Journal of Environmental Management 334 (2023) 117430

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Journal of Environmental Management

journal homepage: www.elsevier.com/locate/jenvman

Research article

Combined use of biochar and alternative management systems for

imazamox induced pollution control in rice growing environments
Jaime Terrón-Sánchez a, Carmen Martín-Franco b, Luis Andrés Vicente b,
Damián Fernández-Rodríguez a, Ángel Albarrán a, José Manuel Rato Nunes c, David Peña d, *,
Antonio López-Piñeiro b
a
Área de Producción Vegetal, Escuela de Ingenierías Agrarias – IACYS, Universidad de Extremadura, Ctra de Cáceres, 06071, Badajoz, Spain
b
Área de Edafología y Química Agrícola, Facultad de Ciencias – IACYS, Universidad de Extremadura, Avda de Elvas S/n, 06071, Badajoz, Spain
c
Instituto Politécnico de Portalegre, Escola Superior Agraria de Elvas, Elvas, Portugal
d
Área de Edafología y Química Agrícola, Escuela de Ingenierías Agrarias– IACYS, Universidad de Extremadura, Ctra de Cáceres, 06071, Badajoz, Spain

A R T I C L E I N F O A B S T R A C T

Keywords: Imazamox (IMZX) is a persistent herbicide having probable risks for non-target organisms in the environment
Biochar ageing and water contamination. Alternatives to conventional flooding rice production, including biochar amendment,
Imazamox may induce changes in soil properties which can greatly modify the environmental fate of IMZX. This two-year
Leaching
study is the first to evaluate how tillage and irrigation practices, with or without fresh or aged biochar (Bc), that
Persistence
Sorption
are alternatives to conventional rice production impact IMZX’s environmental fate. The treatments were: con­
Sprinkler irrigation ventional tillage and flooding irrigation (CTFI), conventional tillage and sprinkler irrigation (CTSI), no-tillage
and sprinkler irrigation (NTSI), and the corresponding Bc-amendment treatments (CTFI-Bc, CTSI-Bc, and
NTSI-Bc). Fresh and aged Bc amendment decreased IMZX’s sorption onto the soil in tillage treatments, with Kf
values decreasing 3.7 and 4.2-fold (fresh case) and 1.5 and 2.6-fold (aged case) for CTSI-Bc and CTFI-Bc,
respectively. The transition to sprinkler irrigation reduced IMZX persistence. Overall, Bc amendment also
reduced chemical persistence with half-life values decreasing 1.6 and 1.5-fold for CTFI and CTSI (fresh year) and
1.1, 1.1, and 1.3-fold for CTFI, CTSI, and NTSI (aged year), respectively. Sprinkler irrigation reduced IMZX
leaching by up to a factor of 2.2. The use of Bc as amendment led to a significant decrease in IMZX leaching only
under tillage conditions, but notable in particular for the CTFI case where leaching losses were reduced in the
fresh year from 80% to 34% and, in the aged year, from 74% to 50%. Hence the change in irrigation from
flooding to sprinkler either alone or in combination with the use of Bc (fresh or aged) amendment could be
considered an effective way to sharply mitigate IMZX contamination of water in environments where rice is
grown, particularly in those managed with tillage.

1. Introduction techniques by reducing the water footprint. In this sense, sprinkler

irrigation using conventional tillage or direct seeding (no-tillage) have
One of the crops that is crucial for the world’s food security is rice been widely proposed as effective management practices to replace
(Oryza sativa L.), but it involves great water consumption, which makes conventional flooding rice production, thereby maximizing water use
it very vulnerable to climate change (Surendran et al., 2021). This is efficiency with savings of up to 75% of water resource requirements
particularly the case in Mediterranean countries and other semi-arid (Sánchez-Llerena et al., 2016) and notable increases in water produc­
regions where hydric resource scarcity compromises the sustainability tivity (Peña et al., 2022). However, the implementation of these prac­
of this crop when it is managed under flooding (Peña et al., 2022). tices may induce relevant changes in soil properties and microbial
Alternative management practices therefore urgently need to be activity and soil properties, and these can strongly influence the fate in
implemented in order to accelerate the transition towards more viable the environment of the pesticides applied in these agro-ecosystems

* Corresponding author. Abades Área de Edafología y Química Agrícola Escuela de Ingenierías Agrarias Universidad de Extremadura Ctra de Cáceres, 06071,
Badajoz, Spain.
E-mail address: davidpa@unex.es (D. Peña).

https://doi.org/10.1016/j.jenvman.2023.117430
Received 28 October 2022; Received in revised form 3 January 2023; Accepted 30 January 2023
0301-4797/© 2023 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
J. Terrón-Sánchez et al. Journal of Environmental Management 334 (2023) 117430

