The Role of Nanoengineered Biochar Activated with Fe for Sulfanilamide Removal from Soils and Water.

Biochar is a nanoengineered sorbent proposed to control the contamination derived from the presence of residual concentrations of sulfonamides in soil. In this work, we evaluated the sorption of sulfanilamide (SFA) in commercial biochar (BC) produced at 500 °C from oak hardwood (Quercus ilex) and its analog activated with 2% (w/w) Fe (BC-Fe). Subsequently, the effect on dissipation and transport of SFA in untreated soil and soil treated with BC and BC-Fe was also assessed. Laboratory batch studies revealed that BC-Fe increased the sorption of SFA as compared to the pristine BC with Kd of 278 and 98 L/kg, respectively. The dissipation of SFA in either untreated soil or soil treated with BC or BC-Fe was similar, displaying half-lives ranging between 4 and 6.4 days. Conversely, the concurrent determination of sorption during the incubation experiment showed that lower amounts of SFA in solution at the beginning of the experiments were bioavailable in BC-Fe-treated soil when compared to the rest of the treatments shortly after application. Leaching column studies confirmed the amendment's capability to bind the SFA compound. Therefore, the decrease in bioavailability and movement of SFA in treated soils suggest that biochar soil application can reduce SFA soil and water contamination. According to our results, BC surface modification after Fe activation may be more appropriate for water decontamination than for soil since there were no significant differences between the two types of biochar when added to the soil. Therefore, these outcomes should be considered to optimize the SFA mitigation potential of biochar.

Soil phenanthrene phytoremediation capacity in bacteria-assisted Spartina densiflora.

Polycyclic aromatic hydrocarbons (PAH) have become a threat for the conservation of wetlands worldwide. The halophyte Spartina densiflora has shown to be potentially useful for soil phenanthrene phytoremediation, but no studies on bacteria-assisted hydrocarbon phytoremediation have been carried out with this halophyte. In this work, three phenanthrene-degrading endophytic bacteria were isolated from S. densiflora tissues and used for plant inoculation. Bacterial bioaugmentation treatments slightly improved S. densiflora growth, photosynthetic and fluorescence parameters. But endophyte-inoculated S. densiflora showed lower soil phenanthrene dissipation rates than non-inoculated S. densiflora (30% below) or even bulk soil (23% less). Our work demonstrates that endophytic inoculation on S. densiflora under greenhouse conditions with the selected PAH-degrading strains did not significantly increase inherent phenanthrene soil dissipation capacity of the halophyte. It would therefore be advisable to provide effective follow-up of bacterial colonization, survival and metabolic activity during phenanthrene soil phytoremediation.

Adsorption of sulfamethoxazole and ethofumesate in biochar- and organoclay-amended soil: Changes with adsorbent aging in the laboratory and in the field.

Biochars and organoclays have been proposed as efficient adsorbents to reduce the mobility of agrochemicals in soils. However, following their application to soils, these adsorbents undergo changes in their physicochemical properties over time due to their interaction with soil components. In this study, the adsorption capacity of a commercial biochar and a commercial organoclay for the antibiotic sulfamethoxazole (SFMX) and the pesticide ethofumesate (ETFM) was evaluated over aging periods of 3 months in the laboratory and 1 year in the field, subsequent to their application to a Mediterranean soil. The results showed that the adsorption of SFMX and ETFM in the soil amended with the adsorbents was greater than in the unamended soil, but for both chemicals, adsorption decreased with aging of the adsorbents in the soil. Characterization of the adsorbents before and after aging revealed physical blocking of adsorption sites by soil components. The loss of adsorption capacity of the adsorbents upon aging led to higher leaching of SFMX and ETFM in the soil containing field-aged adsorbents, although leaching remained lower than in unamended soil. Our findings reveal that, under the Mediterranean environment studied, the efficacy of the studied materials as adsorbents is maintained to a considerable extent for at least one year after their field application, which would have positive implications in their use for attenuating the dispersion of agricultural contaminants in the environment.

Sensory Adaptations to Improve Physiological and Behavioral Distress During Dental Visits in Autistic Children: A Randomized Crossover Trial.

