Enhanced adsorption of bromate from

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mesoporous Mg-Al layered double
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 Journal of Hazardous Materials 334 (2017) 212–222

Contents lists available at ScienceDirect

Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Enhanced adsorption of bromate from aqueous solutions on ordered

mesoporous Mg-Al layered double hydroxides (LDHs)
Huashun Ji 1 , Wenhao Wu 1 , Feihu Li ∗ , Xiaoxue Yu, Jingjing Fu, Luyao Jia
CICAEET Center, AEMPC Lab, School of Environmental Science and Engineering, Nanjing University of Information Science and Technology, 219 Ningliu
Road, Nanjing 210044, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

• A facial method for preparation of

ordered mesoporous Mg-Al LDH was
presented.
• The mesoporous Mg-Al LDH has a
high surface area (126 m2 g−1 ).
• The mesoporous Mg-Al LDH shows a
high adsorption capacity for bromate
uptake.
• Bromate adsorption mechanism
involves both anion-exchange and
reconstruction.

a r t i c l e i n f o a b s t r a c t

Article history: An ordered mesoporous Mg-Al layered double hydroxide (meso-LDH350) with a fairly high Brunauer-
Received 28 December 2016 Emmett-Teller (BET) surface area (126 m2 g−1 ) has been facilely synthesized and then evaluated for the
Received in revised form 3 April 2017 adsorptive removal of bromate from aqueous solutions. Adsorbents were characterized by a variety of
Accepted 5 April 2017
techniques (e.g., XRD, FTIR, SEM, TG-DSC, N2 physisorption, XPS, etc.). The adsorption studies indicated
Available online 6 April 2017
that the presence of background electrolytes and competitive anions can obviously repress the uptake
of bromate on LDHs. The adsorption isotherms agree well with the Langmuir model, giving a maxi-
Keywords:
mum adsorption capacity of 59.34 mg g−1 (pH 7.5, 10 ◦ C) for meso-LDH350, which is much higher than
Bromate
Layered double hydroxides
other LDH-type adsorbents reported in literature. The adsorption kinetic data can be well fitted with the
Mesoporous pseudo-second-order rate model. Based on the macroscopic and microscopic studies, bromate adsorp-
Anion-exchange tion on meso-LDH350 was associated with two mechanisms: the reconstruction of the layered structures
Reconstruction of meso-LDH350 and the anion-exchange between bromate and the intercalated anions.
© 2017 Published by Elsevier B.V.

1. Introduction

Bromate (BrO3 − ) is an oxyhalide that was generally formed as

∗ Corresponding author. one of typical disinfection by-products (DBPs) during the ozonation
E-mail address: favorlee@163.com (F. Li). of bromide-containing water [1]. Bromate has potential carcino-
1
These authors contributed equally to this work.

http://dx.doi.org/10.1016/j.jhazmat.2017.04.014
0304-3894/© 2017 Published by Elsevier B.V.
 H. Ji et al. / Journal of Hazardous Materials 334 (2017) 212–222
genic properties to induce renal cell tumors, thus increasing the
health risks of both humankind and animals [2]. U.S. EPA (1998)
and the Ministry of Health of China (2006) had strictly established
a maximum contaminant level (MLC) of 10 ␮g L−1 for bromate in
drinking water. Efficient removal of bromate from drinking water
is therefore of particular significance with respect to reducing bod-
ies exposure to BrO3 − -contaminated water. Currently, it remains a
big challenge to remove bromate efficiently from aqueous solutions
because bromate is highly soluble and stable in water. A wide vari-
ety of techniques have been developed to sequester bromate from
surface waters, including activated carbon adsorption [3], anion-
exchange [4–7], biodegradation [8], zero-valent iron reduction [9],
catalytic hydrogenation reduction [10] and photocatalytic reduc-
tion [11]. Of these technologies, adsorption or anion-exchange with
inorganic materials, such as layered double hydroxides (LDHs), has
attracted intensive attention due to high effectiveness and low cost
[12].
LDHs are composed of stacks of positively-charged, mixed
metal hydroxide layers between which are sandwiched of water
molecules and various anionic species that are exchangeable with
other aqueous anions in the bulk solution, allowing LDHs to be
one of the most efficient anion-exchangers for sequestration of
toxic anions [13]. As summarized by Goh et al. [12], LDHs have
been widely used to adsorb a wide range of anions from water,
which consequently allows them to be an alternative adsorbent or
anion-exchanger to scavenge bromate in aqueous solution [4–7].
Chitrakar had examined the adsorption of bromate on both Fe(II)-
Al LDH (Cl) and Fe(II)-Al LDH (SO4 ) and found that bromate would
be reduced by structural Fe(II) into bromide, resulting in collapse
of the layered structure of LDHs [14,15]. To avoid the structural
collapse of LDHs during the removal of bromate, nonferrous LDHs
such as Mg-Al LDH [4–7], and Zn-Al LDH [16–18] are preferred to
be employed.
It is obvious that the anion-exchange capacity of LDHs is cor-
related to the anions electrostatically attached on the exchanging
sites in the interlayers of LDHs [19]. Besides, surface adsorption
on the specific adsorption sites also played a crucial role in anions
uptake by LDHs with well-defined pores [20]. How to increase the
density of binding sites in LDHs for enhanced uptake of toxic anions
is still an open question. Recently, it was reported that layered
Mg-Al hydrous oxides (an analog of LDHs) with well-developed
mesopores have a high adsorption capacity and affinity towards
arsenate species and other toxic anions (e.g., fluoride, bromate,
selenate, etc.) [5]. Is it possible to introduce mesopores into LDHs
structure for creating more binding sites for toxic anions (e.g., bro-
mate) clean-up? This question is the initial motivation of current
work. Mesoporous metal and bimetallic oxides and oxyhydrox-
ides have been, in fact, extensively prepared by using a number of
surfactant templates (e.g., cationic, anionic, neutral block copoly-
mers) over the last two decades [21–24]. In the case of preparation
of mesoporous and/or mesostructured Mg-Al LDHs, neutral block
®
copolymers (e.g., Pluronic F-127 or P-123) was more preferable
than anionic surfactants since the latter is more likely to intercalate
into LDHs as guest anions [25].
In this study, a facile method combining fast co-precipitation
and calcination for the synthesis of mesoporous Mg-Al LDH with
high adsorption capacity for bromate was presented. The structural
properties of mesoporous LDH and its non-mesoporous counter-
parts were well characterized prior to a series of batch adsorption
experiments for bromate uptake. In terms of the results of both
batch experiments and molecular spectroscopies, the adsorption
mechanisms were also proposed.
213
2. Experimental section
2.1. Chemicals
All chemicals were of A.R. grade and used without further purifi-
cation. Magnesium nitrate hexahydrate (Mg(NO3 )2 ·6H2 O, 99%) and
aluminum nitrate nonahydrate (Al(NO3 )3 ·9H2 O, 98%) were pur-
chased from Sinopharm Chemical Reagent Co., Ltd. (Shanghai,
China). Pluronic F127 was obtained from Sigma-Aldrich Co. (Shang-
hai, China). Milli-Q ultrapure (18.2 M-cm) water was used to
prepare solutions. Bromate stock solution (0.1 M) was prepared by
dissolving certain amount of G.R. grade sodium bromate (NaBrO3 ,
Sinopharm Chemical) with ultrapure water and stored in refriger-
ator (4 ◦ C).
2.2. Preparation of mesoporous LDHs
Mesoporous Mg-Al LDH was prepared by a modified co-
precipitation method [26] and followed by calcination. Briefly,
2.4 g of the F127 was dissolved with 120 mL of deionized water
under vigorous stirring in a waterbath (60 ◦ C). Then, a mixture
of Mg(NO3 )2 ·6H2 O (12.3 g, 48 mmol) and Al(NO3 )3 ·9H2 O (9.02 g,
24 mmol) was added into the above solution and stirring until
fully dissolved. The mixture was then co-precipitated by drop-
wise addition of NaOH solution (1 M) until pH ∼ 10. To precipitate
all aluminum salt, pH was maintained by intermittently adding
dilute NaOH (0.2 M) in the following 2 h. After reaction, the resul-
tant white suspensions was treated ultrasonically at 60 ◦ C for 1 h,
and then statically aged for 2 h. The as-made white powders were
collected by centrifugation and rinsed thoroughly with deionized
water for several times, followed by freeze-drying under vacuum
overnight. The residual F127 in as-made LDHs was removed by cal-
cination at 350 ◦ C for 3 h in air, giving the mesoporous LDH termed
as meso-LDH350. For comparison, two Mg-Al LDH counterparts
were also prepared following the same procedure in the absence
of F127, and termed as LDH (i.e., the as-made sample) and LDH350
(i.e., the calcinated sample), respectively.
2.3. Characterization of mesoporous LDHs
X-ray diffraction (XRD) analyses of these Mg-Al LDHs were
conducted on an XRD-6100 diffractometer (Shimadzu, Japan) at
a tube voltage of 40 kV and a tube current of 30 mA with Cu-K␣
radiation (␭ = 1.5418 Å, step size: 0.02◦ , scanning rate: 5◦ /min).
Scanning electron micrography (SEM) was recorded by using a
Hitachi SU1510 microscope at an accelerating voltage of 1.5 kV.
Brunauer-Emmett-Teller (BET) surface area of LDHs was deter-
mined by N2 adsorption at −196 ◦ C using a Quantachrome gas
adsorption analyzer (iQ-AG-MP). Prior to BET measurement, the
samples were degassed at 80 ◦ C for at least 6 h. Fourier transform
infrared (FTIR) spectroscopy was performed on a NIKOLET iS5 spec-
trometer (Thermo Fisher, USA) following the KBr–pressed–disc
method. Thermogravimetry-differential scanning calorimetry (TG-
DSC) analysis was carried out on LABSYS EVO TG-DTA/DSC
(SETARAM, France) apparatus. Zeta (␨) potential data were col-
lected on a Zetasizer Nano ZS 90 apparatus (Malvern, UK) using
0.1 mM of NaNO3 solution as background electrolyte. UV–visible
diffuse reflection spectra (UV–vis DRS) were obtained from dry-
pressed disk samples using a UV–visible spectrophotometer (Cary
100, Agilent, USA) with BaSO4 as the reflectance sample. X-ray
photoelectron spectroscope (XPS) (PHI 5000 Versa Probe, UIVAC-
PHI, Japan) equipped with a monochromatized Al K␣ X-ray source
(h = 1486.6 eV) and a hemispherical electron analyzer was used to
analyze the surface properties of samples. The C1s peak (284.6 eV)
was used for the calibration of binding energy values.
214 H. Ji et al. / Journal of Hazardous Materials 334 (2017) 212–222
2.4. Batch adsorption experiments
All batch experiments were performed at room temperature (ca.
25 ◦ C) unless otherwise stated. Briefly, the adsorption slurries were
prepared in 15-mL capped polyethylene centrifuge tubes (Corning,
USA) by combining 10 mg adsorbents with a desired volume (e.g.,
7.8 ␮L for pH envelope experiments, giving a final concentration of
1 ppm bromate) of diluted bromate stock solution (0.01 M) and a
background electrolyte solution (e.g., 1 mM NaNO3 ), giving a total
volume of 10 mL mixture. After adjusting pH with dilute HNO3 and
NaOH, the slurries (10 mL) were bubbled with pure N2 for 5 min to
exclude dissolved CO2 and then rotated on a Labquake tube rota-
tor (Thermo Scientific, USA) for 24 h in a thermostatic chamber.
The supernates were collected by centrifugation (12000 rpm for
15 min) and filtration with 0.45 ␮m PES filter (Navigator, Tianjin)
for the measurement of bromate concentration by ionic chro-
matography (IC). Adsorption isotherms were obtained by varying
the initial bromate concentration in the range of 1.0 −100 mg L−1
(7.82–782 ␮M) with a constant adsorbent dosage (1 g L−1 ) and pH
(i.e., 7.5 ± 0.2) at 10 ◦ C and 30 ◦ C, respectively. The Langmuir and
the Freundlich models as given in Eqs. (1) and (2) were employed
to fit the experimental data.
Langmuir model:
bqm Ce
qe =
1 + bCe
Freundlich model:
1/n
qe = K f C e
where qe (mg g−1 ) is the adsorption capacity at equilibrium, Ce is
the equilibrium BrO3 − concentration in mg g−1 , qm is the maximum
adsorption capacity in mg g−1 , b (L mg−1 ) is Langmuir constant
related to adsorption energy; n and Kf are the Freundlich constant.
The competitive effects of co-anions including Cl− , NO3 − , SO4 2− ,
CO3 2− , PO4 3− , were also investigated individually. Stock solutions
of these anions were prepared by dissolving a certain amount of
their sodium salts (except for Na2 HPO4 ) in deionized water. The
initial concentration of these anions has been set as same as that of
bromate (0.1 mM). The competitive experiments were conducted
individually at pH 7.5 ± 0.2 and 25 ◦ C. The pH of the solutions was
measured by using a Sartorius pH meter (PB-10) calibrated with
standard pH 4.00, 7.00 and 10.01 buffers (Thermo, USA).
2.5. Adsorption kinetic tests
The adsorption kinetics tests were performed at pH 7.5 ± 0.2 and
25 ◦ C with an initial bromate concentration of 10 mg L−1 (78.2 ␮M)
and an adsorbent dosage of 1 g L−1 in a three-necked flask that
loaded with 500 mL of slurries completely mixed by an electri-
cal stirrer (stirring rate: 120 rpm). At varying time intervals 2 mL
of solution was collected using a pipette and filtered for analysis
of bromate concentration. Both pseudo first-order kinetic model
(Eq. (3)) [27] and second-order kinetic model (Eq. (4)) [28] as given
below were used to fit the adsorption kinetic data.
qt = qe (1 − e−kl t )
k2 q2e t
qt =
1+qe k2 t
where qe (mg g−1 ) and qt (mg g−1 ) are adsorption capacity at equi-
librium and contact time t (min), k1 and k2 is the pseudo first-order
and second-order kinetic rate constants, respectively [29].
2.6. Analysis of bromate
The concentration of BrO3 − ions were measured by using an ion
chromatographer (Dionex, ICS-2000, USA). Samples were filtered
with 0.45 ␮m filter to remove adsorbents and then separated on a
Dionex IonPac AS11-HC capillary column (4.0 mm × 250 mm) with
10 mM KOH delivered at a flow rate of 1.0 mL/min. The separation
column was operated at 30 ◦ C.
3. Results and discussion
3.1. Characterization of Mg-Al LDHs
Fig. 1A presents XRD patterns of all Mg-Al LDHs, i.e., meso-
LDH350, LDH350 and LDH. The reflections of LDH at 2 = 11.1◦ ,
22.2◦ , 34.6◦ , 38.6◦ , 45.8◦ and 60.4◦ are corresponding to (003),
(006), (009)/(012), (015), (018), and (110) planes respectively,
which are typical Miller-Bravais indices of poorly crystallized Mg-
Al LDH (NO3 ) phase [30]. The d spacing of (003) reflection is 7.8 Å,
indicating that nitrate (NO3 − ) is the predominant guest anions
intercalated in the interlayers of Mg-Al LDHs [31]. Upon calcina-
ton at 350 ◦ C, the intensity of all reflections were decreased due to
the loss of interlayer water molecules and the partial dehydroxyla-
tion of the double hydroxide sheets as verified by the reflections of
(1)
MgO (JSPDS PDF# 01-1235) in both patterns of meso-LDH350 and
LDH350 [32]. It is worth to note that the introduction of F127 into
the synthetic recipe seems not to affect the lamellar structure of
LDHs since the relative positions of all reflections showed no obvi-
(2) ous shifts, which implies that the characteristic layered structure
of LDHs was preserved after calcination. It is evident that the LDH
particles aggregated to form larger particles during the calculation
treatment, and that this aggregation process was more obvious in
the presence of F127 (Table S1 in the Supplementary data).
The FTIR spectra of Mg-Al LDHs are given in Fig. 1B. The broad
band at 3450 cm−1 is attributed to the stretching of O H groups
associated with the interlayer water molecular or O H groups in
adjacent layers. The band at 1637 cm−1 is assigned to the defor-
mation vibration of H O H (␦H2O ) of interlayer water molecules
[33]. As expected, the intensities of the above two band were
slightly decreased after calcination due to the loss of interlayer
water. The band at 1384 cm−1 refers to the antisymmetric stretch-
ing vibration (v3 mode) of both nitrate (␯NO3 ) and carbonate (␯CO3 )
[6,32,34]. The bands observed in the range of 500−800 cm−1 are
generally assignable to M O, O M O and M O M (M = Mg, Al) lat-
tice vibrations [35,36]. Additional, a weak shoulder band assignable
to the stretching vibration (v2 mode) of CO3 2− (␯CO3 ) was also
observed at 833 cm−1 , which was probably caused by the exposure
of LDHs to the atmosphere during storage [33,34]. Furthermore,
neither stretching vibration bands of C O groups (ca. 1060 cm−1 )
nor vibration bands of CH2 CH2 groups (ca. 2820 and 2910 cm−1 )
was observed, indicating that calcination at 350 ◦ C can efficiently
remove F127 from the as-made mesoporous LDH.
Fig. 1C depicts the TG-DSC curves of as-made mesoporous LDH.
It is clear to note that the thermogravimetric (TG) curve shows
three mass loss steps: the first refers to the range below ∼230 ◦ C,
the second and the third steps were located in ∼ 230–421 ◦ C and
∼421–519 ◦ C, respectively. The first mass loss interval (18.6 wt.%)
(3) was assigned principally to hydration water and physisorbed water
[37]. The second mass loss interval where 18.5 wt.% was lost, corre-
sponded to the partial dehydroxylation of the layers, the pyrolysis
(4)
of the intercalated nitrate and F127 [38]. In the last step, mass
loss (6.6 wt.%) was probably contributed from partial dehydrox-
ylation and pyrolysis of the residual F127 and nitrate. Calcination
of the as-made mesoporous LDH at a desired temperature is cru-
cial for the integrity of layered structure of LDHs [4,30,33,38]. Our
 H. Ji et al. / Journal of Hazardous Materials 334 (2017) 212–222 215