(López-Piñeiro et al., 2016, 2019). practices based on reduced irrigation are applied (Ghosh et al., 2021).
Falls in yield (10%–50%) are frequently observed when sprinkler The herbicide imazamox (IMZX) (2-[4,5-dihydro-4-methyl-4-(1-
irrigation, with or without tillage, is implemented in rice production, methyleth-yl)-5-oxo-1H-imidazole-2-yl]-5-(methoxymethyl)-3-pyridin
especially when the soils are characterized by low levels of organic e-carboxylic acid) is extensively used to control perennial and annual
matter (<25 g kg− 1) as is the case in most Mediterranean region soils grasses and broad-leaf weeds in crops such as sugarcane, peanut, and
devoted to agriculture (e.g., Muñoz et al., 2007). Therefore, in order to soybean, as well as weedy rice in paddies in which imidazolinone
achieve optimal yields and ensure rice’s sustainability when cropped -resistant rice varieties are cultivated (Milan et al., 2017). Nonethe­
under sprinkler irrigation, the use of an organic amendment is required less, as a result of its limited degradation and high solubility in water
in water-stressed regions with poor organic matter soils. Because of its (626 g L− 1; pH 7, 20 ◦ C), this herbicide has a high leaching potential, and
beneficial effects in improving crop productivity and the soil’s chemical, has recently been detected at concentrations of up to 16 μg L− 1 in water
biological, and hydrological properties, biochar has been widely resources of rice-cropping areas (Gosetti et al., 2019) which may nega­
perceived as a particularly interesting organic soil amendment (Haque tively impact aquatic organisms and ecosystems (Xie et al., 2018).
et al., 2021). It reduces greenhouse gas emissions and heavy metal There has been increasing application of biochars in rice cultivation
bioavailability, including in the cases of rice cropping under different to enhance the environmental and agronomic sustainability of this crop.
management systems (Yang et al., 2020; Korai et al., 2021). In several Also, the extensive use of IMZX represents a potent source of water
Mediterranean countries with large areas under rice cultivation, great pollution in rice-growing ecosystems with great potential to threaten
amounts of reasonably priced biochar (Bc) derived from holm oaks may non-target organisms,. Nonetheless, a thorough search of the literature
be available which could promote the maintenance of soil ecosystem revealed no published studies on how the environmental fate of this
services. Compared with biochars derived from other organic materials, chemical is influenced by biochar addition when it is applied in rice
Bc has the characteristic of a greater water retention capacity (Takaya paddies with distinct tillage and irrigation management regimes. There
et al., 2016), and is therefore very well suited for use in sustainable rice have been just two works which studied how biochar impacts IMZX’s
production under deficit irrigation in semi-arid regions. sorption (Dechene et al., 2014) and sorption and bioavailability (Gámiz
Worldwide, more than 4 million tons of pesticides are used every et al., 2019a). Neither of them examined leaching, however, and they
year to maintain agriculture production (FAO, 2020). But when these incorporated the amendment under laboratory conditions, thus high­
compounds are improperly managed they are associated with severe lighting the need for a study looking into the effects of field application.
negative impacts on non-target organisms and environmental quality, Therefore, this study is the first to evaluate how the field addition of
endangering crop production, ecosystem services, and soil enzyme ac­ fresh Bc influences the sorption, persistence, and leaching of IMZX
tivity and biodiversity in agro-ecosystems (e.g.., Varjani et al., 2019; Yu following its application to paddy soils under alternative as well as
et al., 2019; Khalid et al., 2020; Ogura et al., 2021). Although the use of conventional systems of production using sprinkler irrigation with
biochar as organic amendment can influence pesticide tillage or direct seeding (no-tillage). Since the ageing process may
sorption-desorption, mobility, and degradation, distinct trends have greatly change a biochar’s properties, the impacts of two years of Bc
been widely reported that depend both on the properties of the soils or field-ageing on IMZX’s behaviour under different conditions of irriga­
amendments as well as on these compounds themselves (Ogura et al., tion and tillage were measured as well.
2021; Siedt et al., 2021). For instance, while the use of maize biochar as
organic amendment in a loamy sand increased atrazine sorption by 45%, 2. Material and methods
in a silty clay loam soil it only increased it by 25% (Clay et al., 2016).
Khorram et al. (2018) found fomesafen sorption to increase 10.8-fold in 2.1. Soil sampling and field experiments
a soil that had been treated rice straw biochar at a dose of 1%, while
amendment with hardwood biochar was followed by an increase that During 2018 and 2019 a field experiment was conducted in an area
was 13.3-fold. Others have reported that in a soil that had been amended (38◦ 55′ N; 6◦ 57′ W) of Extremadura (Spain) (Fig. S1) which had previ­
with olive mill waste biochar there was a 1.3-fold reduction in the ously been used for rice (O. sativa L.) production (14 years) under con­
sorption of penoxsulam, while the sorption of azimsulfuron increased by ventional tillage and flooding irrigation. This area, with a temperature
a factor of 1.2 (García-Jaramillo et al., 2020). For a soil amended with of 16.2 ◦ C and a mean annual rainfall of 460 mm, is classified as a semi-
2% of biochar, while imidacloprid persistence decreased 1.2-fold, for arid Mediterranean region (Papadakis, 1966). The soil (0–20 cm depth)
clothianidin there was a 1.8-fold increase (Zhang et al., 2020). with 50.3% sand, 28.9% silt, and 20.8% clay was classified as loam (Soil
Furthermore, changes in a biochar’s properties (e.g., surface area and Science Division Staff, 2017). After harvesting rice in November 2017,
pH) have frequently been identified after its ageing in the soil, which can the area was divided into eighteen plots of approximately 180 m2 each
greatly impact the environmental fate of pesticides. While Liu et al. to evaluate six management regimes in triplicate: conventional tillage
(2018) reported that the ageing process can often lead to a reduced and flooding irrigation (CTFI), conventional tillage and sprinkler irri­
biochar sorption potential, Gámiz et al. (2019a,b) noted enhanced gation (CTSI), no-tillage and sprinkler irrigation (NTSI), and the corre­
sorption by biochar after ageing. Khorram et al. (2017) found a signif­ sponding regimes with only first-year Bc amendment (CTFI-Bc, CTSI-Bc,
icant increase in fomesafen leaching after 6 months of rice husk biochar and NTSI-Bc). The Bc was applied manually (April 2018) at a dose of 28
ageing. Nonetheless, Gámiz et al. (2019b) reported that the ageing effect t ha− 1 and incorporated into the soil using a disc harrow. After har­
on the behaviour of mesotrione herbicide varied with the properties of vesting the rice in September (2018 and 2019), composite soil samples
the soils in which oak wood biochar was aged. Further investigations are (four subsamples) were taken from each plot from 0 to 20 cm depth to
therefore needed, preferably under real field conditions, for a better use in the sorption-desorption, leaching, and persistence experiments.
understanding of the implications of biochar ageing on the environ­ The fresh and aged effects were evaluated with the data obtained in
mental fate of these synthetic chemicals (Ogura et al., 2021). 2018 and 2019, respectively. Selected soil characteristics (TN content,
One of the main factors limiting rice production worldwide is weed EC, TOC, pH, and water soluble organic carbon WSOC) of the un­
infestation, with annual losses greater than 45% (Tshewang et al., amended and Bc-amended soils were determined as previously
2016). In this sense, weedy rice is considered to be one of the most described in López-Piñeiro et al. (2022a,b), and are presented in
troublesome weeds. It causes severe yield reduction in rice cultivation, Table S1 (Supplementary Material; SM).
irrespective of whether conventional or alternative management

