiuroid. A1-A4, the first four ambulacra ossicles; Ad1-Ad4, the first four
adambulacral ossicles; J1, the first plate of the interradius (in the Ophiuroid
the scutum buccale); P, the spines borne by the jaw (in the Ophiuroid the
teeth); T, the torus angularis; W, the water-vascular ring; Wr, the radial
water-vessel; I, II, the first two pairs of tube-feet. (After Ludwig.)

The words "jaw" and "tooth" are misleading. There is no evidence

that the jaws of a Brittle Star are ever used for crushing food, but by
means of the muscles attaching them to the first complete vertebra
in the arm they can be rotated downwards so as greatly to enlarge
the mouth, and again rotated upwards and inwards, when they form
an excellent strainer to prevent the entrance of coarse particles. To
permit this extensive movement the articulatory facets on the
proximal surface of the first vertebra have been much modified; the
median knob and pit have disappeared, and the dorso-lateral pits are
raised on to the surface of processes, so that there are in all four
processes, two of which articulate with one half of a jaw.
 Fig. 212.—Lateral view of mouth-frame of Ophiarachna incrassata. × 4. A1?,
peristomial plate, possibly the half of the first vertebra; A2, the half of the
second vertebra; A3, the third vertebra; F1, pores for pair of tentacles; gen,
genital scale lying beside opening of genital bursa; musc, longitudinal
muscles connecting vertebrae; n.r, groove for nerve-ring; p, tooth; p1,
mouth-papilla; t, torus angularis. (After Ludwig.)

The mouth can be narrowed and the jaws forced inwards towards
the centre by the simultaneous contraction of five muscles (musc. tr,
Fig. 213) each, which unite the two halves of a jaw.

Turning now to the skeleton of the disc, we notice that dorsally it

consists of a closely-fitting mosaic of small plates, which are usually
concealed from view by a covering of minute spines. Opposite the
insertion of each arm there are, however, a pair of large triangular
plates ("radials"), which extend outwards to the periphery and
strengthen it, much as the ribs do in an umbrella. These radial plates
are always exposed, in Ophiothrix, even when the rest of the dorsal
plates are concealed by spines. On the under surface there is a
similar plating; but adjoining the jaws are five large, more or less
rhomboidal, plates termed "scuta buccalia" (Fig. 211, J1), on one of
which open the few madreporic pores which the animal possesses.
Attached to the sides of the scuta buccalia are the "lateral mouth
shields," which are in fact the adambulacral plates belonging to the
second pair of ambulacral plates which form the main mass of the
jaws. Further out, on the under side of the disc, there is, on each
side of each arm, a long narrow slit—the opening of the genital bursa
(Fig. 208, g.b), so that there are ten genital bursae. The "genital
bursa" (Fig. 214) is a sac lined by ciliated ectoderm projecting into
the interior of the disc. It is called genital because the openings of
the genital organs are situated on its surface; its main function,
however, is respiratory, the cilia bringing about a constant inward
current of fresh sea-water, the oxygen contained in which diffuses
through the thin wall of the sac into the coelomic fluid. The opening
of the bursa is strengthened on its radial side by a rod-like ossicle,
the "genital plate," and on its interradial side by an ossicle called the
"genital scale" (Fig. 212, gen), and in Ophiothrix the outer end of the
radial plate articulates with the outer end of the genital plate.
Muscles connect the two plates running on either side of the
articulation.

Observations on Ophiothrix[460] show that in this species at any rate

the radial plates can be raised or lowered. When they are raised the
centre of the disc is lifted into a cone and water is sucked into the
genital bursae, whereas when they are lowered the bursae are
compressed and water is expelled. This forced respiration appears
to come into play when the supply of oxygen is getting scanty.

The alimentary canal of Ophiothrix is a simple flattened sac (Fig.

213). It is devoid of an anus and cannot be everted through the
mouth. There is a horizontal pouch given off into each interradial
lobe of the disc. The sac is attached to the dorsal wall of the coelom
by numerous mesenteries, fibrous cords traversing the coelomic
cavity and clothed on the outer side by coelomic epithelium. To the
mouth-frame it is attached by a circular membrane, which we have
reason for believing is a functionless remnant of the retractor
muscles of the stomach of Asteroidea. In the young Asteroid there is
a similar sheet of membrane, which later becomes resolved into the
ten retractor bands.

