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Aluminum Building Scrap Wire, Take-Out Food Container, Potato Peels and Bagasse as Valueless Waste Materials for Nitrate Removal from Water supplies

  • Safaa El-Nahas
  • Hassan M. Salman
  • Wafaa A. Seleeme
Original Article
  • 42 Downloads

Abstract

Purpose

Two types of active acidic alumina derived from aluminum building wire scraps (AlBWS) and aluminum take-out food container waste (AlTFC), as well, two effective types of activated carbon prepared from potato peels (ACPP) and sugarcane bagasse (ACSB) for removal of nitrate ions were utilized in this study.

Methods

Adsorbent samples were prepared with highly porous structure and large specific surface area above 200 m2 g−1. Also, low calcinations temperatures and low-priced chemicals were used.

Results

The results showed that the adsorption of nitrates were rapid. The qmax were found to be 12.4, 8.8, 7.1 and 3.9 (mg g−1) for AlTFC, AlBWS, ACPP and ACSB samples, respectively. The thermodynamic parameters showed the endothermic nature and adsorption of nitrate ions and are considered chemisorption. The total cost of the samples production were 13 USD kg−1 for acidic alumina and 6 USD kg−1 for active carbon.

Conclusion

The adsorption of nitrates were utilized in real and synthetic samples which give an excellent removing capability for nitrate pollution from groundwater samples.

Keywords

Nitrate removal Alumina Activated carbon Building scraps wire Aluminum take-out food container Potato peels 

1 Introduction

Nitrates jeopardize all water reservoirs. Recently, contamination of surface and groundwater with nitrates has emerged as an insistent problem on a global scale [1, 2, 3, 4, 5, 6], due to its toxicity and various pernicious health hazards on both human and animal beings causing in some cases fatal results [7, 8, 9, 10]. Furthermore, the existence of elevated levels of nitrates in water has been globally linked to numerous environmental risks such as eutrophication [11].

Point and non-point sources of nitrate pollution have been linked to the growing agricultural and industrial activities, intensive and uncontrolled application of fertilizers, pesticides and herbicides in the agricultural sectors, drainage of untreated sanitary, septic tank outflow, municipal wastewater, landfill leachate, atmospheric deposition, and local mineral deposits such as potassium nitrate [12, 13, 14, 15, 16, 17]. Besides, chemical manufacturing of explosives and the byproducts of pharmaceutical, nitro-organic compounds, paper industries and processed food [18, 19, 20, 21].

Generally, over-consuming of nitrate-contaminated water can damage human health and even kill. It can cause methemoglobinaemia in the newborn infants, which contribute to a drastic increase in their mortality rate [17, 22, 23, 24, 25]. In adults, exposure to high levels of nitrates is a risk factor for specific cancers like digestive tract cancers [15, 16, 17, 26, 27, 28, 29]. In livestock, nitrate poisoning causes symptoms like abdominal pain, diarrhea, weight loss, abortion of brood animals, dark brown or chocolate colored blood, mucous membranes; furthermore in severe cases, coma and death may happen within a few hours in cattle [7, 17, 27, 28, 29]. For its perniciousness and its possible health risk, The United States Environmental Protection Agency (USEPA) has set a limit of nitrate in drinking water to be 45 mg L−1 as nitrate (10.2 mg L−1 nitrate–N), whereas WHO (the World Health Organization) has set international maximum permissible level of 50 mg L−1 as nitrate (11.3 mg L−1 nitrate–N) [30].

Unlike other environmental pollutants, nitrate is very mobile, highly soluble, cannot bind or be absorbed by the soil layers and undetectable in water, thusly elimination of nitrate ions from water by the traditional treatment processes utilized for water portability are difficult and ineffectual. Thusly, numerous treatment techniques have been developed for nitrate removal from water like, biological denitrification, reverse osmosis (RO), electrodialysis (ED), chemical reduction, ion exchange resins (IX), adsorption and catalytic denitrification [3, 10, 20, 25, 27, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41]. In the last years, the nanoscale catalytic materials such as nano PdAu alloy [42] and indium decorated palladium nanoparticles [43] have been found to be very promising materials for treating nitrate and nitrite polluted water.

Compared to the other nitrate removal technologies, adsorption is considered an excellent technique for removal of nitrates, nitrites and a wide range of organic and inorganic contaminants from aqueous effluents. It is simple, efficient, no post treatment is required, adsorbent material can be easily recycled by low cost-effective method [20, 44]. For the previously mentioned reasons, adsorption technique has been selected in the current study to be utilized in treatment of contaminated water from nitrate.

Herein, tested adsorbents serve as attractive alternative materials for removing of nitrates from water supplies by recycling abundant unused agricultural wastes and industrial by-products. Compared with traditional adsorbent materials, the main advantages of the newly synthesized adsorbents are the high efficiency, large surface areas, controllable pore structures and highly active sites on the surface. The cost of manufacture the adsorbent materials were minimized by two methods. The first one is by utilization of worthless and locally available starting materials; while, the other one is using low cost-effective synthetic technique for production of the selected adsorbents such as utilization low temperatures in calcination of all the adsorbent samples and choosing inexpensive chemicals.

In the present study potato peels, bagasse, aluminum foil waste, and aluminum building wire scrap are four different types of wastes which accumulate in large amounts day after day causing a serious environmental menace. Hence, recovery of useful materials such as activated carbon and active alumina from these wastes to be applied as efficient adsorbent materials for the removal of environmental pollutants is crucial for both economic and environmental necessities.

Waste Al foil and scrap Al wire or cables are the most prevalent sources of the global Al waste. Al building wiring is used as a kind of electrical wiring in many houses [45]. Also, Al takeout food container waste is one of the most important sources of the global Al waste. About 7 billion containers of aluminum foil are produced annually worldwide. That equals 220 containers every second [46]. Generally, the aluminum takeout foil containers are usually made from a 1000-series or 3000-series alloy: aluminum alloys which contains between 92 and 99% aluminum. They are mainly used for food products for their ability to retain and reflect heat.

