Removal of bifenthrin pesticide from aqueous solutions by treated patellidae shells using a new fixed bed column filtration technique

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Highlights

  • A new column filtration technique has been implemented for bifenthrin pesticide removal from aqueous solutions.

  • The column was squeezed by a new low-cost and ecological biomaterial prepared based on Patellidae Shells (TPS).

  • The effectiveness of TPS was tested in batch system and the adsorption results were very significant.

  • TPS is an alternative to commercial adsorbents for the pesticides removal.

Abstract

The Treated Patellidae Shells (TPS) packed in a fixed bed column for the removal of emerging contaminant such as bifenthrin provides novel insights into waste valorisation, application of environmentally harmless sorbents and removal of bifenthrin pesticide with extension possibilities for larger applications. The biosorbent was characterized by XRD, FTIR, SEM-EDS, TGA-DTA, pHPZC, and BET analysis. TPS biosorbent is composed of a single phase of calcium carbonate (CaCO3) having a high specific area of 158 m2/g. The effects of important parameters such as flow rate, bed height, particles size and bifenthrin feed concentration were studied. The results show that the column efficiency is higher with higher flow rate, higher bed height, higher bifenthrin inlet concentration and lower TPS particles size. The optimum adsorption capacity (40.53 mg) is achieved using a flow rate of 8 mL/min, a bed depth of 4 cm (1.6 g), in the TPS particles size range of 50–100 μm and a bifenthrin feed concentration of 20 mg/L. To model the experimental data, the Bohart-Adams (B-A), Thomas (T) and Yoon-Nelson (Y-N) models were used. The mathematical formulas of these three models are equivalent, that is why the Chu logistic model was developed to fit the experimental data with a single value of both adjusted correlation coefficient (Adj. R2) and chi-square (χ2), for each set. The non-linear form of Chu logistic model showed a good fit between predicted and observed values with higher Adj. R2 and smaller χ2 values. The Chu logistic model therefore made it possible to calculate the actual parameter values of B-A, T and Y-N models. The study of the adsorption isotherm allows to show that the Langmuir isotherm is suitable for describing experimental data. This adjustment of the Langmuir model with the observed data indicates the favorable adsorption and the higher bifenthrin adsorption capacity of TPS biosorbent. The TPS regenerative power study reveals that TPS has good regenerative capacity and can be recycled to remove pesticide molecules. The TPS biosorbent is effective in removing pesticides and can be considered as an alternative to the commercial adsorbent.

Introduction

Pyrethroids are classified as the fourth most widely used group of insecticides in the world (Brander et al., 2016). They are used as pesticides instead of organophosphate compounds due to their relatively low toxicity to mammals and high capacity of pest control (Bao et al., 2020). However, studies have confirmed that pyrethroids cause potential endocrine disruption effects and develop neurotoxicity in human body (Guo et al., 2013). Due to its harmful effects, the U.S. Environment Protection Agency (EPA) grants the maximum residue limits for pyrethroids to be not more than 0.05 μg/g (Li et al., 2010).

Various technologies such as UV/ozone (Tran et al., 2014), adsorptive micellar flocculation (Kuipa and Kuipa, 2015) esterase activity (Wheelock et al., 2006) and adsorption (Xu et al., 2012) have been developed to remove pyrethroids from agricultural and industrial effluents. Most of them require significant financial input and their use is limited (Syuhadah and Rohasliney, 2012). Nevertheless, adsorption may be the highly effective (Shamsollahi and Partovinia, 2019). The adsorption on activated carbon generally had a high capacity to retain pesticides (Gupta and Ali, 2001), but the rapid saturation, high cost and the treatment of the spent adsorbent decrease its value. To solve these problems, scientists have directed to another type of adsorption, which is biosorption. Several low-cost biosorbents such as treated eggshells (Bakka et al., 2016), groundnut shell ash (Trivedi and Mandavgane, 2016), pecan shell (Niandou et al., 2016), Neem Bark Dust (Chattoraj et al., 2016), eucalyptus bark (Gebresemati and Sahu, 2016), treated patellidae shells (TPS) (Bakka et al., 2018), have been investigated. These biosorbents are wastes which can be of vegetable or animal origin. Biosorbents can be considered highly effective because of their cheaper cost, simple design, rapidity, ease of use and the availability of biosorbents without hazardous compound formation. The biomaterial (TPS) is obtained by chemically treating the external shells of a marine gastropod widely distributed in the coastal areas of the Atlantic Ocean. Biosorption is considered the most suitable approach until now because it is simple, cheap and high effective and it can be an alternative process for the elimination of pesticides from wastewater (Mushtaq et al., 2016).

