Does poly-3-hydroxybutyrate biodegradation affect the quality of soil organic matter?

The search for eco-friendly substitutes for traditional plastics has led to the production of biodegradable bioplastics. However, concerns have been raised about the impact of bioplastic biodegradation on soil health. Despite these concerns, the potential negative consequences of bioplastics during various stages of biodegradation remain underexplored. Therefore, this study aims to investigate the impact of micro-bioplastics made of poly-3-hydroxybutyrate (P3HB) on the properties of three different soils. In our ten-month experiment, we investigated the impact of poly-3-hydroxybutyrate (P3HB) on Chernozem, Cambisol, and Phaeozem soils. Our study focused on changes in soil organic matter (SOM), microbial activity, and the level of soil carbon and nitrogen. The observed changes indicated an excessive level of biodegradation of SOM after the soils were enriched with micro-particles of P3HB, with concentrations ranging from 0.1% to 3%. The thermogravimetric analysis confirmed the presence of residual P3HB (particularly in the 3% treatment) and underscored the heightened biodegradation of SOM, especially in the more stable SOM fractions. This was notably evident in Phaeozem soils, where even the stable SOM pool was affected. Elemental analysis revealed changes in soil organic carbon content following P3HB degradation, although nitrogen levels remained constant. Enzymatic activity was found to vary with soil type and responded differently across P3HB concentration levels. Our findings confirmed that P3HB acts as a bioavailable carbon source. Its biodegradation stimulates the production of enzymes, which in turn affects various soil elements, indicating complex interactions within the soil ecosystem.

Effects of biodegradable P3HB on the specific growth rate, root length and chlorophyll content of duckweed, Lemna minor.

The extensive production and use of plastics have led to widespread pollution of the environment. As a result, biodegradable polymers (BDPs) are receiving a great deal of attention because they are expected to degrade entirely in the environment. Therefore, in this work, we tested the effect of two fractions (particles <63 µm and particles from 63 to 125 µm) of biodegradable poly-3-hydroxybutyrate (P3HB) at different concentrations on the specific growth rate, root length, and photosynthetic pigment content of the freshwater plant Lemna minor. Microparticles with similar properties made of polyethylene terephthalate (PET) were also tested for comparison. No adverse effects on the studied parameters were observed for either size fraction; the only effect was the root elongation with increasing P3HB concentration. PET caused statistically significant root elongation only in the highest concentration, but the effect was not as extensive as for P3HB. The development of a biofilm on P3HB particles was observed during the experiment, and the nutrient sorption experiment showed that the sorption capacity of P3HB was greater than PET's. Therefore, depleting the nutrients from the solution could force the plant to increase the root surface area by their elongation. The results suggest that biodegradable microplastics may cause secondary nutrient problems in the aquatic environment due to their biodegradability.

Nickel (Ni) phytotoxicity and detoxification mechanisms: A review.

Scientists studying the environment, physiology, and biology have been particularly interested in nickel (Ni) because of its dual effects (essentiality and toxicity) on terrestrial biota. It has been reported in some studies that without an adequate supply of Ni, plants are unable to finish their life cycle. The safest Ni limit for plants is 1.5 µg g-1, while the limit for soil is between 75 and 150 µg g-1. Ni at lethal levels harms plants by interfering with a variety of physiological functions, including enzyme activity, root development, photosynthesis, and mineral uptake. This review focuses on the occurrence and phytotoxicity of Ni with respect to growth, physiological and biochemical aspects. It also delves into advanced Ni detoxification mechanisms such as cellular modifications, organic acids, and chelation of Ni by plant roots, and emphasizes the role of genes involved in Ni detoxification. The discussion has been carried out on the current state of using soil amendments and plant-microbe interactions to successfully remediate Ni from contaminated sites. This review has identified potential drawbacks and difficulties of various strategies for Ni remediation, discussed the importance of these findings for environmental authorities and decision-makers, and concluded by noting the sustainability concerns and future research needs regarding Ni remediation.

Soil Properties and Maize Yield Improvement with Biochar-Enriched Poultry Litter-Based Fertilizer.

