The area of agricultural wastes valorisation to fertilizers is attracting growing attention because of the increasing fertilizer prices of fertilizers and the higher costs of waste utilization. Despite the scientific and political interest in the concept of circular economy, few studies have considered the practical approach towards the implementation of elaborated technologies. This article outlines innovative strategies for the valorisation of different biobased wastes into fertilizers. The present work makes a significant contribution to the field of new ideas for waste biomass management to recover significant fertilizer nutrients. These results emphasize the importance of the biomass use as a base of renewable resources, which has recently gained special importance, especially in relation to the outbreak of pandemia and war. Broken supply chains and limited access to deposits of raw materials used in fertilizer production (natural gas, potassium salts) meant that now, as never before, it has become more important and feasible to implement the idea of a circular economy and a green deal. We have obtained satisfactory results that demonstrate that appropriate management of biological waste (originating from agriculture, food processing, aquaculture, forest, pharmaceutical industry, and other branches of industry, sewage sludge) will not only reduce environmental nuisance (reducing waste heaps), but will also allow recovery of valuable materials, such as nitrogen (especially valuable amino acids), phosphorus, potassium, microelements, and biologically active substances with properties that stimulate plant growth. The results reported here provide information on production of biobased plant protection products (bioagrochemicals) from agri-food waste. This work reports an overview of biopesticides and biofertilisers production technologies and summarizes their properties and the mechanisms of action.

Increasing numbers of studies have demonstrated the existence of nanoplastics (1–999 nm) in the environment and commercial products, but the current technologies for detecting and quantifying nanoplastics are still developing. Herein, we present a combination of two techniques, e.g., scanning electron microscopy (SEM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS), to analyze submicron-sized plastics. A drop-casting of a 20-nL particle suspension on a Piranha solution-cleaned silicon wafer with dry ice incubation and subsequent freeze-drying was used to suppress the coffee-ring effect. SEM images were used to quantify particles, and this technique is applicable for 0.195–1.04-μm polystyrene (PS), 0.311-μm polyethylene terephthalate (PET), and 0.344-μm polyethylene (PE) at a minimum concentration of 2.49 × 10⁹ particles/mL. ToF-SIMS could not quantify the particle number, while it could semi-quantitatively estimate number ratios of submicron PE, PET, polyvinyl chloride (PVC), and PS particles in the mixture. Analysis of submicron plastics released from three hot water-steeped teabags (respectively made of PET/PE, polylactic acid (PLA), and PET) was revisited. The SEM-derived sizes and particle numbers were comparable to those measured by a nanoparticle tracking analysis (NTA) regardless of whether or not the hydro-soluble oligomers were removed. ToF-SIMS further confirmed the number ratios of different particles from a PET/PE composite teabag leachate. This method shows potential for application in analyzing more-complex plastic particles released from food contact materials.

This study investigates a comparison between the photocatalytic action of two nanocomposites (TiO₂ and TiO₂(Ag) doped) on the degradation of phenol from water. The nanocomposites were synthesized by the UV photo-reduction process to get a silver metal loading of 0.25, 0.5, 0.75, and 1% (w/w). In addition to this, Eriochrome Cyanine Red (ECR) and Eosin Yellow (EY) both anionic dyes were used for sensitization of Ag-doped TiO₂ photo-catalyst such as TiO₂(Ag)ECR and TiO₂(Ag)EY. The TiO₂(Ag-1.0)EY photo-catalyst indicated higher absorbance compared to the TiO₂(Ag-1.0)ECR in the 400–700 nm range (visible range). The degradation of phenol was tested by varying the pH, silver loading and catalyst dosage. The maximum degradation of phenol was 98% in 180 min at pH 7 in presence of 1% (w/w) silver loading with 0.5 gL⁻¹ dosage of photo-catalyst TiO₂(Ag-1.0)EY. At this condition, the reduction in the phenol concentration was noticed from 20 mg/L to 0.4 mg/L.

For the first time, we used targeted metabolome to investigate the effects of pH-aluminum (Al) interactions on energy-rich compounds and their metabolites (ECMs) and phytohormones in sweet orange (Citrus sinensis) roots. The concentration of total ECMs (TECMs) was reduced by Al-toxicity in 4.0-treated roots, but unaffected significantly in pH 3.0-treated roots. However, the concentrations of most ECMs and TECMs were not lower in pH 4.0 + 1.0 mM Al-treated roots (P4AR) than in pH 3.0 + 1.0 mM Al-treated roots (P3AR). Increased pH improved the adaptability of ECMs to Al-toxicity in roots. For example, increased pH improved the utilization efficiency of ECMs and the conversion of organic phosphorus (P) from P-containing ECMs into available phosphate in Al-treated roots. We identified upregulated cytokinins (CKs), downregulated jasmonic acid (JA), methyl jasmonate (MEJA) and jasmonates (JAs), and unaltered indole-3-acetic acid (IAA) and salicylic acid (SA) in P3AR vs pH 3.0 + 0 mM Al-treated roots (P3R); upregulated JA, JAs and IAA, downregulated total CKs, and unaltered MEJA and SA in P4AR vs pH 4.0 + 0 mM Al-treated roots (P4R); and upregulated CKs, downregulated JA, MEJA, JAs and SA, and unaltered IAA in P3AR vs P4AR. Generally viewed, raised pH-mediated increments of JA, MEJA, total JAs, SA and IAA concentrations and reduction of CKs concentration in Al-treated roots might help to maintain nutrient homeostasis, increase Al-toxicity-induced exudation of organic acid anions and the compartmentation of Al in vacuole, and reduce oxidative stress and Al uptake, thereby conferring root Al-tolerance. In short, elevated pH-mediated mitigation of root Al-stress involved the regulation of ECMs and phytohormones.

