A hybrid Zr/amine-modified mesoporous silica sorbent (SBA/TMPED/Zr-0.5) was proposed to preconcentrate traces of inorganic As from drinking water before its flow injection hydride generation atomic absorption spectrometry (FI HG AAS) determination.
Microporous and Mesoporous Materials 328 (2021) 111484 Contents lists available at ScienceDirect Microporous and Mesoporous Materials journal homepage: www.elsevier.com/locate/micromeso A hybrid Zr/amine-modified mesoporous silica for adsorption and preconcentration of as before its FI HG AAS determination in water ´ ska a, *, Rafał Olchowski a, Emil Zięba b, Ryszard Dobrowolski a Joanna Dobrzyn a Department of Analytical Chemistry, Institute of Chemical Sciences, Faculty of Chemistry, Maria Curie Skłodowska University in Lublin, Poland Centre for Interdisciplinary Research, Faculty of Biotechnology and Environmental Sciences, The John Paul II Catholic University of Lublin, Ul Konstantyn´ ow 1”J”, 20708, Lublin, Poland b A R T I C L E I N F O A B S T R A C T Keywords: Arsenic adsorption Zr modified silica Preconcentration SBA-15 Hydride generation atomic absorption spectrometry A hybrid Zr/amine-modified mesoporous silica sorbent (SBA/TMPED/Zr-0.5) was proposed to preconcentrate traces of inorganic As from drinking water before its flow injection hydride generation atomic absorption spectrometry (FI HG AAS) determination In order to select the sorbent suitable for As traces preconcentration a series of six hybrid Zr modified and Zr/amine modified SBA-15 materials were synthesized, characterized (SEM, XRD, XPS, nitrogen adsorption/desorption), and compared in terms of As(V) adsorption properties It was stated that the introduction of Zr to the SBA-15 structure results in a slight decrease of the sorbent surface area, the deterioration of hexagonal ordering, and changes in materials morphology The introduction of amine groups into Zr/silica results in the extension of the pH range of effective As(V) adsorption and the increase of the adsorption capacity from to 14 mg g− for SBA/Zr-0.5 and SBA/Zr-1 to 24 and 32 mg g− for SBA/TMPED/Zr0.5 and SBA/TMPED/Zr-1, respectively Taking into account fast adsorption and the possibility of quantitative desorption of As from sorbent surface SBA/TMPED/Zr-0.5 was chosen for arsenic traces preconcentration from drinking waters In order to preconcentrate the total inorganic As, As(III) was initially oxidized to As(V) by KMnO4 Before FI HG AAS measurements preconcentrated arsenic was desorbed from SBA/TMPED/Zr-0.5 by using 10 mol L− hydrochloric acid The linearity of the calibration plot ranges from to 40 μg L− The detection and quantification limits were 0.025 μg L− and 0.086 μg L− 1, respectively The recoveries from spiked water samples range between 95 and 105% Introduction The entering of arsenic into the body through a food chain can lead to serious health consequences Inorganic arsenic species are considered as much more toxic than organic ones Both As(V) and As(III) are known as class carcinogens which significantly increase the risk of liver, skin, kidney, and lung cancer [1] Apart from cancer, inorganic arsenic may also cause respiratory and hematological diseases, diabetes, diarrhea, vomiting, and severe nervous system disorders In this respect, 10 μg L− has been fixed by World Health Organization as a guideline value for As concentration in drinking water [2] The significant exceeding of this limit occurs in West Bengal, where from 29 million to 40 million people are exposed to drinking water containing over 50 μg L− of As [3], which is naturally found in water in two oxidation states: arsenite (AsO33− ) and arsenate (AsO43− ) [4] However, a trivalent form, which is more toxic than a pentavalent one, predominates in groundwaters Although, in most water reservoirs the arsenic content is lower than the mentioned value, as a result of prolonged exposure it may accumulate in edible plants and enter into the food chain [5] Due to the high toxicity of arsenic and its low concentrations in environmental samples, many highly advanced and sensitive analytical methods like atomic fluorescence spectroscopy (AFS) [6], graphite furnace atomic absorption (GFAAS), hydride generation atomic ab sorption (HGAAS) [7], and inductively coupled plasma-mass spec trometry (ICP-MS) [8,9] are employed for its concentration monitoring However, when the