Conversion of poultry litter into fertilizer presents an environmentally friendly way for its disposal. The amendment of stabilizing sorption materials (e.g., biochar) to broiler chicken rearing seems promising, as it protects produced litter from nutrient losses and improves fertilizing efficacy. Thus, a pot experiment was carried out with maize and organic fertilizers produced from biochar-amended chicken bedding. The properties of three types of poultry-matured litter, amended with biochar at 0%, 10% and 20% dose, were analyzed. These matured litters were added to soil and physicochemical, biological properties and dry aboveground crop biomass yield were determined. Both biochar doses improved matured litter dry matter (+29%, +68% compared to unamended litter) and organic carbon (+5%, +9%). All three fertilizers significantly increased dry plant aboveground biomass yield (+3% and +42% compared to control litter-treated variant) and N-acetyl-ß-D-glucosaminidase activity (+51%, +57%) compared to unamended control soil. The 20% biochar poultry-matured litter derived the highest dry plant aboveground biomass, highest respiration induced by D-glucose (+53%) and D-mannose (+35%, compared to control litter-treated variant), and decreased pH (-6% compared to unamended control). Biochar-derived modification of poultry litter maturation process led to organic fertilizer which enhanced degradation of soil organic matter in the subsequently amended soil. Furthermore, this type of fertilizer, compared to conventional unamended litter-based type, increased microbial activity, nutrient availability, and biomass yield of maize in selected biochar doses, even under conditions of significant soil acidification.

Food and agricultural wastes-derived biochars in combination with mineral fertilizer as sustainable soil amendments to enhance soil microbiological activity, nutrient cycling and crop production.

The ever-increasing human population associated with high rate of waste generation may pose serious threats to soil ecosystem. Nevertheless, conversion of agricultural and food wastes to biochar has been shown as a beneficial approach in sustainable soil management. However, our understanding on how integration of biochar obtained from different wastes and mineral fertilizers impact soil microbiological indicators is limited. Therefore, in the present study the effects of agricultural (AB) and food waste derived (FWB) biochars with and without mineral fertilizer (MF) on crop growth and soil health indicators were compared in a pot experiment. In particular, the impacts of applied amendments on soil microbiological health indicators those related to microbial extracellular (C, N and P acquiring) enzymes, soil basal as well as different substrate induced respirations along with crop's agronomic performance were explored. The results showed that compared to the control, the amendment with AB combined with MF enhanced the crop growth as revealed by higher above and below ground biomass accumulation. Moreover, both the biochars (FWB and AB) modified soil chemical properties (pH and electric conductivity) in the presence or absence of MF as compared to control. However, with the sole application of MF was most influential strategy to improve soil basal and arginin-induced respiration as well as most of the soil extracellular enzymes, those related to C, N and P cycling. Use of FWB resulted in enhanced urease activity. This suggested the role of MF and FWB in nutrient cycling and plant nutrition. Thus, integration of biochar and mineral fertilizers is recommended as an efficient and climate smart package for sustainable soil management and crop production.

Influence of Poly-3-hydroxybutyrate Micro-Bioplastics and Polyethylene Terephthalate Microplastics on the Soil Organic Matter Structure and Soil Water Properties.

Adverse effects of microplastics on soil abiotic properties have been attributed to changes in the soil structure. Notably, however, the effects on the supramolecular structure of soil organic matter (SOM) have been overlooked, despite their key role in most soil properties. This work accordingly investigated the influence of plastic residues at various concentrations on the SOM supramolecular structure and soil water properties. To model plastic residues of micro-bioplastics, spherical or spherical-like poly-3-hydroxybutyrate (PHB) was used, while polyethylene terephthalate (PET) was used as a model of conventional microplastics. The results suggest that both types of plastic residues affect SOM properties, including physical stability (represented by water molecule bridges), water binding (represented by decreased desorption enthalpy or faster desorption), and the stability of SOM aliphatic crystallites. The results further showed that the polyester-based microplastics and micro-bioplastics affected the SOM abiotic characteristics and that therefore the observed effects cannot be attributed solely to changes in the whole soil structure. Notably, similar adverse effects on SOM were observed for both tested plastic residues, although the effect of PHB was less pronounced compared to that of PET.