Fig. 1. Characterizations of synthetic Mg-Al LDHs: (A) XRD patterns. Noted that MgO (JCPDS # 01-1235) phase was marked with diamonds (); (B) FTIR spectra; (C) TG-DSC
curves of as-made meso-LDH; (D) N2 adsorption-desorption isotherms of meso-LDH350 and LDH350 at −196 ◦ C. Inset is the corresponding BJH pore size distribution graphs.

attempts to calcinate the as-made mesoporous LDH above 350 ◦ C
has led to a structure-collapsed sample without any mesopores
(data not shown), consistent with previous report that the struc-
tural collapse took place at around 360 ◦ C for Mg-Al LDHs [30]. It
should be stressed that, in our case, calcination at 350 ◦ C would not
only allow the lamellar structure of LDHs to survive, but also effi-
ciently promote the formation of mesoporous structure and MgO
that crystallizes approximately at 400 ◦ C in F127-free Mg-Al LDHs
[30].
The nitrogen adsorption-desorption isotherms and correspond-
ing pore size distribution of meso-LDH350 and LDH350 are shown
in Fig. 1D. The pore size distributions (PSD) of both samples were
calculated with the Barrett-Joyner-Halenda (BJH) method using
the desorption data of the isotherms. The adsorption-desorption
isotherm of meso-LDH350 can be classified as type IV (IUPAC classi-
fication) with a hysteresis loop of type H2 at high relative pressures
(P/P0 = 0.6–1.0), which implies that the mesoporous structure was
ink-bottle-type mesopores [39]. Correspondingly, meso-LDH350
shows a bimodal pore size distribution (upper curve, inset of
Fig. 1D), a uniform pore at the mean value of 12.4 nm along with
another narrow uniform pore at the mean value of 3.8 nm. The
isotherm of LDH350 exhibits a type II isotherm with a hystere-
sis loop of type H3 according the IUPAC classification. This type of
loop are derived from the macropores that are formed by non-rigid
aggregates of plate-like particles [40], which agrees well with the
corresponding pore size result (lower curve, inset of Fig. 1D) show-
ing a broad PSD curve spanning over the macroporous range. The
Brunauer-Emmett-Teller (BET) surface area of meso-LDH350 and
LDH350 are about 126 m2 g−1 and 108 m2 g−1 , respectively, much
greater than that of Mg-Al LDH synthesized via the hydrothermal
method [41].
216 H. Ji et al. / Journal of Hazardous Materials 334 (2017) 212–222

Fig. 2. SEM images of synthetic Mg-Al LDHs: (A) meso-LDH350, (B) LDH350, (C) LDH and (D) LDH synthesized via the hydrothermal method [41].

The morphologies of LDH samples were characterized by SEM

images presented in Fig. 2. The morphological features of the LDH
samples are quite similar irrespective of the addition of F127, con-
sisting of particulate aggregates with irregular shapes and sizes
ranged from several to tens of micrometers (Fig. 2A–C), which
are totally different from the flake-like particles of hydrothermal-
synthesized Mg-Al LDH (Fig. 2D) [41]. Furthermore, it can be noted
that the external surfaces of calcinated LDHs (Fig. 2A, B) are more
coarser than that of as-made LDH (Fig. 2C), and that meso-LDH350
are composited of foam-like particles, whereas LDH350 is con-
sisted of agglomerates likely formed as an aggregation of plate-like
grains. This observation is in good accordance with the results of
N2 adsorption-desorption isotherms as described above.