The simple structure of the alimentary canal appears to be correlated

with the exceedingly simple character of the food. Ophiothrix feeds
on the most superficial layer of mud at the bottom of the sea. This
deposit consists partly of microscopic Algae and partly of decaying
organic matter, and is much more easily disposed of than the living
animals on which the Starfish preys. The food is shovelled into the
mouth by the first two or "buccal" pairs of tube-feet in each ray.

Fig. 213.—Longitudinal section through the disc of a young Ophiuroid passing

along one arm and the middle of the opposite interradius. (Diagrammatised
from an actual section of Amphiura squamata.) ab, Aboral sinus (dorsal in
the radius, ventral in the interradius); ax, axial sinus; coe, dorsal coelomic
canal of the arm; ep, epineural canal; gang.rad, ganglion of the radial nerve;
gen.r, genital rachis contained in the aboral sinus; gen.st, genital stolon;
mp, madreporic pore; musc.long, longitudinal muscle of the arm; musc.tr,
transverse muscle uniting the two halves of each jaw; mv, madreporic
vesicle; nerv.r, nerve-ring; p.c, pore-canal; perih, perihaemal canal; vert,
vertebra; w.vr, radial water-vessel.

The water-vascular system has undergone a most interesting set

of modifications, which can be explained by noticing the fact that the
tube-feet have almost, if not quite, lost their locomotor function and
are now used as tactile organs. The ampulla, or swollen inner end of
the tube-foot, has disappeared, and the upper end of the organ is
directly connected with the radial canal by means of a curved canal,
which traverses the outermost flange of the vertebra, appearing on
its surface in a groove on the outer side of the dorsal lateral knob on
the distal side of the ossicle. As in Asteroidea there are valves,
which regulate the entrance of fluid into the tube-foot. The stone-
canal is a curved tube of simple circular section and excessively
narrow bore which extends from the water-vascular ring downwards
to the madreporite (Fig. 213, mp) situated on one of the scuta
buccalia. The madreporite, in Ophiothrix as in most Brittle Stars, is
an exceedingly rudimentary structure, consisting of one or two pores
leading into as many pore-canals. From each interradius, except that
in which the stone-canal lies, a large Polian vesicle hangs down from
the water-vascular ring into the coelom.
We saw that in the Asteroid the ampulla was used like the bulb of a
pipette to force the fluid in the tube-foot down into the tip, so as to
press the sucker against the substratum. But when the tube-foot is
used as a sense-organ, a few circular fibres around its upper end
suffice to bring about all the extension that is needed. Since the
extension is no longer a very vigorous act, the loss of fluid by
transudation has probably been rendered insignificant, and hence
the stone-canal and madreporite, whose function it is to repair the
loss, have been reduced in size. The curious ventral curvature of the
stone-canal is, however, due to another cause. In the very young
Ophiuroid the madreporite is on the edge of the disc, and the stone-
canal extends horizontally outwards; and in some Asteroidea there is
a similar outward direction in its course. As development proceeds
the dorsal interradial areas of the disc of the young Ophiuroid grow
out into lobes, building up the conspicuous adult disc and forcing the
madreporite, and with it the stone-canal, downwards towards the
ventral surface.

The pores of the madreporite in Ophiothrix, like some of those in the

Asteroid, open not directly into the stone-canal but into the axial
sinus (Fig. 213, ax). This is a large ovoid sac, lined with thin
epithelium, lying between the stone-canal and the mouth-frame,
since of course it has shared in the ventral rotation of the stone-
canal. Its open connexion with the stone-canal was easily
recognised by Ludwig, who termed it, on this account, the "ampulla."
[461] The name "axial sinus" was bestowed mistakenly on another
cavity, which will be mentioned in connexion with the genital organs.