Recycling of these two types of Al waste materials has a number of key environmental and economic benefits. In this work, waste Al foil and scrap Al wire or cables have been recycled at the end of product life rather than wasted to produce a highly efficient active alumina to be used in water purification.

Potato peel is an easily available agricultural waste (as a household and restaurant waste), it has been successfully applied to produce carbon samples for decontamination of water because of its lignocellulosic-rich structure, and its high adsorption capacity for many pollutants such as heavy metals, organic pollutants, and drug compounds [47, 48, 49, 50].

Finally, sugarcane bagasse is dry pulpy residue left after the extraction of juice from sugarcane. In the present study, SB is applied as a raw material for producing activated carbon to remove nitrates from its aqueous solutions by adsorption.

Until now, none of the researchers have attempted to apply activated carbon prepared from potato peels (ACPP), aluminum building wire scrap (AlBWS), or aluminum takeout food containers (AlTFC) in removing of nitrates from aqueous solutions making this work unique and new.

2 Materials and Methods

2.1 Chemicals

All the chemicals and reagents used in this work were of analytical grade and were used without any further purification. Deionized water was used in the preparation of all solutions.

2.2 Apparatus

For the characterization of the prepared adsorbents, the surface functional groups were analyzed by Fourier transform infrared spectroscopy (FTIR, the JASCO 4100). The surface area measurements were determined by Automatic ASAP 2010 Micromeritics spectrometer (USA) for at liquid nitrogen temperature. The morphology of the three adsorbents was characterized using a scanning electron microscope (SEM, JSM-5500LV model) operating at 25 kv.

In batch experiments, the nitrate concentrations were measured using Hanna (HI 96786), whereas the pH measurements were made using precision pH-meter (Model PHS-3C). Temperature-controlled water bath with shaker model (WB-110X) was used for shaking the samples at different time intervals.

2.3 Synthesis of Adsorbent Materials

Al foil waste was successfully recycled and converted into active alumina as follows: 20 g of used Al foil was dissolved in an appropriate volume of hydrochloric acid under vigorous stirring at 60 °C. NH4OH was added drop wise until the pH of the solution was attained to 8.0. A white precipitate of Al(OH)3. The final precipitate was washed, dried, and ignited at 400 °C in dynamic air. The resulted sample was assigned as AlTFC. Also, preparation of active alumina from Al wire scrap AlBWS was prepared by a similar methodology as AlTFC (Fig. 1a).
Fig. 1

a AlTFC and AlBWS alumina, b ACPP carbon, c ACSB carbon

Potatoes were obtained from local markets (Qena, Egypt). Potato peels were washed with tap water, then with deionized water repeatedly to remove dust and impurities.Washed Potato peels were dried at room temperature and then oven-dried at 70 °C for 48 h to minimize the moisture content. The dried peels were grounded and sieved to finer particle size before using. To prepare the activated carbon adsorbent from potato peels, 25 g of dried peels were heated to 500 °C, at 10 °C min−1, and kept for 3 h under N2 flow of 150 ml min−1. Finally, the sample was cooled under N2 flow and named as ACPP (Fig. 1b). For SB, the air-dried material was heated till carbonization and the obtained biochar was referred to as ACSB (Fig. 1c).

2.4 Point of Zero Charge (PZC)–Surface Properties

The surface chemistry of tested adsorbents was characterized by the determination of pH at the point of zero charge (PZC).The PZC or pHPZC is the pH at which the resultants of the adsorbent surface charge is null [51].

Based on methodologies described by [2, 51, 52, 53, 54] with some modification, five bottles, each one contains 50 ml of an aqueous solution of NaCl (0.01 M), and fixed sorbent loading (2.0 g L−1 in case of AlTFC and AlBWS and 3.0 g L−1 in case of ACPP and ACSB), were prepared then the starting pH of the solution (pHi) in each bottle was adjusted by using NaOH (0.5 M) or HCl (0.5 M) solutions at pH range (2–10) in case of AlTFC and AlBWS and (2–12) in case of ACPP and ACSB. The final pH of the solutions (pHf) was measured after 48 h of agitation with the sorbent (long enough time is allowed for diffusive mixing). ΔpH was calculated (ΔpH = pHi − pHf) and plotted versus pHi. The PZCwill be the point which reaches the null value variation (at ΔpH = 0). The pH meter was calibrated at pH values 4, 7, and 10 prior to each run.

For determination of the acidity or basicity of the adsorbent’s surface in pure water, measurements of the surface pH of tested adsorbent samples were performed. 0.1 g of dry adsorbent sample was added to 50 ml of distilled water and stirred for 2 h. The suspension was kept for 48 h at the room temperature to reach equilibrium, then the final pH was measured (developed from methodology described by [48]).

2.5 Adsorption Studies

Adsorption of nitrate ions onto tested adsorbent media was studied by batch experiments. A fixed dosage of sorbent (6 g L−1) were shaken at 150 rpm with 50 ml of KNO3 solution at a concentration equals (50 mg L−1) in a capped glass bottle (250 ml). The above samples for each sorbent were filtered and the nitrate concentration in the supernatant was determined. Experiments were performed in duplicate.

The percentage of removal of nitrates was calculated by the Eq. (1):
$$\% {\kern 1pt} \,Removal = \frac{{\left( {C_{o} - C_{e} } \right)}}{{C_{o} }} \times \text{100}\quad$$
(1)
where Ci, Cf are the initial and the final concentrations of NO3 solution in mg L−1. (qe) is the (mg) amount of the adsorbate per (g) amount of adsorbent, adsorption capacity (mg g−1) was calculated by Eq. (2):
$$q\,_{e} \, = \frac{{\left( {C_{o} \, - C_{e} } \right)\,\,}}{m} \cdot \,\frac{V}{1000}\quad \;$$
(2)
where Co and Ce are the initial and final concentration at equilibrium (mg L−1), m is the mass of adsorbent dose (g); V is the volume of the solution (ml).

