Applied Clay Science 143 (2017) 134–141

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Applied Clay Science

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

Research paper

X-ray coupled Laser Desorption Ionization assessment of layered double

hydroxides for nitrate adsorption based on ion size, affinity and
compromised layer height

Jaybalan Tamahrajah a,b,⁎, Irina Goncharova c, Ivan Pytskii c, Andrey A. Shiryaev c, Alexey A. Averin c,
Michail R. Kiselev c, Alevtina Shaphigulina c, Wan Jefrey Basirun b, Alexey K. Buryak c,
Galina A. Pethukova c, Frank Roessner a
a
Department of Technical Chemistry, Institute of Chemistry, Carl von Ossietzky University of Oldenburg, 26111 Oldenburg, Germany
b
Department of Chemistry, Faculty of Science, University of Malaya, Lingkungan Budi, 50603 Kuala Lumpur, Malaysia
c
A. N. Frumkin Institute of Physical and Electrochemistry, Russian Academy of Sciences, Moscow, Russia

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

Article history: The adsorption of nitrates with NO3(aq) solutions ranging from 20 mg/L to 400 mg/L with Layered-Double-Hy-
Received 21 September 2016 droxides (LDH) PURAL 70 (Mg70) and an Erbium containing LDH (Er40) were investigated. The X-ray Diffraction
Received in revised form 13 February 2017 measurements (XRD) are accompanied by complemented Matrix Assisted Laser Desorption Ionization-Time of
Accepted 16 March 2017
Flight (MALDI-TOF) measurements for prove of NO3- containing LDH. The shift in the XRD reflection angle for
Available online 27 March 2017
both Mg70 and Er40 corresponds to MALDI-TOF Data for presence of nitrate for all LDH except for Er40MW, as
Keywords:
its nitrate adsorption capacity is the lowest. Both methods show the adsorption of nitrates for microwaved
Nitrates LDH and further calcined LDH, proving the memory effect. UV–vis spectroscopy was used to determine the ni-
adsorption trate concentration. The study shows substantial amount of nitrate adsorption for all LDH. Adsorption ranges
MALDI from 2 to 5 mg-NO3(aq)/g-LDH for initial NO3(aq) concentration from 20 mg/L to 400 mg/L. Leaching of element
Layered double hydroxides (LDH) from the LDH structure is done by ICP-MS measurements to guarantee no further pollution of environmental wa-
ters with mentioned elements. Leaching for Mg ranges from170 to 1600 mg/m3 and Al, Er and Fe leaching is less
than 10 mg/m3.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction in the LDH, seem to be reasonable and economic to solve this environ-
mental risk in short time (Cross et al., 2012).
The North German territory of Lower Saxony and Bremen are facing The microwave treatment only removes the excess H2O and the in-
the difficulties of increased nitrate concentration in their aquatic envi- tegrity of the layered structure remains. In this case, the cratering effect
ronments, caused by over-fertilization (Umweltbundesamt, 2015a). Ni- by CO2−3 by calcination is minimized due to the specific targeting of the
trates are feared to be carcinogenic and lead to eutrophication of microwave treatment to remove excess H2O and leave OH-groups in the
mentioned environments (Umweltbundesamt, 2015a, b). brucite-layered structure (Meyer, 2011; Cross et al., 2012).
Subsequent measures must be adopted in the least time possible to Hence, the layered structure is preserved but however, the adsorp-
control further pollution of these environments. Layered double hy- tion capacity may suffer. Hosni and Sasra (Hosni and Srasra, 2008) men-
droxides (LDH) are known to help reduce nitrate contamination in nat- tioned high nitrate adsorption of calcined LDH and retrieval of the
ural-water environments (Torres-Dorante et al., 2008). Hosni et al. and brucite-layer by the memory-effect. However, Torres-Dorrante et al.
Torres et al. have fortunately made investigation akin to this report (Torres-Dorante et al., 2008) reported the nitrate adsorption of uncal-
(Hosni and Srasra, 2008; Torres-Dorante et al., 2008), however with cined LDH. The discrepant amount of nitrate adsorption by uncalcined
other selected layered double hydroxides. Microwave methods for re- and calcined LDH is the aim of this report. This is due to the competi-
moval of excess H2O and hydroxyl groups, which are of most abundance tions of ions involved and the layer height of the LDH of this report
(Wan et al., 2012).
⁎ Corresponding author at: Department of Chemistry, Faculty of Science, University of
The competition between nitrate and other ions, such as OH− CO2− 3