Deciphering the Potential Role of Symbiotic Plant Microbiome and Amino Acid Application on Growth Performance of Chickpea Under Field Conditions.

The unprecedented rise in the human population has increased pressure on agriculture production. To enhance the production of crops, farmers mainly rely on the use of chemical fertilizers and pesticides, which have, undoubtedly, increased the production rate but at the cost of losing sustainability of the environment in the form of genetic erosion of indigenous varieties of crops and loss of fertile land. Therefore, farming practices need to upgrade toward the use of biological agents to maintain the sustainability of agriculture and the environment. In this context, using microbial inoculants and amino acids may present a more effective, safer, economical, and sustainable alternative means of realizing higher productivity of crops. Therefore, field experiments were performed on chickpea for two succeeding years using Rhizobium and L-methionine (at three levels, i.e., 5, 10, and 15 mg L-1) separately and in combinations. The results show that the application of Rhizobium and all the three levels of L-methionine increased the growth and yield of chickpea. There was a higher response to a lower dose of L-methionine, i.e., 5 mg L-1. It has been found that maximum grain yield (39.96 and 34.5% in the first and second years, respectively) of chickpea was obtained with the combined use of Rhizobium and L-methionine (5 mg L-1). This treatment was also the most effective in enhancing nodule number (91.6 and 58.19%), leghemoglobin (161.1 and 131.3%), and protein content (45.2 and 45%) of plants in both years. Likewise, photosynthetic pigments and seed chemical composition were significantly improved by Rhizobium inoculation. However, these effects were prominent when Rhizobium inoculation was accompanied by L-methionine. In conclusion, utilizing the potential of combined use of L-methionine and microbial inoculant could be a better approach for developing sustainable agriculture production.

Cadmium Phytotoxicity, Tolerance, and Advanced Remediation Approaches in Agricultural Soils; A Comprehensive Review.

Cadmium (Cd) is a major environmental contaminant due to its widespread industrial use. Cd contamination of soil and water is rather classical but has emerged as a recent problem. Cd toxicity causes a range of damages to plants ranging from germination to yield suppression. Plant physiological functions, i.e., water interactions, essential mineral uptake, and photosynthesis, are also harmed by Cd. Plants have also shown metabolic changes because of Cd exposure either as direct impact on enzymes or other metabolites, or because of its propensity to produce reactive oxygen species, which can induce oxidative stress. In recent years, there has been increased interest in the potential of plants with ability to accumulate or stabilize Cd compounds for bioremediation of Cd pollution. Here, we critically review the chemistry of Cd and its dynamics in soil and the rhizosphere, toxic effects on plant growth, and yield formation. To conserve the environment and resources, chemical/biological remediation processes for Cd and their efficacy have been summarized in this review. Modulation of plant growth regulators such as cytokinins, ethylene, gibberellins, auxins, abscisic acid, polyamines, jasmonic acid, brassinosteroids, and nitric oxide has been highlighted. Development of plant genotypes with restricted Cd uptake and reduced accumulation in edible portions by conventional and marker-assisted breeding are also presented. In this regard, use of molecular techniques including identification of QTLs, CRISPR/Cas9, and functional genomics to enhance the adverse impacts of Cd in plants may be quite helpful. The review's results should aid in the development of novel and suitable solutions for limiting Cd bioavailability and toxicity, as well as the long-term management of Cd-polluted soils, therefore reducing environmental and human health hazards.

A Simple Method for Quantification of Polyhydroxybutyrate and Polylactic Acid Micro-Bioplastics in Soils by Evolved Gas Analysis.