2.5.1 pH Studies

In order to study the effect of pH of solution on nitrate adsorption onto the selected adsorbent materials, the pH of KNO3 solution (50 mg L−1) was adjusted to different values (2, 3, 4, 6, 8, 10, and 12) by using NaOH (0.5 M) or HCl (0.5 M) solutions. The experiments were performed at sorbent dose 6 g L−1 in the batch method, and then samples were shaken for 2 h at the room temperature. The pH of the resulting solutions was then determined.

2.5.2 Adsorbent Dosage Studies

Different adsorbent doses (from 1 to 20 g L−1) were placed in 50 ml of KNO3 solution at a fixed concentration of (50 mg L−1) without adjusting the pH value, then was shaken for 2 h at 150 rpm and at the room temperature.

2.5.3 Kinetic Studies

For kinetic studies, 50 ml KNO3 solution (50 mg L−1) and fixed adsorbent dose 6.0 g L−1 were used at different contact time intervals (from 0 to 200 min.) at the natural pH value of the solution and the room temperature.

2.5.4 Effect of Initial Concentration

50 ml of nitrates at different initial concentrations (15–85 mg L−1) without adjusting the pH value was added to sorbent dose 6.0 g L−1 and shaken for 2 h to investigate the effect of Initial concentration on adsorption of nitrates onto the three adsorbents at the room temperature.

2.5.5 Effect of Temperature

To evaluate the effect of temperature on sorption of nitrates, 50 ml KNO3 solution (50 mg L−1) and adsorbent dose 6.0 g L−1 were shaken for 2 h at different temperature intervals (25–60 °C).

3 Result and Discussion

In this work, we must point that all the four tested adsorbent materials were prepared using a cost-effective synthetic route at low calcination temperature and without pre-adjustment of the solution pH and achieve high removal efficiency. The nitrate removal efficiency follows the order ACPP > AlSW > AlBWS > AlTFC > ACSB, they were 60.38% for ACPP, 49.18% for AlBWS, 45.57% for AlTFC and 38.52% for ACSB at an initial concentration of 50 mg L−1. As can be seen, the ACPP sample has the highest adsorption removal efficiency. The reasonable high adsorption capacity was due to the nature and the morphology of adsorbent materials which will be discussed below by using SEM, EDX and FTIR analysis.

3.1 Characterizations of the Adsorbent

3.1.1 Surface Area and Pore Volume Measurements

Specific surface area or surface area per unit mass of a solid is an important characteristic in understanding the structure, formation and potential applications of different materials. For this reason, it is necessary to determine and control it accurately. Both surface area and porosity are considered as vital factors that reflect a real image about the structure of any solid material. Therefore, increasing the surface area will improve the concentration of active sites. Consequently, this is expected to increase the rate of ion’s sorption at the adsorbent-solution interface [55, 56]. There are various methods for assessing the surface area of solids, but the most commonly used theory is the BET theory and nitrogen is the most commonly employed gaseous adsorbate used for surface probing by BET methods at 77.35 K [57].

The nitrogen adsorption–desorption isotherms exhibited by the tested samples are presented in Fig. 2, while the corresponding BET isotherm curve (plot of 1/W[(Po/P) − 1] versus relative pressure (P/Po) is demonstrated in Fig. 3. Also, results and the textural parameters calculated from the adsorption isotherms derived by BET-, t-, and BJH-analysis are summarized in Table 1.
Fig. 2

N2 adsorption–desorption isotherms determined at 77.35 K on AlBWS, AlTFC, ACPP and ACSB

Fig. 3

BET adsorption isotherm for AlBWS, AlTFC, ACPP and ACSB at 77.35 K

Table 1

BET-, t-, and BJH-, analysis, results of N2 adsorption data on AlBWS, AlTFC, ACPP and ACSB

Sample

BET theory

t-Theory

BJH theory

SBET (m2 g−1)

CBET

Sext (m2 g−1)

SMP (m2 g−1)

Vmic (cm3 g−1)

Vmes (cm3 g−1)

Scum (m2 g−1)

APD (Å)

MPD (Å)

Vcum (cm3 g−1)

AlBWS

237.6

18.4

201.1

36.55

0.03

0.08

179.5

17.6

18.3

0.27

AlTFC

217.3

25.2

125.3

91.9

0.05

0.05

156.4

17.5

18.6

0.18

ACPP

282.6

2.7

194.3

79.6

0.02

0.06

141.9

11.2

10.9

0.24

ACSB

389.0

13.7

265.3

123.7

0.04

0.13

197.6

17.5

17.5

0.35

The adsorption–desorption isotherms of N2 at 77 K for AlBWS and AlTFC powders in this study showed isotherm belongs to (IV) type in the IUPAC classification, while ACPP and ACSB show isotherms of type (III) [57] as demonstrated in Fig. 2. Obtained data in Table 1 illustrate that tested samples can be precisely described as microporous, i.e. containing pores less than 2 nm (or d < 20 Å). The calculated SBET values were relatively high, they were as following: 389.0 m2 g−1, 282.6 m2 g−1, 237.6 m2 g−1, and 217.3 m2 g−1 for ACSB, ACPP, AlBWS and AlTFC, respectively. The surface areas of test samples exceed the values of a number of commercially available activated carbons [52] as well as other adsorbents reported by other [23, 58, 59, 60]. Thus, it can be reasoned that the selected adsorbents have highly porous structure and are of large specific surface areas, which are fundamental requirements for an efficient adsorbent.

3.1.2 X-ray Diffraction (XRD) Analysis

The XRD analysis of the two alumina samples (Fig. 4a, b) identify the formation of Al2O3 structure according to (JCPDS no.: 10-0425) card. Peaks with diffraction lines are persisting at d = (2.38,1.96, 1.40 Å) for AlBWS and (2.39,1.98, 1.40 Å) for AlTFC at (2θ = 37. 75°, 46.15° and 66. 70°) for AlBWS and (37. 53°, 45. 77° and 66. 52°) for AlTFC. These diffraction lines are corresponding to Miller indices (311), (400) and (440), respectively. Also, no peak was observed for pure Al element which indicates the complete transformation of Al element into the γ-Al2O3. The phase analysis confirmed the presence of gamma alumina phase in the two tested samples. Similar results published for γ-Al2O3 by [61, 62, 63, 64].
Fig. 4

The X-ray diffraction pattern for a AlTFC, b AlBWS

The amorphous structure of carbon cannot monitor by XRD and diffractograms for ACPP and ACSB samples. The composition and purity of our carbon samples are elucidated by EDX analysis. Thus, the spectra of two samples ACPP and ACSB samples are not shown here, but the identity of the surface particles was confirmed using EDX analysis, which found to be more accurate in the case of carbon samples and it provides the purity and elemental composition of various constituent elements in these two tested carbon materials.

