Interactions of Microplastics with Pesticides in Soils and Their Ecotoxicological Implications
Abstract
:Highlights
- Soil pollution by microplastics (MPs) has steadily grown in recent years.
- MPs may interact with pesticides that reach the soil during pest control.
- MPs increase adsorption and reduce transport and degradation of pesticides.
- No major effects of soil properties on MP–pesticide interactions.
- Joint MPs–pesticides exhibit variable toxic effects on soil organisms.
Abstract
1. Introduction
2. Sources of Plastics in Agricultural Soils
3. Effect of MPs on Soil Health and Functioning
4. Plastics and Pesticide Fate/Behavior
4.1. Mechanisms and Factors Governing the Interactions of Pesticides and MPs
4.2. Adsorption/Desorption and Transport Behavior of Pesticides in Soils Contaminated with MPs
4.3. Dissipation Behavior of Pesticides in Soils Contaminated with MPs
5. Effect of Microplastics and Pesticides Interactions on Living Organisms
5.1. Aquatic Ecosystems
5.2. Terrestrial Ecosystems
6. Conclusions
Author Contributions
Funding
Data Availability Statement
Conflicts of Interest
Abbreviations
DOC | dissolved organic carbon |
DOM | dissolved organic matter |
MP | microplastic |
NP | nanoplastic |
OC | organic carbon |
PA | polyamide |
PBAT | polybutylene adipate terephthalate |
PBS | polybutylene succinate |
PE | polyethylene |
PET | polyethylene terephthalate |
PLA | polylactic acid |
PP | polypropylene |
PS | polystyrene |
PVC | polyvinyl chloride |
Tg | glass transition temperature |
WWTP | wastewater treatment plant |
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Pesticide | Log Kow | Soil Properties | MPs Employed (Size and Concentration) | Experimental Design | Results | Refs |
---|---|---|---|---|---|---|
Endosulfan Procymidone Chlorpyrifos Trifluralin Deltamethrin | 4.75 3.3 4.7 5.27 4.6 | Horticultural soil |
|
| Pesticides applied on the plastic mulches reached the soil after 24 h. Pesticides migrate to the interior of the plastic, more for thicker plastics, and were then partially released to the soil and the atmosphere (especially trifluralin, with high vapor pressure). Plastic mulches protected from chemical degradation but not from photodegradation | [128] |
Chlorpyrifos | 4.7 | OECD artificial soil: Kaolin clay 20%, quartz sand 70%, peat 10% |
|
| PE released chlorpyrifos into soil. Desorption rate depended on MP size, being much higher (≈ 135 times) for smaller (1 mm) than bigger (5 mm) PE sizes | [136] |
Atrazine 2,4-DB | 2.7 1.22 | OC 1% Sandy loam texture |
| Adsorption | The MP reduced the adsorption of both herbicides, because of a weak molecular interaction with the aliphatic PE. Likely reduced mobility of both compounds, due to a diminished soil retention capacity | [137] |
Acetamiprid Chlorantraniliprol Flubendiamide | 0.8 2.86 4.14 | pH 7.67 soil OC 2.30% Alluvial soil |
|
| In joint conditions, reduced pesticide adsorption to soil, especially for the more hydrophobic flubendiamide. No effect on acetamiprid adsorption. MPs could act as carriers for apolar pesticides, increasing their risk of mobility in the soil ecosystem | [62] |
Thiacloprid | 1.26 | pH 7.73 OM 3.61% Clay 9.2%, silt 83.4%, sand 7.4% |
|
| Negligible effect of a variety of MP composition and size on the adsorption or dissipation of the relatively polar thiacloprid at the concentrations explored, which are environmentally relevant. | [138] |
Imidacloprid Flumioxazin | 0.57 2.55 | Soil from a cotton field |
|
| MPs slowed down the adsorption rate and the time to reach adsorption equilibrium. Adsorption data were better fitted to the Freundlich equation. The effect depended on the pesticide and MP properties. MPs reduced the adsorption capacity of the soil for the polar imidacloprid, especially for aged and bio-MPs with more functional groups and larger surfaces. For flumioxazin, PBAT increased the sorption capacity and the aged MP reduced it. The degradation of both pesticides was accelerated with pristine MP and delayed with aged and bio-MPs, more at higher MP concentrations. | [139] |
2,4-D Atrazine Glyphosate DDT | −0.82 2.7 −6.28 6.91 | River sediment |
|
| The mixed treatment (MPs+ pesticides) with sediments, did not modify pesticide adsorption, neither in deionized nor in river water, in comparison with the sediment alone. | [124] |
Epoxiconazole Tebuconazole Myclobutanil Azoxystrobin Simazine Terbutylazine Atrazine Metolachlor | 3.3 3.7 2.89 2.5 2.3 3.4 2.7 3.4 | Sediment |
|