concentration of arsenic is lower than the limit of quantification of the chosen analytical technique, the preconcentration of an analyte is necessary Besides the lowering of the detection limit, the preconcentration often leads to the elimination of matrix in terferences It may be accomplished by liquid-liquid extraction * Corresponding author.Department of Analytical Chemistry, Institute of Chemical Sciences, Faculty of Chemistry, Maria Curie Skłodowska University in Lublin, Poland, M C Sklodowska Sq 3, 20-031, Lublin, Poland E-mail address: joanna.dobrzynska@poczta.umcs.lublin.pl (J Dobrzy´ nska) https://doi.org/10.1016/j.micromeso.2021.111484 Received 30 June 2021; Received in revised form 13 September 2021; Accepted October 2021 Available online October 2021 1387-1811/© 2021 The Authors Published by Elsevier Inc This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/) J Dobrzy´ nska et al Microporous and Mesoporous Materials 328 (2021) 111484 techniques such as cloud point extraction (CPE) [10], dispersive liquid-liquid microextraction [11,12] or various types of solid-phase extraction [13] Among the numerous preconcentration techniques solvent-free solid-phase extraction based on the partitioning of the analyte be tween solid sorbent and liquid sample, due to its simplicity, high pre concentration factors, and time-saving, seems to be the most appropriate choice The analyte-loaded sorbent can be analyzed directly, or analyte elution may be required, depending on the employed determination technique With regard to preconcentration and removal of inorganic arsenic a number of materials have been proposed, including activated carbon [14], titanium dioxide [15], iron oxide [16], graphene oxide [17], and silicas [18,19] Hexagonal mesoporous SBA-15 material, modified by ligating groups due to its large surface area, large pore volume, and high hydrothermal stability, seems to be particularly attractive for this purpose [20] However, as presented in [20], the application of amine-functionalized SBA-15 does not ensure the quan titative removal of As(V) ions from the solution, which is crucial for the accurate determination of preconcentrated ion To synthesize the ma terial ensuring the quantitative elimination of As(V) from solution, the simultaneous modification of SBA-15 by ZrOCl2 [21,22] and amine-containing monomer was proposed by us The influence of experimental parameters such as pH of aqueous solution, contact time, presence of chosen anions, initial As(V) ions concentration on their adsorption onto N-[3-(trimethoxysilyl)propyl]-ethylenediamine (TMPED) and ZrOCl2 modified SBA-15 materials were investigated and discussed The hybrid material was successfully applied for the pre concentration of As(V) from water samples before flow injection hydride generation atomic absorption spectrometry (FI HG AAS) determination Table Structural parameters of synthesized materials Material Reaction mixture TEOS/TMPED/ ZrOCl2 [mmol/ mmol/mmol] Total BET surface area, SBET [m2 g− 1]a Pore volume [cm3 g− 1]b Pore diameter, dBJH [nm]b SBA SBA/Zr0.5 SBA/Zr-1 SBA/ TMPED SBA/ TMPED/ Zr-0.5 SBA/ TMPED/ Zr-1 20/0/0 20/0/0.5 760 ± 637 ± 1.29 1.14 5.9 8.1 20/0/1 20/2/0 626 ± 738 ± 1.23 1.30 8.8 6.5 20/2/0.5 613 ± 1.17 8.1 20/2/1 550 ± 0.88 7.3 a b from BET desorption method from BJH desorption method with a surface area analyzer ASAP 2405 N (Micromeritics) The specific surface area and pore volume were calculated using the BET and BJH methods, respectively Powder X-ray diffraction (XRD) patterns were collected with Seifert RTG DRON-3 diffractometer (Cu Kα radiation) with 0.02◦ size step and 10 s time step covering a range of 0.5◦ < 2θ < 5.0◦ at RT The scanning electron microscopy (Carl Zeiss Ultra Plus (Germany)) was adopted to observe the morphologies of synthesized materials All experiments were carried out under 20-kV acceleration voltage and 5nA probe current XPS spectra were collected with Multi-Chamber Analytical System (Prevac, Poland) equipped with a monochromated Kα-Al radiation source (1486.6 eV) (Gammadata Scienta, Sweden) and the X-ray power of 450 W C1s = 284.7 eV line was used for binding energy scaling The vacuum in the analysis chamber was better than 1.5 × 10− Pa Experimental 2.1 Materials and reagents The following compounds were used: tetraethoxysilane (TEOS, 99%, ABCR), N-[3-(trimethoxysilyl)propyl]-ethylenediamine (TMPED, 97%, ABCR), Pluronic P123 (P123, Sigma-Aldrich), ZrOCl2⋅8H2O (Merck), HCl (Suprapure, 36%, POCH), HNO3 (Suprapure, 60%, Merck), standard solution of As(V) (1000 mg L− 1) (Merck), sodium arsenite (Merck), NaOH (POCH), ethanol (EtOH, 99.8%, POCH), sodium chloride (POCH), potassium nitrate (POCH) All reagents were used as received, without further purification Ultrapure water prepared by a Millipore purifica tion system with a resistivity of 18.2 MΩ cm was used throughout The water samples were taken from Lublin’s water supply 2.4 Adsorption experiments Adsorption experiments were carried out in a water batch regime Each measuring point was obtained at 25 ◦ C for the suspension con sisting of mg of modified SBA-15 and mL of the As(V) solution The solid sorbent was separated from the solution by centrifugation The initial and equilibrium concentrations of As(V) in the liquid phase were measured by the AAS method The adsorption value was calculated according to the equation: 2.2 Synthesis of sorbents a= Six SBA-15 type sorbents applied for As(V) preconcentration were synthesized by the one-pot route via co-condensation of TEOS with TMPED in the presence of ZrOCl2 The typical synthesis was as follows: Firstly, g of P123 was added to 72 mL of 1.6 mol L− HCl and dissolved at 40 ◦ C under vigorous stirring Then, powdered ZrOCl2⋅8H2O, TEOS, and functionalizing monomer were added in this order Wherein, TMPED was dropped about h after TEOS The mixture was kept under stirring at 40 ◦ C for 24 h Afterwards, the reaction mixture was heated at 100 ◦ C for 48 h without stirring Finally, the suspension was filtered and P123 was removed by triple 6-h extraction with acidified ethanol carried out at 78 ◦ C The obtained solid material was washed with deionized water and dried at 100 ◦ C for h Six materials of various amounts of zirconyl chloride and TMPED were synthesized The names of the sor bents and the composition of the reaction mixture used for their syn thesis are shown in Table (ci − c) × V m (1) where: ci and c are the initial and equilibrium As(V) concentration (mg L− 1), respectively, V is the volume of the As(V) ions solution (L) and m is the mass of modified SBA-15 (g) The determination of arsenic concentrations in the solutions pre pared for adsorption and in residual solutions separated from adsorption systems was carried out using the FI HG AAS technique FI HG AAS determination of arsenic was realized by using atomic absorption spectrometer Spectr AA800 (Varian) equipped with an electrically heated quartz atomizer Arsine generation was performed with a laboratory-modified commercially available flow analysis VGA-77 Vapor Generation Accessory (Agilent)) system Before the arsine gen eration, As(V) was reduced to As(III) For this purpose, 100 μL of the solution containing 2.5% KI + 2% ascorbic acid was added to the Eppendorf vessel containing 900 μL of the sample solution, the waiting time for the reduction to As(III) was h The generation of arsine was performed in the presence of 0.2% NaBH4 in 0.2% NaOH 100 μL of the sample solution (containing As(III)) was injected by using a micro sy ringe to mol L− HCl Argon containing 3% addition of oxygen was 2.3 Characterization of materials The adsorption/desorption isotherms were measured at − 196 ◦ C J Dobrzy´ nska et al Microporous and Mesoporous Materials 328 (2021) 111484 used as a carrier gas, atomization was carried out at 710 ◦ C The spec trometer settings during measurement were as follows: wavelength – 193.7 nm, lamp current – 10 mA, delay - s, time of measurement - 25 s The peak area was used for integration The desorption studies were carried out in a batch system consisting of about 0.0005 g of As-loaded sorbents and mL of desorption media The suspensions were shaken for 24 h at 20 ◦ C Centrifugation was applied to separate the liquid and the solid The concentration of As in the liquid phase was measured with the FI HG AAS technique In the case of CRMs the recovery of As was calculated as the ratio of concentration measured to certified value, whereas for As-spiked Lublin tap water it was calculated according to the equation: ( ) cmstw − cmptw Recovery = × 100% (2) cstw adhere to the hydrophilic part of the P123 micelle or to the silanol group to form cationic species participating in the self-assembly process [25] The substitution of some protons