Importance: Autistic children have poorer oral health and greater oral care challenges, which are often associated with sensory overresponsivity, than neurotypical peers. It is important to identify innovative solutions enabling dentists to successfully perform standard clinic-based procedures for this population. Objective: To determine whether a sensory-adapted dental environment (SADE) reduces physiological and behavioral distress in autistic children undergoing dental cleanings, compared with a regular dental environment (RDE). Design, Setting, and Participants: This randomized crossover trial was conducted at a pediatric dentistry clinic in a large urban children's hospital between May 2016 and April 2022. Coders were blinded to study condition for physiological but not behavioral measurements. Autistic children aged 6 to 12 years were identified and invited to participate. Interested families were enrolled consecutively; after confirmation of autism diagnosis, children were randomized. Analysis for this per-protocol study were conducted from April to October 2022. Intervention: Each child underwent 1 RDE and 1 SADE dental cleaning, administered in randomized and counterbalanced order approximately 6 months apart. SADE included modified visual, auditory, and tactile stimuli. Main Outcomes and Measures: The primary outcome was physiological stress, assessed by electrodermal activity. The secondary outcome was behavioral distress measured from video recordings. Results: Among 452 families invited to participate, 220 children were enrolled, and 162 children (mean [SD] age, 9.16 [1.99] years; 136 [84.0%] male) with confirmed autism were randomized, with 83 children receiving RDE first and 80 children receiving SADE first. Most children (94 children [58.0%]) had moderate autism severity. Children had significantly lower physiological stress during dental care in SADE compared with RDE (mean difference in skin conductance level, -1.22 [95% CI, -2.17 to -0.27] µS), suggesting decreased sympathetic activity and increased relaxation during SADE dental care. No significant differences were found in nonspecific skin conductance responses (mean difference, -0.30 [95% CI, -0.86 to 0.25] per min). Video-coded frequency and duration of behavioral distress (but not questionnaire) measures were significantly lower in SADE vs RDE (Cohen d = -0.84 to -1.19). Physiological stress was associated with behavioral distress during the dental cleaning (eg, nonspecific skin conductance responses associated with the Frankl Scale: ß = -0.29; 95% CI, -0.39 to -0.19); age, IQ, and expressive communication moderated the intervention's success. No participants withdrew due to adverse effects. Conclusions and Relevance: In this randomized crossover trial of autistic children, using SADE was safe and efficacious in decreasing physiological and behavioral distress during dental care. This is important because enhancing oral care is critical for autistic children; this intervention may also be beneficial for populations beyond autism. Trial Registration: ClinicalTrials.gov Identifier: NCT02430051.

Oral Health Barriers for African American Caregivers of Autistic Children.

The most persistent oral health disparities in the United States impact children from racial and ethnic minoritized groups and children diagnosed as autistic. This paper aims to describe barriers to oral care as depicted by Black/African American (B/AA) parents of autistic children to further explore how and why oral health disparities persist in this population. A purposeful sample of eleven caregivers of autistic children, ages 4 to 14 years, who identified as B/AA were interviewed twice for approximately 60-90 min each. Thematic analysis utilizing a narrative approach was employed. Three themes emerged from the data concerning the barriers that affect oral health experiences: (a) difficulty in maintaining good oral health practices, (b) challenges with access to care and resources, and (c) poor patient-provider relationships. Due to the limited research that examines the intersection of autism, B/AA culture, and oral health practices, this study provides a rich picture of the barriers families face when obtaining oral care. Many families raised issues that other parents of autistic children also identified. B/AA caregivers have demonstrated that despite their own negative dental experiences, they understand the value of good oral care practices and are willing to pursue oral care for their children.

Oral Care Knowledge, Attitudes, and Practices of Black/African American Caregivers of Autistic Children and Non-Autistic Children.

