Home Adsorption and sugarcane-bagasse-derived activated carbon-based mitigation of 1-[2-(2-chloroethoxy)phenyl]sulfonyl-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea-contaminated soils
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Adsorption and sugarcane-bagasse-derived activated carbon-based mitigation of 1-[2-(2-chloroethoxy)phenyl]sulfonyl-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea-contaminated soils

  • Khuram Shahzad Ahmad EMAIL logo , Iqra Amjad and Daoud Ali
Published/Copyright: December 1, 2020
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Open Chemistry
From the journal Open Chemistry Volume 18 Issue 1

Abstract

Burgeoning pesticide usage in agriculture sector required to be evaluated by assessing the adsorption rate in soils. The herbicide triasulfuron was used in this research to analyze its sorption behavior in seven distinct soils using batch equilibrium methodology. The adsorption coefficient (Kd) values ranged from the 3.32 to 29.7 µg/mL. Peshawar soil displayed the highest Kd value because of the distinct physiochemical properties when compared with the other six samples. Gibbs free energy exhibited negative values displaying less contact between soil particles and pesticides, showing the exothermic nature of the phenomena. A negative association was observed between the pH of the soil samples and Kd (R2 = −0.71) but a direct relation with the organic content (R2 = 0.74). Triasulfuron mitigation was performed by the economical remediation of soils using acid-activated charcoal prepped from Saccharum officinarum husk. Activated carbon derived from biomass displayed the great potential for triasulfuron removal from soils.

Keywords: sorption; herbicide; exothermic; removal; activated carbon; sugarcane bagasse

1 Introduction

The protection of environment and food crops from harmful organisms requires utilizing different chemical compounds commonly known as pesticides. Moreover, they are used for mitigating any nuisance-causing organisms that are harmful for the crops. After World War II, pesticides were commonly utilized in agronomic sectors for crop protection and production. Pesticides when sprayed on to the crops not only stop the growth of pests but also cause dreadful impacts on our ecosystem and contaminate the soil. These chemical substances from the soil are leached into the ground water and thus contaminate the water reservoirs. Leaching of pesticides depends upon the concentration, type, persistency into the soil, and life span of the pesticides. Pesticides are also injurious to the human health. It causes many chronic diseases such as cancer and diabetes, disorders such as reproductive disorders and many respiratory problems. Pesticides also have toxic effects on human estrogen. Around 75% of agrochemicals are utilized in the United States for agronomic purposes. The world population is growing very rapidly, which in turn demands more food. Therefore, pesticides are used to increase crop production to meet the demands of the growing population. Disproportionate use of xenobiotics significantly distresses the ecosystem, contaminates the water bodies, and also reduces the soil fertility. Through these pesticides, hazardous chemicals are released into the environment through anthropogenic activities [1]. Although the hazardous effects of pesticides are known, yet it is used excessively to increase crop production. To reduce the contamination of the soil, the use of pesticides has to be limited [2]. To lessen the destructive impacts of pesticides, it is vital to obtain knowledge about their sorption process. The binding of pesticide molecules to soil matrix controls the passage of pesticides through percolation [3]. Basic soils possessing low carbon percentage have the highest level of adsorption [4]. The fate of pesticides in soil can be analyzed using different adsorption parameters [5].

Triasulfuron, 1-[2-(2-chloroethoxy)phenyl]sulfonyl-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea, is from sulfonylurea group and present in white powder form (Figure 1). Triasulfuron is a herbicide used to destroy the broad-leaved herbs. It is adsorbed by the roots and leaves. It also inhibits the synthesis of amino acid in plants. Herbicides belonging to sulfonylurea group possess high potency even at low temperature. It is used to control the weeds that grow in wheat and barley crops [6]. It contaminates the soil, reduces the soil fertility, and changes the soil structure and its formation [7]. It is slightly toxic to bacteria but highly toxic to aquatic plants. Molecular weight of triasulfuron is 401.8 g/mol. Triasulfuron is slightly soluble in methylene chloride, acetone, chloride hexane, and organic solvents. Its melting point is 186°C and it decomposes before boiling. Its solubility in water is 815 mg/L.

Figure 1 Structure of triasulfuron.
Figure 1

Structure of triasulfuron.

Activated carbon (AC) is produced from the materials that naturally contain high amount of carbon content. It is prepared from walnut shells, peanuts shells, coconut shells, wheat bagasse, and saw dust. Through heating, these carbonaceous materials are converted into AC by adjusting temperature. AC is used to remove certain heavy metals from the water [8]. The major and significant application of AC is that it is used to remove pollutants from soil, water, and air. This is only possible because of its large surface area and the pores on its surface. With the help of these pores, AC can purify air, soil, and water. AC adsorption criteria depend upon the pores on its surface, pH, and chemical nature of AC. The physicochemical properties are significant in adsorption capacity [9]. The research about pesticides encourages us to discern the comportment of pesticides in our ecosystem. The investigation of their fate is exceptionally beneficial, so the dangers are detected. Agricultural zones are the main sufferers of agrochemical contamination. The excessive use of pesticides in agriculture can cause serious adverse effects.

The aspiration of the study is to scrutinize the behavior of triasulfuron (herbicide) in the soils of Pakistan and remove the pesticides from the soil using cost-effective AC methodology, which is prepared by using Saccharum officinarum bagasse. Removal through biomass-derived AC is a very effective method because it manages the waste and it is economical [4,10]. Triasulfuron remediation from soils has not been previously reported by using biomass-based AC.

2 Experimental

2.1 Chemicals

Triasulfuron of analytical grade is acquired from Sigma Aldrich. Its analytical standard was 99% pure. NaCl (anhydrous), methanol, and acetone were also used (99% pure). Distilled water (DW) was used to prepare the stock solution of triasulfuron.

2.2 Soil sampling and processing

The soils were sampled from seven regions in Pakistan, including Peshawar, Attock, Taxila, Sohawa, Chakwal, Mirpur, and Karachi (Figure 2). After the collection, soils were stored in polythene bags. Air-drying of soil samples was done in green house for a couple of days. The samples were disintegrated with mortar and pestle followed by passing through 2 mm sieve. These were stored in petri dishes until further experimentation.