3.2. Effect of initial pH and ionic strength

The removal percentages (removal%) of bromate on Mg-Al LDHs

at varied ionic strengths as a function of initial pH are given in
Fig. 3. As initial pH increased from 2 to 11, the removal percentages
of bromate on all LDHs exhibit a similar trend that they increased
gradually in acidic pH range until achieved maxima in pH 6–9, and
then declined slowly at pH > 9. The pHPZC (point of zero charge)
were about 9.5, 10.2, and 11.0 for LDH, LDH350, and meso-LDH350,
respectively (Fig. S1 in the Supplementary data). It is expected that
Fig. 3. Effects of initial pH and ionic strength on bromate adsorption on Mg-Al LDHs.
LDHs have positive surface charges when pH is below pHPZC , which
is favorable for the binding of the negatively charged bromate,
and that the surfaces of LDHs become negatively charged when of bromate increased with increasing pH in the pH range of 2–6
pH is above pHPZC depressing the adsorption of bromate due to (<pHPZC ) for all LDHs, which is somewhat in contrary to the above
the electrostatic repulsion. However, it is shown that the removal% expectation. This is possible due to the changes in the solution pH
 H. Ji et al. / Journal of Hazardous Materials 334 (2017) 212–222 217

(as shown in Fig. S2), which can increase by 3−5 units from the ini-
tial to the equilibrium values during the adsorption processes [17],
resulting in a decreased removal% when the equilibrium pH was
close to and eventually above pHPZC . Another reason would be the
fact that the pHs of all fresh slurries were above 9.0, and more HNO3
was needed to draw back them to more acidic pHs, which conse-
quently depressed bromate uptake due to the competition from the
introduced nitrate [6]. When pH was above pHPZC , the concentra-
tion of OH− increases as pH increases, which results in a decrease
in bromate adsorption due to the competitive effect of hydroxides
[42]. Moreover, Mg-Al LDH could be partly dissolved at pH > 10 [17],
which can also lead to a decrease in removal%. It should be noted
that all the equilibrium pHs were above their initial counterparts
at pH < 10 (Fig. S2), and the smaller the initial pH was, the more
increment was needed to achieve its equilibrium counterpart. This
is probably arisen from the consumption of protons and release
of hydroxide ions to the solution during the adsorption process as
confirmed in the mechanism section. At the ionic strength of 1 mM
NaNO3 , the removal% of bromate on all LDHs decreased in the order
meso-LDH350 » LDH350 > LDH.
Generally, ionic strength dependence (usually 1:1 ionic salts
were used as background electrolytes, e.g., NaNO3 ) of adsorp-
tion has been used to indirectly distinguish between inner- and
outer-sphere adsorption mechanisms for ions at the solid/aqueous
Fig. 4. Effect of competitive anions ([anions]/[bromate] = 1.0) on bromate adsorp-
interface [43]. Ions showing little ionic strength dependence of
tion on meso-LDH350.
adsorption were considered to form strong inner-sphere surface
complexes, whereas ions showing significant ionic strength depen-
dence were regarded as weak attaching as outer-sphere surface ate. The reason of carbonate showing less influence on bromate
complexes. Ions that form weak outer-sphere surface complexes adsorption than chloride was probably attributed to the fact that
must display decreasing adsorption with increasing ionic strength a portion of carbonate from the reaction of atmospheric CO2 and
due to competition from the background electrolyte [43]. Pre- water has been pre-adsorbed on meso-LDH350 during storage. This
vious study suggested that bromate might predominantly form is also evidenced by the above FTIR results (Fig. 1B).
outer-sphere complexes on LDH [7]. The removal% of bromate on For monovalent anions, chloride was expected to suppress bro-
meso-LDH350 dropped down dramatically as the ionic strength mate adsorption more heavily than nitrate since lower hydration
increased from 1 mM to 100 mM (Fig. 3), verifying that the mecha- energy is more favorable for anion-exchange (G ◦ Cl < G0 NO3 )
nism associated bromate adsorption on meso-LDH350 is involved [44]. In contrary, the experimental data suggest that chloride has
in outer-sphere complexes (anion-exchange) rather than inner- less influence than nitrate in bromate adsorption, indicating that
sphere complexes [7]. anion-exchange may not be the only mechanism for bromate
adsorption on meso-LDH350. Furthermore, the presence of indi-
vidual Cl− , NO3 − , and CO3 2− (0.1 mM) decreased the removal%
3.3. Effect of competitive anions of bromate only by 3.8%, 10.9%, and 8.4% respectively (Fig. 4), all
far less than 50%, suggesting that bromate has a high affinity to
Common anions such as Cl− , NO3 − , SO4 2− , CO3 2− , and meso-LDH350 and that anion-exchange should not be the only
PO4 3− in surface water might compete with bromate for the mechanism for bromate adsorption on meso-LDH350.
binding sites of LDHs [6]. Competitive experiments were per-
formed triply with a [anions]/[bromate] molar ratio of 1.0 and 3.4. Adsorption isotherms
the results are given in Fig. 4. Obviously, the competitive
effects of these anions can be ranked in the order sul- The adsorption isotherms are given in Fig. 5, which were fit-
fate > phosphate > nitrate > carbonate > chloride, which is slightly ted by both Langmuir (solid line) and Freundlich (dotted line)
different with that for nanocrystalline Mg-Al LDH [6]. This might models using nonlinear algorithms (Eqs. (1) and (2)). The fitting
arise from the difference in the pore structure of nanocrystalline parameters are tabulated in Table 1. The greater correlation coef-
Mg-Al LDH and that of meso-LDH350. Nevertheless, due to a higher ficients (R2 ) of the Langmuir model as compared to those of the
ionic potential ␮ (4.90–8.70 nm−1 ) of bi- and tri-valent anions, bi- Freundlich model indicate that the adsorption data are better fitted
and tri-valent anions (e.g., SO4 2− , PO4 3− ) are more competitive than by the Langmuir model than by the Freundlich model. The maxi-
monovalent anions (e.g., Cl− , NO3 − ) with the exception of carbon- mum adsorption capacities (qm ) at 10 ◦ C calculated by the Langmuir

Table 1
Adsorption isotherm parameters from the Langmuir and Freundlich models’ fitting.

Samples Temperature (◦ C) Langmuir Freundlich

−1 −1 2
qm (mg g ) b (L mg ) R KF n R2

LDH 10 12.61 0.0606 0.976 1.74 2.42 0.865

30 14.58 0.0645 0.978 2.12 2.45 0.879
LDH350 10 16.36 0.0696 0.995 2.44 2.44 0.921
30 25.69 0.0497 0.983 2.85 2.18 0.902
meso-LDH350 10 59.34 0.0383 0.996 4.43 1.81 0.972
30 54.98 0.0380 0.995 4.21 1.85 0.956
218 H. Ji et al. / Journal of Hazardous Materials 334 (2017) 212–222

equation (Eq. (1)) were 12.61 mg g−1 , 16.36 mg g−1 , 59.34 mg g−1
for LDH, LDH350 and meso-LDH350 respectively (Table 1). LDH350
exhibited a higher adsorption capability as compared with that
of LDH, suggesting that calcination can improve the maximum
adsorption capacity. It was found that calcinated LDHs, when con-
tacting with aqueous solutions, usually reconstructed firstly by
rehydration of the disordered hydroxide sheets, in which bromate
may enter into the interlayers of LDHs [45]. Not surprising, meso-
LDH350 exhibited the highest qm amonge all LDHs in this study,
which was contributed to its highest surface area and the meso-
porous structure as described above. The high surface area offered
abundant binding sites for bromate and the mesoporous networks
afforded a plenty of accessible diffusion pathways for bromate. The
maximum adsorption capacities of bromate on these LDHs fol-
low the order meso-LDH350 » LDH350 > LDH (Table 1). It should
be noted that the qm of meso-LDH350 decreased with increasing
temperature from 10 to 30 ◦ C, whereas the adsorption capacities of
both LDH350 and LDH increased with temperature. This is possibly
arising from the differences in the pore structures of these LDHs.
For comparison, the maximum adsorption capacities of bro-
mate on other LDH-type adsorbents are summarized in Table 2.
Among these adsorbents, meso-LDH350 and LDH350 have max-
imum adsorption capacities (i.e., 59.34 mg g−1 at 10 ◦ C and
25.69 mg g−1 at 30 ◦ C respectively) higher than those of other LDHs
including hydrothermally-treated Zn-Al LDH (calcinated) [4,18],
hydrothermally-treated Zn-Fe(II)-Al LDH [46], hydrothermally-
treated Zn-Al LDH (calcinated) [17], hydrothermally-treated Mg-Al
LDH [6,7], even some of these LDHs had a higher surface area than
both meso-LDH350 and LDH350. When considering the adsorption
density ( = qm /SBET , Table 2), the maximum specific adsorption
density of bromate on meso-LDH350 (0.47 mg m−2 ) is also com-
parable to that of thermally-treated Mg-Al xerogel (0.5 mg m−2 ), in
which the higher surface area and the hierarchical porous structure
(i.e., from macropores to micropores) are believed to contribute
to its highest maximum adsorption capacity (78.0 mg g−1 ) [5]. To
evaluate the recycle performance of mesoporous LDH, spent meso-
LFH350 (0.22 g) was regenerated by collecting centrifugally and
desorbing with a solution (10 mM NaNO3 + 100 mM NaOH, 220 mL),
followed by rinsing with ultrapure water several times before
next adsorption cycle. The adsorption–regeneration experiments
were conducted for five cycles. The removal% of bromate decrease
obviously from over 95% to ∼40% after five cycles of adsorption-
desorption (Fig. S3 in the Supplementary data). This is probably
due to the decrease in crystallinity and the collapse of meso-
porous structure of meso-LDH350. The recycle performance of
meso-LDH350 is not as good as other calcinated LDHs that a thermal
regeneration were employed [17,18], implying that the reconstruc-
tion of layered structure should contribute in part to the adsorptive Fig. 5. Adsorption isotherms of bromate on Mg-Al LDHs at (A) 10 ◦ C, and (B) 30 ◦ C.
removal of bromate by meso-LDH350. Nevertheless, from a practi-
cal point of view, meso-LDH350 with such high adsorption capacity
is expected to use as an alternative to commercial adsorbents for time until reaching the maximum at t ∼ 20 min, and then dropped
bromate removal from aqueous solutions. down gradually and attained saturation in 3.0 −10 h (Fig. 6). The
discrepancy in kinetics between LDH and the calcined LDHs is prob-
ably due to the difference in the pore structures of these adsorbents
3.5. Adsorption kinetics as desicribed above. There is no need for LDH to reconstruct in the
beginning of adsorption, resulting a faster initial adsorption rate
The kinetic curves of bromate adsorption were given in Fig. 6. as compared to that of calcinated LDHs. As adsorption proceeds, an
It was observed that the bromate adsorption capacity (qt ) at time t excess amount of BrO3 − was likely to attach onto the surface of LDH
increased first with the contact time (t) and then attained equi- and further diffused into the interlayers to exchange NO3 − until
librium within a certain period of time (<3 h). The calcinated a saturation was achieved. The slight decline of qt in 50–200 min
adsorbents, meso-LDH350 and LDH350, exhibited a similar initial seems to be due to the transition from an initial multilayer attach-
rapid uptake of bromate within the first 80 min and 120 min respec- ment to a final favorable monolayer adsorption of BrO3 − .
tively, followed by a slow adsorption process to reach saturation in No significant changes in qt were observed from 3.0 to 21 h for
2.0–21 h. This type of fast adsorption involving LDHs is believed to all adsorbents, implying adsorption equilibrium was reaching at
be the anion-exchange reactions [4,47]. However, the as-made LDH that time. Chitrakar et al. has also shown longer equilibration time
showed a different kinetics that qt increased rapidly with contact from 48 h to 72 h for bromate adsorption on calcinated Mg-Al LDHs
 H. Ji et al. / Journal of Hazardous Materials 334 (2017) 212–222 219