| No effect of aging or sunlight irradiation on pesticide adsorption. Good fitting to Freundlich with linear adsorption, pointing to partitioning (correlation of hydrophobicity and adsorption) rather than surface interaction, probably by van der Waals forces. In the liquid phase, pesticide half-lives increased with MPs. However, since PE powder floats in water, its interaction with the sediment is scarce and does not alter the half-lives of the pesticides retained in the sediment. | [140] |
p,p’-DDT o,p’-DDT p,p’-DDE p,p’-DDD α-HCH β-HCH γ-HCH δ-HCH | 6.2–6.9 6.8 5.7–7.0 6.02 3.8 3.8 3.6–3.7 4.1 | pH 7.93 OM 1.37% |
|
| Linear pesticide adsorption, better fitted to the Freundlich equation, with partition as the possible sorption mechanism. Small particle MPs were able to adsorb more pesticides. This MP (rubbery with low crystallinity and high internal area) could enrich the concentration of apolar pesticides in soil | [141] |
Imazamox Imazapic Imazethapyr | 5.36 2.47 1.49 | Sediment | PP |
| Kinetic and isotherm data fitted to pseudo-second-order and Freundlich models, respectively. Higher half-lives of the pesticides in the presence of MPs (after pesticide addition either to the water or to the sediment). Enantioselective dissipation was found for imazapic, but not for the other two herbicides, when they were added to the liquid phase in the microcosm. | [101] |
Glyphosate | −6.28 | Model minerals: Calcite and iron hydroxides |
|
| Glyphosate, possessing + and–charged groups, interacts more with the functionalized PSs, occluding in calcite and Fe hydroxides, by hillock growth and aggregation, respectively. | [112] |
Glyphosate | −6.28 | OM 0.2% Sandy soil |
|
| Glyphosate and its metabolite remained almost completely at the upper soil layers (1–2 cm). Due to limited water availability in the microcosm, L. terrestris would have been responsible for the transport of pesticides to deeper soil layers. | [142] |
Chlorpyrifos | 4.7 | OM 0.2% pH 6.4 Artificial sandy soil: 50% sand, 50% loamy silt |
|
| Both MPs decreased the concentration of one of the insecticide metabolites (TCP) in soil, pointing to an inhibition of insecticide degradation, probably retained on the MPs | [143] |
Simazine | 2.3 | pH 5.7 OC 0.5% Sandy clay loam texture |
|
| Simultaneous application of MPs resulted in slower simazine degradation, releasing less 14CO2 and producing higher residues in soil, especially at the 20% MP level. MPs induced a reduction in soil density and led to a shift in soil microbial composition towards fungi, thus potentially affecting pesticide degradation. | [19] |
Glyphosate | −6.28 | pH 8.6 OM 0.51% Clay 18.5%, silt 25%, sand 55.9% | PP powder |
| Similar decay rates for individual or joint additions. Soil respiration and enzyme activities related to C, N and P cycling changed during the incubation. PP size diminished during the incubation period | [144] |
Glyphosate | −6.28 | pH 8.45 OC 0.87% Clay 18.4%, silt 24.9%, sand 55.85% |
|
| The doses of MPs affected differently glyphosate behavior. Joint application of the herbicide and high PP dose increased soil enzyme activities, DOC, DOP, tryptophan-like material and decreased humic-like material and fulvic acid, but not DON. Overall, the joint addition resulted in positive effects on soil microbial activity and nutrient availability in DOM | [145] |
Prothioconazole | 2.0 | C 9.9% |
|
| Significant changes in MP functional groups. The addition of the fungicide led to accelerated irregularities in MPs and promoted their degradation, more in PBAT than in PE. Prothioconazole also affected the adsorption/desorption of heavy metals on both MPs | [146] |
Propiconazole | 3.72 | pH 5.5 OM 0.74% |
|
| Propiconazole accelerated the degradation of MPs at low concentrations (< 40 mg/kg), by enhancing microbial activity, due to the production of carbonyl groups on MPs. PE and PBAT were more easily degraded in alkaline soil and degradation accelerated under UV radiation + pesticide. More heavy metals were adsorbed on the MPs during the degradation process | [147] |
Pesticide | Log Kow | Soil Properties | MPs Employed (Size and Concentration) | Target Organism(s) Experimental Design | Results | Refs |
---|---|---|---|---|---|---|
Monocrotophos | −0.22 | Soil from an organic field |
|
| The joint application increased the oxidative stress of E. eugeniae, with increased lipid peroxidation level and enzyme activities and a reduction in protein levels | [182] |
Dufulin | n.a. | Artificial OECD soil: 70% quartz sand, 20% kaolinite and 10% peat moss |
|
| For both the individual or joint treatments similar accumulation of dufulin in earthworms and in soil, at low MP concentrations. The combination of MPs and dufulin led to a change in the abundance of 21 metabolites and three metabolic pathways, pointing to a worsening of the interference of the pesticide on the metabolic profile of E. fetida. | [183] |