Malaya, Lingkungan Budi, 50603, Kuala Lumpur, Malaysia. and NO− 3 has to be addressed, as they are present in groundwater and
E-mail address: j.tamahrajah@um.edu.my (J. Tamahrajah). affect the nitrate adsorption capacity depending on their affinity to the

http://dx.doi.org/10.1016/j.clay.2017.03.022
0169-1317/© 2017 Elsevier B.V. All rights reserved.
 J. Tamahrajah et al. / Applied Clay Science 143 (2017) 134–141 135

adsorption/ion-exchange sites. The affinity to the sites decreases in the sample and its respective characterization has already been done by
order by CO2− 3 N SO2−4 N OH− N F− N Cl− N Br− N NO− 3 N I
−
(Meyer, Meyer (Meyer, 2011).
2011). As observed, the nitrates have the lowest affinity compared to It is recommended to take LDH with mid-range NO3 adsorption ca-
other ions, especially doubly-charged ions. The investigation starts pacity. Even if higher adsorption capacity are reported by Hosni et al.
with the usual suspects in the microwaved LDH to hinder nitrate ad- and Torres-Dorrante (Hosni and Srasra, 2008; Torres-Dorante et al.,
sorption, which are OH− and CO2− 3 . Further complexity to the adsorp- 2008), it is important to attain reasonable data by LDH with mid-
tion capacity will follow. range NO3 adsorption capacity. This hence proves feasibility of LDH to
Furthermore, the ion size may affect the adsorption capacity by sim- be used as a potential adsorbent in this case. This proves the feasibility
ply having steric hindrance with consideration to the layer height of the of LDH with high adsorption capacity by default. A portion of 5 g of
LDH of concern (Meyer, 2011; Wan et al., 2012). All the effects men- each LDH was treated by means of a Samsung microwave at 850 W
tioned play an important role in this investigation. for 8 and 12 min. Calcination of the sample is done at 420 °C for 6 h
The Matrix-Assisted Laser Ionisation/Desorption (MALDI) with de- (Meyer, 2011). Formation of oxides is confirmed by XRD analysis for
tection by time-of-flight mode (MALDI-TOF) may shed light to the char- the calcined samples (for XRD data of calcined LDH form see Supporting
acteristics of the LDH before (microwaved) and after calcination and information).
nitrate adsorption in the presence of foreign ions aforementioned.
MALDI-TOF is complementary of determining adsorbed ion in cal-
cined and uncalcined (microwaved) LDH through adsorption of nitrates 2.1.1.3. Adsorption experiment. Sample names (Mg70 or Er40) are given
in the presence of CO2− 3 . The amount adsorbed correlates to the layer by their treatment process (MW or MWC) and NO3(aq) concentration
height of the LDH. In this case, the XRD method prevails in determining in solution (020 for 20 mg/L to 400 for 400 mg/L). An example is
the layer height. Mg70-MW-020 where the LDH concerned is the LDH with 70w% of
magnesium hydroxide in the brucite layer, microwave treated and
treated with an aqueous nitrate solution of 20 mg/L (see Table 1). To
2. Procedure
compensate for the soil pH of 8.5, a higher amount LDHs were used
compared to works of Hosni et al. and Dorres-Torrante et al. (Hosni
2.1. Experimental section
and Srasra, 2008; Torres-Dorante et al., 2008).
200 mg of microwave treated (MW) and further calcined (MWC)
2.1.1. Nitrate adsorption
LDH were added to 1 set of the 4 sample test tubes B020-S to B400-S.
The solutions are shaken for 4 h. The solid phase is filtered and
2.1.1.1. Preparation of solution. A stock nitrate solution with a concentra-
microwaved for 12 min again to remove excess water. This corresponds
tion of 1000 mg/L was prepared by dissolving 1.64 g of KNO3 in 100 mL
to the water release of all LDH concerned in this report (see TGA exper-
of distilled H2O. Two sets of four 20 mL solutions were diluted to a range
iments in Supplementary Information). The filtered supernatant solu-
of 20 mg/L to 400 mg/L respectively and placed in 40 mL test tubes
tion is taken for UV–vis and ICP-MS measurements. MALDI-TOF and