Table 2
Comparison of the maximum adsorption capacity (qm ) of bromate on meso-LDH350 with other LDH-type adsorbents.

adsorbents BET surface area initial pH T qm  ionic strength ref

(m2 g−1 ) (◦ C) (mg g−1 ) (mg m−2 ) (mM)

hydrothermally-treated Zn-Al LDH (calcinated) 91 6.9 20 0.12 0.001 0 [18]

hydrothermally-treated Zn-Fe(II)-Al LDH 55 7.0 22 0.20 0.004 0 [46]
hydrothermally-treated Mg-Al LDH (calcinated) 200 9.6–9.8 RTa 0.99 0.005 0 [4]
hydrothermally-treated Zn-Al LDH (calcinated) 91 6.9 20 1.16 0.01 0 [17]
hydrothermally-treated Mg-Al LDH (FCHT-LDH) 127 9.5 25 12.80 0.10 10.0 [7]
hydrothermally-treated Mg-Al LDH 127 9.5 25 22.40 0.18 0 [6]
thermally-treated Mg-Al LDH xerogel 155 4.5 22 78.0 0.50 10.0 [5]
LDH350 108 7.5 30 25.69 0.24 1.0 This study
meso-LDH350 126 7.5 10 59.34 0.47 1.0 This study
a
RT refers to room temperature.

and the reflections of MgO disappeared after adsorption of bromate

Fig. 6. Adsorption kinetics of bromate on Mg-Al LDHs.
[4]. This indicates that bromate shows faster kinetics onto meso-
LDH350 and LDH350, which are also faster than other LDH-type
adsorbents, such as calcinated Mg-Al LDH [4], and FCHT-LDH [7].
Considering that the reconstruction of calcined LDHs still takes
some time, a 24 h period was therefore believed to be enough
to establish equilibrium for bromate adsorption isotherm exper-
iments in our cases.
The experimental data were fitted by both the pseudo-first and
the pseudo-second-order rate equations (Eqs. (3) and (4)). The fit-
ting results were summarized in Table 3 and plotted in Fig. 6. The
values of qe calculated from Eq. (4) are 5.17 mg g−1 , 8.14 mg g−1 ,
and 8.29 mg g−1 for LDH, LDH350 and meso-LDH350, respectively
(Table 3), close to the experimental data (Fig. 6). Comparison of the
correlation coefficients (R2 ) of both kinetic models indicates that
the pseudo-second-order rate model with R2 above 0.96 is better
to fit the kinetica data of all adsorbents, suggesting a chemisorption
process occurred.
3.6. Adsorption mechanisms
To elucidate the adsorption mechanism responsible for bromate
uptake on meso-LDH350, both fresh and spent adsorbents were col-
lected and handled properly, followed by characterizations with
XRD, FTIR, UV–vis DRS and XPS, and the results are given in Fig. 7.
It was observed that the intensities of all LDH reflections increased
(Fig. 7A), suggesting that a reconstruction of the layered structure in
meso-LDH350 occurred during adsorption. As a consequence, the
d spacing of (003) reflection recovered from 8.1 Å to 7.8 Å, which
is in good agreement to that of FCHT-LDH after adsorption of bro-
mate (i.e., 7.84 Å) [7], implying that bromate was likely to be bond
via anion-exchange with the intercalated anions (the remaining
NO3 − and OH− as evidenced by the FTIR spectra). Nevertheless,
a reconstruction mechanism has been identified by Ulibarri and
coworkers for the enhanced uptake of anionic pollutants on calci-
nated LDHs [48]. It is therefore reasonable to suggest that a second
mechanism−the reconstruction mechanism should be responsible
for the enhanced adsorption of bromate on meso-LDH350. After
adsorption, the FTIR band of nitrate at 1384 cm−1 weakened a lot
and the weak carbonate band at 833 cm−1 disappeared, whereas
a new band at 791 cm−1 contributed to Br−O stretching vibration
appeared (Fig. 7B), confirming that anion-exchange has played an
important role in bromate adsorption on meso-LDH350. This was
also verified by the UV–vis DRS spectra (Fig. 7C), in which two new
peaks at 252 nm and 375 nm associated with the electron transition
(ET) of bromate (see Fig. S4 in the Supplementary data) appeared
and the intensity of both 215 nm (assignable to the ET of Mg-Al
LDH) [49] and 300 nm (assignable to the ET of NO3 − to Mg/Al)
[50] decreased slightly (inset of Fig. 7C) after adsorption, indicating
anion-exchange took place. Fig. 7D presents the survey XPS spectra
of meso-LDH350 before and after bromate adsorption. It is noted
that, besides the main elements including O, Al, and Mg observed
in both spectra, the Br peaks (Br3s, Br3p, and Br3d) appeared in
the bromate-adsorbed meso-LDH350 (see also Fig. S5 in the Sup-
plementary data), confirming that bromate has been sequestered
by meso-LDH350. On the basis of above results, the mechanism
of bromate adsorption on meso-LDH350 is contributed both from
the reconstruction of the layered structure in meso-LDH350 and
from the anion-exchange between bromate in bulk solution and
the intercalated anions as given in Eqs. (5)–(9) and illustrated in
Fig. 8. When adding fresh meso-LDH350 into bromate-containing
solution, the reconstruction occurred likely in a manner that a part
of bromate (Eq. (5)), apart from hydroxyls and nitrates (Eqs. (6) and
(7)), participated to reconstruct the layered structure, which conse-
quently increases the solution pHs (see also Fig. S2) by consumption
of protons and release of hydroxide ions (Eqs. (5)–(7)). It is obvious
that the more acidic the solution was, the more rapid the recon-
struction reaction was. Meanwhile, a portion of bromate replaced
the interlayer anions via anion-exchange (Eqs. (8) and (9)), forming
a BrO3 − -intercalated meso-LDH350. Both the higher BET surface
area and the mesoporous structure of meso-LDH350 facilitate the
efficient and fast removal of bromate in such manners.
Reconstruction:
M O− + 2H+ + BrO3 − → M OH2 + /BrO3 − (5)
M O− + 2H2 O → M OH2 + /OH− + OH− (6)
220 H. Ji et al. / Journal of Hazardous Materials 334 (2017) 212–222

Fig. 7. (A) XRD patterns, (B) FTIR spectra, (C) UV–vis DRS spectra, and (D) XPS spectra of meso-LDH350 before and after adsorption of bromate.

Fig. 8. Schematic illustration of adsorption mechanism for bromate uptake on meso-LDH350.