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J. Terrón-Sánchez et al. Journal of Environmental Management 334 (2023) 117430

2.2. Herbicide and the biochar treatment in different years. A post hoc Duncan test was used to further
elucidate differences among means (p ≤ 0.05). To evaluate the signifi­
IMZX analytical standard (>95% pure) was purchased from Dr cance and interaction of the tested variables (management × year), a
Ehrenstorfer, GmbH (Germany). A description of the herbicide’s char­ two-way ANOVA was performed. Three levels of significance were
acteristics is given in PPDB (2021). The herbicide concentrations were considered: p ≤ 0.05, 0.01, and 0.001. Pearson’s correlation coefficient
assayed by high-performance liquid chromatography (HPLC; Waters was used to test for relationships between dissipation, leaching, and
600 E) equipped with a diode-array detector (Waters 996). The specific adsorption-desorption parameters and selected soil properties.
analytical condition details are given in SM (Text S1).
The commercial fresh biochar (Bc) was procured from Carylevere S. 3. Results and discussion
L. (Spain). Its production is by pyrolysis of holm oak prunings for 48 h at
550 ◦ C. Before its application onto the field, the fresh Bc was ground and 3.1. Adsorption-desorption experiments
sieved (<2 mm). In the second year, after harvest and for the CTFI-Bc,
CTSI-Bc, and NTSI-Bc treatments, Bc particles were separated out from The IMZX sorption-desorption parameters are listed in Table 1. As
(20 cm depth) soil samples. The main properties of the Bc (aged and Table 1 indicates, the Freundlich equation modeled the experimental
fresh) – total hydrogen (TH), total nitrogen (TN), total carbon (TC), ash, sorption data for all treatments appropriately, with R2 values ranging
oxygen, specific surface area (SSA), water-soluble organic carbon from 0.952 to 0.999 for the fresh year, and 0.952–0.985 for the aged
(WSOC) content, electrical conductivity, porosity and pH – are listed in year of the study. In addition, most of the nf values were close to 1,
Table S2 of SM. These properties were determined as previously indicating that IMZX sorption was not dependent on concentration
described in detail in López-Piñeiro et al. (2022a,b) and are provided (Fig. S2; Table 1). The IMZX sorption was affected significantly by the
briefly in SM (Text S2). management regimes (p < 0.001). Moreover, a significant management
regime × year interaction (p < 0.01) was also detected, indicating that
2.3. Adsorption and desorption experiments the fresh and aged years’ effects differed (Table 1). For the original soils,
IMZX Kf values ranged from 0.207 to 1.38 (first year) and from 0.283 to
Determination of the IMZX adsorption-desorption isotherms for the 1.27 (second year) (Table 1). Similar Kf values (0.26–1.30) were re­
Bc-amended and unamended soils was done in triplicate using the batch ported by Bresnahan et al. (2002) in soils of the USA with pH values of
equilibration technique. The Freundlich model was used to fit the IMZX 5.4–7.7 but greater TOC contents (21–23 g kg− 1). However, Saini et al.
adsorption-desorption data. Detailed information can be found in SM (2022) found values of IMZX Kf that ranged from 0.24 to 7.60 in Indian
(Text S3). aridisols with lower TOC contents (3.88–6.32 g kg− 1) but a wider pH
range (5.0–9.0) and different experimental conditions of temperature
2.4. Incubation experiments (25◦ C–40 ◦ C) and solution pH (1.5–8.5). Compared with the conven­
tional flooding management, for both years the IMZX sorption was
Because previous studies under flooded (anaerobic) conditions found reduced in soils under sprinkler irrigation, particularly in those under
that IMZX does not degrade (e.g., DEPORS, 2014), the dissipation of no-tillage, with Kf values which were up to 6.7 and 2.4 times lower in
IMZX in the soil samples of all treatments were assessed only under NTSI and CTSI than in CTFI, respectively (Table 1). This effect was
non-flooded (aerobic) incubation conditions. IMZX was applied at a dose attributable to the alterations observed in the pH values, which were
of 2.2 μg g− 1. In the IMZX residual extraction, triplicate samples of soil greater in the soils irrigated by sprinkler than in those under flooding
from each treatment were periodically (0–70 days) removed after (Table S1). Indeed, a significant negative relationship between Kf and
chemical application. The IMZX was extracted, and residues in the su­ pH was observed when pure soils only were subjected to an analysis of
pernatant were determined by HPLC. A first-order kinetic equation was correlation (r = 0.978, p < 0.01). In coherence with Bresnahan et al.
used to fit the IMZX dissipation data in order to calculate the half-lives
(t1/2) for original and Bc-amended soils. Dehydrogenase activity (DA)
was determined following García et al. (1993) using INT as substrate. Table 1
Further details are provided in Text S4 of SM. Effects of different management regimes on imazamox sorption–desorption
parameters.