3.1.3 SEM and EDX Analyses

Figure 5a–d shows the scanning electron microscopy images of the four applied adsorbent materials (a) AlBWS, (b) AlTFC, (c) ACPP and (d) ACSB at different magnification factor.
Fig. 5

The SEM photo for a AlBWS, b AlTFC, c ACPP, d ACSB (the left coulum has more magnification factor)

The calcinated aluminum oxide for AlBWS samples is appearing as agglomerates (Fig. 5a) with a sub-micron size of primary particles, which are difficult to be resolved by the SEM. This is due to the fact that n-Al2O3 particles have a strong tendency to form agglomerate due to Wander Wall’s forces between particle–particle [65]. While,The shape of the AlTFC sample (Fig. 5b) is different, it has a porous structure. Also, the image shows the pores, steps, and cracks on the surface of adsorbent. Similar results were obtained by other authors [62, 63].

The surface morphology of pyrolized carbon samples derived from potato peels (Fig. 5c) show a lot of cavities and pores with sponge like structure, which can be attributed to the conditions of the synthesis technique It is obvious, that the ACPP samples have larger pores with high internal surface area than other tested samples. While, the ACSB has a milder surface with some straps as appeared in (Fig. 5d). Thus, ACPP samples have more numbers of active sites, suggesting that the adsorption capacities onto ACPP are greater than the respective onto ACSB and onto the other tested sample of alumina. The surface morphology of carbon plays an important role on in its adsorption performance, which was proved after the adsorption evaluation. Similar structure for carbon samples had the same appearance [47, 66, 67].

EDX analysis provides the elemental composition of various constituent elements in these two types of carbon (ACPP and ACSB samples). The elemental analysis indicated that the purified carbon is about C (65.05%), O (28.34%), K (1.80%) and P (0.32%) by weight for ACPP sample and C (71%), O (22.80%), N (2.5%), K (2.40%), Cl (0.37%), Mg (0.17%), Na (0.17%) and P (0.12%) by weight for ACSB sample. The presence of many different elements such as Mg, Na, Cl and P may be due to the origin of these samples as agriculture plant source. Results of EDX analysis were presented in Fig. 6a, b.
Fig. 6

The EDX analysis for a ACPP, b ACSB

3.1.4 FTIR Analysis

The FTIR for the solid adsorbent was performed to indicate the functional groups on the sorbent surface responsible for adsorption of nitrates. The general infrared spectrum of the γ-alumina obtained from two types of alumina after calcinations at 400 °C are shown in Fig. 7a. The peaks at (3428, 1643 cm−1) for AlTFC and (3428, 1643 cm−1) for AlBWS are attributed to stretching and bending modes of strongly adsorbed water. The bands at low wave numbers around 1400, 1091, 779.5 and 548 cm−1 indicate the γ-Al2O3 [8, 24, 68]. Finally, the absorption band located at 548 cm−1 is characteristic to the Al-O vibrations in Al2O3 [1].
Fig. 7

The FTIR Spectra for a AlTFC and AlBWS, b for ACPP and ACSB

Figure 7b the peaks for the two types of carbon around 3428 cm−1 refer to O–H stretching. As to the other the bands around 1719.1, 1417, 1117.3 and 780 cm−1 may be due to various C=C stretching vibrations, C–C and C–O stretching vibration and =C–H stretching vibration. The large number of adsorption peaks displayed in the spectrum indicates the complex nature of the examined carbons [66].

The carbon derived from potato peels has more sharp bands at 2904.5 and 1716.1 and 1117.3 cm−1 more than carbon from bagasse.

The peaks at 2904.5 cm−1 are referred to the symmetric and asymmetric C–H stretching vibration of aliphatic acids. While, the peak observed around 1716.1 cm−1 is attributed to the stretching vibration of bond carboxyl groups that may be indicate the carboxylic acids or their esters. Also, The peak observed at 111.7 cm−1 is due to C–H in plane [66, 69]. In addition, the persisting of O-containing groups of carbons can serve as Lewis-acids, which can play a good route in adsorption mechanism [49].

3.1.5 Point of Zero Charge PZC–Surface Properties

Point of zero charge is a pH value exists at which the sum of negative charges equals the sum of positive charges and the net charge on the surface is zero.

To assess the affinity of the surface of the sorbent to the ionic species, the position of PZC is essential to be determined [70]. It is obvious from Fig. 8 that the adsorption process onto the surfaces of AlBWS and AlTFC is pH-dependent. The initial pH of the nitrate solution is plotted versus (ΔpH) the difference between the initial and final pH values of solutions. The point of intersection of the plot pH initial at ΔpH = 0 is the PZC [61]. For the two active aluminas, this is assembled according to Fig. 9.
Fig. 8

PZC for AlBWS, AlTFC, ACPP and ACSB

Fig. 9

Effect of PZC on alumina samples

The PZC of AlBWS and AlTFC samples were found to be 4.0 and 4.46 respectively. As active alumina is added to a liquid solution below its PZC value, the surface acquires a net positive charge as the surface protonated via the adsorption of excess hydrogen ions H+, whereas, at pH above its PZC value, the surface deprotonated via the desorption process of H+, and consequently acquires a net negative charge [2, 71]. It means that the surface is positively charged at low pH values and negatively charged at high pH values.