Oral health is a vital component of overall health. Children from underserved, minoritized populations (i.e., Black/African Americans, autistic children) are at even greater risk for experiencing oral health disparities. This study aims to illuminate the oral health knowledge, attitudes, and practices of Black/African American caregivers of autistic and non-autistic children. Black/African American caregivers of children (4-to-14 years) on the autism spectrum (n = 65) or not on the autism spectrum (n = 60), participated in a survey, with input from literature reviews, interviews, previous research, and reviews by experts. Caregivers demonstrated basic knowledge of oral health with significantly lower scores for caregivers of autistic children. Caregivers care about oral health and would like to increase their knowledge. Significant differences in oral care practices were found between the autistic and non-autistic groups. Caregivers reported they can access dental services with relative ease, including finding their child a dentist, scheduling a dental appointment, and accessing transportation (personal or public) to attend the visit. Black/African American caregivers of autistic children and children without autism seem to have foundational knowledge about oral health and basic practices; however, they are interested in learning more. Therefore, tailored oral health education programs may help mitigate oral health disparities for Black/African American families.

Biochar changes the bioavailability and bioefficacy of the allelochemical coumarin in agricultural soils.

BACKGROUND: Allelochemicals can act as biopesticides or enhance the action of synthetic pesticides. In this work, we assessed the bioavailability of the allelochemical coumarin in soils amended with fresh or field-aged biochars (BCs). The fresh BC from oak wood (Fresh BC) was prepared at 550 °C and was buried for aging in two different places: in a sandy loam soil in Spain for 15 months (Aged BC_1) and a sandy loam soil in USA for six months (Aged BC_2). RESULTS: Sorption experiments showed that all BCs were able to increase the affinity of soil towards coumarin, with the distribution coefficient following the order: unamended soil < Aged BC_2-amended soil < Aged BC_1-amended soil < Fresh BC-amended soil. All biochars ensure greater persistence of coumarin and the effect was more pronounced at high chemical dose (10 mg kg-1 ). Conversely, leaching studies in soil columns revealed that BCs were able to maintain coumarin within the first 5 cm of top-soil with total amount extracted ranging between 17% and 22% for BC-amended soil and <1% for unamended soil. Leaching was only observed when coumarin was added at the highest rate. Likewise, the bioefficacy of coumarin against lettuce was enhanced only at 10 kg ha-1 with BC-amended soil. CONCLUSIONS: Biochar application to agricultural soils is a promising tool for the management of natural compounds with potential use as biopesticides, such as coumarin, because it increases sorption, persistence and, in some cases, bioefficacy. The results reveal that this effect still persists with aging of BC in soils.

An examination of the role of biochar and biochar water-extractable substances on the sorption of ionizable herbicides in rice paddy soils.

The application of biochar as a soil amendment can increase concentrations of soil organic matter, especially water-extractable organic substances. Due to their mobility and reactivity, more studies are needed to address the potential impact of biochar water-extractable substances (BWES) on the sorption of herbicides in agricultural soils that are periodically flooded. Two paddy soils (100 and 700 years of paddy soil development), unamended or amended with raw (BC) or washed biochar (BCW), were used to test the influence of BWES on the sorption behavior of the herbicides azimsulfuron (AZ) and penoxsulam (PE). The adsorption of AZ to biochar was much stronger than that to the soils, and it was adsorbed to a much larger extent to BC than to BCW. The depletion of polar groups in the BWES from the washed biochar reduced AZ adsorption but had no effect on PE adsorption. The adsorption of AZ increased when the younger soil (P100) was amended with BC and decreased when it was amended with BCW. In P700, which has lower dissolved organic carbon (DOC) content than P100, the adsorption of AZ increased regardless of whether biochar was raw or washed. The adsorption of PE slightly decreased when P100 was amended with BC or BCW and slightly increased when P700 was amended with BC or BCW. In order to evaluate compositional differences in the biochar and BWES before and after the washing treatment, we performed solid-state 13C NMR spectroscopy of BC and BCW, and high resolution mass spectrometry of BWES. Our observations stress the importance of proper consideration of soil and biochar properties before their incorporation into paddy soils, since biochar may reduce or increase the mobility of AZ and PE depending on soil properties and time of application.

Dynamic Effect of Fresh and Aged Biochar on the Behavior of the Herbicide Mesotrione in Soils.