Conventional plastics are being slowly replaced by biodegradable ones to prevent plastic pollution. However, in the natural environment, the biodegradation of plastics is usually slow or incomplete due to unfavorable conditions and leads to faster micro-bioplastic formation. Many analytical methods were developed to determine microplastics, but micro-bioplastics are still overlooked. This work presents a simple method for determining poly-3-hydroxybutyrate and polylactic acid micro-bioplastics in soil based on the thermogravimetry-mass spectrometry analysis of low molecular gases evolved during pyrolysis. For the method development, model soils containing different soil organic carbon contents were spiked with micro-bioplastics. Specific gaseous pyrolysis products of the analytes were identified, while the ratio of their amounts appeared to be constant above the level of detection of the suggested method. The constant ratio was explained as a lower soil influence on the evolution of the gaseous product, and it was suggested as an additional identification parameter. The advantages of the presented method are no sample pretreatment, presumably no need for an internal standard, low temperature needed for the transfer of gaseous products and the possibility of using its principles with other, cheaper detectors. The method can find application in the verification of biodegradation tests and in the monitoring of soils after the application of biodegradable products.

Co-composted Biochar Enhances Growth, Physiological, and Phytostabilization Efficiency of Brassica napus and Reduces Associated Health Risks Under Chromium Stress.

Among heavy metals, chromium (Cr) contamination is increasing gradually due to the use of untreated industrial effluents for irrigation purposes, thereby posing a severe threat to crop production. This study aimed to evaluate the potential of compost, biochar (BC), and co-composted BC on the growth, physiological, biochemical attributes, and health risks associated with the consumption of Brassica grown on Cr-contaminated soil. Results revealed that Cr stress (Cr-25) significantly reduced the growth and physiological attributes and increased antioxidant enzyme activities in Brassica, but the applied amendments considerably retrieved the negative effects of Cr toxicity through improving the growth and physiology of plants. The maximum increase in plant height (75.3%), root length (151.0%), shoot dry weight (139.4%), root dry weight (158.5%), and photosynthetic rate (151.0%) was noted with the application of co-composted BC under Cr stress (Cr-25) in comparison to the control. The application of co-composted BC significantly reduced antioxidant enzyme activities, such as APX (42.5%), GP (45.1%), CAT (45.4%), GST (47.8%), GR (47.1%), and RG (48.2%), as compared to the control under Cr stress. The same treatment reduced the accumulation of Cr in grain, shoot, and roots of Brassica by 4.12, 2.27, and 2.17 times and enhanced the accumulation in soil by 1.52 times as compared to the control. Moreover, the application of co-composted BC significantly enhanced phytostabilization efficiency and reduced associated health risks with the consumption of Brassica. It is concluded that the application of co-composted BC in Cr-contaminated soil can significantly enhance the growth, physiological, and biochemical attributes of Brassica by reducing its uptake in plants and enhanced phytostabilization efficiency. The tested product may also help in restoring the soils contaminated with Cr.

Rhizosphere Bacteria in Plant Growth Promotion, Biocontrol, and Bioremediation of Contaminated Sites: A Comprehensive Review of Effects and Mechanisms.

Agriculture in the 21st century is facing multiple challenges, such as those related to soil fertility, climatic fluctuations, environmental degradation, urbanization, and the increase in food demand for the increasing world population. In the meanwhile, the scientific community is facing key challenges in increasing crop production from the existing land base. In this regard, traditional farming has witnessed enhanced per acre crop yields due to irregular and injudicious use of agrochemicals, including pesticides and synthetic fertilizers, but at a substantial environmental cost. Another major concern in modern agriculture is that crop pests are developing pesticide resistance. Therefore, the future of sustainable crop production requires the use of alternative strategies that can enhance crop yields in an environmentally sound manner. The application of rhizobacteria, specifically, plant growth-promoting rhizobacteria (PGPR), as an alternative to chemical pesticides has gained much attention from the scientific community. These rhizobacteria harbor a number of mechanisms through which they promote plant growth, control plant pests, and induce resistance to various abiotic stresses. This review presents a comprehensive overview of the mechanisms of rhizobacteria involved in plant growth promotion, biocontrol of pests, and bioremediation of contaminated soils. It also focuses on the effects of PGPR inoculation on plant growth survival under environmental stress. Furthermore, the pros and cons of rhizobacterial application along with future directions for the sustainable use of rhizobacteria in agriculture are discussed in depth.

A critical review of the possible adverse effects of biochar in the soil environment.