 H. Ji et al. / Journal of Hazardous Materials 334 (2017) 212–222
Table 3
Kinetics parameters from the Pseudo-first-order and Pseudo-second-order rate models’ fitting.
Samples Pseudo-first-order
k1 (min−1 ) qe (mg g−1 )
LDH 5.20 0.97
LDH350 0.031 7.50
meso-LDH350 0.083 7.91
M O− + 2H+ + NO3 − → M OH2 + /NO3 −
Anion-exchange:
M OH2 + /NO3 − + BrO3 − ↔ M OH2 + /BrO3 − + NO3 −
+ − − + − −
M OH2 / OH + BrO3 ↔ M OH2 /BrO3 + OH
4. Conclusions
In summary, we have presented a facile method for the prepa-
ration of mesoporous Mg-Al LDH (termed as meso-LDH350) by fast
co-precipitation of Mg-, Al-nitrate precursors and F127 in alka-
line solution, followed by calcination. The mesoporous Mg-Al LDH
exhibits a pretty high surface area (SBET = 126 m2 g−1 ) and foam-
like mesopores, which allows it to have a much higher adsorption
capacity (59.34 mg g−1 , 10 ◦ C, pH 7.5) and excellent potentiality to
sequester bromate from aqueous solution as compared with other
LDH-type adsorbents. The adsorption isotherms of meso-LDH350,
and its non-mesoporous counterparts, LDH350 and LDH, agree
well with the Langmuir algorithm. The kinetic data of bromate
adsorption on all adsorbents can be well fitted with the pseudo-
second-order rate model. The mechanism for bromate adsorption
on meso-LDH350, in terms of the results of XRD, FTIR, UV–vis DRS
and XPS, is mainly contributed both from the reconstruction of
layered structures in meso-LDH350 and from the anion-exchange
between bromate in bulk solution and the intercalated anions. In
summary, this work provides a facile approach to prepare ordered
mesoporous Mg-Al LDH with a high surface area and a high adsorp-
tion capacity for bromate, making it a potential candidate for
adsorptive removal of bromate from aqueous solutions.
Acknowledgements
The work was partially supported by National Natural Science
Foundation of China (NSFC) (51002080), Nature Science Foundation
of Jiangsu (BK20171480), the open fund of AEMPC Lab (KFK1505),
SPITP Program (201510300058, 201610300050, 201610300273),
Top-notch Academic Programs Project of Jiangsu Higher Education
Institutions (PPZY2015C222) and the Priority Academic Program
Development of Jiangsu Higher Education Institutions (PAPD). Spe-
cial thanks are due to Dr. Wonyong Choi and all anonymous
reviewers for their helpful comments and suggestions on the earlier
version of this paper.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jhazmat.2017.04.
014.
References
[1] U. von Gunten, J. Holgne, Bromate formation during ozonation of
bromide-Containing waters—interaction of ozone and hydroxyl radical
reactions, Environ. Sci. Technol. 28 (1994) 1234–1242.
[2] Y. Kurokawa, A. Maekawa, M. Takahashi, Y. Hayashi, Toxicity and
carcinogenicity of potassium bromate—a new renal carcinogen, Environ.
Health Perspect. 87 (1990) 309–335.
221
Pseudo-second-order
R2 k2 (g mg−1 min−1 ) qe (mg g−1 ) R2
0.927 – 5.17 0.963
0.955 0.005 8.14 0.966
0.943 0.017 8.29 0.981
(7) [3] M.L. Bao, O. Griffini, D. Santianni, K. Barbieri, D. Burrini, F. Pantani, Removal of
bromate ion from water using granular activated carbon, Water Res. 33
(1999) 2959–2970.
[4] R. Chitrakar, A. Sonoda, Y. Makita, T. Hirotsu, Calcined Mg-Al layered double
(8) hydroxides for uptake of trace levels of bromate from aqueous solution, Ind.
Eng. Chem. Res. 50 (2011) 9280–9285.
[5] N. Chubar, New inorganic (an)ion exchangers based on Mg-Al hydrous oxides:
(9)
(Alkoxide-free) sol-gel synthesis and characterisation, J. Colloid Interface Sci.
357 (2011) 198–209.
[6] K.H. Goh, T.T. Lim, Influences of co-existing species on the sorption of toxic
oxyanions from aqueous solution by nanocrystalline Mg/Al layered double
hydroxide, J. Hazard. Mater. 180 (2010) 401–408.
[7] K.H. Goh, T.T. Lim, A. Banas, Z.L. Dong, Sorption characteristics and
mechanisms of oxyanions and oxyhalides having different molecular
properties on Mg/Al layered double hydroxide nanoparticles, J. Hazard. Mater.
179 (2010) 818–827.
[8] C.G. van Ginkel, A.M. van Haperen, B. van der Togt, Reduction of bromate to
bromide coupled to acetate oxidation by anaerobic mixed microbial cultures,
Water Res. 39 (2005) 59–64.
[9] L. Xie, C. Shang, The effects of operational parameters and common anions on
the reactivity of zero-valent iron in bromate reduction, Chemosphere 66
(2007) 1652–1659.
[10] H. Chen, Z.Y. Xu, H.Q. Wan, J.Z. Zheng, D.Q. Yin, S.R. Zheng, Aqueous bromate
reduction by catalytic hydrogenation over Pd/Al2O3 catalysts, Appl. Catal.
B—Environ. 96 (2010) 307–313.
[11] X. Zhao, H.J. Liu, Y.L. Shen, J.H. Qu, Photocatalytic reduction of bromate at C-60
modified Bi2MoO6 under visible light irradiation, Appl. Catal. B—Environ. 106
(2011) 63–68.
[12] K.H. Goh, T.T. Lim, Z.L. Dong, Application of layered double hydroxides for
removal of oxyanions: a review, Water Res. 42 (2008) 1343–1368.
[13] D.G. Evans, R.C.T. Slade, Structural aspects of layered double hydroxides, in: X.
Duan, D.G. Evans (Eds.), Layered Double Hydroxides, 2006, pp. 1–87.
[14] R. Chitrakar, Y. Makita, A. Sonoda, T. Hirotsu, Fe-Al layered double hydroxides
in bromate reduction: synthesis and reactivity, J. Colloid Interface Sci. 354
(2011) 798–803.
[15] R. Chitrakar, A. Sonoda, Y. Makita, T. Hirotsu, Synthesis and bromate reduction
of sulfate intercalated Fe(II)-Al(III) layered double hydroxides, Sep. Purif.
Technol. 80 (2011) 652–657.
[16] L. Lv, T. Jiang, S.H. Zhang, X. Yu, Exposure to mutagenic disinfection
byproducts leads to increase of antibiotic resistance in pseudomonas
aeruginosa, Environ. Sci. Technol. 48 (2014) 8188–8195.
[17] Y. Zhang, X.L. Li, H.Y. Liu, A novel process for bromate removal from water
using calcined Zn-Al layered double hydroxides, Desalin. Water. Treat. 55
(2015) 1325–1332.
[18] Y. Zhang, X.L. Li, Preparation of Zn-Al CLDH to remove bromate from drinking
water, J. Environ. Eng.—ASCE 140 (2014) 04014018.
[19] Y. Kuroda, Y. Miyamoto, M. Hibino, K. Yamaguchi, N. Mizuno, Tripodal
ligand-Stabilized layered double hydroxide nanoparticles with highly
exchangeable CO32−, Chem. Mater. 25 (2013) 2291–2296.
[20] K.H. Goh, T.T. Lim, Z.L. Dong, Enhanced arsenic removal by hydrothermally
treated nanocrystalline Mg/Al layered double hydroxide with nitrate
intercalation, Environ. Sci. Technol. 43 (2009) 2537–2543.
[21] P.D. Yang, D.Y. Zhao, D.I. Margolese, B.F. Chmelka, G.D. Stucky, Generalized
syntheses of large-pore mesoporous metal oxides with semicrystalline
frameworks, Nature 396 (1998) 152–155.
[22] F.H. Li, H. Fu, J.P. Zhai, Q. Li, Synthesis of mesostructured ferric oxyhydroxides
templated by alkyl surfactants: effect of pH, F- and solvents, and their
adsorption isotherms for As(V), Microporous Mesoporous Mater. 123 (2009)
177–184.
[23] F.H. Li, X.R. Fu, J. Huang, J.P. Zhai, Synthesis of mesostructured iron oxides
with potential As(V) adsorption application, Chem. Res. Chin. Univ. 28 (2012)
559–562.
[24] F.H. Li, D.Y. Nie, Iron-based inorganic mesoporous materials, Prog. Chem. 26
(2014) 961–975.
[25] T. Itoh, N. Ohta, T. Shichi, T. Yui, K. Takagi, The self-assembling properties of
stearate ions in hydrotalcite clay composites, Langmuir 19 (2003) 9120–9126.
[26] J. Wang, J.D. Zhou, Z.S. Li, Y. He, S.S. Lin, Q. Liu, M.L. Zhang, Z.H. Jiang,
Mesoporous mixed metal oxides derived from P123-templated Mg-Al layered
double hydroxides, J. Solid State Chem. 183 (2010) 2511–2515.
[27] B.J. Pan, L.L. Xiao, G.Z. Nie, B.C. Pan, J. Wu, L. Lv, W.M. Zhang, S.R. Zheng,
Adsorptive selenite removal from water using a nano-hydrated ferric oxides
(HFOs)/polymer hybrid adsorbent, J. Environ. Monit. 12 (2010) 305–310.
222 H. Ji et al. / Journal of Hazardous Materials 334 (2017) 212–222
[28] S. Mandal, S. Tripathy, T. Padhi, M.K. Sahu, R.K. Patel, Removal efficiency of
fluoride by novel Mg-Cr-Cl layered double hydroxide by batch process from
water, J. Environ. Sci.—China 25 (2013) 993–1000.
[29] F.H. Li, Layer-by-layer loading iron onto mesoporous silica surfaces: synthesis,
characterization and application for As(V) removal, Microporous Mesoporous
Mater. 171 (2013) 139–146.
[30] J.S. Valente, M. Sanchez-Cantu, E. Lima, F. Figueras, Method for large-scale
production of multimetallic layered double hydroxides: formation
mechanism discernment, Chem. Mater. 21 (2009) 5809–5818.
[31] Y.L. Wang, P.X. Wu, Y.W. Li, N.W. Zhu, Z. Dang, Structural and spectroscopic
study of tripeptide/layered double hydroxide hybrids, J. Colloid Interface Sci.
394 (2013) 564–572.
[32] V. Rives, Layered Double Hydroxides: Present and Future, Nova Science
Publishers, Huntington, N.Y, 2001.
[33] F.R. Costa, A. Leuteritz, U. Wagenknecht, D. Jehnichen, L. Haussler, G. Heinrich,
Intercalation of Mg-Al layered double hydroxide by anionic surfactants:
preparation and characterization, Appl. Clay Sci. 38 (2008) 153–164.
[34] V. Rives, M.A. Ulibarri, Layered double hydroxides (LDH) intercalated with
metal coordination compounds and oxometalates, Coord. Chem. Rev. 181
(1999) 61–120.
[35] K. Nejati, Z. Rezvani, Synthesis and characterisation of nanohybrids of
olsalazine-intercalated Al-Mg layered double hydroxide, J. Exp. Nanosci. 7
(2012) 412–425.
[36] D.S. Tong, C.H. Zhou, M.Y. Li, W.H. Yu, J. Beltramini, C.X. Lin, Z.P. Xu, Structure
and catalytic properties of Sn-containing layered double hydroxides
synthesized in the presence of dodecylsulfate and dodecylamine, Appl. Clay
Sci. 48 (2010) 569–574.
[37] X.X. Ruan, S. Huang, H. Chen, G.R. Qian, Sorption of aqueous organic
contaminants onto dodecyl sulfate intercalated magnesium iron layered
double hydroxide, Appl. Clay Sci. 72 (2013) 96–103.
[38] T. Bujdoso, A. Patzko, Z. Galbacs, I. Dekany, Structural characterization of
arsenate ion exchanged MgAl-layered double hydroxide, Appl. Clay Sci. 44
(2009) 75–82.
[39] M. Thommes, B. Smarsly, M. Groenewolt, P.I. Ravikovitch, A.V. Neimark,
Adsorption hysteresis of nitrogen and argon in pore networks and
characterization of novel micro- and mesoporous silicas, Langmuir 22 (2006)
756–764.
[40] M. Thommes, K. Kaneko, A.V. Neimark, J.P. Olivier, F. Rodriguez-Reinoso, J.
Rouquerol, K.S.W. Sing, Physisorption of gases, with special reference to the
evaluation of surface area and pore size distribution (IUPAC Technical
Report), Pure Appl. Chem. 87 (2015) 1051–1069.
[41] Y.M. Ren, P.X. Liu, J. Feng, J. Ma, Q. Wen, M.L. Zhang, Selective recognition of
molybdenum(VI) from water by Mo(VI) oxy ion-imprinted particle as an
adsorbent, Chem. Eng. J. 219 (2013) 286–294.
[42] C. Forano, Environmental remediation involving layered double hydroxides,
Interface Sci. Technol. 1 (2004) 425–458.
[43] S. Goldberg, Application of surface complexation models to anion adsorption
by natural materials, Environ. Toxicol. Chem. 33 (2014) 2172–2180.
[44] A. Bhatnagar, Y. Choi, Y. Yoon, Y. Shin, B.H. Jeon, J.W. Kang, Bromate removal
from water by granular ferric hydroxide (GFH), J. Hazard. Mater. 170 (2009)
134–140.
[45] M.A. Ulibarri, I. Pavlovic, M.C. Hermosin, J. Cornejo, Hydrotalcite-like
compounds as potential sorbents of phenols from water, Appl. Clay Sci. 10
(1995) 131–145.
[46] Y. Zhang, S. Jing, H.Y. Li, Reactivity and mechanism of bromate reduction from
aqueous solution using Zn-Fe(II)-Al layered double hydroxides, Chem. Eng. J.
266 (2015) 21–27.
[47] M.C. Hermosin, I. Pavlovic, M.A. Ulibarri, J. Cornejo, Hydrotalcite as sorbent for
trinitrophenol: sorption capacity and mechanism, Water Res. 30 (1996)
171–177.
[48] M.A. Ulibarri, I. Pavlovic, C. Barriga, M.C. Hermosin, J. Cornejo, Adsorption of
anionic species on hydrotalcite-like compounds: effect of interlayer anion
and crystallinity, Appl. Clay Sci. 18 (2001) 17–27.
[49] G. Mendoza-Damian, F. Tzompantzi, A. Mantilla, R. Perez-Hernandez, A.
Hernandez-Gordillo, Improved photocatalytic activity of SnO2-ZnAl LDH
prepared by one step Sn4+ incorporation, Appl. Clay Sci. 121 (2016) 127–136.
[50] J.F. Mcintyre, R.T. Foley, B.F. Brown, Ultraviolet-Spectra of aluminum
salt-solutions, Inorg. Chem. 21 (1982) 1167–1172.
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are usually from two to three feet long, and beautifully flowered after
the manner of the Damascene blades. The inhabitants rarely employ
themselves in ship-building, but obtain their smaller prahus from the
Ki Islands, and the larger ones from Bali. I have already described
these vessels, and will only now remark the simplicity of the
materials with which they are fitted out. A paduakan has only one
sail, and is steered by two rudders (one on each quarter), which can
readily be raised out of the water. The two cables, each from thirty to
fifty fathoms long, are made of twisted rattans, and the anchors are
composed of hard wood, having the flukes a little sharpened, and a
large stone fastened to the stock. A small canoe is carried on the
deck. The bottom of the vessel is covered with a composition of lime,
and the top sides are painted with a black mixture made from burnt
rattans and husks of cocoa-nuts. Some pots of fresh water, a little
salt, a quantity of sago bread, and some fishing-hooks and lines,
complete their equipments.
The Goram Islands are rather high, and extremely fertile. Rice is
grown on the main island; but the inhabitants of Manovolko and
Salawatta dare not plant it, as its cultivation is considered as an
exclusive hereditary right of the people of Goram. In the interior of
the islands many fugitives from Bali and Sumbawa reside, who are
forced to pay a slavish obedience to the old inhabitants. The wants
of these people are few, and are supplied by the forests, which afford
plenty of hogs and other wild animals; even snakes, as I was
informed, being esteemed a delicacy among them.
Fishing is but little attended to here, fowls and goats, which here
abound, being preferred as food. The Papuan slaves fish with lines,
but seroos, or stake-traps, with which fish are caught on the banks,
are here rarely used. The women often employ themselves in
catching crabs in the shallow water, adopting rather a singular mode.
They place baskets over each foot, and walking over the mud-banks
they are enabled to feel the crabs when they tread upon them, which
they secure by thrusting a sharp-pointed stick into them through the
basket. The mode of line-fishing adopted in the Archipelago is very
simple. The lines are from sixty to one hundred fathoms long, having
at the end a piece of copper wire, four or five fathoms in length, to
which the hook is fastened. The bait consists of hen's feathers,
which are tied fast to the hook, and when in the water have the
appearance of small fish. There are several other modes adopted,
which it will be unnecessary to explain at length.
We saw no land until the 16th, when we made the Arru Islands, and
sailing close along the west coast of Wassia, hauled in, and came to
an anchor in the strait between that island and Wadia. The Orang
Kaya of Wadia immediately came on board, and in the afternoon I
went on shore to return his visit. Hoping to gain some information at
Dobbo about the coast of New Guinea, and wishing also to know
how they got on there, I proceeded there the same night with the
armed boats. I there met with the Orang Kaya of Wama, who
informed me of the death of the head chief of Wokan, which took
place about a month previous, and of his office being filled by his
brother, who arrived among us during the same day.
A brig from Sourabaya, and several other vessels, lay at anchor off
the town, while thirteen paduakans from Macassar and Boni were
hauled up on the beach, the commanders of which had gone to
some of the more distant islands of the group, especially Vorkay, to
purchase trepang, mother-o'pearl-shell and tortoise-shell. Two other
large paduakans lay at anchor behind Maykor, the trade being
conducted in a very regular manner. Several differences had,
however, occurred, the most important of which were the following.
The Nakhoda, or commander of a jonko from Ghissa, complained to
me that the Raja of Amma, a village situated on the Goram Islands,
having come here to trade, had forbidden him (the Nakhoda) from
disposing of his goods, with a view to obtain a better price than his
own; the Raja being enabled to enforce his prohibition, by the aid of
two armed prahus. As no reason existed for the trade being open to
one and not to another, it became necessary for me to make known
to the people of Goram my displeasure at such arbitrary
proceedings. The Raja, however, alarmed at our arrival, had
departed no one knew whither, his prahu having been seen standing
out to sea as we came in. The Orang Kaya of Wama remarked to
me, that the Raja was well aware that his conduct would not bear the
test of examination.
A second affair was as follows:—A juro-batu, or pilot (literally,
watcher for rocks), named Seyid-Ed-Din, complained to me that the
Nakhoda of a prahu from Amboyna had turned him ashore, so that
he was now without the means of subsistence. The Nakhoda had
gone to the back part of the group; but I soon learned that the juro-
batu was not entirely free from blame, and was thus prevented from
coming to a decision on the case, being only able to order the
commanding officer of the prahu to take the man back to Amboyna,
as it was improper that any of the crew should be put on shore in a
foreign place.
In the year 1824, a prahu belonging to Kilwari, while on her voyage
from New Guinea to the Ki Islands, put into Wadia, having received
damage at sea from bad weather, and being in want of fresh water.
The Orang Kaya of Wadia wished to purchase the trepang which
formed part of her cargo, but the parties not being able to come to
terms, the crew of the prahu made preparations to depart. This,
however, was prevented by the Orang Kaya, who endeavoured to
decoy the strangers into the river, but being unable to succeed he
boarded the vessel with several prahus, and plundered her of some
pieces of cloth, some gunpowder, and other trifles. The Ceramese,
to avoid further violence, fled the same night, and continued their
voyage to the Ki Islands. It accidentally happened, that several of
those who formed the crew of the prahu, some of whom were
relatives of my interpreter for New Guinea, were now in a vessel at
Dobbo, and came to me to request that I would obtain the restitution
of the goods which had been taken from them. The chiefs of the
different villages were present at the time, the Orang Kaya of Wadia
being among them. He did not deny the circumstance, but, as
usually occurs, laid all the blame on the villagers. I requested the
proprietors of the plundered goods to return with me to Wadia, where
I obtained the property for them, but forgave, for this time, the
villagers, threatening them with severe punishment should they ever
transgress in like manner again.
The Christian teachers of Wakan, Wama and Maykor, stated to me,
that they could remain no longer on the islands, as they were unable
to obtain even sufficient provisions for their maintenance. On
examination I found that these useful men received nothing whatever
from the villagers, so that I could not be surprised at their desire to
return to Amboyna, especially those of Wama and Maykor. I took the
opportunity of a general meeting of chiefs on the Island Wokan, to
mention the subject to those who professed Christianity. These did
not deny that the teachers had been left to their own resources; but
stated in excuse, that as M. Bik had promised the teachers a
monthly salary of ten rupees, they must have sufficient to subsist
upon. I observed to them the injustice of their conduct, on which they
begged the teachers to remain, and promised to provide for their
maintenance.
Some of the teachers appeared to me as not being on the most
friendly footing with the natives, which, I believe, was owing greatly
to their presuming too much on the protection of the Government,
and wishing to be masters in reality. I therefore remonstrated with
them on the impropriety of attempts at rule, and sent the teacher of
Maykor back again to his home, at the same time exhorting them to
perform their duties better for the future than they had hitherto, and
give the natives clearer ideas of Christianity. The dispositions of the
Arru Islanders are excellent, and it is truly to be regretted that their
instruction in the tenets of our religion has hitherto been so slight.
Were a missionary to be sent among them, his labours would be
attended with very good results. The distribution of some Malayan
Bibles, hymn books, and tracts, which I had received from M. Kam,
gave much delight to the Christian natives.
At the earnest request of the three teachers, I gave to each twenty
rupees (£1. 15s.), together with some rice and other provisions. One
of the three whom I brought with me from Amboyna, was installed at
Duryella.
On the 19th of April we departed in the boats for Wokan. The Orang
Kaya of Wadia, who had remained with me up to this time, returned
to his village to await my arrival there. On the following morning the
chiefs and elders of the Christians assembled, when Zadrak
Hermans was appointed as head chief of Wokan, with the usual
ceremonies, and received a golden-knobbed baton, together with the
certificate of appointment which had been provided for his father, to
which an appendix was attached, naming him his successor. I also
delivered certificates to the chiefs of Wama and Maykor, with which I
had been furnished by the Government. The ceremonies were
concluded with an appropriate address, and a salute of lelah shots.
The people here are not less desirous than those of most other
islands of this Archipelago, to have a Dutch garrison among them.
At noon I returned on board, accompanied by five vessels,
containing a number of my native friends, whom I entertained on
board at dinner, after which they returned home with many
expressions of thanks for the kind proofs of remembrance on the
part of the Government.
On the 21st I presented the Orang Kaya of Wadia with an act of
appointment, after which I arranged the affair of piracy, of which I
have previously made mention. During our stay among the islands,
the weather had been continually calm and rainy. I was disappointed
in my expectations of receiving important information, concerning the
coasts of New Guinea. When the people heard that I intended to go
there, they expressed much satisfaction, hoping that they would be
benefitted by the results of the expedition. The Ceramese I met with
here, who had lately left the coast of New Guinea, informed me that
the Papuas to the northward of the Arru Islands had assured them,
that Orang Pati, or white people, dwelt further to the south-eastward
of them.[44]