In this study, we assessed the sorption, dissipation, and leaching of the herbicide mesotrione in soil amended with fresh and field-aged biochars, when added to the soil. The aging process was performed by burying the fresh biochar at 10 cm depth in three soils located in different points across the USA [Wisconsin (ABC_WI), Idaho (ABC_ID), and South Carolina (ABC_SC)] for six months. ABC_ID and ABC_SC slightly increased the sorption of mesotrione in soils, whereas ABC_WI removed greater amounts of herbicide from the solution. This was attributed to differences in water-soluble components and metal content of this aged biochar. Consequently, the persistence of the herbicide in the amended soils with fresh biochar and ABC_ID and ABC_SC were similar to that in unamended soils, while ABC_WI slightly increased mesotrione half-life. Differences between treatments were detected in leaching studies although no direct relationship with the dissipation batch studies was observed. Mesotrione leaching could not be detected in soil columns amended with ABC_WI and was high for the rest of treatments. The outcomes from this work demonstrate that temporal variability of biochar sorption capacities due to soil exposure can occur altering mesotrione's behavior in biochar-amended soils.

Optimizing a low added value bentonite as adsorbent material to remove pesticides from water.

A local low value bentonite from Southern Spain (Raw Bentonite), previously decarbonated (Bent), was modified to improve its pesticide adsorption capacity with Fe3+, hexadecyltrimethylammonium (HDTMA) and the biopolymer chitosan (CH). Adsorption of pesticides on powdered samples showed that Fe3+ and HDTMA were appropriate modifiers for this purpose. The modification was optimized by saturation with Fe3+ (Bent-Fe) and hexadecyltrimethylammonium (Bent-HDTMA) and the obtained adsorbents were characterized by several physicochemical techniques (X-ray diffraction, thermogravimetric analysis, X-ray fluorescence, physisorption of N2). Their adsorption capacity to remove three widely used pesticides in Andalusian crops (terbuthylazine, tebuconazole and MCPA) from water was assessed and compared with the commercial organoclay Cloisite® 10A (Clo10). The modified bentonites adsorbed the selected pesticides in a percentage ranging from 30 to 100%, whereas sorption on Clo10 ranged from 30 to 90%. For their possible use as filtering beds, Bent-HDTMA, Bent-Fe and Clo10 were granulated by using three different binders (colophony resin and carnauba and bee waxes) at three different mixing ratios and the water resistance and pesticide adsorption of the granules were measured. Results showed that the granulation process did not alter the pesticide adsorption capacity of the powdered modified bentonites, and both waxes granules (carnauba and bee wax) showed better behavior than resin granules. In this work, we succeeded in the preparation of granulated adsorbents derived from a low cost material with similar behavior against a high purity smectite (precursor of Cloisite® 10A). This raises an alternative for this waste material to be used in filter systems for removing pesticides from contaminated water.

Availability of triazine herbicides in aged soils amended with olive oil mill waste.

Amendments are frequently added to agricultural soils to increase organic matter content. In this study, we examined the influence of alperujo, an olive oil mill waste, on the availability of two triazine herbicides, terbuthylazine and atrazine, in two different sandy soils, one from Sevilla, Spain, and the other from Minnesota. The effect of aging on herbicide sorption and bioavailability was also studied. Soils were amended with alperujo at a rate of 3-5% (w:w) in laboratory studies. Apparent sorption coefficients for the triazine herbicides were calculated as the ratio of the concentrations of each herbicide sequentially extracted with water, followed by aqueous methanol, at each sampling time. These data showed greater sorption of terbuthylazine and atrazine in amended soils as compared to nonamended soils, and an increase in the amount of herbicide sorbed with increasing aging time in nonamended soils. The triazine-mineralizing bacterium Pseudomonas sp. strain ADP was used to characterize triazine bioavailability. Less mineralization of the herbicides by Pseudomonas sp. strain ADP was observed in soils amended with alperujo, as compared to the unamended soils, and, despite the increase in sorption with aging in unamended soils, herbicide mineralization also increased in this case. This has been attributed to Pseudomonas sp. strain ADP first using alperujo as a more readily available source of N as compared to the parent triazines. In summary, addition of alperujo to the soils studied was shown to increase triazine herbicides sorption and hence to reduce its availability and potential to leach.

