**Abstract**

Biochar is a solid material derived from different feedstocks that is added to the soil for various agronomic and environmental purposes, such as nutrient sources and CO2 emission mitigators. In modern agriculture, the application of herbicides directly in the soil is common for pre-emergent weed control; however, biochars may interfere in the degradation processes of these agrochemicals, increasing or decreasing their persistence. Long persistence is desirable for some herbicides in determined cultivation systems, especially in monoculture, but persistence is undesirable in crop rotation and/or succession systems because the subsequent cropping can be sensitive to the herbicide, causing carryover problems. Therefore, knowing the interactions of biochar-herbicide is essential, since these interactions depend on feedstock, pyrolysis conditions (production temperature), application rate, biochar aging, among other factors; and the physical-chemical characteristics of the herbicide. This chapter shows that the addition of biochar in the soil interferes in the persistence or remediation processes of the herbicide, and taking advantage of the agricultural and environmental benefits of biochars without compromising weed control requires a broad knowledge of the characteristics of biochar, soil, and herbicide and their interactions.

**Keywords:** bioavailability, sorption, weed control, pollution soil

## **1. Introduction**

Herbicides are the pesticides most applied in modern agriculture for weed control worldwide, in pre-emergency, directly in the soil, or in post-emergence in leaves. Regardless of the application of herbicides, these reach the soil and may persist with residual effect (carryover) or contaminate the non-target organism and environment. The behavior of the herbicide in the soil is governed by the physico-chemical properties of the molecule and the soil and can have retention, transport, and transformation processes [1]. In transformation processes, the herbicide molecule is degraded into secondary compounds (metabolites) by physical (photodegradation), chemical, and biological processes (**Figure 1**) [2].

**Figure 1.** *Degradation process (chemical, biological, and photodegradation) of herbicides in the soil.*

Biological degradation is the most common way to dissipate the herbicides in the environment, and it is carried out mainly by the soil microbiota which use the herbicide molecules as an energy source and transforms it into compounds without herbicidal action, the process is also known as detoxification [3, 4]. The chemical complexity of the herbicide determines the higher or lower facility of microorganisms to degrade the molecules, characterizing it in low or high persistence in the soil [5], being measured by degradation or dissipation half-life time (DT50) in laboratory or field conditions, respectively [2].

The degradation of herbicides in the soil by microorganisms can be aerobic (with oxygen) or anaerobic (without oxygen). In the presence of oxygen, the herbicide is mineralized in CO2 and water. Without oxygen, the herbicide is mineralized in CH4, CO2, and water [6]. The efficiency of aerobic degradation of herbicides is higher than the anaerobic. The aerobic bacteria oxygen act as an oxidizing agent, and they are present in the region of the soil where there is a higher content of organic matter (OM) and an excellent soil-water-air ratio for the microbiota [7]. In conditions of absence of oxygen, the herbicide can become more persistent in the soil and its degradation pathways are different from microorganisms with aerobic metabolism [8].

The addition of organic materials, like biochar, in the soil directly influences the microbial community, responsible for herbicide degradation [9]. Biochar is a carbonaceous material produced by different feedstocks in pyrolysis conditions with the limited presence of oxygen. Naturally, biochar is found in the anthropogenic soil, known as "Terra Preta de Índio", i.e., Amazonian Dark Earths in the Amazon, which gave rise to synthetic biochar produced worldwide [10]. Pyrolyzed feedstocks and pyrolysis conditions determine the physico-chemical properties of biochar, such as nutrient content, porosity, specific surface area, among others.

In agricultural soils, the biochar has been added to increase porosity, waterholding capacity, reduce acidity, sequester carbon, reduction of greenhouse gas emissions, plant growth promotion, improve soil fertility, and immobilize (remediation) herbicides by increasing sorption and microbial diversity [11]. This chapter showed that is possible to recommend the addition of biochar in the soil to interfere in the persistence or remediation processes of the herbicide.

### **2. Biochar characteristics**

Biochar is the carbon-rich product resulting from the pyrolysis of organic residues such as wood, animal wastes, crop residues, and biosolids [12]. The feedstock usually determines the chemical composition, quantity of macropores, and nutrient content in biochar. Pyrolysis conditions (such as temperature, heating rate, and residence time) determine the morphology and surface structure changes in feedstock and C/H content [11]. The dominant properties affecting herbicide sorption and degradation by biochar include porosity, specific surface area, pH, functional groups, carbon content and aromatic structure, and mineralogical composition [13].