by zirconyl cations probably leads to the increase of the diameter of P123 micelles and, the same, to the extension of SBA-15 pore diameters 2.5 Analytical procedure 3.1.2 XRD The application of the XRD technique allows assessing the influence of ZrOCl2 addition during the synthesis on the order degree of the ob tained materials In the case of pristine SBA-15, three intensive (100), (110), and (200) reflections are observed at the small-angle XRD pat terns (Fig 1), which indicate the ordered hexagonal structure of the material The addition of ZrOCl2 to the reaction mixture leads to a slight decrease in the intensity of (100) reflex and a significant one in the in tensity of two other reflections, as evidenced by patterns of SBA/Zr-0.5 and SBA/Zr-1 Thus, the ordering of SBA-15 deteriorates in the presence of zirconyl chloride The deterioration of ordering is also observed when SBA-15 is modified by TMPED However, it is worth mentioning that the ordering of TMPED-modified SBA-15 is slightly improved when 0.5 mmol of ZrOCl2 is added to the reaction mixture, which is reflected by the increase of the (110) and (200) reflects on SBA/TMPED/Zr-0.5 compared to SBA/TMPED First, to oxidize As(III) to As(V), KMnO4 was added to the water sample to obtain the concentration of 5∙10− mol L− [23] After an hour, the pH of 20 mL of the water sample was adjusted to 3.5 by the addition of HNO3 Then 20 mg of sorbent SBA/TMPED/Zr-0.5 was added to the sample and the mixture was shaken for 24 h at 25 ◦ C After that, the sorbent was separated from the solution through filtration and dried at 100 ◦ C to constant weight About 10–14 mg of dry sorbent as weighted in the Eppendorf vessel, and 0.25 mL of 30% HCl was added In order to obtain the total desorption of As from sorbent, the Eppendorf vessel was placed in an ultrasound bath for 20 The determination of As in the solution obtained after desorption was performed by the FI HG AAS technique Before the arsine generation, As(V) was reduced to As (III) For this purpose, 100 μL of the solution containing 2.5% KI + 2% ascorbic acid was added to the Eppendorf vessel containing sorbent and 0.25 mL of 30% HCl Then 650 μL of water was added to reach the volume to mL The waiting time for the reduction of As(III) was h Before the FI HG AAS determination, the solution was separated from the sorbent by centrifugation The measurement conditions were the same as for the determination of As in the solutions used for adsorption (See Paragraph 2.4.) 3.1.3 SEM SEM analysis were carried out to shed the light on the morphologies of the hybrid Zr/silica and Zr/organosilica materials The formation of disc-like SBA/Zr and egg-like particles of SBA/TMPED/Zr materials is presented in Fig Both discs of SBA/Zr and eggs of SBA/TMPED/Zr are arranged in chains, reaching about 20 μm for SBA/Zr and about 10 μm for SBA/TMPED/Zr The formation of SBA/Zr and SBA/TMPED/Zr hy brids was proved by SEM-EDX (See ESM - Table S1) In the case of SBA/ Zr-0.5 except of disk-like, also spherical particles which were not found for the other studied materials are observed Increasing the amount of ZrOCl2 from 0.5 to mmol added during synthesis of SBA-15 favors the formation of narrow discs, which are especially clearly visible for SBA/ Zr-1 Increasing the amount of ZrOCl2 from 0.5 mmol to mmol during the synthesis of TMPED-modified SBA-15 does not significantly affect the morphology of the obtained particles Despite the morphological differences between SBA/Zr and SBA/ TMPED/Zr samples, it has to be emphasized that the synthesis of both pristine and TMPED-modified SBA-15 in the presence of ZrOCl2 leads to the complete change of the morphology of the obtained particles As can be seen in our previous work [26] for pristine and amine-modified where:cmstw – As concentration measured for As-spiked tap water,cmptw As concentration measured for pristine tap water (without any addition of As) containing only naturally occurring As,cstw – theoretical As con centration being a result of tap water spiking Results 3.1 Characterization of materials 3.1.1 Nitrogen adsorption/desorption isotherms In order to access the impact of ZrOCl2 on the porosity of SBA-15 type materials, nitrogen adsorption/desorption isotherms were determined (see Supplementary Fig S1) All of the relations were classified as type IV isotherms with H1 hysteresis loops according