2.5. Leaching experiments nf Kf R2 D (%) R2

2018
The leaching of IMZX was evaluated using triplicated disturbed PVC NTSI 1.01 aA 0.207 abA 0.953 2.66 aA 0.955
columns (30 cm × 5 cm i. d.) filled with soils from the original and Bc- NTSI-Bc 0.896 aA 0.249bA 0.954 3.05 aA 0.971
CTSI 0.904 aA 0.568 dB 0.999 3.24 aA 0.923
amended treatments, and conditioned with 0.01 M calcium chloride CTSI-Bc 1.02 aA 0.152 aA 0.958 1.70 aA 0.937
solution, allowing 24 h for the excess to drain. Then a solution of IMZX CTFI 0.992 aA 1.38eA 0.994 37.6 cB 0.999
was added to the top of each soil column to reach a dose equivalent of CTFI-Bc 0.994 aA 0.324 cA 0.952 10.3bA 0.954
0.4 kg a. i./ha. Following 24 h after the IMZX had been applied, columns 2019
NTSI 0.856 aA 0.283 aA 0.954 2.87 aA 0.998
were rinsed through each day by adding 0.01 M CaCl2 solution (50 mL),
NTSI-Bc 0.891 aA 0.361abB 0.956 2.19 aA 0.972
and the leachates were assayed by HPLC. Finally, the soils of the col­ CTSI 0.853 aA 0.462bA 0.981 2.47 aA 0.937
umns were sectioned into four 5-cm segments to assay the IMZX that CTSI-Bc 0.826 aA 0.300 aB 0.958 1.89 aA 0.974
remained. IMZX was extracted as in the dissipation experiments detailed CTFI 0.942 aA 1.27 cA 0.985 28.3 cA 0.952
above. Additional information on these studies of leaching is given in SM CTFI-Bc 0.929 aA 0.474bB 0.952 21.8bB 0.997
Y NS 5.91* – 4.67* –
(Text S5). M NS 327*** – 355*** –
YxM NS 7.50** – 75.3*** –
2.6. Statistical analysis
The data for nf, Kf, and desorption (D) are mean values. ANOVA factors are: M,
management regime; Y, year; M × Y, interaction management regime × year,
Statistical analyses were done using the SPSS (vn.22) program significant at ap < 0.05, **p < 0.01, and ***p < 0.001, respectively, and NS: not
package. Selected soil properties and adsorption–desorption, dissipation significant. Different letters indicate significant differences (p < 0.05) between
and leaching parameters were subjected to one-way ANOVA considering management regimes in the same year (lower case letters) and between years
each variable alone (management and year), to evaluate statistical dif­ within the same management regime (upper case letters).
ferences between the treatments within each year, and for the same a
The percentage of D was obtained after three cycles of desorption.