More porous structures and higher specific surface area will result in higher sorption capacities and lower degradation of herbicides [13]. Higher pH of biochar can accelerate the hydrolysis of organophosphorus and carbamate herbicides in the soil through the alkali catalysis mechanism [14]. Surface functional groups including carboxylic (–COOH), hydroxyl (–OH), lactonic, amide, and amine groups are essential for the sorption capacity of biochar [15, 16]. Carbon content and aromatic structure can increase herbicide sorption and reduce their bioavailability to be degraded [13]. The mineralogical composition can reduce the bioavailability of herbicides through surface chelation and/or surface acidity mechanisms [17].

Biochar amendment also affects the degradation of herbicides in the soil in several ways and the effects can be either stimulatory or suppressive [18]. Biochar may contain available nutrients that stimulate overall microbial activity and, thus, degradation of herbicides [19, 20]. However, the degradation of herbicides in biochar-amended soils is most commonly reduced because herbicide sorption increases [21]. Biochar also sorbs dissolved organic carbon (OC), which can contribute to co-metabolic biodegradation [22]. Some changes in the degradation rate can be a result of indirect effects of biochar amendment, e.g., changes in soil pH, albedo, and aeration [18].

#### **3. Microbial diversity in biochar-amended soils**

Soil correction with biochar can affect the soil microbiota in different ways: (1) It can provide an increase in the microbiota [23, 24]; (2) It can negatively affect the resident microbiota by the amount of organic substances (volatile compounds) formed in the production of biochar [25, 26]; or (3) It may not effect the soil microbiota [27, 28]. The possible interaction mechanisms of biochar and soil microbiota are exemplified in **Figure 2** [29, 30]. The physical–chemical structures of the biochar surface (macro and micropores, roughness, surface load, and hydrophobicity) are a refuge for the soil microbiota [31, 32], where microorganisms can find nutrients and ions adsorbed in biochar particles useful for their growth [29, 33]. In addition, biochars can contain significant amounts of organic substances (volatile organic compounds and free radicals) [34, 35], improve the soil's physical–chemical properties, which are important for microbial growth by modifying habitats (aeration, water content, and pH) [36], affect the enzymatic activity of the soil [37, 38],

#### **Figure 2.**

*Interactions between biochar and soil microbiota and environmental effects. Source: Adapted from Zhu et al. [29].*

and increase the sorption of herbicides, reducing the bioavailability and toxicity of these agrochemicals for the soil microbiota [29, 39, 40].

Biochar-amended soil has a higher respiratory rate and microbial communities due to carbon mineralization by soil microorganisms [41]. Microbial biomass carbon and nitrogen increased by 18% and 63% with the application of 1% of sugarcane bagasse biochar [42]. The role of biochar nutrients in the biodegradation of coexisting dichlobenil and atrazine in soil by their respective bacterial degraders was evaluated. The degradation increased with increasing biochar content, due to nutritional stimulation on microbial activities [43]. The application of hardwoodderived biochar increased atrazine mineralization by stimulating atrazine-adapted microflora compared to unamended soil [19]. Soil amended with biochar derived from wheat straw increased the abundance and diversity rate of bacteria and fungi beneficial to plants in the rhizosphere of wheat seedlings [24]. In addition, these microorganisms use fomesafen as a source of nutrients, which favors their proliferation from the soil [24]. The change and proliferation of the soil microbiota with the addition of biochar is related to the chemical characteristics of biochar (mainly pH and nutrient content) and physical properties (pore size, pore-volume, and specific surface area), OM content, and water retention that provide favorable conditions for soil microbiota [28]. Although soil microbial biomass is generally benefited with the addition of biochar, the response depends on the type of raw material, pyrolysis temperature, and biochar application rate, since these factors directly interfere with the physical–chemical characteristics of biochar and consequently on the response of the microbiota in herbicide degradation. The proposed mechanisms involved in biochar and microbiota interactions require further studies to elucidate the impact of biochar on soil microbial activity.

### **4. Influence of biochar amendment in soil on the herbicide degradation**

Herbicides are applied to the soil to control weeds during a certain time after application; however, long persistence may affect the subsequent crop, a process known as carryover. Therefore, the process of degradation of the herbicide is

important for the dissipation of herbicides in the soil when the intention is the remediation of the product. However, under agronomic conditions in which a residual effect of the herbicide on the soil is desired for weed control, the addition of biochar can reduce the persistence of the product, consequently reducing its effectiveness in management [2, 9, 44].