to the International Union of Pure and Applied Chemistry (IUPAC) classification, which are typical for mesoporous materials [24] The structural parameters calculated based on experimental data are presented in Table The modification of SBA-15 by TMPED does not change the surface area and pore volume of the material Whereas the introduction of ZrOCl2 into the reaction mixture results in the decrease of the mentioned parameters Wherein the decrease is proportional to the amount of added zirconyl chloride Both the lowest surface area of 550 m2 g− and pore volume of 0.88 cm3 g− are observed for SBA/TMPED/Zr-1 The increase of the pore diameter of the materials synthesized in the presence of ZrOCl2 suggests that zirconyl ions influence on self-assembly of the polymer micelle and the silica precursor for both unmodified and amine-modified SBA-15 It seems that zirconyl cation may replace hydrogen ions and Fig Small angle XRD patterns of synthesized materials J Dobrzy´ nska et al Microporous and Mesoporous Materials 328 (2021) 111484 Fig SEM images of synthesized materials SBA-15 synthesized without the addition of ZrOCl2 worm-like particles are obtained, while the addition of ZrOCl2 leads to the creation of discs or eggs probably originates from H2AsO4− ions Thus As(V) is boned as oxoan ions both by Zr and N atoms The positively charged Zr(IV) ions present in the Zr–O groups and the positively charged amine groups cause the attraction of As(V) anions, which facilitates the formation of bonds be tween As and N or O atoms 3.1.4 X-ray photoelectron spectroscopy In order to determine the mechanism of As(V) adsorption onto SBA/ TMPED/Zr type materials, XPS spectra of SBA/TMPED/Zr-0.5 and Asloaded SBA/TMPED/Zr-0.5 were recorded and compared In SBA/ TMPED/Zr-0.5 and As-loaded SBA/TMPED/Zr-0.5 zirconium is pre sent in the fourth oxidation state, as evidenced by the doublet of 3d 5/2 and 3/2 peaks at 183.2 and 185.6 eV, respectively (See ESM Fig S4 a and S4 b.) [27] The doublet of Cl 2p 3/2 and ½ at 198.3 and 199.9 eV observed for the pristine SBA/TMPED/Zr-0.5 indicates the presence of chlorine which is probably bonded with Zr atoms The peak of chlorine disappears when As(V) is adsorbed, thus it can be concluded that Cl− ions are released to the solution due to the adsorption of arsenic The comparison of the XPS signals of oxygen obtained for pristine and As-loaded sorbent (Fig S4 c and d, respectively) leads to the conclusion that arsenic is adsorbed as oxo-anion For both materials two forms of oxygen are distinguished O 1s peak at 532.9 eV reflects the presence of Si–O bonds [28], while the one at 530.9 eV [27] is the evidence of oxygen-metal bonds The participation of the second form of oxygen increases almost twice (from 3.4 to 7.8 atomic %), as the result of arsenic adsorption The energies of As 3d 5/2 and 3d 3/2 peaks equal to 45.5 and 46.2 eV (Fig S4 e), respectively indicate the presence of As(V) on the surface [29] However, As(V) oxo-anions are bonded not only with Zr but also with amine groups For the spectrum of N 1s region of pristine SBA/TMPED/Zr-0.5 three peaks at 400.0, 401.5, and 402.4 eV (Fig S4 f) corresponding to primary, secondary, and protonated amine groups can be distinguished after deconvolution [30] After adsorption the fourth peak appeared at the N1s region, the binding energy of 407.3 eV (Fig S4 g) proves that N atoms are bonded with oxygen [31], which 3.2 Adsorption studies 3.2.1 pH influence As(V) species dissociate according to the reactions [32]: H3 AsO4 (aq) ⇌ H+ (aq) + H2 AsO4− (aq)K1 = 10− 2,5 (3) H2 AsO4 − (aq) ⇌ H+ (aq) + HAsO4 2− (aq)K2 = 10− 6,96 (4) HAsO4 2− (aq) ⇌ H+ (aq) + AsO4 3− (aq) K3 = 10− 11,24 (5) Due to the fact that the speciation of As(V) and the sorbent surface protonation are pH-dependent, the relation of adsorption vs initial pH value was determined and presented in Fig In the case of pristine SBA-15, As(V) uptake is negligible in the studied pH range For SBA/Zr0.5 and SBA/Zr-1 materials, adsorption significantly increases compared to pristine SBA-15 The highest values are reached for initial pH between 1.6 and 2.9 Higher pH is favorable for the deprotonation of the sorbent surface, which results in the repulsion of As(V) anions and a significant decrease of adsorption It was concluded that the adsorption of As(V) onto SBA/Zr-0.5 and SBA/Zr-1 is associated with the presence