FOOTNOTES:
[43] Morinda citrifolia. Lin.—Translator.
[44] It is possible that our colony of New South Wales was here
alluded to. The natives of the islands in Torres Straits, from their
frequent intercourse with ships from Sydney, must be well aware
of the existence of the colony, and might have communicated it to
the Papuas of the south part of New Guinea, with whom they
maintain a constant intercourse.—Translator.
 CHAPTER XIX.
NEW GUINEA.
Voyage towards the St. Bartholomeus River.—Encounter
a Multitude of Whales.—Discover a Sand-bank.—Nautical
Remarks.—Difficulty in approaching the Land.—Sharks.—
Crocodiles.—Discover a River.—The Author ascends it.—
Remarkable Behaviour of the Natives.—Their Wild State.
—Unable to land.—Arrival at an uninhabited Bay on the
Island of Lakahia.—Visit from some of the Chiefs.
Having filled up our water-casks, and put the rigging in order, we left
our anchorage off Wadia on the morning of the 22nd of April, and
continued our voyage towards New Guinea. Owing to calms we were
unable to advance far during the day, but we afterwards were
favoured by a steady breeze, which soon carried us out of view of
the Arru Islands. Bartholomeus River, (on the south coast of New
Guinea), being the point to be first visited, we shaped our course for
the south-west extreme of that great island. The winds and weather
we experienced during the passage, were very unsteady, the former
being generally from the northern quarter. As soon as we passed the
Arru Islands, the pilots stated to me that they were unacquainted
with the navigation beyond, and were even afraid to proceed any
farther. The traders from Ceram, and the islands to the westward, do
not penetrate beyond the Arrus.
A number of birds usually came on board the brig towards evening,
to roost, most of which appeared to me to be land-birds. The colours
of some were very beautiful, and in many we could trace a
resemblance to our small ducks, magpies and larks.
When to the north-east of the Arru Islands we obtained soundings,
for the first time, on a corally bottom; but as we stood to the south-
west the depth gradually decreased, the bottom changing from coral
to sand, and from sand to soft mud. We encountered daily an
immense number of large Noord-kapers (a species of whale), which
collected around the brig, and on two occasions one of these sea-
monsters passed under her bottom, grazing the keel, and shaking
the entire vessel.
At noon, on the 26th, we passed over a small patch of hard sand, on
which we had only nine fathoms, the depth around being nineteen
and twenty fathoms mud. This, which was named Kolff Bank, was
found to lie in latitude 7 deg. south, longitude 136 deg. 4 min. east.
[45]