Biochar has received extensive attention because of its multi-functionality for agricultural and environmental applications. Despite its many benefits, there are concerns related to the long-term safety and implications of its application, mainly because the mechanisms affecting soil and organism health are poorly quantified and understood. This work reviews 259 sources and summarises existing knowledge on biochar's adverse effects on soil from a multiangle perspective, including the physicochemical changes in soil, reduced efficiency of agrochemicals, potentially toxic substances in biochar, and effects on soil biota. Suggestions are made for mitigation measures. Mixed findings are often reported; however, the results suggest that high doses of biochar in clay soils are likely to decrease available water content, and surface application of biochar to sandy soils likely increases erosion and particulate matter emissions. Furthermore, biochar may increase the likelihood of excessive soil salinity and decreased soil fertility because of an increase in the pH of alkaline soils causing nutrient precipitation. Regarding the impact of biochar on (agro)chemicals and the role of biochar-borne toxic substances, these factors cannot be neglected because of their apparent undesirable effects on target and non-target organisms, respectively. Concerning non-target biota, adverse effects on reproduction, growth, and DNA integrity of earthworms have been reported along with effects on soil microbiome such as a shift in the fungi-to-bacteria ratio. Given the diversity of effects that biochar may induce in soil, guidelines for future biochar use should adopt a structured and holistic approach that considers all positive and negative effects of biochar.

A critical review of the overlooked challenge of determining micro-bioplastics in soil.

Currently, non-biodegradable oil-based plastics are gradually being replaced by bio-based biodegradable plastics to prevent the formation of microplastics. For biodegradable materials to decompose completely, however, they require specific conditions that are rarely met in ecosystems. Paradoxically, this may lead to the fast production of microplastics from biodegradable materials, i.e. micro-bioplastics. Until recently, the scientific focus has been solely on the estimation of conventional microplastics. As a result, there is a lack of analytical methods for determining the amount of micro-bioplastics in soil. In this review, we address this problem by summarising sample pre-treatments and analytical techniques suitable for the determination of conventional microplastics, which serve as inspiration for the determination of micro-bioplastics from polyhydroxybutyrates, polylactic acid and polybutylene adipate terephthalate in soil. The analytical techniques include both pyrolysis-based techniques, i.e. thermoanalytical and non-thermoanalytical approaches including sample pre-separation and respective detection limits. We conclude that due to the incomplete knowledge of the production rate of micro-bioplastics, fate, sorption properties and toxicity, it is necessary to develop and validate a rapid and suitable method for their determination. Indeed, the use of thermoanalytical approaches seems to be the most promising strategy. Furthermore, we suggest how the development and analysis of micro-bioplastics should be addressed in future research.

Small-sized platinum nanoparticles in soil organic matter: Influence on water holding capacity, evaporation and structural rigidity.

Engineered and anthropogenic nanoparticles represent a new type of pollutants. Up until now, many studies have reported its adverse effect on biota, but the potential influence on the properties and functions of environmental compartments has largely been ignored. In this work, the effect of Pt nanoparticles on the functions and properties of model soil organic matter has been studied. Using differential scanning calorimetry and molecular modeling, the effect of a wide range of 3 nm Pt nanoparticles concentrations on water holding capacity, the strength of water binding, the stability of water molecule bridges and the content of aliphatic crystallites was studied. It was found that strong hydration of the nanoparticles influences the 3D water structural network and acts as kosmotropic agents (structure-forming) in water bridges and as chaotropic agents (i.e. water destructuring) in larger water volumes. Contrarily, the interaction with soil organic matter moieties partially eliminates these effects. As a result, the 3 nm Pt nanoparticles decreased the evaporation enthalpy of water in soil organic matter and supported soil desiccation. They also increased the strength of water molecule bridges and increased the soil structural rigidity even at low concentrations. Additionally, at high concentrations, they decreased the water content in soil organic matter and induced the aliphatic moieties' crystallization. It is concluded that the small-sized Pt nanoparticles, and perhaps other types as well, may affect the local physicochemical processes in soils and may consequently contribute to enhanced evapotranspiration and deterioration of soil functions.