For activated carbon samples, their surface chemistry is controlled by the functional groups present on the surface of the carbonaceous adsorbents. These functional groups play an essential role in the adsorption processes because they have a great influence on the reactivity of the surface of ACs. Oxygen-containing functional groups (also known as surface oxides) as previously confirmed by FTIR analyses (Fig. 7b). In case of ACPP and ACSB samples, PZC values were found to be 10.0 and 8.80, respectively. Depending on the nature of these groups and the pH of the solution in the aqueous solutions, these surface groups give rise positive or negative charges. At pH values lower than PZC, AC’s surface becomes positively charged and vice versa [54, 72, 73]. Similar results obtained from [48].

The surface pH measurements were performed to determine the acidity or basicity of the adsorbent’s surface in distilled water. Obtained experimental data indicated that both active aluminas AlBWS and AlTFC have acidic character (4.43 and 4.66 respectively), whereas the activated carbon sample (ACPP) was found to be a basic character (pH = 9.80) and ACSB was found to have a neutral character (pH = 7.52).

3.2 Effect of pH

The influence of pH values of the adsorption capacity of nitrates onto AlBWS, AlTFC, ACPP and ACSB has been illustrated in Fig. 10. The effect of pH on the percentage removal of nitrates by the tested samples was studied for a variety of initial pH from 2.0 to 12.0 in 2 h of adsorption time. It was noted that the PZC is the key parameter that controls the adsorption uptake of nitrates onto the test samples [53].
Fig. 10

Effect of pH on  % Removal of nitrate ions by AlBWS, AlTFC, ACPP and ACSB

It is clear that higher adsorption capacities for nitrates were observed at lower pH values (at acidic pH, when pH < PZC), this may be attributed to the positive surface charges of the applied adsorbents resulting from protonation reactions, which increases the coulombic force of attraction between positively charged surface and negatively charged nitrate ion [2, 8, 74] as it illustrated in Fig. 11a, b.
Fig. 11

Mechanism of nitrate ion removal on a alumina, b carbon

In case of AlBWS sample; percentage removal of nitrates didn’t strongly affected by the change in the pH value of the solution.

3.3 Effect of Adsorbent Dose

The influence of the adsorbent dose on the adsorption of nitrate was also studied at ambient temperature (22 ± 2 °C) and contact time of 2 h as shown in Fig. 12a. For all selected adsorbent samples, there was an increase in nitrate removal by increasing the adsorbent dosage. This may be due to the increase in the active sites on the surface of the adsorbent materials by increasing the dosage. Similar results have been published by [75]. In case of AlTFC sample, it was found that further increase in dose beyond 10.0 g L−1 rarely affected the adsorption efficiency of adsorbent, while the ACPP have high adsorption capacity and give 100% of nitrate removal using an adsorbent dose of 10.0 g L−1. The results also clearly indicate that beyond the AlBWS dosage of 6.0 g L−1, the percent removal increases slowly, which indicates that 6.0 g L−1 is the optimum adsorbent dosage.
Fig. 12

Factors affected the percentage removal of nitrate by ACPP, AlBWS, AlTFC, and ACS: a Effect of dose. b Effect of initial conc. c Effect of time. d Effect of temperature

3.4 Effect of Initial Nitrate Ions Concentrations

Initial concentrations of nitrate ions play an important role in the mass transfer between the aqueous and solid phase. It is evident from experimental data plotted in Fig. 12b that nitrate removal efficiency is strongly dependent on the initial concentration of nitrate ions in the solution. By increasing initial nitrate concentration, the nitrate removal efficiency decreases for all the applied samples. When the initial nitrate concentration increased from 15.0 to 85.0 mg L−1 at fixed adsorbent dose (6.0 g L−1), the percentage removal of nitrates decreased from 90.0 to 52.36% in case of ACPP, from 38.19 to 63.09% in case of AlBWS, from 54.2 to 41.05% in case of AlTFC and from 72.67 to 24.20% in case of ACSB sample. This phenomenon may be reasoned to the saturation of the most active sites at a fixed dose of the adsorbent surface with increasing concentration as more nitrate molecules would be provided. Also, increasing the initial nitrate concentration increases the diffusion rate of nitrate ions to adsorption. This result is in agreements with other studies published [1, 76].

3.5 Effect of Contact Time

Adsorbent/adsorbate contact time is an important factor in the adsorption process since contact time depends on the nature of the used system [77]. The influence of time on nitrate uptake by ACPP, ACSB, AlBWS, and AlTFC is illustrated in Fig. 12c. For all adsorbent samples, nitrate removal efficiency increases with increasing the contact time till it reached an equilibrium value beyond which no more nitrate is further adsorbed from the solution. Generally, the adsorption process was initially rapid and became slower near the equilibrium. All the adsorbent materials under study, exhibit short time to reach the equilibrium state, which give us an initial prediction that the type of nitrate adsorption onto these materials is chemisorption process. Equilibrium was attained after about 45, 60, 30 and 150 min for AlBWS, AlTFC, ACPP and ACSB, respectively. It is clear from the results constructed in Fig. 12c that the initial uptake of nitrates onto ACPP was rapid, where about 50% of the nitrate ions are adsorbed within the first 5 min indicating that the ACPP possesses superior adsorption performance with high adsorption kinetics. Similar trends were observed by other researchers [8, 78].

3.6 Effect of Temperature

Temperature plays an essential role in the adsorption process [79]. Obtained results in Fig. 12d showed that the percentage of nitrate adsorption increased with the increase of the temperature from 25 to 55 °C, that may be attributed to the acceleration of some originally slow adsorption steps and enhancement of the mobility of nitrate ions from the bulk solution towards the adsorbent surface which gives a proof of the endothermic nature of the adsorption process of nitrates onto the selected adsorbents. Many authors published similar results [1, 2, 19].