Terbuthylazine persistence in an organic amended soil.

The aim of this work was to study the effect of the application of a solid waste from olive oil production (alperujo) on the movement and persistence of the herbicide terbuthylazine (N2-tert-butyl-6-chloro-N4-ethyl-1,3,5-triazine-2,4-diamine). An experimental olive grove was divided in two plots: (i) Plot without organic amendment (blank) and (ii) Plot treated with alperujo during 3 years at a rate of 17920 kg of alperujo ha(- 1). Terbuthylazine was applied to both plots at a rate of 2 kg ha(- 1) a.i. Triplicates from each plot were sampled at 3 depths (0-10, 10-20 and 20-30 cm), air-dried, remains of olive leaves, grass roots, and stones removed and sieved through a 5 mm mesh sieve. Terbuthylazine was extracted with methanol 1:2 weight:volume ratio, the extracts were evaporated to dryness, resuspended in 2 mL of methanol, filtered and anylized by high performance liquid chromatography (HPLC). Higher amounts of terbuthylazine were detected at each sampling depth in plots treated with alperujo. The increase in soil organic matter content upon amendment with alperujo slightly increased sorption, suggesting that other factors beside sorption affect terbuthylazine degradation rate in organic amended soils.

Glyphosate sorption/desorption on biochars - interactions of physical and chemical processes.

BACKGROUND: Biochar, a carbon-rich product of biomass pyrolysis, could limit glyphosate transport in soil and remediate contaminated water. The present study investigates the sorption/desorption behavior of glyphosate on biochars prepared from different hardwoods at temperatures ranging from 350 to 900 °C to elucidate fundamental mechanisms. RESULTS: Glyphosate (1 mg L-1 ) sorption on biochars increased with pyrolysis temperature and was highest on 900 °C biochars; however, total sorption was low on a mass basis (<0.1 mg g-1 ). Sorption varied across feedstock materials, and isotherms indicated concentration dependence. Biochars with a greater fraction of micropores exhibited lower sorption capacities, and specific surface groups were also found to be influential. Prepyrolysis treatments with iron and copper, which complex glyphosate in soils, did not alter biochar sorption capacities. Glyphosate did not desorb from biochar with CaCl2 solution; however, up to 86% of the bound glyphosate was released with a K2 HPO4 solution. CONCLUSION: Results from this study suggest a combined impact of surface chemistry and physical constraints on glyphosate sorption/desorption on biochar. Based on the observed phosphate-induced desorption of glyphosate, the addition of P-fertilizer to biochar-amended soils can remobilize the herbicide and damage non-target plants; therefore, improved understanding of this risk is necessary. © 2017 Society of Chemical Industry.

Fate of diuron and terbuthylazine in soils amended with two-phase olive oil mill waste.

The addition of organic amendments to soil increases soil organic matter content and stimulates soil microbial activity. Thus, processes affecting herbicide fate in the soil should be affected. The objective of this work was to investigate the effect of olive oil production industry organic waste (alperujo) on soil sorption-desorption, degradation, and leaching of diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] and terbuthylazine [N2-tert-butyl-6-chloro-N4-ethyl-1,3,5-triazine-2,4-diamine], two herbicides widely used in olive crops. The soils used in this study were a sandy soil and a silty clay soil from two different olive groves. The sandy soil was amended in the laboratory with fresh (uncomposted) alperujo at the rate of 10% w/w, and the silty clay soil was amended in the field with fresh alperujo at the rate of 256 kg per tree during 4 years and in the laboratory with fresh or composted alperujo. Sorption of both herbicides increased in laboratory-amended soils as compared to unamended or field-amended soils, and this process was less reversible in laboratory-amended soils, except for diuron in amended sandy soil. Addition of alperujo to soils increased half-lives of the herbicides in most of the soils. Diuron and terbuthylazine leached through unamended sandy soil, but no herbicide was detected in laboratory-amended soil. Diuron did not leach through amended or unamended silty clay soil, whereas small amounts of terbuthylazine were detected in leachates from unamended soil. Despite their higher sorption capacity, greater amounts of terbuthylazine were found in the leachates from amended silty clay soils. The amounts of dissolved organic matter from alperujo and the degree of humification can affect sorption, degradation, and leaching of these two classes of herbicides in soils. It appears that adding alperujo to soil would not have adverse impacts on the behavior of herbicides in olive production.