Introducing a soil universal model method (SUMM) and its application for qualitative and quantitative determination of poly(ethylene), poly(styrene), poly(vinyl chloride) and poly(ethylene terephthalate) microplastics in a model soil.

Methods for analysis of microplastic in soils are still being developed. In this study, we evaluated the potential of a soil universal model method (SUMM) based on thermogravimetry (TGA) for the identification and quantification of microplastics in standard loamy sand. Blank and spiked soils (with amounts of one of four microplastic types) were analyzed by TGA. For each sample, thermal mass losses (TML) in 10 °C intervals were extracted and used for further analysis. To explain and demonstrate the principles of SUMM, two scenarios were discussed. The first refers to a rare situation in which an uncontaminated blank of investigated soil is available and TML of spiked and blank soils are subtracted. The results showed that the investigated microplastics degraded in characteristic temperature areas and differences between spiked and blank soils were proportional to the microplastics concentrations. The second scenario reflects the more common situation where the blank is not available and needs to be replaced by the previously developed interrelationships representing soil universal models. The models were consequently subtracted from measured TML. Sparse principal component analysis (sPCA) identified 8 of 14 modeled differences between measured TMLs and the universal model as meaningful for microplastics discrimination. Calibrating various microplastics concentrations with the first principal component extracted from sPCA resulted in linear fits and limits of detection in between environmentally relevant microplastics concentrations. Even if such an approach using calculated standards still has limitations, the SUMM shows a certain potential for a fast pre-screening method for analysis of microplastics in soils.

Factors influencing structural heat-induced structural relaxation of dissolved organic matter.

Physical and chemical structure affect properties of dissolved organic matter (DOM). Recent observations revealed that heating and cooling cycles at higher temperature amplitude lead to a change in DOM physical conformation assumingly followed by a slow structural relaxation. In this study, changes at lower temperature amplitudes and their relation to DOM composition were investigated using simultaneous measurements of density and ultrasonic velocity in order to evaluate the adiabatic compressibility, which is sensitive indicator of DOM structural microelasticity. Six fulvic acids (FAs) having various origins were analyzed at concentrations of 0.12, 0.6 and 1.2 g L-1 and at different temperature amplitudes. First, we validated that the used technique is sensitive to distinguish conclusively the structural changes upon heating and cooling of DOM with heating/cooling amplitude of ±â€¯3 °C and higher. This amplitude was then applied to observe the relationship between change in adiabatic compressibility and chemical composition of FA. No correlation was observed with elemental composition and aromatic structures. Positive correlations were observed with content of alkyl moieties, carboxylic and carbonyl carbons and biological activity. Based on literature data, it was concluded that alkyl moieties undergo (re)crystalization during thermal fluctuation and their structural relaxation back is very slow (if occurs). The polar moieties form a flexible hydrogel responding to thermal fluctuation by moderate dissolution and re-aggregation. Negative correlation was observed in relation to the amount of peptide and O-alkyl systems, which can be attributed to very fast structural relaxation of proteinaceous materials, i.e. their larger content leads to lower difference between original and heat-induced compressibility. Last, the increase of the heating/cooling amplitude from ±â€¯3 to ±â€¯15 °C resulted in an increase of the change of the adiabatic compressibility and in the extension of the relaxation time needed for DOM structure to return to the equilibrium. We conclude that this increase is caused by the increase in inner energy, and DOM conformation can reach a cascade of energy minima, which may influence DOM reactivity and biodegradability.

Formation of Water Molecule Bridges Governs Water Sorption Mechanisms in Soil Organic Matter.