(B020, B050, B200, B400). One set is used for nitrate adsorption with a
XRD analysis were done for the dried solid phase.
time of 4 h (e.g. B020-S) and the other set serve as reference solutions
(e.g B020-R). The nitrate concentration was increased to 400 mg/L
due to neutral pH conditions. The system deserves a higher driving
2.1.2. Phase analysis by XRD
force to accommodate to the higher ion exchange capacity at slightly
XRD measurements with Copper Kα-source in reflective mode mea-
higher groundwater pH-value of around 8 to 8.5. Nevertheless, a
surements were done before and after microwave treatment (Mg70–8/
lower value of 20 mg/L is also considered.
12 MW, Er40–8/12 MW) measurements and for all samples introduced
For UV–vis measurement purposes, the solutions were diluted 100
to the nitrate solution (LDH-MW-020-400 and LDH-MWC-020-400).
times again (C020-C400). This is done due to limitations of Navone's
The phase analysis of LDH gives a reflex at 10–12° in the
method to perform well to a maximum NO3-concentration of 8.8 mg/L
diffractogram. This corresponds to the 001 basal plane of the respective
(Navone, 1964). 200 μL of each solution was diluted in 19.8 mL of dis-
LDH. This corresponds to the layer height of the LDH.
tilled H2O. This was again done twice for both sets of sample (S) and ref-
There exists a combined effect of the partial substitution of
erence solutions (R) (B020-S to B400-S and B020-R to B400-R). 200 mg
Al(OH)3−6 as by Er(OH)3−6 and further Er2O3-clusters on the layer sur-
of prepared Zinc-Copper couple is added to the one set of C020-R/S to
face at excess of Erbium precursor during synthesis (Meyer, 2011).
C400-R/S solutions (Navone, 1964). It is to suppress nitrate concentra-
Upon removal of additional OH-groups by calcination, rehydration and
tion in the reference and sample solutions and freely measure nitrate
further microwaving, two distinct reflexes are observed in this case.
concentration without interference other ions in the solutions. The
The cation size of Erbium and Magnesium is similar and allows for
rest of the B020-S to B400-S solutions are taken for ICP-MS measure-
proper substitution without distortion of the layer height. The cation
ment for leaching analysis for the elements of Magnesium (Mg), Alu-
size of potassium may distort the layer upon treatment with nitrate so-
minium (Al), Iron (Fe), and Erbium (Er) originating from the LDH.
lutions (see Table 2). This is due to the preparation of the nitrate solu-
tion by K2CO3 (see section 2.1.1). The incorporation of the cation in
2.1.1.2. Preparation of solid phase. Mg70 is a commercial hydroxy-car- the lattice is less possible as this would distort the layer structure and
bonate based hydrotalcite from SASOL named PURAL. It has a the reflex at 10–12° may disappear, which is not observed in this inves-
MgO:Al2O3 ratio of 70:30, whereas Er40 is a hydroxy-carbonate based tigation. Cluster formation due to K2O may also be possible. However,
hydrotalcite already synthesized by Meyer (Meyer, 2011). It has a this is not observed, as two distinct peaks in Mg70-MW and
base MgO:Al2O3 ratio of 85:15 and Er40 being 40% of the Aluminium Mg70MWC is absent.
being substituted by Erbium. Both are brucite layered structures. Car-
bonate based LDH are studied to investigate the NO3-adsorption capac-
Table 1
ity in the presence of carbonate and hydroxyl ions, as these LDH are The designation of samples used in this report.
reported to have a higher affinity to OH− and CO23 − than to NO3
Sample Microwaved sample Microwaved and
(Hosni and Srasra, 2008, 2009; Meyer, 2011).
name (uncalcined) calcined sample NO3-concentration
Data for Mg70 (PURAL Mg70) and Er40 are readily available as liter-
ature data. Mg70 was purchased from SASOL and the necessary data re- Mg70 MW MWC 020-400
Er40 MW MWC 020-400
quired is provided by the respective company. The syntheses of the Er40
136 J. Tamahrajah et al. / Applied Clay Science 143 (2017) 134–141