Figure 2 Map of Pakistan displaying sampling sites for triasulfuron adsorption.
Figure 2

Map of Pakistan displaying sampling sites for triasulfuron adsorption.

2.3 Adsorption experiment

Stock solution of triasulfuron was prepared following the standard protocol [11,12]. Triasulfuron (10.3 mg) was weighed and dissolved in a few drops of acetone followed by mixing in DW to prepare 10 ppm stock solution. Multiple dilutions were prepared to assess the adsorption process. These dilutions were prepared in the following concentrations: 0, 0.25, 0.5, 0.75, 1, 2.5, 5, and 7.5 ppm. Triasulfuron adsorption experiments were performed following the methodology adopted by Ahmad [13]. Standard batch equilibrium method was followed according to the OECD guidelines. One control and one blank sample was also prepared for the adsorption experiments. NaCl of 10 mL 0.1 M was also added to each dilution for electrolyte balance. The vials were placed in shaker for 24 h at 90 rpm. The vials were then centrifuged for 20 min at 3,500 rpm. They were filtered through 0.2 µm nylon filters and analyzed by UV-visible spectrophotometer. Adsorbed triasulfuron was calculated following the adsorption distribution coefficient equations [14]. Univariate ANOVA and regression were applied on the experimental results in Microsoft Excel (2013) and Minitab 17 statistical package.

2.4 Synthesis of biomass-derived AC

Saccharum officinarum-bagasse-derived activated carbon (SAC) was prepared by the technique followed by Ahmad [14]. Prepared SAC was stored in airtight media bottle.

2.5 Iodine test

The synthesized SAC was characterized by iodine test devised by Hassler [15]. The adsorption of iodine to SAC was tested and confirmed by the change in the color of the iodine solution from brown to yellow.

2.6 FTIR characterization

The change in functional groups in raw S. officinarum bagasse and SAC, i.e., before and after the formation of AC was studied through FTIR spectrometry. Sample pallets were prepared following the methodology devised by Nabiyouni and Ghanbari [16]. Sample was run in FTIR from 400 to 4,000 cm−1.

2.7 SAC-aided triasulfuron removal

Removal of triasulfuron from soils through SAC was done by the methodology of Ahmad [12]. Herbicide removal was checked in two concentrations, i.e., 5 and 7.5 ppm. Removal was checked as a function of time at 3 and 6 h by UV-visible spectrophotometric analysis. A 10-mL quantity of each, 5 and 7.5 ppm, dilution, previously prepared from the stock solution, was added to the 15-mL centrifuge tube. Soil sample of 0.5 g was then added to each tube. Absorbance was measured by UV-visible spectrophotometer. UV was again checked before and after (3 and 6 h) the addition of the synthesized biomass-based AC. This process was repeated for all the soil samples.

  1. Ethical approval: The conducted research is not related to either human or animal use.

3 Results and discussion

3.1 Properties of soil samples

Physicochemical properties of the soil samples were observed (Table 1). These properties play a significant role in predicting the soil–pesticide association. The pH values of the soil samples were in the range of 7.05–7.68. It was noted that the soil from Peshawar possessed the lowest pH among all soils, whereas the soil from Karachi possessed the highest pH value. Pakistani soils displayed an overall alkaline trend. Previous research revealed an abundance of sodium content in soils from this location [17]. The organic matter (OM) percentage of the samples ranged from 0.52 to 1.4, with the highest percentage from Peshawar region. Peshawar district possesses very fertile land. A main reason for this might be the two rivers flowing through it, giving it a rich soil [18]. Uzoma et al. stated that alkaline soils tend to possess less OM [19]. The elevated pH levels cause the paucity of organic biomass in soils resulting in reduced OM and organic carbon contents [20]. OM in turn is responsible for influencing several other soil properties. Soils were also analyzed for the amount of total carbon (TC). Soils of Peshawar contained the most amount of the TC content (0.81%). Furthermore, soil textural examination displayed the highest percentage of clay content in Peshawar soil (38%), whereas Karachi possessed the most amount of sand (82%), due to its coastal setting near the Arabian sea [21]. The Peshawar soil was thus classified as clay loam, whereas the soil of Karachi region was categorized as loamy sand. Electrical conductivity was used to assess the extent of salinity hazard in soils [22]. The highest value of electrical conductivity was observed in soil from Karachi region (2,120 µS/cm). Hence, the soil from Karachi can be excogitated to be the most probable to soil salinity risk. Heavy metal analysis of soils was also performed to assess the risk associated with the heavy metal concentration in soils. Previous research have shown that the pH of soils greatly influences the metal toxicity of soils [9]. The soil from Chakwal was found to possess the highest amount of lead (3.9 ppm). It has been concluded in a previous research by Raza et al. that high amount of lead in soils from this region is mainly due to the inherent nature of ground rock of that geographical strata [23]. The highest amount of nickel was found in Peshawar soil (0.414 ppm). It was stated by Ishaq et al. that in the Peshawar region nickel was distributed by the flow of river water followed by evaporation [24]. Most of the zinc was found in the Attock soil (0.27 ppm). The the soil of the Taxila region demonstrated the highest amount of cadmium (0.7 ppm). Various researchers have shown that cadmium adsorption by soil particles increased with the elevated pH levels [25]. Chang et al. displayed the increasing cadmium adsorption by soil particles with high pH values [26].

Table 1

Physiochemical properties of the soil

SamplespHOM (%)TextureSand (%)Slit (%)Clay (%)TC (%)TN (%)EC (µS/cm)Saturation (%)Heavy metals (ppm)
PbNiZnCd
Attock7.591.10Loamy sand5436100.640.55143.0353.4—0.2770.04
Mirpur7.621.35Silty clay loam3.062350.780.67334.0480.1—0.1590.04
Karachi7.680.70Loam823.0150.410.352,120260.70.290.0250.12
Taxila7.621.15Clay loam4439170.660.57280.0502.90.200.0150.70
Peshawar7.051.40Silty clay loam/clay loam2042380.810.70397.0291.10.410.1240.04
Chakwal7.500.52Clay loam53389.00.300.26291.0503.90.350.0050.06
Sohawa7.281.25Sandy loam4441140.720.620.710312.90.040.1010.05

3.2 Adsorption isotherms

Triasulfuron adsorption phenomenon in soils was investigated by UV-visible analysis. Two adsorption isotherm models, i.e., linear and Freundlich, were utilized to evaluate the adsorption parameters of triasulfuron on soils (Table 2 and Figure 3). All soils exhibited varying adsorption rates due to their diverse soil physicochemical properties. The linear adsorption coefficient (Kd) values of all soils for triasulfuron adsorption ranged from 3.32 to 29.7 µg/mL. The adsorption distribution constant (Kd) trend in all soils was S3 > S7 > S4 > S5 > S2 > S6 > S1.