Assessing the Effect of Organoclays and Biochar on the Fate of Abscisic Acid in Soil.

The potential use of allelopathic and signaling compounds as environmentally friendly agrochemicals is a subject of increasing interest, but the fate of these compounds once they reach the soil environment is poorly understood. This work studied how the sorption, persistence, and leaching of the two enantiomers of the phytohormone abscisic acid (ABA) in agricultural soil was affected by the amendments of two organoclays (SA-HDTMA and Cloi10) and a biochar derived from apple wood (BC). In conventional 24-h batch sorption experiments, higher affinity toward ABA enantiomers was displayed by SA-HDTMA followed by Cloi10 and then BC. Desorption could be ascertained only in BC, where ABA enantiomers presented difficulties to be desorbed. Dissipation of ABA in the soil was enantioselective with S-ABA being degraded more quickly than R-ABA, and followed the order unamended > Cloi10-amended > BC-amended > SA-HDTMA-amended soil for both enantiomers. Sorption determined during the incubation experiment indicated some loss of sorption capacity with time in organoclay-amended soil and increasing sorption in BC-amended soil, suggesting surface sorption mechanisms for organoclays and slow (potentially pore filling) kinetics in BC-amended soil. The leaching of ABA enantiomers was delayed after amendment of soil to an extent that depended on the amendment sorption capacity, and it was almost completely suppressed by addition of BC due to its irreversible sorption. Organoclays and BC affected differently the final behavior and enantioselectivity of ABA in soil as a consequence of dissimilar sorption capacities and alterations in sorption with time, which will affect the plant and microbial availability of endogenous and exogenous ABA in the rhizosphere.

Biochar Soil Additions Affect Herbicide Fate: Importance of Application Timing and Feedstock Species.

Biochar (BC), solid biomass subjected to pyrolysis, can alter the fate of pesticides in soil. We investigated the effect of soil amendment with several biochars on the efficacy of two herbicides, clomazone (CMZ) and bispyribac sodium (BYP). To this aim, we evaluated CMZ and BYP sorption, persistence, and leaching in biochar-amended soil. Sorption of CMZ and BYP was greater in soil amended with BC produced at high temperature (700 °C). Significant sorption of the neutral CMZ herbicide also occurred in amended soil with BC prepared at low temperature (350 and 500 °C). For both herbicides, desorption possessed higher hysteretic behavior in soil amended with BC made at 700 °C (pyrolysis temperature). Dissipation of CMZ was enhanced after addition of BCs to soil, but no correlation between persistence and sorption was observed. Persistence of BYP was up to 3 times greater when BC made at 700 °C was added to soil. All BCs suppressed the leaching of CMZ and BYP as compared to the unamended soil. Amendment with 700 °C BC inhibited the action of CMZ against weeds, but 350 and 500 °C BCs had no such effect when added to soil. BYP activity was similar to that exhibited by unamended soil after the addition of 700 °C BC. From these results, biochar amendments can be a successful strategy to reduce the environmental impact of CMZ and BYP in soil. However, the phytotoxicity of soil-applied herbicides will depend on BC sorption characteristics and the pesticide's chemical properties, as well as the pesticide application timing (e.g., pre- or postemergence). According to our results, proper biochar screening with intended pesticides in light of the application mode (pre- or postemergence) is required prior to use to ensure adequate efficacy.

Sorption-desorption of imidacloprid and its metabolites in soil and vadose zone materials.