Table 2 calcined (LDH-MWC-020-400) LDH (Mg70 and Er40) and compared

The Ionic Radii of the possible cations incorporated in to reference solutions C020-400. All solutions were measures against
the LDH structure with a coordination number of 6
(Lide, 2006).
air. Results of calibrated UV–vis spectra is shown is in the following sec-
tion (see Supporting information).
Element Ionic radii/Å

Al 0.54 3. Results and discussion

Mg 0.89
Er 0.89
3.1. Experimental section
K 1.38

3.1.1. Nitrate adsorption

2.1.3. Matrix Assisted Laser Desorption Ionization-Time of Flight (MALDI- The adsorption isotherms are described according to the Freundlich
TOF) analysis and Dubinin isotherms. The Freundlich isotherm has been used to de-
MALDI-TOF Analysis was done in a MALDI Device by Bruker of the scribe nitrate adsorption in LDH (Freundlich, 1907; Halajnia et al.,
Series Ultraflex-Bruker Daltonics. Intensities were measured by the 2012, 2013; Hosni and Srasra, 2008). However, the Dubinin Isotherm
Flexcontrol Ultraflex software. Analysis of intensities was executed by has better flexibility to describe the adsorption at higher equilibrium
the Flex Analysis software from the same company. The deflection in concentration (Schütz, 1988). This is attempted in this investigation.
positive and negative mode was applied down to 20 Da to suppress in- μ n
terference of the matrix, dihydroxy benzoic acid (DHB) with the sample. Vads ¼ Vo exp ð1Þ
The intensity of the Nitrogen Laser was at 90% of the total laser intensity E
to totally ensure the sample is in the plasma form. where μ is the Polanyi Potential (Chen and Yang, 1994; Dubinin, 1960;
Dihydroxy-benzoic acid (DHB) was used as matrix to carry the sam- Schütz, 1988), given as:
ple to the gaseous phase with little fragmentation. Samples were pre-
 
pared on the target by means of the sandwich model (DHB-sample- Ceq
μ ¼ RTln ð2Þ
DHB). Cads
Reference measurements for MgO (distinct spectra) and PURAL
(Al(OH)4-pseudoboehmit) were taken first. Al2O3 is MALDI inactive Ceq is the equilibrium concentration and Cads is the adsorbed amount of
due to its high stability. However, its hydroxide form can be mildly de- NO3(aq) in the LDH of concern. R is the ideal gas constant and T is the
tected. The departure of Mg70 and Er40 from the reference measure- temperature. It is the normal temperature in this report, taken to be
ment gives qualitative view of the nitrate presence in the LDH for 298.15 K.
microwaved and calcined samples upon nitrate adsorption. The depar- The results of adsorption are shown in Fig. 1 and Table 3. The adsorp-
ture of the spectra for LDH-MW and LDH-MWC after treatment with tion isotherms are described according to the theory of Freundlich (top
NO3(aq) were attributed to nitrate adsorption into the LDH in the pres- sub-figure) and Dubinin (bottom sub-figure). The experimental results
ence of CO2−3 , which form C-clusters (Bloomfield et al., 1985). MALDI- are given from the UV–vis results given in the Supplementary material.
TOF measurements were done for reference compounds MgO from Results are shown up to 400 mg/L Moreover, the maximum values of ni-
Sigma Aldrich, and Pseusobohmite PURAL, Mg70 from SASOL. Er40 trate pollution in groundwater in North German territories are only up
was already synthesized in a previous work by Meyer (Meyer, 2011). to 200 mg/L (Umweltbundesamt, 2015a). Therefore, only the part of in-
terest is shown here.
2.1.4. ICP-Q-MS (inductively coupled plasma quadrupole mass
spectrometry)
ICP-Q-MS measurements were done in the device by Agilent Tech-
nologies 7500 Series (7500ce) and employ a quadrupole prior to
detection.
The element concentrations of Iron (Fe), Magnesium (Mg), Alumin-
ium (Al) originating from Mg70 and Erbium (Er) originating from Er40
is measured by means of Ion Coupled Plasma Mass Spectrometry. Argon
gas is used as carrier gas, make-up gas in the nebulizing chamber and in
the torch. The torch is water-cooled to 16 °C together with the chamber
of the Mass Spectrometer. The nebulizer is thermostated at 2 °C and the
torch is supplied a power of 1500 W. The samples are directed to the
nebulizer by a peristaltic pump, operating at 0.1 revolutions/sec (rps).
For washing, H2O or HNO3 (for sample with Erbium) is used after each
sample measurement and the speed is increased to 0.5 rps. ICP-MS mea-
surements were done for LDH-MW-020-400 and LDH-MWC-020-400.