Table 2

Triasulfuron linear and Freundlich adsorption parameters in soil

Sample #LocationKd (µg/mL)R2Kom (µg/mL)∆G (kJ/mol)Koc (µg/mL)Kf (µg/mL)R2Kfoc (µg/mL)na
S1Karachi3.320.73475.0−15811.00.920.91231.00.6
S2Chakwal10.70.722,065−183,5562.620.95868.00.8
S3Peshawar29.70.902,126−183,6754.120.97510.01.3
S4Mirpur24.30.811,804−183,1223.950.92508.01.1
S5Taxila11.90.931,039−171,8112.940.80447.01.2
S6Attock6.240.71568.0−15976.01.220.87191.00.5
S7Sohawa24.90.921,993−183,4604.020.91559.00.9
Figure 3 Comparative linear and Freundlich isotherm model of triasulfuron adsorption on soils.
Figure 3

Comparative linear and Freundlich isotherm model of triasulfuron adsorption on soils.

Soil sample S3 displayed the highest rate of triasulfuron adsorption (29.7 µg/mL). According to the experiment, the soil samples with the highest OM and lowest pH exhibited the highest rate of adsorption. Furthermore, the sample was clay in nature. Kd is the most crucial linear adsorption parameter which can be used to assess the potential and risk of pesticide transport. Higher values of Kd are indicative of a vigorous interaction of pesticide and soil molecules. On the contrary, the low Kd determines a more probability for the movement of pesticide in soils. In this research, sample S3 displays the highest rate of adsorption, thus exhibiting the strongest affinity for pesticide attachment. In this regard, sample S1 shows the lowest affinity for pesticide binding, thus increasing the likelihood for triasulfuron leaching. The R2 value for linear isotherm ranged from 0.71 to 0.92, representing goodness of fit to this model. Triasulfuron mobility in soils can be determined by another parameter for organic carbon-based adsorption coefficient (Koc). Different pesticide mobility groups have been made based on the Koc values [27]. The Koc values below 50 comprise the highest pesticide movement group. Values from 50 to 100 indicate a great mobility group and the values between 150 and 500 depict mediocre mobility of pesticide in soils. Current experiments displayed the Koc ranging from 811 to 3,675 µg/mL. It is quite obvious from the results that triasulfuron displayed very low percolation. It was also perceived that soil exhibiting the greatest triasulfuron adsorption displayed highest Koc. This justified the fact that pesticide mobility and its Koc values were inversely proportional to each other. In another research, Ahmad (2017b) exhibited mediocre mobility potential of triasulfuron in soils [13]. The change in mobility pattern of triasulfuron depends upon the physicochemical properties of each soil sample. The soils were also assessed for Kom values, which ranged from 475 to 2,126 µg/mL. Sample S3 displayed the highest Kom value and also possessed the highest Kd and OM values. The Gibbs free energy (ΔG), a thermodynamic parameter, was also studied to evaluate the interface between soil particles and pesticide molecules. The value of ΔG ≤ −40 kJ/mol represents the phenomena of physisorption and exothermic reaction [28]. It further implies that the reaction is spontaneous with weak van der Waal’s forces between the pesticide and the soil particles.

Triasulfuron adsorption pattern was also assessed by Freundlich isotherm. The Freundlich adsorption coefficient (Kf) values ranged 0.92–4.12 µg/mL. Freundlich adsorption constants in Italian soils revealed lower values of Kf in loamy and clay loam soils with comparatively higher pH values of 8.0 and 8.3 [29]. In an experiment by Pusino et al., triasulfuron has exhibited similar rate of adsorption to montmorillonite mineral in soil [30]. In another research conducted by Pusino et al., triasulfuron exhibited high rate of Freundlich adsorption, which can be attributable to the presence of comparatively higher percentages of OM [4]. The R2 for Freundlich adsorption ranged from 0.80 to 0.97, indicating the best fit for adsorption isotherm. The Kfoc in all samples varied significantly based on the organic content present in the soils. In the current research, the values of Kfoc were from 191 to 868 µg/mL. Previously, Ahmad had reported the Kfoc value of triasulfuron in four distinct soils ranging from 177 to 909 µg/mL [13].

3.3 Soil physicochemical properties and adsorption

The interaction of soil and pesticides depends greatly on the soil physicochemical properties. The soils with high Kd values were found to possess low pH but rich in OM content and carbon percentage. On the contrary, the soils with low Kd value showed high pH but low carbon content and low OM content. In the current study, Peshawar soil possessed high OM content and organic carbon (1.40 and 0.81%) but a low pH was observed (7.05) among all samples, thus displaying the highest rate of adsorption (Kd = 29.7 µg/mL). Karachi’s soil pH was 7.68 and contained low OM (0.70%) and organic carbon (0.41%) and consequently Kd value (3.32 µg/mL) was lowest among all soil samples. Furthermore, Karachi soil sample contained the highest sand content (82%). More the amount of sand content hinders the attachment of molecules to soil. Peshawar soil possessed highest clay percentage, which also aided in more adsorption. Previous adsorption studies of various pesticides have shown the same trend of dependency of the rate of adsorption on soil properties [5,12,13,14].

3.4 FTIR spectrometry of AC

Analysis of functional groups of the raw material and SAC was performed through FTIR. These functional groups could act as potential attachment sites for the pesticide molecules. The difference in functional groups before and after the activation of AC is presented in Table 3.