3
J. Terrón-Sánchez et al. Journal of Environmental Management 334 (2023) 117430

(2002) and Saini et al. (2022), our findings appear to confirm that the for pure soils, the significant D decrease observed in CTFI after Bc
increase in the soil pH values promoted by the transition to sprinkler addition may be due to the increases detected in soil pH, but also to the
irrigation can also lead to a deprotonation of the carboxyl groups, increases in soil organic matter which were greater in this treatment
thereby decreasing the amounts of cationic and/or neutral IMZX mole­ (Table S1). Thus, in concordance with Saini et al. (2022), the IMZX
cules, which could be immediately sorbed onto soil colloids. Based on desorption process may become less reversible when its molecules
these results, a greater potential for IMZX water pollution could be ex­ penetrate more deeply into the organic fraction, which in our case at
pected therefore when this chemical is applied in rice under a sprinkler least was twice as great in CTFI-Bc than in CTFI (Table S1), getting
instead of a flooding regime. strongly bound to these substances. Although we could only find one
For fresh and aged years, the Bc application influenced IMZX sorp­ study in the literature (Dechene et al., 2014) regarding how biochar
tion in soils subjected to conventional and alternative production re­ impacts IMZX desorption, lessened sorption reversibility of different
gimes, although in the latter this was not significant (p > 0.05) under no- chemicals (ionic and non-ionic) has often been demonstrated in
tillage (Table 1), coinciding with those showing the greatest values of biochar-amended soils, mainly being explained by entrapment in mi­
pH (>6.4) (Table S1), and indicating that the strong effect of this cropores or partitioning into condensed structures (Sopeña et al., 2012;
property on IMZX sorption contributed to masking the minor effects of Khorram et al., 2016; López-Piñeiro et al., 2022a,b). It is interesting to
Bc in these soils. Fresh and aged Bc reduced IMZX sorption in CTSI-Bc highlight that the IMZX sorption reversibility observed in CTFI-Bc was
and CTFI-Bc when compared with the corresponding cases without Bc 2.1-fold greater after Bc ageing (Table 1) which, in accordance with
addition. However, while in the fresh case the IMZX Kf values declined Khorram et al. (2018) and López-Piñeiro et al. (2022a,b), might be due
3.7 and 4.2-fold, in the aged case they decreased 1.5 and 2.5-fold for to the detected lesser micropore volume percentage in the fresh (74%)
CTSI-Bc and CTFI-Bc, respectively (Table 1), indicating that the Bc than in the aged Bc (82%) (Table S3). Our desorption data suggest that,
amendment’s impact on IMZX sorption was affected not only by the although a greater potential for IMZX pollution should be expected in
different management practices, but also by an expected temporal rice soils subjected to conventional flooding as a consequence of their
variability of the Bc properties (Table S2) due to soil exposure. These observed much greater D values compared with those under sprinkler
decreases in the sorption of IMZX might be ascribed to the increases in irrigation, Bc used as amendment could decrease IMZX desorption,
the soil pH induced by the Bc amendment with these increasing from thereby contributing to potentially reducing water pollution by this
6.27 to 5.53 to 7.09 and 6.40 (fresh year) and from 6.29 to 5.65 to 7.15 chemical in flooded rice environments, although this also could decrease
and 6.50 (aged year), for CTSI-Bc and CTFI-Bc treatments, respectively, its bioavailability.
compared with the corresponding no Bc-addition cases (Table S1).
Indeed, Kf was inversely related to pH of soils (r = 0.874; p < 0.01)
corroborating the key part it plays in IMZX sorption (Bresnahan et al., 3.2. Dissipation studies
2002; Saini et al., 2022). According to those authors, in a high-pH soil a
greater amount of IMZX anionic form in solution should be expected The IMZX dissipation curves and DA are shown in Fig. S3. The IMZX
than in a low-pH soil, which would be repulsed by negatively charged Bc concentrations were fitted to the first-order model for the fresh
particles or soil colloids. However, Dechene et al. (2014) did not find (R2>0.850) and aged (R2>0.858) years (Table 2). After Bc application,
any effect on the sorption of IMZX in a sandy loam with fresh and the values of DA increased (p < 0.05) in all management regimes for
composted beech wood biochar amendments, although in their study both years (Table 2), indicative of microbial stimulation in Bc-amended
neither were the pH values affected by the biochar additions, high­ soils. This could be attributed to the improvement of the pH coupled
lighting that specific research for each type of soil and biochar is needed with the greater organic matter content (by up to 2.2 times) of the Bc-
before their use in agro-ecosystems. A slight significant (p < 0.05) rise amended than of the pure soils. Indeed, positive correlations were
was observed in IMZX sorption in the NTSI-Bc (from 0.249 to 0.361), found for DA with both TOC and pH, although they only were significant
CTSI-Bc (from 0.152 to 0.300), and CTFI-Bc (from 0.324 to 0.478) soils
from the fresh to the aged year (Table 1), despite the changes in pH Table 2
between years being ≤0.1 for each treatment (Table S1). In agreement Effects of different management regimes on dehydrogenase activity and ima­
with Gámiz et al. (2017), this slight increase in IMZX sorption could be zamox dissipation parameters.
attributed to the higher SSA values found in the aged than in the fresh Bc t1/2 R2 DHAT (μg INTF g− 1
h− 1)
(Table S2) which may have led to new sorption sites. 2018
Similar to sorption, the desorption experimental data were appro­ NTSI 87.9bA 0.859 5.37 cA
priately fitted by the Freundlich equation (R2>0.937). The IMZX NTSI-Bc 88.9bA 0.901 6.15 dA
CTSI 108 cA 0.907 3.10 aA
desorption (D) was significantly affected (p < 0.001) by the manage­
CTSI-Bc 70.5 aA 0.947 6.70 dA
ment regime applied, and the aged and fresh year effects differed as CTFI 125 dA 0.852 4.67bA
shown by the management regime × year interaction (Table 1; p < CTFI-Bc 75.5 abA 0.881 11.6eB
0.001). For pure soils (both years), sorption reversibility was much 2019
greater in those under flooding (lower soil pH) than under sprinkler NTSI 107bB 0.876 7.53bB
NTSI-Bc 83.0 aA 0.891 13.6 dB
irrigation (higher soil pH), with D values ranging from 28.3 to 37.6
CTSI 115 cA 0.953 4.81 aB
(CTFI), 2.66 to 2.87 (NTSI), and 2.47 to 3.24 (CTSI) (Table 1). Similarly, CTSI-Bc 105bB 0.902 7.24bB
Aichele and Penner (2005) also found a lesser percentage of IMZX des­ CTFI 120 cA 0.858 7.69bB
orbed at pH 7 than at pH 5. The trend of our findings agree with Bres­ CTFI-Bc 105bB 0.890 8.90 cA
M 30.4*** 166***
nahan et al. (2002) who reported that at low soil pH the amount of IMZX –
Y 37.4*** – 644***
sorbed was greater than at high soil pH, but the amount readily desorbed MxY 13.4*** – 284***
was also greater. There was indeed a negative correlation of D with pH
(r = − 0.794; p < 0.05). However, despite Bc addition promoting a sig­ Half-lives: t1/2 in soils at 80% field water capacity. DHAT, total dehydrogenase
activity considering all the incubation times in soils conditioned to 80% field
nificant increase in soil pH for all treatments (Table S1), a significant (p
capacity. The data are presented as mean values. ANOVA factors are: M, man­
< 0.05) decrease in D values was only observed in CTFI-Bc relative to
agement regime; Y, year; M × Y, interaction management regime × year, sig­
CTFI (the treatment with the lowest pH) (Table 1), which could decrease nificant at *p < 0.05, **p < 0.01, and ***p < 0.001, respectively. Different
the risk of IMZX release into the environment but also compromise its letters indicate significant differences (p < 0.05) between management regimes
weed control effectiveness in rice growing-areas subjected to flooding in the same year (lower case letters) and between years within the same man­
irrigation, particularly before the Bc has aged. As was mentioned above agement regime (upper case letters).