2.1.5. UV–vis spectroscopic measurements

Navone's method was employed to measure nitrate concentrations
(Navone, 1964). Calibration curves of NO3(aq) solutions were made for
concentrations from 20, 50, 200, 400 mg/L (C020-S to C400-S). Calibra-
tion curves were made by subtracting the intensity of the solution con-
cerned (sample or reference) with the same solution treated with ZnCu-
couple-. This measures only nitrates concentration while suppressing
intensities of other impurities in both respective solutions. The spec-
trometer used is a Perkin-Elmer Lambda 35 UV–vis spectrometer.
UV–vis measurements are done for filtered supernatant nitrate solu- Fig. 1. The agreement of the Freundlich and Dubinin Isotherm relation to the experimental
tions treated with microwaved (LDH-MW-020-400) and further data for nitrate adsorption on Er40MW, Er40-MWC, Mg70MW and Mg70-MWC.
 J. Tamahrajah et al. / Applied Clay Science 143 (2017) 134–141 137

Table 3 concentration gradient is absent in the calcined structure of Mg70-

The experimental data for the NO3 adsorption data for all LDH. MWC. The layer is first flooded by hydroxyl groups and subsequent
Initial concentration Equilibrium concentration Adsorption capacity NO3 adsorption is limited. Hence, upon reconstruction affinity plays a
(mg-NO3/L) (mg-NO3/L) (mg-NO3/g-LDH) role with lowering the nitrate adsorption capacity.
Er40-MW-exp This does not happen to the Er40-MW and Er40MWC sample. Al-
20 19.8 0.0183 though substation of Al(OH)3− 6 by Er(OH)3−6 was successful, the layer
50 48.5 0.1515 height of the non-calcined Er40MW is compromised by premature
200 188.6 1.1365
Er2O3-clusters on the LDH layer. The cluster compromises the layer
400 384.4 1.5503
Mg70-MW-exp height at its deposited locations. This is proven by the broad but distinct
20 0.3 1.9720 reflex of Er40-MW. Hence very less NO3(aq) is adsorbed.
50 27.3 2.2702 Upon calcination to Er40-MWC, the layer is reconstructed to a higher
200 159.3 4.0715 crystallinity, causing two distinct reflexes to occur. The lower reflex is
400 353.8 4.6227
Er40-MWC-exp
the layer height caused by the Er2O3-cluster formation with adsorbed
20 19.7 0.0310 nitrate on the layered structure. This causes an increase in adsorbed ni-
50 49.3 0.0671 trate compared to the non-calcined microwaved structure (Er40-MW).
200 177.5 2.2499 The latter reflex is the conventional Al(OH)36 − and Mg(OH)46 − layer
400 366.8 3.3166
construct reflex. The sharper reflex shows more defined layer passage.
Mg70-MWC-exp
20 14.0 0.5962 This shows that NO3 participates in the reconstruction of the layer ac-
50 40.9 0.9128 cording to the concentration in the solution, which has a larger layer
200 172.0 2.7966 height than without calcination (Er40-MW).
400 365.3 3.4670 The results according to the Freundlich isotherm show good agree-
ment to the experimental data for all LDH involved in the investigation,
with regression values of Er40-MW at 0.8761, Er40-MWC at 0.9320,
For Er-40-MW show the lowest adsorption capacity at just 1 mg- Mg70-MW at 0.7200, and Mg70-MWC at 0.8774.
NO3/g-LDH, as the UV–vis results show still high intensity of the sample The results of the Dubinin-Isotherm show the agreement to experi-
solution. Hence a low adsorption for the LDH of concern is observed. mental data for Er40-MW at 0.8512, Er40-MWC at 0.9036, Mg70-MW at
Er40-MWC shows a higher adsorption capacity at nearly 4 mg-NO3/g- 0.5537 and Mg70-MWC at 0.7891. The Freundlich-Isotherm is favoured
LDH. This is partly due to the calcination of the LDH. The adsorption ca- due to better data representation, as mentioned in literature (Halajnia
pacity increased by exploiting the memory effect of respective calcined et al., 2012, 2013; Hosni and Srasra, 2008).
LDH. More NO3(aq) is adsorbed upon reconstruction of the layer. This is
manifested in the emergence of a double reflex of the XRD data upon re-
construction of calcined Er40MW upon NO3(aq) treatment. The calcined 3.1.2. ICP-MS results
sample prior to NO3 treatment is amorphous (See Supplementary mate- The elemental compositions of Mg, Al, Er, and Fe of the sample solu-
rial for XRD of LDH-MWC prior to NO3(aq) treatment). tion containing the LDH of concern is shown for leaching effects of the
However, Mg70-MW shows a higher adsorption capacity at almost LDH in Fig. 2. The top-left figure shows values for Magnesium leaching
6 mg-NO3/g-LDH than Mg70-MWC (4 mg-NO3/g-LDH). The XRD reflex for all LDH. All LDH except for Er40MW show low leaching effect. The
for Mg70-MW shows a layer height of 0.65 nm. The layer shows a lower leaching of Magnesium is the highest at 1600 mg/m3 for Er40MW.
but less compromised layer height by NO3 in the XRD data with high Other LDH have a leaching effect at lower than 500 mg/m3 the lowest
crystallinity and allows for highest adsorption capacity. being for Mg70 MW and Mg70MWC at about 150 mg/m3.
The layer is further saturated with OH and partially with CO2−3 sub- The bottom-left sub-figure shows the elemental leaching effect of
stitutions already (see MALDI data). This causes a concentration gradi- Erbium. All LDH leach at lower than 5 mg/m3. Measurements for
ent which surpasses the force of affinity for CO23 − and OH− groups. Mg70-MW and Mg70MWC show nearly no Erbium, since Er is absent
This hence causes more NO− 3 to be adsorbed to attain equilibrium. The in the Mg70-type LDH. This data is comparable to data for Er40MW