Adsorption is the main mechanism of capturing water in soil organic matter (SOM) under arid conditions. This process is governed by hydrophilic sites, which are gradually bridged via water molecule bridges (WaMB). Until now, the link between WaMB and other types of water molecules occurring in SOM during sorption has not been systematically investigated. In this work, we compared the formation and stability of WaMB simultaneously with the total water content, strength of water binding, and kinetics of water sorption in a vacuum-dried model SOM (sapric histosol) exposed to different relative water pressures. The same parameters were then determined in SOM exposed to reduced relative pressures. The adsorption resulted in an adsorption isotherm with a Langmuir-like part below a relative pressure of 0.5 and a Brunauer-Emmett-Teller-like isotherm at higher relative pressures. The WaMB formation was observed at a relative pressure of 0.32, which represented the pressure at which Langmuir-like part reached a plateau. The binding energy showed a linear decrease with an increasing pressure; the slope increased at a relative pressure of 0.46. Reduction of relative pressures above 0.46 showed that the water content remained constant, but the binding energy was lowered. In contrast, below a relative pressure of 0.46, the water content decreased, but the binding energy was not changed. The results indicate that in SOM exposed to different relative pressures, water exists in three types: first, it is strongly bound to primary sorption sites (Langmuir-like), second, it occurs in the form of WaMB water, which bridges functional groups and where predominates water-water interactions, and third, it occurs in the form of phase water, which is located in larger pores similar to the pure water phase. The latter either surrounds the WaMB and destabilizes it or, for higher water content, links individual WaMB and successively reduces their stabilizing effect. Formation of phase water leads to swelling processes including plasticizing effects and potential volume changes of SOM. Accordingly, the results suggest that at lower water relative pressures WaMB stabilizes the SOM structure, whereas at higher water relative pressures, it influences the formation of phase water and thereby the total water content in SOM.

Quantitative Analysis of Poly(ethylene terephthalate) Microplastics in Soil via Thermogravimetry-Mass Spectrometry.

The use of plastic materials in daily life, industry, and agriculture can cause soil pollution with plastic fragments down to the micrometer scale, i.e., microplastics. Quantitative assessment of microplastics in soil has been limited so far. Until now, microplastic analyses in soil require laborious sample cleanup and are mostly restricted to qualitative assessments. In this study, we applied thermogravimetry-mass spectrometry (TGA-MS) to develop a method for the direct quantitative analysis of poly(ethylene terephthalate) (PET) without further sample pretreatment. For this, soil samples containing 1.61 ± 0.15 wt % organic matter were spiked with 0.23-4.59 wt % PET bottle recyclate microplastics. dl-Cysteine was used as the internal standard (IS). Sample mixtures were pyrolyzed with a 5 K min-1 ramp (40-1000 °C), while sample mass loss and MS signal intensity of typical PET pyrolysis products were recorded. We found MS signal intensities linearly responding to microplastic concentrations. The most-promising results were obtained with the IS-corrected PET pyrolysis product vinylbenzene/benzoic acid ( m/ z = 105, adj. R2 = 0.987). The limits of detection and quantification were 0.07 and 1.72 wt % PET, respectively. Our results suggest that TGA-MS can be an easy and viable complement to existing methods such as pyrolysis or thermogravimetry-thermal desorption assays followed by gas chromatography/mass spectrometry detection or to spectral microscopy techniques.

Influence of Organic Chemicals on Water Molecule Bridges in Soil Organic Matter of a Sapric Histosol.

Water molecules in soil organic matter (SOM) can form clusters bridging neighboring molecular segments (water molecule bridges, WaMBs). WaMBs are hypothesized to enhance the physical entrapment of organic chemicals and to control the rigidity of the SOM supramolecular structure. However, the understanding of WaMBs dynamics in SOM is still limited. We investigated the relation between WaMBs stability and the physicochemical properties of their environment by treating a sapric histosol with various solvents and organic chemicals. On the basis of predictions from molecular modeling, we hypothesized that the stability of WaMBs, measured by differential scanning calorimetry, increases with the decreasing ability of a chemical to interact with water molecules of the WaMBs. The interaction ability between WaMBs and the chemicals was characterized by linear solvation energy relationships. The WaMBs stability in solvent-treated samples was found to decrease with increasing ability of a solvent to undergo H-donor/acceptor interactions. Spiking with an organic chemical stabilized (naphthalene) or destabilized (phenol) the WaMBs. The WaMBs stability and matrix rigidity were generally reduced strongly and quickly when hydrophilic chemicals entered the soil. The physicochemical aging following this destabilization is slow but leads to successive WaMBs stabilization and matrix stiffening.