Investigation of Atrazine Sorption to Biochar With Titration Calorimetry and Flow-Through Analysis: Implications for Design of Pollution-Control Structures

Abstract

Atrazine is one of the most common broad-leaf herbicides used in the world. However, due to extensive use for many years, atrazine often appears in surface and groundwater. Atrazine transport is inhibited by degradation or sorption to soil components, especially organic matter. Biochar is a charcoal-like material produced from pyrolysis of biomass. Due to the amount and type of functional groups found on biochar, this product has shown potential for sorption of atrazine from solution. There is an interest in developing best management practices utilizing biochar to filter atrazine from non-point drainage with pollution-control structures such as blind inlets. The objective of this study was to explore the kinetics and thermodynamics of atrazine sorption to biochar using two different approaches: flow-through sorption cells and isothermal titration calorimetry (ITC). Twenty-five milligrams of an oak (Quercus spp.)-derived biochar was suspended in water and titrated 25 times (0.01 mL per titration) with atrazine at three different concentrations, and by a single titration (0.25 mL), with heat of reaction directly measured with ITC. A benchtop atrazine sorption study that simulated the titration experiment was also conducted. A continuous flow-through system was used to quantify the impact of contact time on atrazine sorption to biochar. Atrazine sorption to biochar displayed both exothermic and endothermic signals within each titration, although the net reaction was exothermic and proportional to the degree of sorption. Net enthalpy was −4,231 ± 130 kJ mole−1 atrazine sorbed. The existence of both exotherms and endotherms within a single titration, plus observation of an initial fast reaction phase from 0 to 300 s followed by a slower phase, suggested multiple sorption mechanisms to biochar. Results of flow-through tests supported kinetics observations, with the 300 s contact time removing much more atrazine compared to 45 s, while 600 s improved little compared to 300 s. Based on flow-through results, annual atrazine removal goal of 50%, and typical Midwestern U.S. tile drainage conditions, a pollution-control structure implementing this biochar sample would require 32 and 4 Mg for a design utilizing a contact time of 45 and 300 s, respectively. Future work is necessary for estimating degradation of atrazine sorbed to biochar.

Isothermal Titration Calorimetry to Explore the Parameter Space of Organophosphorus Agrochemical Adsorption in MOFs

“…Fortunately, isothermal titration calorimetry (ITC) allows for the direct quantification of the binding association constant (K a ), enthalpy change (Δ H ), entropy change (Δ S ), and Gibbs free energy change (Δ G ) of a chemical process. − Most commonly, researchers in the biological sciences use this technique to investigate substrate-active site interactions. , Similarly, we envisioned the value of this technique for illuminating adsorptive processes in MOFs. Only recently have materials chemists begun exploring the applicability of this technique for the study of porous sorbents. − Therefore, we undertook a proof-of-concept study using ITC to explore the parameter space of glyphosate adsorption in Zr-MOFs (Figure ). Glyphosate, the active ingredient of the widely used pesticide Roundup, possesses both a carboxylic acid and a phosphonic acid .…”

Valorisation of agricultural waste derived biochars in aquaculture to remove organic micropollutants from water – experimental study and molecular dynamics simulations

“…In most cases, we observed good fits to the BET, Freundlich and Langmuir models, indicating non-linear sorption. In the literature, good fits to Langmuir have been reported for tetracycline ( Jang and Kan, 2019 ), enrofloxacin ( Zhao et al, 2019 ) or atrazine ( Penn et al, 2018 ). Nonetheless, the fits to the Freundlich isotherm were often of similar quality, and such behavior was confirmed in terms of atrazine sorption on soils ( Yue et al, 2017 ).…”

Adsorptive Removal of Atrazine From Contaminated Water Using Low-Cost Carbonaceous Materials: A Review

“…Lower pH might be an advantageous factor for the sorption of ionizable substances (Oh and Seo, 2016;Mandal et al, 2017), which proposes the role of negative surface charges in the biochar adsorption capacity. In a study by Penn et al (2018), it was reported that pH did not affect the sorption process and heat release. The atrazine-biochar solution with a neutral pH does not alter the state of atrazine, thus reducing the possibility of cationic exchange in the sorption process (Weber, 1993).…”

“…However, the sorption capacities of biochar for atrazine largely depend on feedstock sources, pyrolysis temperature, rate of pyrolysis, and resident time. Moreover, the type and number of surface functional groups (Penn et al, 2018), surface area, and strong binding affinity may also influence the sorption potential of biochar for atrazine (Zhao et al, 2013;Mandal et al, 2017). Biochar's sorption capacities for atrazine vary largely with the type of feedstock used for biochar production.…”