Herbicide pollution is persistent, which not only has a negative impact on individual organisms, but also may endanger the interspecific relationship between predators and prey. Cladocerans, i.e. zooplankton that plays an important role in the energy flow and material circulation in freshwater ecosystem, usually develop induced defense in response to predation risk. We used atrazine, one of the most used herbicides in the world, and Daphnia pulex, a representative cladocerans, to test the possible interference effect of herbicides on the induced defensive traits of cladocerans in response to predator fish (Rhodeus ocellatus) kairomone, including morphological defense, life history strategies, and the expression of defense-related genes. Atrazine reduced the body size, spine size, growth rate, total offspring, and the relative reproductive output of D. pulex, which further affected the response strength of the morphological and life history defenses, i.e., atrazine significantly reduced the spine size, relative spine size, and fecundity of D. pulex in response to R. ocellatus kairomone. Exposure to atrazine affected the expression of defense-related genes, and we speculated that atrazine affected the signaling process in the induced anti-predation defense of cladocerans. Specially, fish kairomone attenuated the negative effects of high concentrations of atrazine on the life history traits of D. pulex. Our results will help to accurately assess the potential risk of artificial compounds in freshwater ecosystems from the perspective of interspecific relationships, and help to understand the impact of environmental changes on the inducible anti-predator defense of prey in aquatic ecosystems.

Understanding the arsenic (As) enrichment mechanisms in the subsurface environment relies on a systematic investigation of As valence species and their partitioning with the Fe (oxyhydr)oxide phases in the subsoil profile. The present study explored the distribution, speciation, partitioning, and (im)mobilization of As associated with Fe in four subsoil cores (∼30 m depth) from Hong Kong using sequential chemical extraction and X-ray absorption near edge spectroscopy. The subsoil profiles exhibited relatively high concentrations of As at 26.1–982 mg/kg (median of 112 mg/kg), and the As was dominated by As(V) (85–96%) and primarily associated with the residual fraction (50.7–94.7%). A small amount of As (0.002–13.2 mg/kg) was easily mobilized from the four subsoil profiles, and a concentration of water-soluble As higher than 100 μg/L was observed for only some subsoil layers. The molar ratios of As:Fe in the oxalate-extractable Fe fraction ranged from 1.2 to 76.5 mmol/mol (median of 11.1 mmol/mol), revealing the participation of poorly crystalline Fe (oxyhydr)oxides in immobilizing most of the high geogenic As. The primary phases of ferric (oxyhydr)oxides were characterized as ferrihydrite (16–53%), lepidocrocite (0–32%), and goethite (0–62%), and these phases contributed to the sufficient ability of the subsoil to sequester 45.3–100% (median of 98.8%) of the exogenous As(V) (1.0 mg/L) in adsorption experiments. In contrast to As(V), exogenous As(III) showed a lower removal percentage (3.9–79.1%, median of 45.1%). The study revealed that the chemical speciation of As and Fe in the subsoil profiles is useful for predicting the immobilization of high geogenic As in the region, which is also helpful for the safe utilization of As-containing soil during land development worldwide.

Despite several studies having addressed the bioaccumulation of Dechlorane Plus (DP) flame retardant in wildlife, there is still a dearth of information for reptiles in general and for snakes in particular. Here, we report the residue levels and trophic transfer of syn-, anti-, and anti-Cl₁₁-DP in a frog-eating snake—namely, the striped keelback snake Amphiesma stolata—from a DP hotspot in South China. The concentrations of syn-, anti-, and anti-Cl₁₁-DP in A. stolata ranged from 1.06–21.2, 2.13–21.5, and 0.16–10.6 ng/g lipid weight, respectively, with significantly higher levels in males compared with females. Statistical analysis showed that the concentrations of these chemicals were negatively correlated with body sizes (length and mass) of the snake. The fractional abundance of anti-DP (fₐₙₜᵢ) did not significantly differ either between the sexes or between A. stolata and its diet (i.e., frogs). However, fₐₙₜᵢ showed positive correlations with the snake's body size and negative correlations with ∑DP concentrations (summed concentrations of syn- and anti-DP), indicating that body size and DP residue levels are important factors influencing DP isomeric profiles in these snakes. Biomagnification factors estimated based on the relationship between A. stolata and frogs were 0.49 ± 0.01 (mean ± SE), 0.44 ± 0.09, and 1.79 ± 0.54 for syn-, anti-, and anti-Cl₁₁-DP, respectively, suggesting trophic dilution of syn- and anti-DP and a mild biomagnification of anti-Cl₁₁-DP from frogs to snakes.