Sorption-desorption is one of the most important processes affecting the leaching of pesticides through soil because it controls the amount of pesticide available for transport. Subsurface soil properties can significantly affect pesticide transport and the potential for groundwater contamination. This research characterized the sorption-desorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) and three of its metabolites, 1-[(6-chloro-3-pyridinyl)methyl]-2-imidazolidinone (imidacloprid-urea), 1-[(6-chloro-3-pyridinyl)methyl]-4,5-dihydro-1H-imidazol-2-amine (imidacloprid-guanidine), and 1-[(6-chloro-3-pyridinyl)methyl]-1H-imidazol-2-amine (imidacloprid-guanidine-olefin), as a function of changing soil properties with depth in two profiles extending from the surface to a depth of 1.8 or 8 m. Sorption of each compound was highly variable and hysteretic in all cases. Normalizing the sorption coefficients (K(f)) to the organic carbon or the clay content of the soil did not reduce the variability in sorption coefficients for any compound. These results illustrate the importance of evaluation of the sorption data used to predict potential mobility. Understanding the variability of soil properties and processes as a function of depth is necessary for accurate prediction of pesticide dissipation.

Organic amendments affecting sorption, leaching and dissipation of fungicides in soils.

Metalaxyl and tricyclazole are two fungicides widely used in Spain in vineyard and rice crops respectively. In this study an investigation has been made of the effect of three organic amendments [two commercial amendments, solid fertiormont (SF) and liquid fertiormont (LF), and a residue from the olive oil production industry, alperujo (OW)] on fungicide fate in soils. Changes in soil porosity on amendment were studied by mercury intrusion porosimetry, sorption-desorption studies were performed by the batch equilibration method, dissipation of metalaxyl and tricyclazole in the soil was studied at - 33 kPa moisture content and 20 degrees C and leaching was studied in hand-packed soil columns. Amendments with SF and LF reduced soil porosity, while OW increased porosity through an increase in pore volume in the highest range studied. Tricyclazole sorbed to soils to a much higher extent than metalaxyl. With some exceptions, sorption of both fungicides increased on amendment, especially in the case of SF-amended soils, which rendered the highest K(oc) values. In soils amended with the liquid amendment LF, sorption either remained unaffected or decreased, and this decrease was much higher in the case of metalaxyl and a soil with 70% clay. In this clay soil, amendment with OW, of very high soluble organic matter content, also decreased metalaxyl sorption. Tricyclazole is more persistent in soil than metalaxyl, and both fungicides were found to be more persistent in amended soils than in unamended soils. Leaching of metalaxyl and tricyclazole in soil columns was inversely related to sorption capacity. The low recoveries of tricyclazole in leachates and in soil columns when compared with metalaxyl, a less persistent fungicide, were attributed to diffusion into micropores and to increase in sorption with residence time in the soil, both processes favoured by the low mobility of tricyclazole.

Environmental fate of the fungicide metalaxyl in soil amended with composted olive-mill waste and its biochar: An enantioselective study.

A large number of pesticides are chiral and reach the environment as mixtures of optical isomers or enantiomers. Agricultural practices can affect differently the environmental fate of the individual enantiomers. We investigated how amending an agricultural soil with composted olive-mill waste (OMWc) or its biochar (BC) at 2% (w:w) affected the sorption, degradation, and leaching of each of the two enantiomers of the chiral fungicide metalaxyl. Sorption of metalaxyl enantiomers was higher on BC (Kd ≈ 145 L kg(-1)) than on OMWc (Kd ≈ 22 L kg(-1)) and was not enantioselective in either case, and followed the order BC-amended>OMWc-amended>unamended soil. Both enantiomers showed greater resistance to desorption from BC-amended soil compared to unamended and OMWc-amended soil. Dissipation studies revealed that the degradation of metalaxyl was more enantioselective (R>S) in unamended and OMWc-amended soil than in BC-amended soil. The leaching of both S- and R-metalaxyl from soil columns was almost completely suppressed after amending the soil with BC and metalaxyl residues remaining in the soil columns were more racemic than those in soil column leachates. Our findings show that addition of BC affected the final enantioselective behavior of metalaxyl in soil indirectly by reducing its bioavailability through sorption, and to a greater extent than OMWc. BC showed high sorption capacity to remove metalaxyl enantiomers from water, immobilize metalaxyl enantiomers in soil, and mitigate the groundwater contamination problems particularly associated with the high leaching potential of the more persistent enantiomer.