Fig. 2. ICP-MS results for Er40-MW (top-right), Er40-MWC(bottom-right), Mg70-MW (top-left) and Mg70-MWC(bottom-left) for leaching effects of the hydrotalcites for Mg, Er, Fe and Al.
138 J. Tamahrajah et al. / Applied Clay Science 143 (2017) 134–141

and Er40MWC. Hence, the leaching effect of Erbium in Er40-MW-020-

400 and Er40-MWC-020-400 is relatively low.
Furthermore, the leaching for Aluminium is shown in the top-right
sub-figure. All LDH leaches aluminium at lower than 10 mg/m3.
The leaching effect of iron to clarify overlapping MALDI data for MgO
is shown in the bottom right. All LDH have a leaching effect of lower
than 1 mg/m3. The ICP-MS results show that no iron is present in the
samples. Hence clarification to the absence of iron in the samples is
achieved. The ICP-MS results show that Magnesium leaches at high con-
centrations in nitrate solutions. Other elements considered do not have
a substantial leaching effect.
No LDH contains Fe-ions, however it is done to ensure that the MgO-
MALDI data is truly that of MgO as FeO clusters show identical and over-
lapping peaks. This conflict was reconciled by attaining ICP-MS data for
Fe2+ which may have originated from the distilled water even in the
microgram/l region. By studying the elemental composition of Fe2+ in
the solution, we have successfully concluded that the Fe ions are absent
in the solution.

3.1.3. XRD results

Fig. 3 shows the XRD data for Er40-MW-020-400 and Er40-MWC-
020-400 in the top sub-figure and for Mg70-MW-020-400 and Mg70-
MWC-020-400 for the bottom sub-figure.
The data for Er40-MW-020-400 are thicker than of Er40-MWC. The
XRD data for Er40-MW show one reflex 13°. Another low intensity re-
flex at 62° is of periclase structure of MgO (Meyer, 2011). This corre-
sponds to a layer height of 0.75 nm, with Er(OH)3− 6 incorporated into Fig. 4. The MALDI-MS results for Er40-MW (top sub-figure) and Mg70-MW (bottom
the layer. The layer is saturated with CO2− 3 and OH-substitutions. This subfigure) in the positive mode.
should give an advantage for NO− 3 to be adsorbed due to high concen-
tration gradient compared to OH− and CO23 −. However, the reflex is Upon calcination and nitrate adsorption, two reflexes are observed
broad, which shows a low crystallinity due to presence of unsubstituted for Er40-MWC-020-400, one at 11° and another at 13°. The reflex at
Er2O3-cluster on the layer surface. This is confirmed by Meyer as crystal- 11° corresponds to the larger Er2O3 clusters on the layer (Meyer,
linity decreases with higher amounts of Erbium precursor used for sub- 2011), combined with partial the nitrate substitution, causing higher
stitution (Meyer, 2011). This compromises the layer height and hinders adsorption capacity. The reflex at 13° is the conventional LDH layer by
adsorption. Al(OH)3− 4−
6 . And Mg(OH)6 , which are octahedrally coordinated.