3.7 Adsorption Isotherms

The adsorption equilibrium and its mathematical description are of outstanding significance. The knowledge of adsorption equilibrium data provides the basis for assessing the adsorption processes and, in particular, for adsorber design purposes. Information about the adsorption equilibrium in a considered adsorbate/adsorbent system is essential, for instance, to characterize the adsorbability of water pollutants, to select an appropriate adsorbent, and to design batch, flow-through, or fixed-bed adsorbers [73]. The most famous models are Langmuir and Freundlich models, which were given by the following equations mentioned below:

3.7.1 Langmuir Isotherm Model

This model is used to describe the maximum adsorption capacity of the adsorbent material. The Langmuir equation is written by Eq. (3):
$$q_{e} = \frac{{q_{\text{max} } K_{L} C_{e} }}{{1 + K_{L} C_{e} }}$$
(3)
And its linear form can be expressed by Eq. (4):
$$\frac{1}{{q_{e} }} = \frac{1}{{K_{L} q_{\text{max} } }} \cdot {\kern 1pt} \frac{1}{{C_{e} }} + \frac{1}{{q_{\text{max} } }}$$
(4)
where Ce and qe are as mentioned above. While qm (mg g−1) is the maximum adsorption capacity and KL (L mg−1) is Langmuir constant related to the affinity of binding sites or bonding energy. An essential feature of Langmuir isotherm is the dimensionless constant separation factor or equilibrium parameter is KR which can be used to predict whether an adsorption system is favorable or unfavorable [8] can be expressed by Eq. (5):
$$K_{R} = \frac{1}{{1 + K_{a} C_{o} }}$$
(5)
where Ka is the Langmuir constant and Co is the initial metal ion concentration.

3.7.2 Freundlich Isotherm Model

The Freundlich model assumes that the uptake of metal ions occurs on a heterogeneous surface by monolayer adsorption. The model can be described by the Eq. (6):
$$q_{e} = K_{f} C_{e}^{{\frac{1}{n}}}$$
(6)
The linear form of the Freundlich equation can be written as:
$$\log q_{e} = \frac{1}{n}\log C_{e} + \log K_{f}$$
(7)
where Kf (L g−1) and n are Freundlich constants characteristics of the system and indicate the adsorption capacity and adsorption intensity, respectively [8].

3.7.3 Temkin Isotherm Model

The Temkin isotherm is usually used for heterogeneous surface energy systems (non-uniform distribution of sorption heat). The Temkin equation suggests a linear decrease of the adsorption energy as the degree of completion of the adsorptional centers of an adsorbent is increased. The heat of adsorption of all the molecules in the layer would decrease linearly with coverage due to adsorbent-adsorbate interactions. As mentioned before, the adsorption is characterized by a uniform distribution of binding energies, up to some maximum binding energy. The Temkin isotherm can be expressed in a linear form as presented in Eq. (8):
$$q_{e} = B\ln A + B\ln C_{e}$$
(8)
where B = RT/b, B is a constant related to the heat of sorption (J mol−1) obtained from the Temkin plot (qe versus ln Ce). A is the equilibrium binding constant (L mg−1), R is the universal gas constant (J mol−1 K−1), T is temperature K, and b is the heat of adsorption which is directly related to coverage of nitrate ions onto a solid surface due to adsorbent-adsorbate interaction
The linearized Freundlich, Langmuir, and Temkin plots for adsorption of nitrates are presented in Fig. 13a–c and their constants were calculated and tabulated in Table 2.
Fig. 13

Adsorption Isotherms plots for ACPP, AlBWS, AlTFC, and ACSB at 22 ± 2 °C: a Langmuir isotherm. b Freundlich isotherm. c Temkin isotherm

Table 2

Langmuir, Freundlich, and Temkin Constants for Nitrate Adsorption onto ACPP, AlBWS, AlTFCand ACSB at 22 ± 2 °C

Sample

Freundlich constants

Langmuir constants

Temkin constants

n

1/n

Kf

R2

qm

KL

R2

B

b

A

R2

AlTFC

1.33

0.75

1.64

0.997

12.42

0.02

0.999

2.21

1121.5

0.25

0.964

AlBWS

1.71

0.58

0.63

0.966

8.76

0.04

0.993

1.95

1269.3

0.39

0.957

ACPP

2.24

0.45

1.47

0.996

7.11

0.24

0.989

0.35

1558.2

144

0.945

ACSB

3.94

0.25

1.33

0.984

3.87

0.28

0.980

3.12

3519

3.32

0.979

In this study, Langmuir isotherm model with the higher value of regression correlation coefficient (R2 = 0.999, 0.993, 0.989 and 0.980 for AlTFC, AlBWS, ACPP and ACSB, respectively) presented a better fit to the experimental data of nitrate adsorption onto the applied adsorbents as compared to the other two isotherm models in Table 2. The high correlation coefficient of Langmuir isotherm suggested that It is very suitable for describing the adsorbent/adsorbate interaction in the studied nitrate concentration range. It is obvious that the R2 values of both Langmuir and Freundlich equations are high (> 0.96) for the all samples, which imply that both monolayer adsorption and heterogeneous surface conditions are provided. Also of note was that the R2 values of two models were very close to one another, suggesting that the adsorption of nitrate onto test samples is complex and include multiple processes [53].

The values of constants for each adsorption isotherm model were calculated to evaluate the surface properties and affinity limit of the test adsorbent materials for nitrate ions. All the obtained results of the equilibrium study suggest that these adsorbents are effective ones for the nitrate adsorption from aqueous solution, where the obtained values of the Freundlich isotherm constants (Kf and n) showed easy uptake and good adsorption process of nitrate ions from aqueous solutions with high adsorptive capacity. The values obtained from Freundlich isotherm constant n for the four samples were higher than 1, giving an indication that the removal of nitrate ions onto these materials is an efficient adsorption process. Also, the high value of Kf indicates the high adsorption efficiency for nitrates by the selected adsorbents [8].

Additionally, the b value derived from Temkin equation for nitrate adsorption was found to be higher than 80 kJ mol−1 for all solid samples, which indicating a chemical adsorption process. Moreover, all b values were quite higher that reveals the strong ionic interaction between nitrate ions and the studied adsorbents [80].

3.8 Kinetic Studies

The adsorption kinetics deal with the rate at which sorption occurs. The order of adsorbate-adsorbent interactions has been described by using various kinetic models. Of these, pseudo-first order, pseudo-second order, and intra-particle diffusion models are used. The equation parameters of these models often provide some insight into both adsorption mechanism and the affinity of the sorbent.