2,4–D | −0.82 | pH 7.45 OM 2.4% Sandy loam |
|
| No differences in the earthworm’s weight for mixed or individual treatments. Plastic ingestion occurred, especially for particles >3 µm. Higher ingestion of 2,4–D when mixed with MPs. The mixture MPs + 2,4–D was more toxic, increasing glutathione S–transferase and catalase and accumulating malondialdehydes. Likewise, the DNA integrity in Eisenia andrei was significantly affected | [184] |
Atrazine | 2.7 | Agricultural soil |
|
| The integrated biological response showed that the co-exposure increased oxidative stress but no clear trend for abnormal expression of genes in E. fetida. Aged MPs induced higher effects than non-aged MPs. | [185] |
Glyphosate | −6.28 | OM 0.2% Sandy soil |
|
| The mixed treatment, at higher doses, had a negative effect on gallery volume and dry weight, and diminished earthworm activity. Increased concentrations (>65%) of smaller MPs (<50 µm) were found in the burrow’s walls. High concentration of glyphosate and its metabolite inside the burrows suggests pesticide and MP transport via earthworms, even to deeper soil layers. | [133,142] |
Chlorpyrifos | 4.7 | OECD artificial soil: Kaolin clay 20%, quartz sand 70%, peat 10% (pH 6.5) |
|
| Earthworms escaped from the soil layer treated with the insecticide and MPs, by moving to the bottom of the microcosm. Though earthworms can ingest small-sized MPs, in which the concentration of the insecticide increased, no effect on AcChe was observed, then avoidance by moving away from the pollutant was the mechanism proposed. | [136] |
Chlorpyrifos | 4.7 | Artificial sandy soil: 50% sand, 50% loamy silt OM 0.2% pH 6.4 |
|
| The growth and survival of the earthworms remained unchanged with PE alone, while the bio-MP reduced both endpoints. In combination with the insecticide, PE was more toxic than bio-MP, possibly due to the different adsorption capacities of the MPs | [143] |
Simazine and three pharmaceuticals | 2.3 | pH 5.5 Total OC 1.77% |
|
| Adsorption depended on the pollutant and type of MP. The combined addition (MPs + pollutants) decreased the toxicity to V. fischeri in comparison with single additions. No effect on C. elegans (likely due to the big plastic size). A negative effect on the root development of Z. mays was assessed, possibly due to physical blockage of the roots by MPs. Disturbance of soil microbiome by the simultaneous presence of MPs and the pollutants, but not different from MPs alone. MP or mixed treatment enriched Proteobacteria (in particular, Alphaproteobacteria) and both had a potential impact on the C and N cycling in the soil | [126] |
Glyphosate | −6.28 | Agricultural soil |
|
| Residues of glyphosate were detected in the invertebrate’s tissue. No significant differences in invertebrate diversity between the joint treatment or the one with glyphosate, but both were lower than the control. No relationship between MP amount and glyphosate concentration in soil, nor with the concentration of glyphosate in the tissue of invertebrates. | [186] |
Chlorpyrifos | 4.7 | Standard agricultural soil |
|
| Total haemocyte count increased for the co-exposure, more with fibers than with crumb rubber. Plastics reduced the bioavailability of chlorpyrifos. However, no consistent results were found for the immune processes. | [154] |
Chlorpyrifos | 4.7 | Lufa 2.2, agricultural soil Loamy sand pH 5.5 OC 1.72% |
|
| Joint addition decreased AChe and induced a change in ETS, in comparison with the insecticide alone, but depended on the MP type and concentration. Higher effects of tire particles than PE, especially for P. scaber, more sensitive. | [187] |
Glyphosate | −6.28 | Model minerals: Calcite and iron hydroxides |
|
| Glyphosate, adsorbed by the functionalized PSs, reduces the potential toxicity to O. sativa cells | [112] |
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Peña, A.; Rodríguez-Liébana, J.A.; Delgado-Moreno, L. Interactions of Microplastics with Pesticides in Soils and Their Ecotoxicological Implications. Agronomy 2023, 13, 701. https://doi.org/10.3390/agronomy13030701
Peña A, Rodríguez-Liébana JA, Delgado-Moreno L. Interactions of Microplastics with Pesticides in Soils and Their Ecotoxicological Implications. Agronomy. 2023; 13(3):701. https://doi.org/10.3390/agronomy13030701
Chicago/Turabian StylePeña, Aránzazu, José Antonio Rodríguez-Liébana, and Laura Delgado-Moreno. 2023. "Interactions of Microplastics with Pesticides in Soils and Their Ecotoxicological Implications" Agronomy 13, no. 3: 701. https://doi.org/10.3390/agronomy13030701