The radial perihaemal spaces of the arms open into a "perihaemal

ring" representing the outer perihaemal ring of Asteroids; but the
axial sinus does not have any such extension as constitutes the
inner perihaemal ring in Starfish. So-called oral circular and radial
blood strands are to be found in similar positions to the
corresponding structures in Asteroidea.
The nervous system might have been expected to have become
very much modified, since the activities of the Brittle Stars are so
different from those of the Starfish. It is indeed a universal rule in the
Animal Kingdom that, concomitantly with the increase in size and
activity of a muscle, there is a corresponding increase in the number
of ganglion-cells which control it. An accurate radial section of an
arm shows that there is, corresponding to the interspaces between
the two vertebrae, a ganglionic swelling of the nerve-cord. As in
Asteroids, there are not only ectodermic ganglion-cells on the under
surface of the cord abutting on the epineural canal, but also coelomic
ganglion-cells derived from the floor of the radial perihaemal canal.
Both these categories of cells are largely increased in number in the
ganglion. From the dorsal-cells arise a pair of large nerves which
pass directly up and supply the great intervertebral muscles. From
the interspace between the ganglia a direct prolongation of the
ventral part of the nerve-cord, the so-called pedal nerve, extends out
along the side of the tentacle, as in Asteroids. In Ophiuroids it swells
out into a ganglion, completely surrounding the tentacle and giving
off nerves to the surfaces of the arm which terminate in the cuticle.

There is a large ganglion where the radial cord joins the nerve-ring,
and, owing to the more specialised condition of the nervous system,
a severed arm in an Ophiuroid is much more helpless than an arm of
an Asteroid. It will not carry out "escape movements," and is for a
long time rigid under the shock of section; at last it simply gives
reflex movements on stimulation.

Preyer[462] endeavoured to test the "intelligence" of Ophiuroids by

observing how they would adapt themselves to circumstances which
it might be fairly assumed they had never encountered in their
ordinary experience. To this end he passed over the arm of a
specimen a piece of indiarubber tubing, which clung to it tightly. He
found that the animal first tried walking off, pressing the encumbered
arm against the ground, so that the piece of tubing was rubbed off. It
was then replaced more tightly than before; the animal, having tried
the first method without result, waved the arm to and fro in the water
till the rubber floated off. In a third experiment the animal held the
rubber against the ground by a neighbouring arm, and drew the
encumbered arm out. When the rubber was replaced a fourth time,
the animal kicked it off by alternately pressing neighbouring arms
against it. Finally, when the rubber was put on so firmly that all the
above-mentioned methods failed, the arm was broken off. Preyer
concludes from this that Ophiuroids have a high degree of
intelligence; but this may be doubted, and the reader is referred to
the account of Uexküll's experiments given in the next chapter.
There is, however, no doubt at all that Ophiuroidea are by far the
most active of all Echinoderms, and one would naturally correlate
this with higher psychic development.

The radial nerve ends in a terminal tentacle sheltered by a median

plate at the end of the arm; but eyes, such as are found in Asteroids,
are wanting, and the animal does not appear to be sensitive to light.

The reproductive system in Ophiuroids consists of a genital stolon

giving rise at its distal end to a genital rachis, which extends in a
circular course round the disc, ensheathed in an "aboral sinus" (Fig.
213, ab) and swelling out so as to form the gonads (testes or
ovaries), where it passes over the inner side of the genital bursae.
The genital stolon (Fig. 213, gen.st) is a compact ovoid organ, often
termed on account of its shape the "ovoid gland." It is situated close
to the stone-canal, and, as in Starfish, it indents the outer wall of the
axial sinus; but, unlike the stolon of the Asteroid, it is separated from
the general coelom by a space, of which it forms the inner wall, but
whose outer wall is formed by a sheet of membrane. This cavity
must be carefully distinguished from the axial sinus of Asteroidea, to
which it was supposed at one time to correspond; it is really formed
by a pocket-like ingrowth of the general coelom into the septum
dividing it from the axial sinus. The cells forming the inner side of this
pocket form the primitive germ-cells, which constitute the main mass
of the ovoid gland; those of the outer side remain thin. The cavity of
the ingrowth is shut off from the general coelom, but persists
throughout life. In Asteroids a similar ingrowth takes place, but both
walls thicken and become converted into germ cells, and the cavity
disappears, and, as in Asteroidea, a considerable number of the
germ-cells in the stolon degenerate.

Fig. 214.—Diagram of a tangential section through the edge of the disc of an

Ophiuroid to show the relations of the disc, arm, and genital bursae. ep,
Epineural canal; musc, longitudinal muscle of the arm; nerv.rad, radial nerve
cord; ov, ovary; perih, radial perihaemal canal; w.v.r, radial water-vessel.