3.8.1 Pseudo-First Order Model

The Lagergren first-order equation describes the adsorption of liquid–solid systems based on the solid capacity. The linear form of Lagergren is written as in Eq. (9):
$$Log\,(q_{e} - q_{t} ) = \log \,\,q_{e} - \frac{{K_{1} }}{2.303}t$$
(9)
where the qe and qt (mg g−1) are the amounts of adsorbate per amount of adsorbent at equilibrium and at any time t and K1 (min−1) is the rate constant of pseudo-first order.

3.8.2 Pseudo-Second Order Model

Pseudo-second order equation indicates the sorption system of nitrates and can be express as Eq. (10):
$$\frac{t}{{q_{t} }} = \frac{1}{h} + \frac{1}{{q_{e} }} \cdot t$$
(10)
where h = k2qe2

K2 (g mg−1 min) is the rate constant of pseudo-second order model.

3.8.3 Intra-particle Diffusion Model

Beside the adsorption on the outer surface of adsorbent, there is a possibility of transport of adsorbate ions from the solution to the pores of adsorbent due to stirring in a batch process. This possibility was tested in order to show the existence of intra-particle diffusion in the adsorption process, (qt). The most-widely applied intra-particle diffusion equation expressed by Weber and Morris equation, the amount of nitrate ions sorbed per unit mass of sorbent at time t was plotted as a function of the square root of time (t 0.5) [53]. The intra-particle diffusion model equation is written by Eq. (11):
$$q_{t} = K_{\text{ad}}\,\, t^{0.5}$$
(11)
Kad is the intra-particle diffusion rate constant (mg g−1 min0.5).
The plots of pseudo-first order, pseudo-second order, and intra-particle diffusion model are presented in Fig. 14a–c, while their constants are shown in Table 3.
Fig. 14

Kinetic Studies for nitrate removal by ACPP, AlBWS, AlTFC and ACSB at 22 ± 2 °C: a Linear Lagergren plots. b Linear second order plots. c Linear intraparticle diffusion plots

Table 3

Pseudo–first, pseudo–second and intraparticle diffusion model constants for nitrate adsorption by AlBWS, AlTFC, ACPP, and ACSB at 22 ± 2 °C

Sample

Pseudo-first order

Pseudo-second order

Intra-particle diffusion

qe (Exp)

K1

qe

R2

K2

qe

R2

Kad

R2

AlTFC

1.57 ×  10−2

2.09

0.845

1.93 ×   10−2

5.007

0.988

0.19

0.765

5.003

AlBWS

8.98 ×   10−3

1.95

0.754

3.0 ×   10−2

5.277

0.994

0.166

0.804

5.83

ACPP

4.38 ×   10−3

1.61

0.335

1.86 ×   10−2

5.767

0.982

0.136

0.808

5.80

ACSB

1.17 ×   10−2

4.88

0.860

2.42 ×   10−3

4.950

0.926

0.361

0.960

4.73

According to the correlation factors R2 values, the obtained results are well fitted for the pseudo-second order model (R2 = 0.988, 0.994, 0.982 and 0.926 for AlTFC, AlBWS, ACPP and ACSB, respectively). Furthermore, the experimental values of the equilibrium uptake qe(exp.) of nitrate adsorption by testing materials are closer to those of the calculated values qe(cal.) of the pseudo-second order model, which confirm the chemisorptions mechanism. This phenomenon was observed for different adsorbents studied by other researchers such as [3, 11, 24].

3.9 Thermodynamic Parameters

To evaluate the feasibility and the nature of the adsorption reaction, the thermodynamic parameters such as standard Gibbs free energy change (ΔG°), standard enthalpy (ΔH°) and standard entropy (ΔS°) should be determined. thermodynamic parameters can be expressed by the following equations:
$$\Delta G^{ \circ } = - RT\,\,\ln \,\,Kc^{ \circ }$$
(12)
$$\Delta G^{ \circ } = \Delta H - T\Delta S$$
(13)
Herein, Thermodynamic parameters were estimated from the Van’t Hoff equation. A plot of ln Kc versus 1/T as shown in Fig. 15 and Table 4 was used to determine ΔH° (= − slope. R) and ΔS° (= intercept. R) from the slope and intercept by the following equation:
Fig. 15

Linear plots of ln KC versus 1/T nitrate removal by ACPP, AlBWS, AlTFC, and ACSB at 22 ± 2 °C

Table 4

Thermodynamic constants for nitrate adsorption by AlBWS, AlTFC, ACPP, and ACSB at 22 ± 2 °C

Sample

R2

∆G (kJ mol−1)

∆H (kJ mol−1)

∆S (J mol−1 K)

298 K

318 K

328 K

AlTFC

0.995

377.88

264.28

207.48

2070.52

5.68

AlBWS

0.937

490.60

273.40

165.60

3719.43

10.84

ACPP

0.837

− 750.00

− 2670.00

− 3630

27378

96.00

ACSB

0.970

− 5.02

− 21.71

− 355.68

9836

31.01

$$\ln {\kern 1pt} \,Kc\, = \,\frac{{\Delta S^{o} }}{R}\, - \frac{{\Delta H^{o} }}{RT}$$
(14)

The positive values of ∆H indicate the endothermic nature of the adsorption process of nitrates onto the surface test samples, as well as all the values of ∆H > 40 kJ mol−1, which indicates that adsorption of nitrates onto the studied adsorbents is chemisorption. Whereas, the negative values of ΔG° at the different temperature values in case of activated carbon samples indicate that It is a spontaneous and feasible process. Finally, The positive ∆So values show the increase in the degree of freedom of the adsorbate. Similar results have demonstrated by [48].

4 Field Study (Applied to Real Water Samples)

Suitability of the newly prepared adsorbent materials was tested with field samples taken from the study area at Qena Governorate in order to better investigation of their behavior under field conditions.