As tricresyl phosphate (TCrP) is commonly found in global water sources, its potential reproductive toxicity to fish is of increasing concern. Japanese medaka larvae were exposed to TCrP at 657.9, 1,511, and 4042 ng/L for 100 days. We identified significant fertilization inhibition (6.9%–12.8%) in all exposure groups. Intersex was significantly induced at 4042 ng/L, with an incidence of 22.0%. TCrP exposure also caused dilation of the efferent duct in the testes with maximum duct widths of 83.3, 93.2, and 149.7 μm in the 657.9, 1,511, and 4042 ng/L exposure groups, respectively. These widths were all significantly larger than that observed in the control group (37.7 μm) and likely contributed substantially to fertilization inhibition. The TCrP metabolites 4-OH-MDTP and 3-OH-MDTP, were detected at high concentrations in the liver and elicited 5.8-fold and 5.3-fold greater androgen receptor antagonistic activity than that elicited by TCrP (39.8 μM), which may explain the intersex observed in low exposure groups. 4-OH-MDTP and 3-OH-MDTP elicited anti-estrogenic activities by blocking the estrogen receptor, and the concentrations at which its responses were equal to the IC₂₀ of tamoxifen were 16.1 μM and 18.9 μM, respectively, as detected using the yeast two-hybrid assay. Such anti-estrogenic activities were likely the main driver of dilation of the efferent duct. Observed adverse outcomes after exposure to TCrP all occurred under environmentally relevant concentrations, suggesting considerable ecological risk to wild fish.

Triclinic birnessite (TB), a typical layered Mn oxide which is abundant naturally occurring minerals with a vital impact on the transformation of arsenite (As(III)) by adsorption and oxidation. As one of the most common critical metalloids, ammonium ion (NH₄⁺) universally coexists with birnessite in marine, sediments or groundwater where are contaminated with As(III). In this study, we investigated the impacts of NH₄⁺ on TB towards the transformation of As(III). Compared with the original TB (40.1%), the As(III) removal efficiencies of three different concentration (0.5 M, 1 M and 2 M) NH₄⁺ impressed triclinic birnessite (TB-0.5 N, TB-1N and TB-2N) are increased rapidly in the order of: TB-2N (80.4%) > TB-1N (75.8%) > TB-0.5 N (71.5%). In addition, TB-2N exhibited the highest initial oxidation rate of 0.0031 min⁻¹ which exceeds twice as much as this of TB (0.0014 min⁻¹). And TB-2N could reach the max oxidation efficiency when the As concentration is 0.08 mM. Due to two different mechanisms of As(III) oxidation on birnessites under acidic and alkaline conditions, TB-2N showed a higher removal efficiency than TB at pH 3.0, 5.0, 7.0 and 9.0. Hence, there are two main reasons for the advanced As(III) oxidation capacity of TB-2N. One is the improvement of the average oxidation state of Mn, the other is the increase of oxygen vacancy with the coexistence of NH₄⁺. Moreover, the larger specific surface area of TB-2N also contribute to enhancing As(III) oxidation capacity. This study holds a fundamental understanding of the behavior of triclinic birnessite which is coexisted with ammonium ion towards the transformation of As(III) in the environment.

Microplastic beads are an emerging contaminant that can cause serious environmental and public health problems. Potential bypass of microplastic beads from wastewater to sludge treatment systems is a key challenge in the conventional wastewater treatment process. Moreover, there are no systematic studies on microplastic bead degradation by hydrolytic enzymes that are rich in concentration within wastewater and sludge treatment processes (e.g., anaerobic digestion (AD)). In this study, lab-scale experiments were conducted to investigate the degradation of high-density polyethylene beads by hydrolytic enzymes (e.g., lipase) under various experimental conditions (e.g., temperature). In a 3-day batch experiment, protease was most effective in polyethylene bead degradation as 4.0% of the initial bead mass was removed at an enzyme concentration of 88 mg/L under thermophilic temperature (55 °C). It was also found that the increasing enzyme concentration and high temperature enhanced the polyethylene bead degradation. In a separate 7-day experiment with repeated doses of protease, 23.3% of the initial mass of beads was removed at thermophilic temperature, indicating that AD with a long retention time (e.g., 20 days) and heated temperature has a significant potential for polyethylene bead degradation. A mathematical model was developed and calibrated using the experimental results to estimate the kinetic constant of the high-density polyethylene bead reduction by an enzyme (k1,i) and enzyme self-decay constant (k2,ii). The calibrated k1,i ranged from 5.0 to 8.1× 10⁻⁴ L/mg/hr while k2,ii was 0.44–1.10 L/mg/hr. Using the calibrated model, degradation of polyethylene beads using a mixture of cellulase and protease was simulated, considering an interactive-decay reaction between the two enzymes. The calibrated model was used to simulate the polyethylene bead degradation in AD where 70–95% of the initial bead mass was removed at typical retention time under mesophilic digestion (37.5 °C). Based on the experimental and simulation results, it can be concluded that hydrolytic enzymes can be an efficient technology for large-scale high-density polyethylene bead removal applications.