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J. Terrón-Sánchez et al. Journal of Environmental Management 334 (2023) 117430

with the former parameter (r = 0.622, p < 0.01), corroborating that soil (from 63 to 53 d) in a soil after oak wood biochar application. However,
enzyme activity increases after biochar application are mainly influ­ those authors found no differences in IMZX persistence between ageing
enced by TOC as has previously been noted (e.g., Liao et al., 2022; treatments (p > 0.05), although their study involved a shorter (6
López-Piñeiro et al., 2022a). months) biochar ageing period than ours, and the effects of different
The IMZX dissipation was significantly (p < 0.001) affected by the regimes (tillage and irrigation) were not measured. Although there is no
management regime. Furthermore, a significant management regime × more published information on IMZX dissipation in soils after biochar
year interaction (p < 0.001) was also detected, indicating differences application, other imidazolinone herbicides (imazapic and imazapir)
between the aged and the fresh years’ effects (Table 2). For pure soils, have also shown faster biodegradation (by factors of up to 1.7) using
the IMZX t1/2 values ranged from 87.9 to 125 d (first year) and from 107 biochars produced from two different biomasses, but in a laboratory
to 120 d (second year). These are in the range of previous studies study with no ageing effect investigated (Yavari et al., 2019). However,
reporting t1/2 values from 15 to 142 d (USEPA-United States Environ­ several studies using different biochars as soil amendment found de­
mental Protection Agency, 2008) and from 2 to 120 d (Buerge et al., creases in dissipation of chemicals (simazine, isoproturon, and for­
2019), corroborating that IMZX is a persistent herbicide whose mesafen) due to their increased sorption and thus lesser availability to
remaining residues in the soil could impact negatively both future sen­ be degraded by microorganisms (Liu et al., 2018). These results
sitive crops and non-target organisms. However, our values are greater corroborate that the bioavailability of pesticides and thus their envi­
than the 63 d found by Gámiz et al. (2019a), though that was for a silty ronmental fate in biochar-amended soils is largely dependent on the
loam having a smaller percentage of clay (11%) and higher pH (7.9) management systems applied, but also on the particular characteristics
than in our study (Table S1). This is consistent with findings by Gianelli of both the biochar and the pesticide.
et al. (2014) and López-Cabeza et al. (2017) who also reported a faster
degradation rate of imidazolinone herbicides in soils with lower clay 3.3. Leaching experiments
content and higher pH values. For both years, the IMZX persistence was
greater (p < 0.05) in soils under conventional flooding than under Fig. 1 illustrates the IMZX breakthrough curves for pure and Bc-
sprinkler irrigation, particularly in those under no-tillage in the first year amended soils. Table 3 lists the IMZX proportions extracted and
(higher pH values; Table S1), with t1/2 values which were 1.4 and 1.2 leached from the soil columns once the experiment on leaching had
(First year) and 1.1 (second year) times lower in NTSI and CTSI than in finished. For all treatments, the IMZX breakthroughs were below 0.8
CTFI, respectively (Table 2). The reduction in the IMZX persistence was (first year) and 0.7 (second year) pore volumes (Fig. 1), coherent with it
due to the rise noted in the pH values as a result of the change from being a very mobile chemical with a major potential to pollute water
flooding irrigation to sprinkler (Table S1), which led to a decrease in resources. The leaching of IMZX was affected with significance (p <
IMZX sorption and thus to greater bioavailability. Indeed, significant 0.001) by the management regime. Also, a significant management
relationships between t1/2 and pH (r = 0.865, p < 0.01) and Kf (r = regime × year interaction (p < 0.05) was detected, indicating that the
0.791; p < 0.01) were observed when only pure soils were considered. aged and the fresh years’ effects differed (Table 2). For pure soils, the
Our findings agree with Aichele and Penner (2005) and Gehrke et al. amount of IMZX leached reached up to 80% (year 2018) and 74.5%
(2021) who reported that imidazolinone herbicides were more available (2019) of the total applied chemical (Table 3), proportions that are
for degradation with increasing pH of the soil because of these com­ slightly below the 96% reported by Khatem et al. (2019) although that
pounds’ diminished sorption capacity at higher pH levels. Therefore, the was for an alkaline (pH 8.2) sandy-loam soil. Despite IMZX sorption
transition to sprinkler irrigation in rice cultivation could be considered being significantly lower under NTSI and CTSI than under CTFI, the total
as an alternative practice to the traditional flooding irrigation, which of IMZX leached was significantly (p < 0.05) lower in NTSI and CTSI in
could mitigate the accumulation of IMZX residues and its probable the first year (by factors of up to 1.7 and 2.2, respectively) and second
carry-over effect on potential rotational crops and its negative impact on year (by 1.3 and 1.2 times, respectively) (Table 3; Fig. 1). The expla­
non-target organisms in the environment. nation for these results may be the much greater reversibility in sorption
The persistence of IMZX was reduced by the Bc application in all together with the greater persistence observed in management regimes
treatments except NTSI-Bc in the fresh year in which, compared with under flooding irrigation, with values of D and t1/2 in CTFI greater by
NTSI, the differences were not significant (Table 2), coherent with the factors of up to 14.1 and 11.6 (Table 1) and 1.4 and 1.2 (Table 2) than in
unamended soil presenting the highest pH value (>6.7) (Table S1). This NTSI and CTSI, respectively. Indeed, when only pure soils were selected,
decrease was mainly noticed in the fresh year in which, compared to the the percentage of IMZX leached was positively correlated with D (r =
corresponding pure soils, the t1/2 values decreased by factors of 1.5 and 0.725; p < 0.01) and t1/2 (r = 0.611; p < 0.01).
1.6 for CTSI and CTFI, while in the aged year these factors of decrease After Bc addition, significant differences in the amount of IMZX
were 1.3, 1.1, and 1.1 for NTSI, CTSI, and CTFI, respectively (Table 2). leached were found only in tillage treatments for both years (Table 3).
Hence, the use of Bc as amendment could also lead to a reduction of Notwithstanding the decline in IMZX sorption that was observed in
IMZX residues in soils, thereby decreasing its potential risk of environ­ managements under tillage accompanied by amendment with Bc (CTSI-
mental pollution. The explanation for the observed IMZX dissipation Bc and CTFI-Bc) for both years (Table 1), the addition of Bc declined
increase after Bc amendment might be IMZX’s expected greater avail­ IMZX leaching from 35.5% to 80% and from 60.8% to 74.5% in CTSI and
ability for dissipation with increasing soil pH, which would have led to a CTFI to 26.7% and 34.3% and 51.1% and 50.5% in the corresponding
decline in its sorption capacity as was mentioned above. Indeed, t1/2 was Bc-amended CTSI-Bc and CTFI-Bc treatments for the fresh and the aged
positively correlated with Kf (r = 0.713; p < 0.01). In addition, the soil years, respectively (Table 3; Fig. 1). This effect could be attributed to the
pH and organic matter content increases as a result of Bc addition might lower levels of desorption and of persistence detected in CTSI-Bc and
have promoted changes in microbial activity and nature, also leading to CTFI-Bc compared to the corresponding cases without Bc amendment
increases in IMZX dissipation rates (e.g., Khorram et al., 2016; Su et al., (Tables 1 and 2). Indeed, the IMZX leached was positively correlated
2019). In fact, t1/2 was negatively correlated with pH (r = − 0.697; p < with D (r = 0.605; p < 0.01) and t1/2 (r = 0.683; p < 0.01) values. As
0.01) and TOC (r = − 0.574; p > 0.01). Significant (p < 0.05) IMZX expected mainly because of the greater t1/2 values, there was observed a
persistence increases were detected in the Bc-amended soils (CTSI and significant rise in the amount of IMZX leached for the treatments with
CTFI) in the aged year compared with those in the fresh year (Table 2), and without Bc addition of the first (fresh) compared with those of the
indicating that Bc ageing may impact not just the soils’ capacity to sorb second (aged) year, with percentages of IMZX leached up to 1.7 and 1.9
IMZX but also the herbicide’s bioavailability, as would mainly be ex­ greater for treatment without and with Bc amendment, respectively
pected in soils that are tilled regardless of the type of irrigation applied. (Tables 2 and 3). This indicates that the impact of irrigation and tillage
Gámiz et al. (2019a) also found a slight decrease in IMZX persistence practices and Bc amendment on the IMZX leaching was time dependent,