On the night of the 27th, while steering to the south-south-east, the

depth gradually decreased, but the bottom still continued muddy.
This made me suspect that we were approaching False Cape, (or
Cape Valsche), the south-west extreme of New Guinea. On steering
south the depth increased to twenty-six fathoms, but after hauling up
north-east and east-north-east we had only five and six fathoms,
which, coupled with a swell from the south and south-east, led me to
conclude that we had passed the Cape. In the evening, when the
atmosphere cleared up, we saw the land to the northward, and soon
brought up to await the day. During the night we experienced north-
east winds, with heavy rain, and a current of six miles from the east-
south-east. Rise and fall between seven and eight feet.
As opportunity offered, we stood in and out from the shore—never
being able to approach nearer than eight miles, the depth at that
distance being only three fathoms, but further to seaward it
increased very rapidly, the first cast of the lead, when standing off
the edge of the bank, giving five fathoms. The land was everywhere
low, and covered with large trees. I endeavoured as much as
possible to approach the land, either with the brig or with the boats,
but was always prevented by the mud-bank. Between the Cape and
St. Bartholomeus River, we saw no opening that would admit our
entrance.
Having arrived off the mouth of the St. Bartholomeus River, which is
easily distinguished, as the points forming the entrance are a
considerable distance apart, the unfavourable state of the weather,
coupled with an increasing swell raised by the strong south-east
wind, determined me to return towards False Cape; being the more
inclined to do so, from the brig, which was anchored nine miles from
the shore, rolling heavily, from being forced by the tide to lie across
the swell, and having already carried away several of the shrouds of
the lower rigging.
The large islands in the Indian Archipelago, generally, have a
considerable influence on the wind, causing land and sea breezes;
but here it was not the case. This circumstance was injurious to the
objects of the voyage, as we were unable to contend against the
strength of the south-east monsoon, being thus prevented from
passing farther to the eastward. To have fully examined and laid
down this part of the coast would have required more time than we
could bestow upon it. We ascertained the south extreme of the land
to lie in latitude 8 deg. 25 min. south, while the longitude of the
mouth of St. Bartholomeus River, by chronometers and lunar
observations, was found to be 139 deg. 2 min. 25 sec. east of
Greenwich. I have laid down the trending of the land in the
accompanying chart as accurately as I could, and am confident of
the correctness of the positions assigned to the principal points.
On the 3rd of May we stood back to the westward, and passed round
False Cape without having any opportunity of landing, although,
being now on a weather shore, we were able to employ the boats
with more safety. An immense number of large and small sharks
always attended the brig, many of which were caught by the ship's
company. On the 7th, while the boats were rowing as usual along the
mud-bank, smoke was seen to arise from the shore, and on nearing
the spot a number of people were seen climbing up into the trees,
who fled into the forest as the boats approached. We were here
again disappointed, for the low marshy land was fronted by an
extensive mud-bank, which forbade our approach. This bank was
covered with crocodiles, which took flight on seeing the boats.
We continued running along shore until the 8th, when we entered a
wide channel, carrying a depth of six and seven fathoms close into
the south shore, while the land on the opposite side was scarcely
visible. We anchored in seven fathoms within the entrance, and the
same night I left the brig in the boats, accompanied by the surgeon,
the clerk, and the interpreters, for the purpose of ascending the river.
We passed up along the south shore, which was still low, marshy,
and well-wooded, and having ascended about twenty-eight miles we
turned back towards the brig, as I judged it inadvisable to proceed
further, the continued rain being likely to give rise to sickness among
the boats' crews. The breadth of the river throughout was about five
miles, the depth being about eight fathoms in mid-channel, and three
fathoms within half a cable's length from the shore. The tides were
very regular, the ebb appearing to be rather the stronger. Rise and
fall ten feet. The water abounded with fish, and the shores were
covered with birds bearing much resemblance to geese, white
ducks, snipes, &c. No natives were seen during the excursion, nor
were any traces of them seen, with the exception of two old canoes,
formed of hollowed trees, which were half buried in the mud. The
tameness of the birds would lead to the conclusion that they were
but little acquainted with man. Only one of the numerous small
creeks we met with produced fresh water, and this was sixteen miles
from the sea. From the creek to the sea, the shore was inaccessible
on account of the mud-bank which fronted it.
This previously unknown river received the name of Dourga River.
The mouth was found to lie in lat. 7 deg. 12 min. south, long. 138
deg. 44 min. east.[46]
Having arrived on board on the 12th, we weighed and stood west-
north-west, north-west, and north, along the edge of the mud-bank;
the water was yellow and muddy, the shadows of the clouds thrown
upon it giving it the appearance of being full of reefs and banks. The
coast, which we could not approach nearer than from ten to twelve
miles, formed several bays hereabouts.
On the 13th, being between the parallels of 6 deg. and 6 deg. 30
min. south, we were enabled to near the land, and seeing smoke
arise to the northward of us we stood towards it, and shortly
perceived a number of small houses on the sandy beach, off which
we came to anchor in three fathoms, about four miles distant from
the shore. A number of men were running to and fro on the beach,
and I lowered one of the boats down for the purpose of
communicating with them. Several small prahus, containing seven or
eight men each, now came towards the vessel, and having
approached within musket-shot, turned back towards the shore. With
a view to give them confidence I sent the crew down below, and
caused the pilots and interpreters to call out to them; but their
answers were unintelligible. Seeing that they were afraid to come on
board, I sent one of the interpreters with six native seamen in the
boat, unarmed, with a view to conciliate them by presents of spirits,
tobacco, &c., which were shown to them, and then launched towards
them on a plank. Our endeavours, however, were unsuccessful; for
they were as much afraid of the boat as of the brig, and retreated on
its approach. I therefore called the boat on board again, on which the
natives remained quiet for some time, until the number of their
prahus were increased to twelve, when they suddenly rowed towards
the brig with a loud shout, stopping, however, when still at a little
distance. I again showed them the presents, and called to them in
the Papuan language, but with the same result as before. I again
sent the boat towards them, without the interpreter, being able to get
near, and it had no sooner commenced returning than the natives
followed with loud cries, taking up their bows and arrows, but
stopping short when the people in the boat ceased rowing. This
mode of proceeding continued for some time, and, at length, seeing
that the natives had their bows strung ready for attack, I fired a blank
shot towards them, on which they all threw themselves flat on their
faces for a few moments, and then paddled away for the shore with
all their might.
These people appeared to be of large stature, with jet-black skins,
and curled hair. They went entirely naked, and no scarifying of the
skin, or other mode of ornamenting, was visible on their persons. In
two of the prahus I remarked several men whose skins were of a
whitish colour. They appeared to be chiefly young men, not one
among them being advanced in years. Two of the eldest-looking
wore the skins of animals.
While the prahus were pulling towards shore, a man stood up in one
of them, with a thick bamboo in his hand, out of which he threw
something that appeared to me to be ashes.[47] When the boats
approached them they also threw water up in the air, and showed
their teeth like enraged dogs. My interpreter assured me that these
people were so inhuman as to devour their prisoners taken in war,
which appeared probable enough, if we may judge from the above
grimaces.
The huts of these negroes, which are scattered along the beach, are
low and open on all sides, the roof being composed of palm leaves.
The soil around the village was white sand, on which many large
trees grew, many carwarinas being among them. A small river ran
into a bay immediately opposite to our anchorage. On going on
shore we were as unsuccessful as on the water, in our attempts to
communicate with these shy people, as they always fled on our
approach, and climbed into the trees at a distance. To judge from the
number of houses and men that we saw, the coast hereabouts must
be very populous. We saw at a distance some other houses, which
appeared to be much larger than those on the beach. Some bones,
probably those of buffaloes, were met with, but not the least trace of
agriculture, arts or civilization. I was sorry, nevertheless, at not being
able to communicate with the natives, for the next morning I
continued my voyage, it being tolerably certain that all endeavours to
make friends with them would be fruitless.
Shortly after our departure we suddenly struck soundings in two and
a half fathoms, having had from ten to fifteen fathoms immediately
before. We continued for several successive days standing along
shore, as close as we could with safety, without finding a spot in
which we could anchor within a convenient distance of the shore.
During the nights we had bad weather, the rain continually pouring
down; and the swell from the southward increasing every day.
On the 16th we saw high land for the first time, the extreme being far
in the interior, between the meridians of 137 deg. and 138 deg. east.
We remarked that several rivers here entered the sea, but so heavy
a surf prevailed everywhere that we could not approach, being
repeatedly obliged to bring up at a distance of from seven to eight
miles from the shore, owing to our coming suddenly from five to
three and a half fathoms. On the 17th, while sailing along shore, we
often attempted to stand in, but were always stopped by reefs; while
at six miles off the shore we had twenty to twenty-five fathoms. I
regretted much that the strong winds and heavy sea prevented me
from examining the different creeks which we saw, although the
interpreters assured me that the inhabitants were in a state of the
utmost barbarism. On the following day we again stood in, and
obtained no bottom with the lead at a distance of four miles off
shore, the hills here running steep off into the sea. We saw some
dwellings about the meridian of 130 deg. east, but were unable to
approach them. The coast was now known to the pilot, who assured
me that he knew a spot in the neighbourhood where we might obtain
fresh water, and having stood off for the night, we endeavoured at
daylight to enter under his direction between an island and the
northern part of a deep bay. The decrease of the depth, however,
soon caused us to stand out to sea again, the pilot excusing himself
by saying, that he always entered here with prahus, and thought that
there was water enough for the brig also.
Being desirous of communicating with the people of the island, and if
possible to obtain fresh water, I again stood in towards the island,
and anchored in five fathoms west-south-west of it. We had
previously seen smoke arise from the shore, which our interpreters
stated to be a signal of welcome, which induced me, after anchoring,
to send the boat on shore with the interpreters, for the purpose of
bringing some of the natives on board the brig. In the afternoon the
boat returned with three of the chiefs, who at first appeared afraid;
but after I had given them some rice and arrack they became more
at their ease. The Raja, an aged man, danced, sang, and made a
number of curious gestures. He could not speak Malayan, but with
the aid of the interpreters we were enabled to converse in their own
language. As a proof of friendship I gave the old Raja a kabya and a
handkerchief for the head, distributing presents of the same
description among the others, with a promise of more if they would
come on board the next day.
I informed them, that the only object of my visit to these parts was to
offer the friendship of the Dutch Government to the natives, and at
the same time to afford protection to the traders who frequent the
neighbourhood. They shouted in praise of the Company and of the
Ceramese, especially the Raja of Kilwari; and, on the other hand,
expressed their detestation of the Chinese, the Bughis, and the
Macassars. On my enquiry whether any of the last-mentioned people
were in the habit of visiting them, they answered that they were not,
but that they gained much information concerning them from the
Ceramese.[48]
I mentioned to the Raja and his friends, that I should send the boats
on shore next morning to obtain water, and that our men, as usual,
would be armed, which they must not suppose to arise from any
want of confidence. I also stated my intention of visiting their village
in person towards noon, at which they expressed much satisfaction,
and taking leave, with a hearty shake of the hand, promised that the
villagers should employ themselves in fishing, and send the greater
part of the produce on board the brig. At seven o'clock the boat
carried them ashore, after they had received a parting present of
arrack and tobacco.