The genital rachis (Fig. 213, gen.r) is an outgrowth of the distal end
of the genital stolon, which extends in a complete circle round the
disc. The rachis does not, however, lie everywhere in the same
plane, but by its undulating course bears witness to the distortion
which the disc has undergone. In the radii it is, as in the Asteroid,
dorsal; but in the interradii it is ventral, this ventral portion having,
like stone-canal and axial sinus, been carried down by the
preponderant growth of the dorsal parts of the disc. It is everywhere
ensheathed by the aboral sinus, which, as in Asteroids, is an
outgrowth of the coelom. The rachis is embedded in a strand of
modified connective tissue, to which we may (as in the case of
Asterias) apply the name "aboral blood-ring." Both on the central and
peripheral sides of this sinus are vertical muscles connecting the
genital and the radial plates, which bring about the respiratory
movements already referred to. Just above the madreporite, at the
end of the genital stolon, is a small, completely closed space, which
by its position corresponds with the madreporic vesicle of Asteroids
and represents the right hydrocoel (Fig. 213, mv). As the rachis
passes over the genital bursa it gives off branches, which swell up to
form the genital organs. In Ophiothrix there is one such organ on
each side of each bursa, but in other genera (cf. Ophiarachna) a
large number of small ones. The genital products are shed into the
water through the bursae.
 Classification of Ophiuroidea.
Before proceeding to study the classification of Brittle Stars, it is
necessary to give some account of the range of structure met with in
the group.

Number of Radii.—The number of arms is rarely increased, and

hardly ever exceeds six; a few species (each an isolated one in its
genus) have six arms, and in one case (Ophiactis virens), at any
rate, this is associated with the power of transverse fission. In many
Cladophiurae the arms fork repeatedly, so that although there are
only five radii, there is quite a crowd of terminal branches.

Vertebrae.—The vertebrae differ in the manner in which they

articulate with one another. In Ophiothrix fragilis taken as the type,
which in this respect resembles the vast majority of species
(Zygophiurae), the knobs and pits on the faces of the vertebrae
prevent the arms from being coiled in the vertical plane. In
Ophioteresis (Fig. 210, A) and some allied genera (Streptophiurae)
the knobs are almost obsolete, and the arms are free to coil in the
vertical plane; whilst in Gorgonocephalus and Astrophyton
(Cladophiurae) the arms are repeatedly branched and the vertebrae
have saddle-shaped articulating surfaces, so that they have quite a
snake-like capacity for coiling themselves round external objects. In
Ophiohelus (Fig. 216) each vertebra consists of two rod-like plates
placed parallel with the long axis of the arm and fused at both ends,
but divergent in the middle, leaving a hole between them.

Covering Plates of the Arms.—The upper arm-plates are the most

variable. They may be surrounded by small supplementary plates
(Ophiopholis) or double (Ophioteresis). In all (?) Cladophiurae and
most Streptophiurae they are absent, being replaced by minute
calcareous granules. Under arm-plates are absent in Ophioteresis
and in the distal portion of the arms in many Cladophiurae. Side arm-
plates are constantly present, and in most Cladophiurae meet in the
middle line below.
Arm-Spines.—The spines borne by the lateral covering plates of the
arms vary greatly in character. In Ophiura and its allies they are short
and smooth, and are borne by the hinder edge of the arm and
directed backwards; but in the larger number of genera they are
borne nearer the centre of the plate, and are directed outwards at
right angles to the arm. They may be covered by small asperities, as
in Ophiothrix (Fig. 215, C), when they are said to be rough; or these
asperities may become secondary spines, as in Ophiacantha (Fig.
215, B), when they are said to be thorny. In Ophiopteron all the
spines borne by a single plate are united by a web of skin so as to
constitute a swimming organ. The small plates guarding the ends of
the tentacles (tentacle-scales) may be absent, or more rarely double.
In Cladophiurae there is a regular transition from tentacle-scale to
arm-spine; the tentacle-scale being merely the smallest of the series
of lateral spines.

True pedicellariae are unknown amongst Ophiuroidea, since there

is no longer a soft ectoderm to protect, but in some cases, as for
instance in Ophiohelus, small hooks movable on a basal piece
attached to the arms are found which may represent the vestiges of
such organs (Fig. 216). Similar hooks are found in the young
Ophiothrix fragilis just after metamorphosis and in all Cladophiurae,
replacing in the latter case the arm-spines in the distal portion of the
arm.

Fig. 215.—Three types of mouth-frame found in Zygophiurae. A, Ophioscolex, ×

10; B, Ophiacantha, × 6; C, Ophiothrix, × 6. (After Lyman.)