5
J. Terrón-Sánchez et al. Journal of Environmental Management 334 (2023) 117430

Fig. 1. Effects of treatments on the relative and cumulative breakthrough curves of imazamox. Vertical bars represent one standard error of the mean.

particularly in the CTSI and CTSI-Bc treatments (Table 3). Although no was recovered (Table 3), the chemical was homogeneously distributed
work was found in the literature regarding on how biochar impacts through the 20-cm soil column depth (four sections) for all treatments
IMZX leaching, our findings in line in part with Yavari et al. (2021) who (data not shown). The absence of detectable IMZX in CTFI soil columns
also observed reduced leaching of other imidazolinone herbicides seems to indicate that, at least for this treatment, the differences be­
(imazapyr and imazapic) in a paddy soil (pH 6.3) after biochar addition. tween the IMZX applied and leached could mainly be attributable to
However, those authors attributed the decline in the amount of chem­ microbial degradation. For both years, in soils without Bc addition, the
icals leached to the increase in their sorption capacity, although in their amount of IMZX recovered followed the order: CTSI > NTSI > CTFI,
study the biochars used presented much lower pH values (pH < 6.4) which is inverse to that followed by the total amount of IMZX leached.
than those of the present study (pH > 9.0), and different types of Indeed, the amounts of IMZX leached and recovered were negatively
management (tillage and irrigation) and dissipation studies were not correlated (r = 0.857; p < 0.01). Furthermore, the proportions of IMZX
included. Our findings indicate that the alterations in soil properties recovered were higher in CTSI than in NTSI by factors of 2.0 (first year)
induced by the change to alternative sprinkler rice production from and 1.3 (second year) (Table 3), which is consistent with results from the
conventional flooding could greatly mitigate IMZX water contamination experiment of dissipation, with the greater amount of IMZX recovered in
risk, regardless of the type of tillage management applied. Furthermore, tilled soils due to its greater persistence. After Bc amendment, the
the use of (aged or fresh) Bc may also cause this effect under flooding, amounts of IMZX recovered were up to 2.5 and 4.1 times greater in
with it being enhanced under irrigation by sprinkler, but not signifi­ flooded (CTFI-Bc) than in non-flooded (NTSI-Bc and CTSI-Bc) treatments
cantly unless accompanied by tillage. for the fresh and aged years, respectively (Table 3). Furthermore, IMZX
At the end of the leaching study, IMZX retention was found to be recovered decreased in non-flooded treatments, particularly in CTSI-Bc
significantly affected (p < 0.05) by the management regime (Table 3). where the residues were 2.2 (fresh year) and 2.0 (aged year) times less
Furthermore, a significant management regime × year interaction (p < than in the CTSI treatment (Table 3). These results are consistent with
0.01) was detected, indicating that the effects of the aged and the fresh those found for the total IMZX leached, and are also coherent with the
years differed (Table 3). Except for CTFI in which no amount of IMZX lesser chemical persistence observed in Bc-amended soils. Indeed,

6
J. Terrón-Sánchez et al. Journal of Environmental Management 334 (2023) 117430

Table 3
Effects of different management regimes on imazamox leaching parameters.
Initial Pore volumea Max. Concentration leached (μM) Total leached (%) Total extracted (%) Not recovered (%)