FOOTNOTES:
[45] In the chart prepared by M. Kolff, the longitude assigned for
this bank is 136 deg. 48 min. east.—Translator.
[46] This opening was also entered two years subsequently by
the Dutch corvette Triton and schooner Iris, when it was still
supposed to be a river; but in 1835, Lieut. Kaal, of the Dutch navy,
passed through it out to sea, proving the Dourga and St.
Bartholomew Rivers to be the north-west and south-east
entrances of a strait which cuts off the south-west extreme of New
Guinea, and forms an island about one hundred miles long and
sixty broad.—Translator.
[47] Captain Cook, during his first voyage, touched at a village on
the south-west coast of New Guinea, whose position agrees with
this, and had an encounter with the natives, in which lives were
lost on the part of the latter. The people of the Endeavour
observed, also, the singular proceeding above alluded to, and at
first supposed that the natives had fire-arms. From the remarks of
M. Modera, of the Dutch corvette Triton, it appears that the
composition thrown out of the bamboos consists of lime, ashes
and sand, which were ejected for the purpose of making signals
to friends at a distance.—Translator.
[48] This disgraceful information of the Ceramese was influenced,
probably, by their envy and jealousy of the others.
 CHAPTER XX.
NEW GUINEA.
Armed Boats sent on Shore.—Treacherous Attack of the
Natives.—A Soldier killed.—Cowardly Conduct of the
Officers in Charge of the Watering-Party.—The Author
personally visits the Bay.—Causes of the Barbarism of the
Natives of New Guinea.—Faithless and arbitrary Conduct
of the Ceramese.—Profitable Nature of the Trade.—
Departure from New Guinea.
The friendly meeting with the chiefs, coupled with the assurances of
the interpreters, who had been in the habit of making yearly visits to
the coast, determined me to obtain here a supply of water, this
necessary of life having become scarce on board. On the morning of
the 20th, therefore, I caused the empty casks to be put into the
tender, which was armed with a one-pounder gun, and manned with
an European warrant-officer and a seaman, eighteen rowers, and a
corporal with six soldiers. The chief command was given to a
midshipman, who, with six European and four native seamen, went
in the jolly-boat in company with the tender.
The command of the armed party, who were to cover the waterers,
was entrusted to the corporal, who had been highly recommended to
me at Amboyna, and to whom I gave a written order to guide his
proceedings. As I wished to superintend the watering in person, and
also to visit the village, I caused another of the boats to be lowered,
and sent, in the first place, to examine the depth of water to the
north-east and north-west, the result proving the impossibility of
approaching nearer to the land with the brig. An affection in the
chest, with which I had been afflicted since my voyage to the Bay of
Boni, being more than usually troublesome in the morning, forced
me, however, to defer my visit to the afternoon.
About noon, hearing guns fired on shore, I sent an officer with an
armed boat to enquire the cause, furnishing them with ammunition
for the tender. When close to the island he encountered the boats
returning, and remarked that great disorder prevailed among their
crews, three of the number being badly wounded. They stated that
all their cartridges being wet, and some of the soldiers having thrown
away their arms, they had nothing remaining with which they could
defend themselves. Although the officer sent to their assistance had
with him a dozen good muskets, and cartridges both for them and for
the small cannon, he thought it best to return on board, which I did
not regret when I heard of the events that had occurred. It appeared
that our people met with a friendly reception from the Papuas, who
showed them the watering-place, while those who had visited the
brig the previous night brought them presents of cocoa-nuts and
sagoweer, or palm wine. On his first arrival the midshipman made
arrangements according to his instructions, and had scarcely
finished filling his casks in readiness to be put on board the tender,
when the natives suddenly attacked our party with a shower of
spears and arrows. The Javanese seamen, who had been stupid
enough to leave their arms behind them, immediately left the water
casks, and fled towards the tender, while the corporal, who should
have been the last to retreat, left his post at the first shout of the
Papuas, and throwing away his musket and sword, followed their
example. The Javanese Mandor,[49] however, took up the musket
and fired it at the attackers. The shameful flight of the corporal
created great confusion among the covering party, to whom the
former cried out that they were to follow him, which they did, after
making a short stand. The Papuas naturally acquired fresh courage
on seeing this, and fell on the hindmost, whom they could easily
wound as they fled, while little opposition could be made on our side,
as the tender had already shoved off, and the muskets of the people
in the boat had become useless from their being wetted as their
owners waded on board.
The soldiers and seamen made heavy complaints against the
corporal, to whose cowardice the unfortunate result of the affair was
to be attributed, he having caused the greatest confusion by cutting
the grapnel rope of the tender, and shoving her off. Concerning the
conduct of the midshipman I would rather be silent. On subsequent
examination I discovered, alas! that my orders had not been
followed, and that some had thought more of amusing themselves
than of executing the duty on which they had been sent.
At the commencement of the attack, H. Smit, a seaman who was
sentry at the well, was wounded by two spears, and Ziengo, a
soldier, who had stoutly maintained his post, was dreadfully injured,
being pierced with no less than two-and-twenty wounds; while
another of the seamen, Van Grieken, was wounded slightly by an
arrow in the shin-bone. The courageous Ziengo died immediately
after his arrival on board, while under the hands of the doctor.
Several small casks, a couple of muskets, some cartridge-boxes,
and a quantity of clothing, having been left on shore, I determined to
send the tender (into which a carronade had now been placed) and
an armed boat to bring them off, and to efface the shame which our
people had brought upon them. Being still too unwell to leave the
brig, I entrusted the command of the boats to one of the officers, with
orders to obtain the last articles if possible; but should circumstances
render this unadvisable, he was to keep the natives in check during
the night, and await my arrival in the morning with additional force. A
strong easterly wind, accompanied by heavy showers of rain,
prevented them, however, from reaching the island; and at daylight
the signal for their return to the brig was made, and they came
alongside. The carronade was now taken out of the tender, and two
one-pounder guns placed on board her in its stead, when we stood
towards the island, the tender and the boat carrying in all thirty men.
We soon reached the shore, when the spot on which the encounter
had taken place was pointed out to me. I landed with a portion of the
men, and reached the thick forest that bounded the path to the well,
this being about a pistol-shot distant from the beach. Every thing that
our party left on shore was found, but several of the casks were in
pieces. Much blood was seen scattered about, especially near the
well, where the natives had probably washed their wounds.
From the information I could collect concerning this unfortunate
occurrence, it appeared that the Papuas, who were probably
unacquainted with the deadly effect of our weapons, attacked our
people in great numbers when the latter were off their guard, and
probably without arms.[50] Several shots were fired at them from the
muskets, and from the one-pounder loaded with grape-shot, which
must have done great execution. The courageous Javanese Mandor,
who had remained ashore with the jolly-boat for some time after the
midshipman had retreated with the tender, in order to bring off the
wounded men, had kept up a constant fire at the natives with two
muskets, and declared that he had seen three fall, who were carried
into the forest by their companions. The unfortunate soldier, Ziengo,
had been set upon by a number at once, and had received the most
deadly of his numerous wounds from an axe that had been thrown
away by some of our party. The natives would not have left him but
for the continued fire from the jolly-boat. Notwithstanding the
superior numbers of the natives, our people would never have been
routed had they been on their guard. Unfortunately, my orders were
not followed, and they separated from each other, thinking more of
amusing themselves by bathing and walking, than of preparing
against attack, which gave the natives an opportunity of falling upon
them unawares, and had the latter known how to avail themselves of
the confusion they had created, our loss must have been much
greater than it was. The conduct of my countrymen grieved me
deeply.
At the watering-place we could find no traces of people having been
there since the previous night. The arms that had been thrown away,
and the clothes left by the bathers, remained untouched. The
ground, from the beach to the forest, was strewed with arrows and
spears, among which were two intended for striking fish; these were
provided with iron points, but the others were merely bamboos, the
ends of which had been pointed and hardened in the fire. The arrows
had wooden points and barbs; the bows, by which they were
discharged, being formed merely of a bamboo-stick with a string of
rattan. The force with which these arrows were shot was so small,
that even from a short distance they scarcely did more than
penetrate the clothes of our people, many of whom found the
wooden points of the arrows sticking in their garments after the affair
was over.
As the cocoa-nut trees are not numerous on the coast, while their
produce forms an indispensable article of subsistence, I caused
those scattered along the coast to be cut down, partly to show that
we had not been driven away by fear, and partly to deter them from
committing similar misdeeds in future. The interpreters assured me
this would be a severe chastisement, and that they were in the habit
of killing the relatives of those who injured the cocoa-nut trees.
We now went further into the bay to Kayu Merah, and pulled down
some huts we found standing at the bottom of the heights,
immediately behind the island. Men were occasionally seen, who
took flight on our approach, and climbed into the trees, the better to
observe our motions. Having rowed round the bay without meeting
with any occurrence we turned towards the brig, on which a number
of the natives made their appearance on the beach, who took flight,
however, when we turned the boats' heads to the shore.
The treacherous conduct of the Ceramese cannot be sufficiently
reprehended. It was related to me, and I afterwards had evidence of
its truth, that these people, on their arrival with their prahus at New
Guinea, endeavoured to pick a quarrel with the natives. If the
Ceramese Raja has two or three men killed, it will be of little
consequence, as they will probably be Papua slaves, and even if the
natives take and plunder one of his vessels the loss will still be
trifling. The Raja will be rejoiced at having an excuse for chastising
the natives, and will not only attack and plunder the village, but also
catch as many of the inhabitants as he can, whom he will carry
away, under the plea of taking satisfaction for the injury that has
been done to his people. Similar transactions occur but too often.
Be this as it may, it grieved me deeply to meet with so unfavourable
a reception, as I had so anxiously wished to bring these people
under our Government, and to show them, by the distribution of
presents, that we entertained none but the most peaceable and
friendly intentions towards them. Their barbarism is mainly to be
attributed to the sinister dealings of the Ceramese, who, to retain
their exclusive trade with the coast, inspire them with hatred and
aversion to all foreigners but themselves. Until the rapacious and
inhuman people of Kilwari, Keffing, and the Goram Islands are
stopped in their arbitrary career, and are taught in an impressive
manner to pay a proper respect to the Dutch Government, the coast
of New Guinea will never be available to us for commercial
purposes. Traders would gladly visit these parts could they do so
with safety, for the productions, as massoy-bark, nutmegs, trepang,
tortoise-shell, pearls, edible birds'-nests, birds of paradise, and other
articles of value, would support an important commerce. The
quantity of these rich productions purchased by the Ceramese on
the coast for an almost nominal price, and carried by them to Bali
and Singapore, is incredible. It may appear surprising that under
these circumstances the Ceramese are not in a more flourishing
state, but it must be taken into consideration that a restless people,
constantly at war, do not hoard their riches, but squander it in leading
a luxurious life. I have often been assured that traders, who have left
their homes with a valuable cargo, have returned without sufficient
property to pay their men, the whole having been lost by gambling,
or similar modes of getting rid of wealth.
The people of Kilwari visit the bay of Lakahia regularly once or twice
a year, with coarse white calico, arrack, tobacco, iron ware, &c., to
give in exchange for the productions of the country. The natives of
this part of the coast bear much resemblance in stature and
complexion to those of the easternmost of the Arrus. According to
the account of the interpreters they lead a wild and idle life.
The east monsoon now drawing to a close rendered it inadvisable to
trace the coast to the westward, which should be examined during
the other season; for the coast lies open to the southerly winds,
while the steep nature of the shore affords but insecure anchorage.
My opinions on this point were confirmed by those of intelligent
natives.
As one of the principal objects of the present expedition was to visit
the Tenimber Islands, so important to the native trade, during the
return voyage, (while, were I to remain longer on the coast of New
Guinea, this could not be effected,) I determined to take my