Table 3

Functional group in AC identified with the help of FT-IR

Sr. no.Before activation by acidAfter activation by acidFunctional groups
Peak position (cm−1)BondsAssignmentsaPeak position (cm−1)BondsAssignmentsa
1563C–Hoop597C–HoopAromatic compounds (phenolic compounds)
2665–C═C–H:C–Hδ———Unsaturated hydrocarbons alkynes
3———800N–Hω1° and 2° amines and aromatics
4868C–Hoop 873C–Hoop Aromatic compounds (phenolic compounds)
5908C–Hoop Aromatic compounds
61,051C–Oʋ1,030C–OʋAlcohol and carboxylic acid
C–N1,097C–NAliphatic amines
71,161C–Oʋ1,161C–OʋAlcohol and carboxylic acid
81,244C–Oʋ1,199C–OʋAlcohol and carboxylic acid
C–NC–NAliphatic amines
91,323C–Nʋ1,261C–NʋAliphatic amines
101,373C–H, N–O ρ, ʋ———Alkane (saturated hydrocarbons) and nitro compounds
111,427C–Hδ1,415C–CʋAlkane (saturated hydrocarbons)
121,514C–Cʋ———Aromatics
N–OʋNitro compounds
131,604N–Hδ1,620N–H δPrimary amines
141,633N–Hδ———Primary amines
151,732C═O ʋ1,703C═O ʋCarboxylic acid
162,931C–Hʋ2,962C–H ʋAlkanes
173,389OH and Hʋ and δ3,429O–H ʋAlcohols and phenols
  1. a

    ʋ = stretching, δ = bending, ρ = rocking, ω = wagging.

In both the samples, before and after activation, very minor vibrations appeared at peak frequency of 563 and 597 cm−1, respectively, in the finger print region (400–500 cm−1). These bands are indicating the C–H oop of the aromatic compounds [39,40]. Moreover, in accordance with the references [34,35,39], the presence of these minor figure print vibrations may also be associated with the alkyl halides [34,35,39].

The analysis of raw S. officinarum bagasse revealed small vibration of 665.46 cm−1, representing the alkynes bending. The presence of alkynes is indicative of different unsaturated hydrocarbons, which are part of the natural composition of the different flora such as S. officinarum [31,32]. The C–H oop of aromatics was observed at the frequencies of 868 and 908 cm−1. The observance of the aromatics was due to the presence of bioactive compounds such as phenolic compounds. The phenolic compounds are the prime representatives of the aromatic compounds [34,36]. Therefore, C–H was proposing the phenol chemical compounds of S. officinarum. The presence of phenolic compounds was furthered validated by C–O stretching, representing the alcohol and carboxylic acid at 1,051, 1,161, and 1,244 cm−1. The peaks at frequencies of 1,051 and 1,244 cm−1 were also signifying the presence of C–N stretching of the aliphatic amines, indicating the presence of amines in the raw material without aromatic ring [36,37]. Furthermore, Table 3 and Figure 4 are depicting the alkane at 1,373 and 1,427 cm−1, exhibiting C–H rock and C–H bending, respectively. The presence of alkane was attributed to the saturated hydrocarbons [34,35,36,37]. The peak at 1,372 cm−1 is also indicating the N–O stretching of nitrocompounds which is supported by another vibration at 1,541 cm−1. This peak vibration is corresponding to the C–C of aromatic compounds and may also represent N–O stretching of nitro compounds that can be observed in the raw S. officinarum. The presence of amines in the raw sugarcane bagasse was again shown by N–H bend at two peak frequencies of 1,604 and 1,633 cm−1. This N–H bending is related to the category of primary amines [34,36,37]. In Figure 4, the vibrational peak at 1,732 cm−1 is corresponding to C═O stretching, which was attributed to the presence of carboxylic acid in the raw material. However, this stretching vibration is also related to the chelated ketone group [31]. The minor peak of alkanes was again observed at 2,931 cm−1 in the raw sugarcane. Nevertheless, a broad and strong vibration was found at 3,389 cm−1 corresponding to OH stretching and H bending, proposing the presence of alcohols and phenols. This broad vibration is endorsing the phenolic compounds in consistency with the earlier described aromatic and carboxylic groups. Thus, the overall FTIR vibrational analysis was demonstrating that S. officinarum was composed of different compounds having aromatic, amine, carboxylic and phenol groups. The major constitutes of the raw S. officinarum (before activation) were amines and phenolic compounds, according to the interpreted functional groups in Table 3 and Figure 4.

Figure 4 FTIR spectrum of raw sugarcane bagasse and SAC.
Figure 4

FTIR spectrum of raw sugarcane bagasse and SAC.

However, after activation by acid, nearly same groups were observed but with different intensities of vibrational peaks. The peak of phenolic compounds at 3,429 cm−1 became much broader when compared with that of the raw material, and the peak intensities of alkanes (2,962 cm−1) and nitro compounds (1,703 cm−1) comparatively reduced. The broader and stronger peak was observed at 1,620 cm−1 of primary amines. It can further be seen in Figure 4 that numerous minor peaks were removed after activation such as the peaks in the frequency range of 1,500, 1,300, 900 and 600 cm−1 disappeared after acid treatment. It is also worth noticing that after activation a very strong sharp peak was observed at 800 cm−1 corresponding to the functional groups of N–H wag, indicating that emergences of primary (1°) and secondary (2°) amines after activation with acid [31,32]. Further, this peak can be associated with C–H oop of aromatics compounds [34,36,37], thereby verifying the 1° and 2° amines having nitrogen atom attached to the aromatic ring [38]. As discussed earlier that the raw sugarcane bagasse material mainly consisted of amines and aromatic compounds, accordingly, the presence of these functional groups was also observed after activation. However, the change in vibration peak position of the respective functional group was due to reaction with acids for activation. Moreover, the FTIR spectra obtained by Carrier et al. of sugarcane bagasse biochar were well matched with the FTIR of SAC from the current experiments. Almost similar bonds were observed with slight shifting at wavelengths, most probably due to the difference in the synthesis method. C═O stretch was observed at 1,702 cm−1; whereas in the current experiment, it was observed at 1,703 cm−1. The C–C stretch was observed at 1,598 cm−1; however, in the present research it was found at 1,415 cm−1. The C–O stretch was observed at 1,092 cm−1, which was detected at 1,097 cm−1 in this research. The C–H bending was observed at 798 cm−1, which was observed at 873 cm−1 in the present research [31]. Furthermore, the FTIR spectra of AC was also compared with the study by Foo et al., which displayed a close resemblance to the AC also prepared from sugarcane bagasse [32]. In summary, FTIR after acid activation successfully demonstrated the preparation of SAC from the raw sugarcane bagasse. The well-defined and prominent functional groups of SAC related to raw sugarcane bagasse are reported as the efficient active sites for organic molecules, such as pesticides, to adsorb by soil amendment [31].