In this study, selected water samples were collected from the surrounded environment in Qena city, Upper Egypt: (1) irrigation water from an irrigation canal derived from the Nile river (sample 1) and (2) two groundwater samples (sample 2 and 3) Fig. 16a. Water samples were then chemically analyzed and the results summarized in Table 5. Two locations in Dandara and Taramsa villages, which consist of several farms, were selected to collect groundwater samples (2) and (3), which have polluted by nitrates. The first well (sample 2) is located between latitude 26°07′ 39.4″ N and longitude 32°41′25.2″ E, whereas the second wall (sample 3) is located between latitude 26°08′00.6″ N and longitude 32°41′17.80″ E. According to the chemical analysis of these samples constructed in Table 5, they have elevated nitrate concentrations. The collected groundwater samples (2) and (3) are not suitable for drinking purposes because they have nitrate concentrations more than the maximum permissible limit recommended (50 mg L−1) [30]. This elevated concentration of nitrates is due to its high solubility in water, which indicates possible hazardous risk to public health, environment, and soil organisms. Also, nitrate concentrations in all water samples are above naturally occurring levels as reported by [81], which indicate an anthropogenic (human-related) source of nitrate. These samples are used for irrigation purposes with limited restriction.
Fig. 16

a Location map for the selected groundwater samples, b Field trial results of tested adsorbent materials on real water samples at optimized conditions

Table 5

Chemical analysis of untreated water samples

Parameter

Sample (1)

Sample (2)

Sample (3)

TDS (mg L−1)

239.0

230.0

134.0

Conductivity (mS cm−1)

447.0

588.0

514.0

Total hardness (mg L−1)

166.0

584.0

664.0

Calcium hardness (mg L−1) as CaCO3

88.0

232.0

302.0

Alkalinity (mg L−1) as CaCO3

204.0

240.0

224.0

Chloride (mg L−1)

11.0

255.0

380.0

Nitrite (mg L−1)

0.112

0.67

0.85

Nitrate (mg L−1)

13.30

138.60

110.00

Mn2+ (mg L−1)

0.193

0.30

0.10

Al3+ (mg L−1)

0.046

0.09

0.12

Fe2+ (mg L−1)

0.238

0.06

0.09

pH

7.87

7.82

8.10

The efficiency of each adsorbent for nitrate removal from the field samples was tested under the same optimized conditions used in single nitrate solution (at an adsorbent loading dose 6 g L−1 ml water sample, 25 °C and time 2 h). According to results presented in Fig. 16b, all the selected adsorbent media have good removal efficiency for nitrates. The produced activated carbon from potato peels (ACPP) has the highest efficiency for nitrate ion removal from the tested field samples, while activated carbon from sugarcane bagasse (ACSB) has the lowest adsorption capacity for nitrate ions. The maximum percentage removal of nitrate ions from field water samples was found to be 98, 42, and 50% for water sample (1), water sample (2), and water sample (3), respectively. Based on the experimental data, it was concluded that the tested adsorbents can be effectively employed for removing the nitrate ion from surface and ground water even though at relatively low adsorbent doses, and in the presence of organic matter and other competing inorganic ions (i.e.: Ca2+, Al3+, Fe3+, chloride or sulfate) in the real samples according to data in Table 5.

5 Cost Evaluation of Tested Materials

In this study, the cost of the tested materials has been minimized by the following:
  1. 1.

    Using locally available waste materials in the production process.

     
  2. 2.

    All samples were calcined at low temperature (400 °C in case of alumina and 500 °C in case of active carbon). This is below the calcination temperature published by [82].

     
  3. 3.

    No expensive chemicals were used and simple preparation method was used. Table 4 shows a comparison between costs estimated for production of our selected materials with the price of the international products.So we can suggest that our tested materials are very cheap and attractive compared to the traditional materials.

     

6 Conclusion

This study highlights nitrates as a potent pollutant in water with its different hazardous effect on health and the environment. In this study, four adsorbent materials were prepared from waste materials from the surrounded environment in the study area. All the prepared adsorbent samples have highly porous structure and are of large specific surface areas (> 200 m2 g−1). They were tested for the removal of nitrates from aqueous solutions. Batch experimental tests on nitrate adsorption by these adsorbent media showed that they have high affinities for adsorbing nitrate pollution. The adsorptive properties of the selected adsorbents pH, initial nitrate ion concentration, contact time, adsorbent dose and temperature were studied. It was found that pH and PZC of solid adsorbents have a high influence on the removal efficiency of nitrate ions. The adsorption processes were rapid and the results of this study showed also that the rate of adsorption of nitrates obeys only pseudo–second order rate equation. The obtained results are best fitted to the Langmuir adsorption isotherm model. Additionally, all the equilibrium and kinetic studies proved that adsorption of nitrates onto prepared adsorbent media is chemisorption (Table 6).
Table 6

Cost evaluation of tested materials

Samples

AlTFC

AlBWS

ACPP

ACSB

Disposal and raw materials (USD kg−1)

1.3

1.8

0.5

0.5

Reagent and chemicals and electricity (USD kg−1)

8.52

10.72

5.29

3.04

Total cost (USD kg−1)

9.82

12.52

5.79

3.54

International price (USD kg−1)

100 $

100 $

10$

10$

From the thermodynamic parameters, the tested adsorbents show endothermic nature for sorption of nitrate ions. The thermodynamic parameters free Gibb’s energy (ΔG°); enthalpy (ΔH°) and entropy (ΔS°) are calculated. The ΔH° value was positive for all tested materials, which confirms the endothermic nature for nitrate adsorption, whereas, the positive value of ΔS° indicates that degrees of freedom of the adsorbed ions are increasing. The negative values of ΔG° for ACPP and ACSB samples revealed that the adsorption process is favorable and spontaneous. At the end of this study, the newly synthesized adsorbent materials were found to be effective and efficient when they were applied to real water samples.

Finally, obtained results showed that the tested adsorbent materials have high capacities for nitrate adsorption in a short time and considered as a low cost, efficient and environment-friendly adsorbent materials.

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Copyright information

© The Tunisian Chemical Society and Springer Nature Switzerland AG 2018

Authors and Affiliations

  1. 1.Chemistry Department, Faculty of ScienceSouth Valley UniversityQenaEgypt

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