of pro tonated zirconium species Zr − OH+ , which electrostatically attract H2AsO4− ions In the studied pH range, solvated H2AsO4− ions form the stable inner-sphere complexes with the Zr modified silica surface [33] The maximum adsorption efficiency onto SBA/Zr-0.5 and SBA/Zr-1 was attained at pH 2.9 Consequently, all the subsequent adsorption exper iments with the application of SBA/Zr-0.5 and SBA/Zr-1 were carried J Dobrzy´ nska et al Microporous and Mesoporous Materials 328 (2021) 111484 Fig The effect of initial pH on the adsorption of As(V), t = 24 h, T = 25 ◦ C, cAs(V)=10 mg L− 1, m = 0.005 g, V = mL Fig Adsorption isotherms of As(V) onto studied materials, t = 24 h, T = 25 ◦ C, pHSBA, SBA/Zr-0.5, SBA/Zr-1 = 2.9, pHSBA/TMPED, SBA/TMPED/Zr-0.5, SBA/TMPED/ Zr-1 = 3.5, m = 0.005 g, V = mL out at pH 2.9 SBA/TMPED/Zr materials also adsorb H2AsO4− ions; however, the maximum uptake is reached at initial pH of 3.5 Contrary to SBA/Zr materials, in the case of SBA/TMPED/Zr, the rapid decrease of adsorp tion associated with the increasing of initial pH is not observed It was stated that the modification of SBA/Zr materials with TMPED leads to the creation of the material, which efficiently sorb As(V) anions in a wide pH range The presence of amine groups probably facilitates the adsorption of As(V) caused by electrostatic interactions between pro tonated amine groups and H2AsO4− anions Thus, to obtain sorbent quantitatively removing As(V) from the solutions of various pH, the introduction of Zr and amine groups to organosilica structure is neces sary Further studies using SBA/TMPED/Zr and SBA/TMPED sorbents were carried out at a pH of 3.5 adsorption, when even small changes of the size of the mesopores and micropores significantly change the adsorption properties [34,35] The initial run of isotherms obtained for all four ZrOCl2 modified materials proves the possibility of quantitative removal of As(V) from the solutions of initial As(V) concentration not exceeding mg L− and hereby ensures the usefulness of sorbents for analytical purposes The ideal sorbent used for analyte preconcentration is expected to ensure quantitative adsorption over the widest possible pH range because the possibility of preconcentration in a wide range of pH considerably simplifies the sample preparation procedure Among the synthesized sorbents, this requirement is met by materials SBA/TMPED/Zr-0.5 and SBA/TMPED/Zr-1 In Table the comparison of chosen sorbents used for As species preconcentration is presented 3.2.3 Interferents The effects of coexisting anions found in natural waters (such as chlorides, nitrates, and phosphates) on As(V) adsorption onto SBA/ TMPED/Zr-0.5 and SBA/TMPED/Zr-1 were investigated (Fig 5) Chlo rides and nitrates in the range of concentration between 0.0001 and 0.01 mol L− have no significant effect on the adsorption of arsenate on SBA/TMPED/Zr-0.5 and SBA/TMPED/Zr-1 For higher concentrations of both anions, the adsorption of arsenate slightly decreases; however, for mol L− coexisting anions solution, the adsorption value is not lower than 60% of the value obtained in the solution containing no chlorides or nitrates Thus, both sorbents can be useful for preconcen tration of As(V) from the waters containing low concentrations of chlorides and nitrates The adsorption of arsenates is significantly impaired when only 0.001 mol L− of phosphates are present in the solution When As(V) is adsorbed from 0.1 mol L− phosphate solution the adsorption is only 3% of the value obtained in a phosphate-free solution Thus SBA/TMPED/Zr-0.5 and SBA/TMPED/Zr-1 materials are not suitable for the preconcentration of As(V) from the solutions containing more than 0.0001 mol L− of phosphates; however, both materials can be successfully applied for the preconcentration of As(V) from drinking water Phosphates decrease the As(V) adsorption because of the similar coordination chemistry and affinity for zirconium (hydr) oxides as arsenate Phosphates form the same inner-sphere complexes and hereby effectively reduce sorbent’s capacity for adsorption of ar senates [33] 3.2.2 Adsorption capacity In Fig 4, As(V) adsorption isotherms are presented The maximum static adsorption capacities are strictly dependent on the TMPED modification and the amount of Zr used for the synthesis of sorbents The maximum adsorption capacity of As(V) obtained onto