3.5 Iodine test

Iodine solution turned to light yellow after the addition of SAC. This indicated the adsorption of iodine molecules to SAC, resulting in the decoloration of the solution. The change in color displayed the correct synthesis of SAC.

3.6 Statistical analysis

Statistical analysis of triasulfuron adsorption was performed based on their physiochemical properties (Table 4). Regression analysis on the samples displayed an indirect relation of Kd with pH and a direct relation with OM and total organic content. This confirms the fact that greater the amount of OM, higher the rate of adsorption, whereas the trend will be opposite to the pH value of soil samples. The statistical analysis justified the experimental results of the current research exhibiting the highest Kd value for Peshawar soil which possessed the highest OM. ANOVA was also performed on the adsorption results. Univariate ANOVA revealed p value less than the α value (0.05), indicating the significance of the results. Residual plots were graphed in Minitab 17 to observe the association of adsorption coefficient Kd with pH, OM, and TOC (Figure 5). The plots displayed the normal distribution of data and a constant variance indicating the goodness of fit.

Table 4

Statistical analysis of regression and correlation of triasulfuron with soil physicochemical properties

Adsorption coefficientProperty (x)Correlation coefficient (r)Probability level (p)Intercept (a)Slope (b)
Kd adspH−0.710.0717.7−0.017
OM0.740.0120.60.024
TOC0.910.0100.30.013
Figure 5 Residual plots of adsorption coefficient Kd with soil properties pH, OM, and TOC.
Figure 5

Residual plots of adsorption coefficient Kd with soil properties pH, OM, and TOC.

3.7 Removal of triasulfuron

Prepared SAC was utilized as an environmental remediation, i.e., for the decontamination of soil from pesticides. Triasulfuron was removed in two concentrations from the soil samples (Table 5). A maximum triasulfuron removal of 44% was observed in 5 ppm concentration. Removal from 7.5 ppm concentration triasulfuron solution was 63%. Mirpur soil sample displayed the highest removal of triasulfuron through SAC (63%), whereas the lowest removal was from Karachi (21%). Time and concentration can play a significant role in the removal of pesticide from soils through SAC (Figure 6). Laurella et al. adsorbed carbendazim on silica for its removal [33]. The experimental data fitted best to the first-order reaction kinetics. Their results indicated the formation of type I isotherm, depicting the difficulty in adsorption with the increase in concentration. The researchers fitted their data to Langmuir and Freundlich models. Based on the r2 values, their experimental data fitted well to Langmuir model.

Table 5

SAC-aided elimination of triasulfuron from various soils

Triasulfuron concentration 5 ppmTriasulfuron concentration 7.5 ppm
LocationBefore addition of ACAfter 3 hAfter 6 hAverage removalPercentage (%)Before addition of ACAfter 3 hAfter 6 hAverage removalPercentage (%)
Attock1.080.330.110.38350.260.150.080.1975
Chakwal1.360.510.160.59430.500.450.020.4693
Karachi2.060.430.030.45210.210.020.020.0316
Mirpur1.220.740.190.84630.170.080.030.0742
Peshawar1.350.490.200.60440.310.040.110.0930
Sohawa1.390.430.140.50360.200.010.680.1365
Taxila1.070.360.160.44410.180.050.050.0742
Figure 6 Triasulfuron elimination from soils via SAC (a) 5 ppm initial herbicide concentration and (b) 7.5 ppm initial herbicide concentration. UV spectrum of triasulfuron removal (c) highest elimination in Mirpur (5 ppm), (d) lowest elimination in Karachi (5 ppm), (e) highest exclusion in Chakwal (7.5 ppm), and (f) lowest exclusion in Karachi (7.5 ppm).
Figure 6

Triasulfuron elimination from soils via SAC (a) 5 ppm initial herbicide concentration and (b) 7.5 ppm initial herbicide concentration. UV spectrum of triasulfuron removal (c) highest elimination in Mirpur (5 ppm), (d) lowest elimination in Karachi (5 ppm), (e) highest exclusion in Chakwal (7.5 ppm), and (f) lowest exclusion in Karachi (7.5 ppm).

4 Conclusion

Diverse soils from various different areas were analyzed for the triasulfuron adsorption alongside its exclusion by AC prepared from sugarcane bagasse. It can be concluded from the results that triasulfuron adsorption depends largely upon the physiochemical properties of soils. Highest Kd and Kf values reveal that soils have greater ability of adsorption. AC-mediated elimination of triasulfuron was beneficial both economically and environmentally. Around 50% triasulfuron was easily detached from soils by this methodology. This method provides promise for future remediation studies because of its less cost and nonrequirement of synthetic AC. It is advisable to use different waste materials to prepare AC pesticide remediation from soils as it not only removes the pesticides but is also an auspicious method for waste reduction. It is the first report on triasulfuron removal by biomass-derived AC, thus acting as a milestone for further studies for herbicide remediation.

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Acknowledgments

The authors acknowledge Higher Education Commission of Pakistan, the Department of Environmental Science (Lab E-21), and Fatima Jinnah Women University, Pakistan. This work was funded by Researchers Supporting Project number (RSP-2020/165), King Saud University, Riyadh, Saudi Arabia.