The biosorption of bifenthrin, as a representative pesticide of the pyrethroid family, has already been studied by other authors under operational conditions in batches using different adsorbents (Domingues et al., 2005). Nevertheless, agro-industrial wastewater is generated in large quantities, which requires the use of dynamic techniques that can treat a large volume of effluent in a short time, such as column filtration. For this reason, dynamic adsorption experiments on a fixed bed column were necessary to obtain practical information on the adsorption efficiency under its flow conditions. Few authors have reported on the adsorption of pesticides at dynamic operational conditions using fixed-bed columns (Deokar et al., 2016a; Cobas et al., 2016; Dichiara et al., 2015).

In this work, the effectiveness of treated patellidae shells (TPS) was investigated as a gastropod waste, eco-friendly, low cost and widespread biosorbent to remove bifenthrin insecticide, widely used in Souss-Massa’s agriculture, from aqueous solutions using fixed-bed column process. The TPS biosorbent was characterized using XRD, FTIR, SEM-EDS, TGA-DTA, pHPZC, and BET analysis techniques. In order to model the experimental data, the Chu logistic model was established. This model allows to computerize the parameter values of the B-A, Thomas and Y-N models through a single function with a single Adj.R2 and χ2 for each data set. Comparison between the both linear and non-linear forms of the Chu logistic model reveals the appropriate form giving the best fit with the observed data. The adsorption isotherm was also measured and fitted to two mathematical models Langmuir and Freundlich. The desorption and recycling study of the fixed-bed column was also performed.

Section snippets

Biosorbent and biosorbate

Analytical grade bifenthrin of 99.9 % purity was purchased from Sigma Aldrich Company Casablanca (Morocco) and a stock solution was prepared in methanol. The bifenthrin molecular formula is C23H22ClF3O2, the molar mass is 422.87 g/mol, the solubility in water is 0.1 mg/L. Patellidae shells were collected from the coast of Massa city in Morocco. The shells were washed with distilled water and treated for 10 min with HCl acid 0.1 M, rinsed and placed in an oven at 110 °C for 12 h. The shells were

Characterization of biosorbent

The XRD spectrum, shown in Fig. 2, reveals the presence of calcite as a major phase and aragonite as a minor phase. The major peak is located at 2θ = 29.47° in addition to 23 other small peaks. The identification of the calcite phase has been confirmed by the JCPDS standard No. 96-900-9668 which has a hexagonal crystalline system, a space group R-3c and a space number of 167. The Miller indices attributed to the Bragg peaks are: a = b = 4.9910 Å; c = 17.0680 Å; α=β = 90°; γ = 120°. The identification of the

Conclusion

The purpose of this study was to determine the efficacy of Treated Patellidae Shells (TPS) for bifenthrin pesticide removal from aqueous solutions under dynamic conditions using a fixed bed column. The most important conclusions are as follows:

  • 1

    The characterization of TPS reveals that it is a biomaterial composed of calcium carbonate with a large specific surface area.

  • 2

    The study of breakthrough curves of bifenthrin biosorption on TPS fixed bed column shows that the breakthrough and exhaustion

Declaration of Competing Interest

We wish to confirm that there are no known conflicts of interest associated with this publication and there has been no significant financial support for this work that could have influenced its outcome. We confirm that the manuscript has been read and approved by all named authors and that there are no other persons who satisfied the criteria for authorship but are not listed. We further confirm that the order of authors listed in the manuscript has been approved by all of us. We confirm that

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