2018
NTSI 0.715bA 0.650bA 46.7 cA 4.08bA 49.3bB
NTSI-Bc 0.379 aA 0.430 abA 44.7 cA 3.57bA 51.7bB
CTSI 0.357 aA 0.316 aA 35.5bA 8.11 cB 56.4bB
CTSI-Bc 0.380 aA 0.248 aA 26.7 aA 3.76 bA 69.5 cB
CTFI 0.345 aA 0.504abB 80.0 dA 0.00 aA 20.0 aA
CTFI-Bc 0.725bA 0.232 aA 34.3bA 9.07 cA 56.6bB
2019
NTSI 0.687 aA 0.602bA 59.6abB 4.99 cA 35.4 abA
NTSI-Bc 0.670 aB 0.628bA 54.1 aB 2.59bA 43.3bA
CTSI 0.695 aB 0.710bB 60.8bB 6.46 dA 32.7 abA
CTSI-Bc 0.651 aB 0.660bA 51.1 aB 3.16bcA 45.7bA
CTFI 0.664 aB 0.268 aA 74.5 cA 0.00 aA 25.5 aA
CTFI-Bc 0.641 aA 0.189 aA 50.5 aB 13.0eB 36.1 abA
M 1681*** 4.86* 33.9*** 4.52* 32.3***
Y 96.4*** 8.35** 20.7*** 44.2*** 14.0***
MxY 292*** 4.37* 3.85* 8.07** 3.51*

The data are presented as mean values. ANOVA factors are: M, management regime; Y, year; M × Y, interaction management regime × year, significant at ap < 0.05,
**p < 0.01, and ***p < 0.001, respectively. Different letters indicate significant differences (p < 0.05) between management regimes in the same year (lower case
letters) and between years within the same management regime (upper case letters).
a
Initial Pore Volume indicates the value of pore volume to commencement imazamox breakthrough.

residual IMZX was negatively correlated with the total chemical leached Investigation. Luis Andrés Vicente: Methodology, Software, Formal
and the t1/2 values, although this was only significant for the former (r = analysis, Investigation. Damián Fernández-Rodríguez: Methodology,
0.463; p < 0.05). Software, Formal analysis, Investigation, Visualization. Ángel
Albarrán: Conceptualization, Methodology, Software, Formal analysis,
4. Conclusions Investigation, Data Curation, Visualization. José Manuel Rato-Nunes:
Methodology, Software, Formal analysis, Investigation, Data Curation,
Sprinkler rice production under tillage and no-tillage systems alone Visualization. David Peña: Conceptualization, Methodology, Software,
or in combination with the use of Bc as amendment induced changes in Validation, Formal analysis, Investigation, Data Curation, Writing-
soil properties leading to a great impact on IMZX’s environmental fate. Reviewing and Editing, Visualization.
As a consequence mainly of soil pH increases, IMZX’s sorption and its
reversibility and persistence decreased when sprinkler instead of Declaration of competing interest
flooding irrigation was implemented in soils without Bc addition,
although only in those subjected to tillage. After Bc addition, as a The authors declare that they have no known competing financial
consequence also of the changes this amendment induced in the soil pH, interests or personal relationships that could have appeared to influence
while IMZX sorption decreased for the two tillage Bc-amended soils, its the work reported in this paper.
reversibility only decreased in those under flooding irrigation, which
could lead to reducing IMZX’s weed control efficacy in rice-growing Data availability
areas managed under this traditional system of irrigation. These ef­
fects of Bc on IMZX sorption and its reversibility were less evident after Data will be made available on request.
Bc ageing when the SSA values were greater than before ageing, leading
therefore to new sorption sites. Overall, enhancements in microbial Acknowledgment
activity and potential changes in their nature promoted by the increases
in pH and organic matter in Bc-amended soils reduced IMZX’s persis­ This work was supported by Grants GR21038 from the Junta de
tence, although this effect was dependent on the Bc’s temporal vari­ Extremadura-Fondo Europeo de Desarrollo Regional (European
ability. The transition to sprinkler irrigation greatly reduced the loss of Regional Development Fund), and by GrantsRTI 2018-095461-B-I00
IMZX by leaching regardless of whether or not the soils were tilled. and PID 2021-123062OB-100 funded by MCIN/AEI/10.13039/
Furthermore, the use of Bc amendment improved IMZX’s effectiveness 501100011033 and by “ERDF A way of making Europe”. Luis Vicente is
in minimizing its leaching in flooded and non-flooded soils under tillage, recipient of a grant-in-aid promoting the hiring of research support staff,
particularly prior to field Bc-ageing. Therefore, the transition to sprin­ awarded by the Extremadura Regional Government’s SEXPE co-
kler irrigation alone or in combination with the use as amendment of financing ESF Investing in your future (TE-0042-18). Carmen Martín
holm oak biochar, particularly under tillage conditions, could be and Jaime Terrón Sánchez are recipients of a grant from the Extrem­
considered as an invaluable tool with which to strongly mitigate adura Regional Government’s Consejería de Economía, Comercio e
contamination of water in rice paddy environments by IMZX and its Innovación co-financing ESF A way of making Europe (PD18026;
potential negative impact on non-target species. PD18025).

Credit author statement Appendix A. Supplementary data

Antonio López-Piñeiro: Conceptualization, Methodology, Soft­ Supplementary data to this article can be found online at https://doi.
ware, Validation, Formal analysis, Investigation, Resources, Data org/10.1016/j.jenvman.2023.117430.
Curation, Writing Original Draft, Writing - Review & Editing, Supervi­
sion, Project administration, Funding acquisition. Jaime Terrón-
Sánchez: Methodology, Software, Formal analysis, Investigation. Car­
men Martín-Franco: Methodology, Software, Formal analysis,

7
J. Terrón-Sánchez et al. Journal of Environmental Management 334 (2023) 117430

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