  1. Conflict of interest: The authors declare no conflicts of interest.

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Received: 2019-07-09
Revised: 2020-09-30
Accepted: 2020-10-19
Published Online: 2020-12-01

© 2020 Khuram Shahzad Ahmad et al., published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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https://doi.org/10.1515/chem-2020-0185
Keywords for this article
sorption; herbicide; exothermic; removal; activated carbon; sugarcane bagasse
Creative Commons
BY 4.0

Articles in the same Issue

  1. Regular Articles
  2. Electrochemical antioxidant screening and evaluation based on guanine and chitosan immobilized MoS2 nanosheet modified glassy carbon electrode (guanine/CS/MoS2/GCE)
  3. Kinetic models of the extraction of vanillic acid from pumpkin seeds
  4. On the maximum ABC index of bipartite graphs without pendent vertices
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  6. Molecular dynamics simulation of sI methane hydrate under compression and tension
  7. Spatial distribution and potential ecological risk assessment of some trace elements in sediments and grey mangrove (Avicennia marina) along the Arabian Gulf coast, Saudi Arabia
  8. Amino-functionalized graphene oxide for Cr(VI), Cu(II), Pb(II) and Cd(II) removal from industrial wastewater
  9. Chemical composition and in vitro activity of Origanum vulgare L., Satureja hortensis L., Thymus serpyllum L. and Thymus vulgaris L. essential oils towards oral isolates of Candida albicans and Candida glabrata
  10. Effect of excess Fluoride consumption on Urine-Serum Fluorides, Dental state and Thyroid Hormones among children in “Talab Sarai” Punjab Pakistan
  11. Design, Synthesis and Characterization of Novel Isoxazole Tagged Indole Hybrid Compounds
  12. Comparison of kinetic and enzymatic properties of intracellular phosphoserine aminotransferases from alkaliphilic and neutralophilic bacteria
  13. Green Organic Solvent-Free Oxidation of Alkylarenes with tert-Butyl Hydroperoxide Catalyzed by Water-Soluble Copper Complex
  14. Ducrosia ismaelis Asch. essential oil: chemical composition profile and anticancer, antimicrobial and antioxidant potential assessment
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  16. Influence of Chemical Osmosis on Solute Transport and Fluid Velocity in Clay Soils
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  18. Antiplasmodial Activity of Stigmastane Steroids from Dryobalanops oblongifolia Stem Bark
  19. Rapid identification of direct-acting pancreatic protectants from Cyclocarya paliurus leaves tea by the method of serum pharmacochemistry combined with target cell extraction
  20. Immobilization of Pseudomonas aeruginosa static biomass on eggshell powder for on-line preconcentration and determination of Cr (VI)
  21. Assessment of methyl 2-({[(4,6-dimethoxypyrimidin-2-yl)carbamoyl] sulfamoyl}methyl)benzoate through biotic and abiotic degradation modes
  22. Stability of natural polyphenol fisetin in eye drops Stability of fisetin in eye drops
  23. Production of a bioflocculant by using activated sludge and its application in Pb(II) removal from aqueous solution
  24. Molecular Properties of Carbon Crystal Cubic Structures
  25. Synthesis and characterization of calcium carbonate whisker from yellow phosphorus slag
  26. Study on the interaction between catechin and cholesterol by the density functional theory
  27. Analysis of some pharmaceuticals in the presence of their synthetic impurities by applying hybrid micelle liquid chromatography
  28. Two mixed-ligand coordination polymers based on 2,5-thiophenedicarboxylic acid and flexible N-donor ligands: the protective effect on periodontitis via reducing the release of IL-1β and TNF-α
  29. Incorporation of silver stearate nanoparticles in methacrylate polymeric monoliths for hemeprotein isolation
  30. Development of ultrasound-assisted dispersive solid-phase microextraction based on mesoporous carbon coated with silica@iron oxide nanocomposite for preconcentration of Te and Tl in natural water systems
  31. N,N′-Bis[2-hydroxynaphthylidene]/[2-methoxybenzylidene]amino]oxamides and their divalent manganese complexes: Isolation, spectral characterization, morphology, antibacterial and cytotoxicity against leukemia cells
  32. Determination of the content of selected trace elements in Polish commercial fruit juices and health risk assessment
  33. Diorganotin(iv) benzyldithiocarbamate complexes: synthesis, characterization, and thermal and cytotoxicity study
  34. Keratin 17 is induced in prurigo nodularis lesions
  35. Anticancer, antioxidant, and acute toxicity studies of a Saudi polyherbal formulation, PHF5
  36. LaCoO3 perovskite-type catalysts in syngas conversion
  37. Comparative studies of two vegetal extracts from Stokesia laevis and Geranium pratense: polyphenol profile, cytotoxic effect and antiproliferative activity
  38. Fragmentation pattern of certain isatin–indole antiproliferative conjugates with application to identify their in vitro metabolic profiles in rat liver microsomes by liquid chromatography tandem mass spectrometry
  39. Investigation of polyphenol profile, antioxidant activity and hepatoprotective potential of Aconogonon alpinum (All.) Schur roots
  40. Lead discovery of a guanidinyl tryptophan derivative on amyloid cascade inhibition
  41. Physicochemical evaluation of the fruit pulp of Opuntia spp growing in the Mediterranean area under hard climate conditions
  42. Electronic structural properties of amino/hydroxyl functionalized imidazolium-based bromide ionic liquids
  43. New Schiff bases of 2-(quinolin-8-yloxy)acetohydrazide and their Cu(ii), and Zn(ii) metal complexes: their in vitro antimicrobial potentials and in silico physicochemical and pharmacokinetics properties
  44. Treatment of adhesions after Achilles tendon injury using focused ultrasound with targeted bFGF plasmid-loaded cationic microbubbles
  45. Synthesis of orotic acid derivatives and their effects on stem cell proliferation
  46. Chirality of β2-agonists. An overview of pharmacological activity, stereoselective analysis, and synthesis
  47. Fe3O4@urea/HITh-SO3H as an efficient and reusable catalyst for the solvent-free synthesis of 7-aryl-8H-benzo[h]indeno[1,2-b]quinoline-8-one and indeno[2′,1′:5,6]pyrido[2,3-d]pyrimidine derivatives
  48. Adsorption kinetic characteristics of molybdenum in yellow-brown soil in response to pH and phosphate