Fig. 3. XRD analysis of LDH Er40 (top sub-figure) and Mg70 (bottom sub-figure) in their
microwaved (MW) and calcined (MWC) forms treated with NO3 solutions from 20 to Fig. 5. MALDI-MS results for Er40-MW (top sub-figure) and Mg70-MW (bottom sub-
400 mg/L. figure) in the negative mode.
 J. Tamahrajah et al. / Applied Clay Science 143 (2017) 134–141 139

The XRD diffractogram for Mg70-MW-020-400 is given as dashed attained should follow a composition of these elements. All other
lines in the bottom figure. The reflex at 15° gives a layer height of peaks are considered as impurities.
0.65 nm. Other low intensity reflexes at 37°, 43° and 62° are that of Reference data is shown in Fig. 4 with Er40 and Mg70 in the positive
the periclase structure of MgO (Meyer, 2011). The high reflex show mode. Due to the existence of Mg, O and H, the mass-to-charge ratio
only an OH− and CO2− 3 substituted layer, giving a lower layer height. from 236 to 291 is identified with reference data as follows:
The saturation of OH and CO2− 3 and a non-compromising layer height OH2Mg4C+ +
9 -(m/z − 221), O2Mg4C9 (m/z − 236), (OH)2Mg6 C6 (m/
+

(absence of large Er(OH)36 −) gives opportunity for a high adsorption z − 249), O3Mg6C+ +
6 (m/z − 263) and O3Mg5C9 (m/z − 277).
of NO3(aq) as concentration gradient dominates the adsorption The trend could be followed from m/z = 221 (OH2Mg4C+ 3 ) to m/z −
phenomena. 291). This shows that the peaks are related compounds. However, m/z
However, the further calcined and nitrate-treated structure of from 236 to 277 is the most prominent and will be considered in this in-
Mg70-MWC-020-400 shows a lower reflex at 12° (solid lines). However vestigation. The question of the distribution for Erbium in the MALDI
adsorption is lower than Mg70-MW-020-400. This is because access for spectra of Er40-12 MW arises, as no Erbium peaks are pronouncedly ob-
further nitrates is hindered as the height is compromised height by the served. This may be due to the mass of Erbium, which is inadequately
readily bound NO3 on the layer. However, the adsorption is sufficient to excited by the low intensity nitrogen laser beam. To find Erbium
increase the layer height after being flooded by predominant hydroxyl peaks, the Er(NO)3 was investigated in a matrix of silver nitrate (highly
groups in the layer. Near identical adsorption capacity of Er40-MWC active in MALDI), which yields the blue peak (Fig. 4-top sub-figure). The
and Mg70MWC is observed in Fig. 1. elemental distribution of Erbium is shown in the inset graph. This is not
observed in Er40-12 MW due to the aforementioned reason.
3.1.4. MALDI-TOF analysis The bottom sub-figure in Fig.4 show the comparison of carbon con-
The MALDI data are divided into positive and negative mode for all taining MgO clusters with Mg70-12MW. Furthermore, Mg(OH)2 clus-
samples of concern (LDH-MW-020-400 and LDH-MWC-020-400, ters are also shown. This reference data is taken from Magnesium
LDH-Er40 and Mg70). It is clear that the LDH considered in this work sulphate heptahydrate (MgSO4-7H2O). Proof of Mg(OH)2-cluster
contains dominant amounts of Mg, Al, O, H and C. Hence, the m/z ratio peaks will be shown, as Mg70-MWC-020-400 shown identical peaks

Fig. 6. Representation MALDI MS Data for Er40-MW (top-right), Er40-MWC (bottom-right), Mg70-MW (top-left) and Mg70-MWC (bottom-left) by agreement to the diagonal reference
data in the positive mode.
140 J. Tamahrajah et al. / Applied Clay Science 143 (2017) 134–141