pristine SBA-15 is only mg g− 1, whereas, for SBA/Zr-0.5 and SBA/Zr-1, and 14 mg g− are reached, respectively A further increase of adsorption capacities is observed for sorbents modified by both ZrOCl2 and TMPED Maximum static adsorption capacity of SBA/TMPED, SBA/TMPED/Zr-0.5 and SBA/TMPED/Zr-1 are 5, 24 and 32 mg g− 1, respectively The slight decrease of the specific surface area and the simultaneous widening of the mesopores being the result of SBA-15 modification with increasing amounts of ZrOCl2 does not cause the decrease of As(V) adsorption Increasing the amount of ZrOCl2 used for the synthesis resulted in an improvement of the adsorption capacity of the materials towards As(V) ions Similar relationship was obtained for the series of SBA/TMPED materials modified with increasing amounts of ZrOCl2 In this case, despite the decrease of the specific surface area from 738 m2 g− for SBA/TMPED to 550 m2 g− for SBA/TMPED/Zr-1 and the decrease of the pore volume, the adsorption of As(V) increased over times Thus, the surface chemistry is of key importance for the adsorp tion of As(V) ions on the studied materials Minor changes in the porous structure of modified SBA-15, including changes of micropores, not have such a significant effect on the adsorption properties shown in relation to As(V) present in aqueous solutions as it is in the case of gas J Dobrzy´ nska et al Microporous and Mesoporous Materials 328 (2021) 111484 Table Comparison of the condition of As species preconcentration by solid phase extraction method Analyte Adsorbent Matrix Detection technique Eluent LOD [ng L− 1] Adsorption capacity [mg g− 1] EF Ref As(III), As(V), AsBet, cacodylate As(III), As(V) PSTH-functionalized magnetic NP/GO Water, biological samples Water HPLC-ICP-MS 1.1 - As(III), 0.2 - As (V), 3.8 - AsBet, 0.5 - cacodylate – 1.6 - As(III), 5.0 - As (V), 3.2 – cacodylate, 1.1 - AsBet 2.68 – [36] ICP-OES 0.1% m/v TU + 0.1% m/v CS in NaOH pH 12.0 mol L− HNO3 [37] As(III), As(V) CdS nanoflowers food ICP-OES mol L− 0.5 – As(III), 0.8 - As (V) 0.23–1.85 137 As(III) 145 As(V) – As(III) – 400, As(V) − 300 100 [39] Inorganic and organic As species As(V) As(III), As(V) As(III) As(III), As(V) As(III), As inorganic As inorganic As(V) As(V) Polyaminesfunctionalized silica Ti (IV)-modified vinyl phosphate magnetic nanoparticles Amine/ALIQUAT 336/ CNTs composite Nickel–zinc ferrite NP HNO3 − [38] Fish, meat HPLC-ICP-MS 0.1 mol L NaOH Cannabis oil XRF – 100 10 10,000 [40] Water spectrophotometry HG AAS ICP-OES HG AAS mol L− Fe3O4/MnO2 composite Water 0.5 mol L− HCl – – [45] Al2O3/GO Zr/amine-modified silica Water Water Slurry sampling HG AAS XRF HG AAS 20 - As(III), 30 - As inorganic 2.9 966 900 As(III) 833 As(V) 20.4 [42] [43] Seawater 35.8 As(III) 62.5 As(V) 140 45 - As(III), 50 As(V) – [41] Water, food Water 150 - As(III), 100 As(V) 1.3 30 100 Protein laminated GO 2D carbon sheets/ MnFe2O4 composite PTFE mol L− NaOH mol L− HCl 0.5 mol L− HCl – 10 mol L− HCl 20 25 43.9 32 294 12.5 [46] This work HCl [44] AsBet – arsenobetaine, CNTs - carbon nanotubes, CS – 1-cysteine, EF – enrichment factor, GO - graphene oxide, HPLC-ICP-MS - high-performance liquid chroma tography in combination with inductively coupled plasma mass spectrometry, XRF - X-ray Fluorescence Spectroscopy, ICP OES - Inductively Coupled Plasma Optical Emission Spectrometry, NP – nanoparticles, PSTH - [1,5-bis(2-pyridyl)3-sulfophenylmethylene] thiocarbonohydrazide, PTFE – polytetrafluoroethylene, TU – thiourea 3.2.4 Desorption The possibility of quantitative As species desorption from SBA/ TMPED/Zr sorbents was studied using hydrochloric and nitric acids As can be seen in Fig As species are totally removed from SBA/TMPED/ Zr-0.5 and SBA/TMPED/Zr-1 when at least mol L− HNO3 is applied When 10 mol L− hydrochloric acid is used desorption reaches 75 and 93% for SBA/TMPED/Zr-1 and SBA/TMPED/Zr-0.5, respectively However, after 20-min, sonication of SBA/TMPED/Zr-0.5/HCl suspen sion quantitative desorption of As is observed Hence, to ensure the Fig The effect of chlorides, nitrates and phosphates on the adsorption of As (V) onto SBA/TMPED/Zr-0.5 and SBA/TMPED/Zr-1, t = 24 h, T = 25 ◦ C, pH = 3.5, m = 0.005 g, V = mL, c = 8.8 mg L− Fig Desorption of As in the presence of HCl and HNO3, m = 0.0005 g, Vr = mL, ASBA/TMPED/Zr-0.5 = 20.2 mg g− 1, ASBA/TMPED/Zr-1 = 28.9 mg g− 1, t = 24 h, T = 25 ± 0.5 ◦ C J Dobrzy´ nska et al Microporous and Mesoporous Materials 328 (2021) 111484 quantitative desorption of As from SBA/TMPED/Zr-0.5 to 10 mol L− HCl, a 20-min sonication step was introduced to the analytical proced ure The As desorption by HNO3 before HG AAS determination was not recommended due to oxidative properties of the acid, which potentially could hinder the reduction of As(V) to As(III) before arsine generation Despite the necessity to use small volumes of concentrated hydro chloric acid for As species desorption, the proposed materials allow quantitative preconcentration of As(V) even from solutions of a con centration exceeding mg L− 1, therefore their recommendation is justified Ideally, As species could be desorbed using milder reagents, but be aware that much larger amount of hydrochloric acid is used in the hydrogen generation step from NaBH4 than in the arsenic desorption step Table Results of As(V) determination in tap water and certified reference materials by FI HG AAS CRM Determined concentration [μg L− 1] Certified concentration [μg L− 1] Recovery [%] NRCAQUA-1 SRM 1640a 0.212 ± 0.045 0.222 ± 0.014 95 7.92 ± 0.088 8.01 ± 0.067 99 Sample Spiked concentration [μg L¡1] 0.2 0.5 1.0 2.0 Determined concentration [μg L¡1] 0.201 ± 0.014 0.407 ± 0.013 0.708 ± 0.032 1.18 ± 0.028 2.31 ± 0.037 Recovery [%] – 102 101 98 105 Lublin tap water 3.2.5 Analytical figures of merit and validation Analytical figures of merit of the method were studied using SBA/ TMPED/Zr-0.5 as solid sorbent and the analytical procedure described in section 2.5 The good linearity of the calibration curve was observed in the range of 2–40 μg L− with an the acceptable correlation coefficient of 0.9989 The limits of detection (LOD) and quantification (LOQ) were calculated as LOD = 3SD/a and LOQ = 3SD/a, where SD is the standard deviation of 10 replicate blank signals and a is the slope of the cali bration curve after the extraction process, assuming that the enrichment factor was 12.5 LOD ad LOQ were 0.025 μg L− and 0.086 μg L− 1, respectively The relative standard deviation (RSD%) of the method (0.5 μg L− of As(V) ions, n = 5) was 4.5% The accuracy of the method was verified by determining the ele ments in the standard reference materials NRC-AQUA-1 (drinking water) and SRM 1640a (freshwater) as well as by analyzing the spiked amount of arsenic to real samples The experimental results presented in Table are in good agreement with certified and spiked values The recoveries are justifiable for trace analysis, in the range of 95–105% – review & editing, Supervision Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work 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https://doi.org/10.1016/j.microc.2021.105974 Conclusion In this work, a Zr/amine-modified SBA-15 was synthesized, charac terized, and applied for simple As(V) preconcentration before its further FI HG AAS determination Zr/amine-modified SBA-15 was found to be the effective sorbent of As(V) in a wide pH range The comparison of sorption properties of Zr/silica and Zr/amine-modified silica for As(V) shows that the introduction of amine groups to Zr/silica results in the extension of the pH range of effective adsorption and the increase of the adsorption capacity The adsorption capacity of SBA/Zr-0.5, SBA/Zr-1, SBA/TMPED/Zr-0.5, and SBA/TMPED/Zr-1 materials with respect to As (V) were found to be 8, 14, 24, and 32 mg g− 1, respectively XPS results revealed that both Zr and N atoms are responsible for As(V) oxoanions adsorption It was stated that nitrates and chlorides coexisting in the solution with As(V) not cause a sharp decrease in its uptake, whereas even 0.01 mol L− phosphates 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10.1016/j.talanta.2018.03.090 ... - As (V) 0.23–1.85 137 As( III) 145 As( V) – As( III) – 400, As( V) − 300 100 [39] Inorganic and organic As species As( V) As( III), As( V) As( III) As( III), As( V) As( III), As inorganic As inorganic As( V)... In this work, a Zr/amine-modified SBA-15 was synthesized, charac terized, and applied for simple As( V) preconcentration before its further FI HG AAS determination Zr/amine-modified SBA-15 was... Slurry sampling HG AAS XRF HG AAS 20 - As( III), 30 - As inorganic 2.9 966 900 As( III) 833 As( V) 20.4 [42] [43] Seawater 35.8 As( III) 62.5 As( V) 140 45 - As( III), 50 As( V) – [41] Water, food Water