  49. Enhancement of thermal properties of bio-based microcapsules intended for textile applications
  50. Exploring the effect of khat (Catha edulis) chewing on the pharmacokinetics of the antiplatelet drug clopidogrel in rats using the newly developed LC-MS/MS technique
  51. A green strategy for obtaining anthraquinones from Rheum tanguticum by subcritical water
  52. Cadmium (Cd) chloride affects the nutrient uptake and Cd-resistant bacterium reduces the adsorption of Cd in muskmelon plants
  53. Removal of H2S by vermicompost biofilter and analysis on bacterial community
  54. Structural cytotoxicity relationship of 2-phenoxy(thiomethyl)pyridotriazolopyrimidines: Quantum chemical calculations and statistical analysis
  55. A self-breaking supramolecular plugging system as lost circulation material in oilfield
  56. Synthesis, characterization, and pharmacological evaluation of thiourea derivatives
  57. Application of drug–metal ion interaction principle in conductometric determination of imatinib, sorafenib, gefitinib and bosutinib
  58. Synthesis and characterization of a novel chitosan-grafted-polyorthoethylaniline biocomposite and utilization for dye removal from water
  59. Optimisation of urine sample preparation for shotgun proteomics
  60. DFT investigations on arylsulphonyl pyrazole derivatives as potential ligands of selected kinases
  61. Treatment of Parkinson’s disease using focused ultrasound with GDNF retrovirus-loaded microbubbles to open the blood–brain barrier
  62. New derivatives of a natural nordentatin
  63. Fluorescence biomarkers of malignant melanoma detectable in urine
  64. Study of the remediation effects of passivation materials on Pb-contaminated soil
  65. Saliva proteomic analysis reveals possible biomarkers of renal cell carcinoma
  66. Withania frutescens: Chemical characterization, analgesic, anti-inflammatory, and healing activities
  67. Design, synthesis and pharmacological profile of (−)-verbenone hydrazones
  68. Synthesis of magnesium carbonate hydrate from natural talc
  69. Stability-indicating HPLC-DAD assay for simultaneous quantification of hydrocortisone 21 acetate, dexamethasone, and fluocinolone acetonide in cosmetics
  70. A novel lactose biosensor based on electrochemically synthesized 3,4-ethylenedioxythiophene/thiophene (EDOT/Th) copolymer
  71. Citrullus colocynthis (L.) Schrad: Chemical characterization, scavenging and cytotoxic activities
  72. Development and validation of a high performance liquid chromatography/diode array detection method for estrogen determination: Application to residual analysis in meat products
  73. PCSK9 concentrations in different stages of subclinical atherosclerosis and their relationship with inflammation
  74. Development of trace analysis for alkyl methanesulfonates in the delgocitinib drug substance using GC-FID and liquid–liquid extraction with ionic liquid
  75. Electrochemical evaluation of the antioxidant capacity of natural compounds on glassy carbon electrode modified with guanine-, polythionine-, and nitrogen-doped graphene
  76. A Dy(iii)–organic framework as a fluorescent probe for highly selective detection of picric acid and treatment activity on human lung cancer cells
  77. A Zn(ii)–organic cage with semirigid ligand for solvent-free cyanosilylation and inhibitory effect on ovarian cancer cell migration and invasion ability via regulating mi-RNA16 expression
  78. Polyphenol content and antioxidant activities of Prunus padus L. and Prunus serotina L. leaves: Electrochemical and spectrophotometric approach and their antimicrobial properties
  79. The combined use of GC, PDSC and FT-IR techniques to characterize fat extracted from commercial complete dry pet food for adult cats
  80. MALDI-TOF MS profiling in the discovery and identification of salivary proteomic patterns of temporomandibular joint disorders
  81. Concentrations of dioxins, furans and dioxin-like PCBs in natural animal feed additives
  82. Structure and some physicochemical and functional properties of water treated under ammonia with low-temperature low-pressure glow plasma of low frequency
  83. Mesoscale nanoparticles encapsulated with emodin for targeting antifibrosis in animal models
  84. Amine-functionalized magnetic activated carbon as an adsorbent for preconcentration and determination of acidic drugs in environmental water samples using HPLC-DAD
  85. Antioxidant activity as a response to cadmium pollution in three durum wheat genotypes differing in salt-tolerance
  86. A promising naphthoquinone [8-hydroxy-2-(2-thienylcarbonyl)naphtho[2,3-b]thiophene-4,9-dione] exerts anti-colorectal cancer activity through ferroptosis and inhibition of MAPK signaling pathway based on RNA sequencing
  87. Synthesis and efficacy of herbicidal ionic liquids with chlorsulfuron as the anion
  88. Effect of isovalent substitution on the crystal structure and properties of two-slab indates BaLa2−xSmxIn2O7
  89. Synthesis, spectral and thermo-kinetics explorations of Schiff-base derived metal complexes
  90. An improved reduction method for phase stability testing in the single-phase region
  91. Comparative analysis of chemical composition of some commercially important fishes with an emphasis on various Malaysian diets
  92. Development of a solventless stir bar sorptive extraction/thermal desorption large volume injection capillary gas chromatographic-mass spectrometric method for ultra-trace determination of pyrethroids pesticides in river and tap water samples
  93. A turbidity sensor development based on NL-PI observers: Experimental application to the control of a Sinaloa’s River Spirulina maxima cultivation
  94. Deep desulfurization of sintering flue gas in iron and steel works based on low-temperature oxidation
  95. Investigations of metallic elements and phenolics in Chinese medicinal plants
  96. Influence of site-classification approach on geochemical background values
  97. Effects of ageing on the surface characteristics and Cu(ii) adsorption behaviour of rice husk biochar in soil
  98. Adsorption and sugarcane-bagasse-derived activated carbon-based mitigation of 1-[2-(2-chloroethoxy)phenyl]sulfonyl-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea-contaminated soils
  99. Antimicrobial and antifungal activities of bifunctional cooper(ii) complexes with non-steroidal anti-inflammatory drugs, flufenamic, mefenamic and tolfenamic acids and 1,10-phenanthroline
  100. Application of selenium and silicon to alleviate short-term drought stress in French marigold (Tagetes patula L.) as a model plant species