The degradation of herbicide molecules into secondary compounds (metabolites) can occur by biotic (biological degradation) or abiotic (hydrolysis, reduction, oxidation, and photolysis) processes [45]. Biodegradation, carried out by the soil microbiota (bacteria, fungi, protozoa, and actinomycetes), is the main decomposition pathway for most herbicides [13, 46]. Microorganisms can use herbicide molecules as an energy source and transform them into compounds without herbicide action, a process known as catabolism, or through co-metabolism, in which herbicide degradation requires the presence of a growth substrate that is used as primary carbon and energy source [3, 47], i.e., microorganism does not obtain energy or benefit from the herbicide degradation. The transformation process is usually mediated by non-specific enzymes that are capable to transform various organic compounds [4]. Herbicides have varied susceptibility to microbial degradation depending on the complexity of the molecule that influences low or high persistence in the soil [5].

Microbial degradation generally reduces the DT50 of herbicides in the soil; however, the addition of biochar, according to studies performed, may increase or decrease the DT50 values, depending on the herbicide and pyrolyzed feedstock (**Table 1**). The high sorption capacity for herbicides in the biochar-amended soil decreases herbicide degradation, providing a higher DT50 than the unamended soil [46, 49]. For example, less atrazine degradation was observed in amended soils with sugarcane bagasse biochar (0.5% w/w) (**Table 1**), increasing in 15 days the DT50 of the herbicide in relation to unamended soil [49]. Flumioxazin DT50 increased by ~10 days when bamboo biochar (10% w/w) was added compared to unamended soil (**Table 1**) [51]. The DT50 of 2-methyl-4-chlorophenoxyaceticacid (MCPA) increased from 5.2 days (unamended soil) to 21.5 days in amended soil with 1% of wheat straw biochar [59].

The application of biochar can also increase soil microbial activity, improving herbicide degradation [29, 60]. The increase in microbial biomass may be due to the addition of available organic substrates, which are the main energy source readily available to soil microorganisms [55]. The high content of dissolved OC in the soil MO can reduce herbicide sorption by biochar particles, as dissolved OC competes with herbicide molecules to occupy available biochar sorption sites [61]. Biochar also sorbs dissolved OC, which can contribute to co-metabolic biodegradation [22]. Some changes in degradation rate may result from indirect effects of biochar amendment, e.g., changes in soil pH and aeration [18]. The highest degradation of oxyfluorfen was observed in amended soils with different rates of application of rice husk biochar, decreasing DT50 between 2 and 23 days compared to unamended soil (**Table 1**) [50]. Alachlor mineralization increased up to 50% using biochar derived from soybean stoves, sugarcane bagasse, and wood chips compared to unamended soil (**Table 1**) [58].

Photolysis and hydrolysis are the main abiotic processes involved in herbicide degradation [48, 62]. Photolysis or photodegradation occurs when herbicides are exposed to sunlight [63] and can be direct (a herbicide molecule absorbs light energy, is later excited and transformed) or indirect (species photochemically produced in the soil matrix react with the herbicide molecule triggering its degradation) [64]. Water degrades herbicides by dividing large molecules into smaller molecules, breaking them in the process called hydrolysis [65]. The hydrolysis of herbicides in the soil can be influenced by several factors such as dissolved ion


*Biodegradation Technology of Organic and Inorganic Pollutants*







**Table 1.**

*Effect of biochar amendment in soil on the degradation half-live time (DT50 - days) of different herbicides.*

*Biodegradation Technology of Organic and Inorganic Pollutants*

**14**

concentration, soil pH, and content of clays and metal oxides capable of catalyzing this herbicide degradation process [14, 66].

The application of biochar can influence the degradation of herbicides by hydrolysis and photolysis, since persistent free radicals existing or photogenerated in biochars can react with the herbicide by the activation of other free radicals such as hydroxyl, sulfate, anion, and superoxide [67, 68]. In addition, the increase in soil pH, the presence of active groups on the mineral surface of biochar, and the high sorption of herbicides have a direct effect on the chemical degradation processes of herbicides [64, 66]. Atrazine was hydrolyzed by 27.9% in the presence of biochar derived from pig manure (700°C) after 12 h due to the mineral surface and dissolved metal ions released from biochars that catalyze hydrolysis [66]. In contrast, imazapic and imazapyr were resistant to degradation by hydrolysis in amended soil with biochar derived from empty fruit bunch of oil palm and rice husk, and their DT50's increased by ~6 to 12 days because the photodegradation rate diminished [53] (**Table 1**). The addition of biochar to the soil at 1 or 5% inhibited the photodegradation of metribuzin and its metabolites deamino (DA), deaminodiketo (DADK), and diketometribuzin (DK), which increased their DT50's due to the immobilization of these compounds the surface layer of the biochar [64]. Therefore, the application of biochar has a direct impact on herbicide degradation processes and should be constantly examined for its application in the soil.