in Fig.6, which does not contain sulphate ions. The following mass to The single peak at m/z = 330 is observed. This corresponds to
charge ratio are seen: [3(Al(OH)3) + Al(OH)4)]− in the negative mode. This is not observed
[5 Mg(OH)2 5MgO 2H2O H]+ (m/z = 526), [6 Mg(OH)2 5MgO H]+ in Mg70-12 MW and Er40-12 MW. However, its peak is important
(m/z = 549), [5 Mg(OH)2 5MgO 4H2O H]+ (m/z = 565), [5 Mg(OH)2 upon treatment with nitrate solutions.
5MgO 5H2O H]+ = 580.
Other set of mass to charge ratio follow an addition of [2MgO MgC6]
(m/z = 176), with C6 attained from carbon clusters (Bloomfield et al., 3.1.5. MALDI-TOF analysis by correlation of XRD results
1985). Other m/z's are: Fig. 6 shows the MALDI-TOF spectra correlation of LDH-MW-020-400
702 (526 + 176), 725 (549 + 176), 741 (565 + 176), 746 (570 and LDH-MWC-020-400 for LDH Er40 and Mg70 in positive mode. The
+ 176), 878 (526 + 2 × 176), 901 (549 + 2 × 176), 917 (565 + 2 spectra increases in concentration clockwise from the top spectra of
× 176), 922 (570 + 2 × 176), 1054 (526 + 3 × 176), 1077 (549 + 3 LDH-MW/MWC-020, with the lowest nitrate concentration at the top.
× 176), 1092 (565 + 3 × 176), 1108 (580 + 2 × 176). The correlation of all LDH follow the reference spectra for MgO with
The Fig. 5 shows the peaks for Er40-12MW and Mg70-12MW in m/z = 236, 249, 263 and 277, except for Mg70-MWC-020-400 (bottom
comparison to C-cluster peaks in the negative mode (Bloomfield et al., left). The mass to charge ratio observed for this LDH is 526, 549, 565,
1985). 580, 702, 725, 741, 746, 878, 901, 917, 922, 1054, 1077, 1092 and
In Fig. 5, we attained m/z from 36 to 108 with separation of 12 a.m.u 1108 respectively. This corresponds to the Mg(OH)2 cluster peak from
respectively. The formation of carbon cluster is affirmative, as we inves- MgSO4-7H2O seen in the bottom sub-figure of Fig. 4. As Mg70-MWC-
tigate the carbonate-form of the LDH. Upon impact of the nitrogen laser 020-400 does not contain sulphates, this must correspond to Magne-
beam, the carbonates form clusters as follows (Bloomfield et al., 1985): sium hydroxide clusters.
C− − − −
3 (m/z = 36), C4 (m/z = 48), C5 (m/z = 60), C6 (m/z = 72, C9
−
This is a sign that the calcined form of Mg70 has attained increased
−
(m/z = 84), C12 (m/z = 108). hydration upon treatment with nitrate solutions, as the carbonates
As the LDHs contain aluminium hydroxide in its lattice structure and have been released upon calcination. Other LDHs only attain the oxide
due to its low intensity, pure aluminium hydroxide (PURAL) is taken as form of magnesium cluster due to lower hydration effect upon inci-
reference for both sub-figures. dence of the laser beam.

Fig. 7. Representation MALDI MS Data for Er40-MW (top-right), Er40-MWC (bottom-right), Mg70-MW (top-left) and Mg70-MWC (bottom-left) by agreement to the diagonal reference
data in the negative mode.
 J. Tamahrajah et al. / Applied Clay Science 143 (2017) 134–141 141

Fig. 7 above shows the negative mode mass spectra for LDH-MW- for further nitrate adsorption after being flooded by hydroxyl groups in
020-400 and LDH-MWC-020-400 for LDH Er40 and Mg70. The spectra the layer. This reduces the nitrate adsorption.
attained increases with treated nitrate concentration clockwise. The
lowest nitrate concentration is at the top of each figure (LDH-MW/ Acknowledgement
MWC-020).
All spectra show a new mass to charge ratio at m/z = 330, 530, and We thank the European Union for funding of the project
552 after treatment with nitrate solution, except Er40-MW-020-400. ECONANOSORB particularly for the visit to Institute of Physical and
The only mass to charge ratio corresponding to the reference Fig. 5 is Electrochemistry at the Russian Academy of Sciences (IPCE-RAS)
that of aluminium hydroxide (m/z = 330). As the only difference is (295260) in Moscow to perform exclusive MALDI measurements.
the treatment with nitrate solutions, the proof of high nitrate adsorption Analytical work was performed using equipment of CKP FMI IPCE RAS.
by Er40-MWC, Mg70-MW and Mg70-MWC is supported by these
MALDI spectra from concentrations of 20 mg/L to 400 mg/L with m/z Appendix A. Supplementary data
= 530 and 552. The mass to charge ratio correspond to
[Al(NO3)3 Mg(NO3)2 3H2O MgO Mg(OH)2 OH]− (m/z = 530) and Supplementary data to this article can be found online at http://dx.
[Al(NO3)3 Mg(NO3)3 4H2O Mg(OH)2]− (m/z = 552). This is not ob- doi.org/10.1016/j.clay.2017.03.022.
served for Er40-MW-020-400, which gives the impression of low ni-
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