  101. Screening and analysis of xanthine oxidase inhibitors in jute leaves and their protective effects against hydrogen peroxide-induced oxidative stress in cells
  102. Synthesis and physicochemical studies of a series of mixed-ligand transition metal complexes and their molecular docking investigations against Coronavirus main protease
  103. A study of in vitro metabolism and cytotoxicity of mephedrone and methoxetamine in human and pig liver models using GC/MS and LC/MS analyses
  104. A new phenyl alkyl ester and a new combretin triterpene derivative from Combretum fragrans F. Hoffm (Combretaceae) and antiproliferative activity
  105. Erratum
  106. Erratum to: A one-step incubation ELISA kit for rapid determination of dibutyl phthalate in water, beverage and liquor
  107. Review Articles
  108. Sinoporphyrin sodium, a novel sensitizer for photodynamic and sonodynamic therapy
  109. Natural products isolated from Casimiroa
  110. Plant description, phytochemical constituents and bioactivities of Syzygium genus: A review
  111. Evaluation of elastomeric heat shielding materials as insulators for solid propellant rocket motors: A short review
  112. Special Issue on Applied Biochemistry and Biotechnology 2019
  113. An overview of Monascus fermentation processes for monacolin K production
  114. Study on online soft sensor method of total sugar content in chlorotetracycline fermentation tank
  115. Studies on the Anti-Gouty Arthritis and Anti-hyperuricemia Properties of Astilbin in Animal Models
  116. Effects of organic fertilizer on water use, photosynthetic characteristics, and fruit quality of pear jujube in northern Shaanxi
  117. Characteristics of the root exudate release system of typical plants in plateau lakeside wetland under phosphorus stress conditions
  118. Characterization of soil water by the means of hydrogen and oxygen isotope ratio at dry-wet season under different soil layers in the dry-hot valley of Jinsha River
  119. Composition and diurnal variation of floral scent emission in Rosa rugosa Thunb. and Tulipa gesneriana L.
  120. Preparation of a novel ginkgolide B niosomal composite drug
  121. The degradation, biodegradability and toxicity evaluation of sulfamethazine antibiotics by gamma radiation
  122. Special issue on Monitoring, Risk Assessment and Sustainable Management for the Exposure to Environmental Toxins
  123. Insight into the cadmium and zinc binding potential of humic acids derived from composts by EEM spectra combined with PARAFAC analysis
  124. Source apportionment of soil contamination based on multivariate receptor and robust geostatistics in a typical rural–urban area, Wuhan city, middle China
  125. Special Issue on 13th JCC 2018
  126. The Role of H2C2O4 and Na2CO3 as Precipitating Agents on The Physichochemical Properties and Photocatalytic Activity of Bismuth Oxide
  127. Preparation of magnetite-silica–cetyltrimethylammonium for phenol removal based on adsolubilization
  128. Topical Issue on Agriculture
  129. Size-dependent growth kinetics of struvite crystals in wastewater with calcium ions
  130. The effect of silica-calcite sedimentary rock contained in the chicken broiler diet on the overall quality of chicken muscles
  131. Physicochemical properties of selected herbicidal products containing nicosulfuron as an active ingredient
  132. Lycopene in tomatoes and tomato products
  133. Fluorescence in the assessment of the share of a key component in the mixing of feed
  134. Sulfur application alleviates chromium stress in maize and wheat
  135. Effectiveness of removal of sulphur compounds from the air after 3 years of biofiltration with a mixture of compost soil, peat, coconut fibre and oak bark
  136. Special Issue on the 4th Green Chemistry 2018
  137. Study and fire test of banana fibre reinforced composites with flame retardance properties
  138. Special Issue on the International conference CosCI 2018
  139. Disintegration, In vitro Dissolution, and Drug Release Kinetics Profiles of k-Carrageenan-based Nutraceutical Hard-shell Capsules Containing Salicylamide
  140. Synthesis of amorphous aluminosilicate from impure Indonesian kaolin
  141. Special Issue on the International Conf on Science, Applied Science, Teaching and Education 2019
  142. Functionalization of Congo red dye as a light harvester on solar cell
  143. The effect of nitrite food preservatives added to se’i meat on the expression of wild-type p53 protein
  144. Biocompatibility and osteoconductivity of scaffold porous composite collagen–hydroxyapatite based coral for bone regeneration
  145. Special Issue on the Joint Science Congress of Materials and Polymers (ISCMP 2019)
  146. Effect of natural boron mineral use on the essential oil ratio and components of Musk Sage (Salvia sclarea L.)
  147. A theoretical and experimental study of the adsorptive removal of hexavalent chromium ions using graphene oxide as an adsorbent
  148. A study on the bacterial adhesion of Streptococcus mutans in various dental ceramics: In vitro study
  149. Corrosion study of copper in aqueous sulfuric acid solution in the presence of (2E,5E)-2,5-dibenzylidenecyclopentanone and (2E,5E)-bis[(4-dimethylamino)benzylidene]cyclopentanone: Experimental and theoretical study
  150. Special Issue on Chemistry Today for Tomorrow 2019
  151. Diabetes mellitus type 2: Exploratory data analysis based on clinical reading
  152. Multivariate analysis for the classification of copper–lead and copper–zinc glasses
  153. Special Issue on Advances in Chemistry and Polymers
  154. The spatial and temporal distribution of cationic and anionic radicals in early embryo implantation
  155. Special Issue on 3rd IC3PE 2020
  156. Magnetic iron oxide/clay nanocomposites for adsorption and catalytic oxidation in water treatment applications
  157. Special Issue on IC3PE 2018/2019 Conference
  158. Exergy analysis of conventional and hydrothermal liquefaction–esterification processes of microalgae for biodiesel production
  159. Advancing biodiesel production from microalgae Spirulina sp. by a simultaneous extraction–transesterification process using palm oil as a co-solvent of methanol
  160. Topical Issue on Applications of Mathematics in Chemistry
  161. Omega and the related counting polynomials of some chemical structures
  162. M-polynomial and topological indices of zigzag edge coronoid fused by starphene
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