Discarded micro/nano-plastic inputs into the environment are emerging global concerns. Yet the quantification of micro/nanoplastics in complex environmental matrices is still a major challenge, notably for soluble ones. We herein develop in-laboratory built nanostructures (zinc oxide, titanium oxide and cobalt) coupled to mass spectrometry techniques, for picogram quantification of micro/nanoplastics in water and snow matrices, without sample pre-treatment. In parallel, an ultra-trace quantification method for micro/nanoplastics based on nanostructured laser desorption/ionization time-of-flight mass spectrometry (NALDI-TOF-MS) is developed. The detection limit is ∼5 pg for ambient snow. Soluble polyethylene glycol and insoluble polyethylene fragments were observed and quantified in fresh falling snow in Montreal, Canada. Complementary physicochemical studies of the snow matrices and reference plastics using laser-based particle sizers, inductively coupled plasma tandem mass spectrometry, and high-resolution scanning/transmission electron microscopy, produced consistent results with NALDI, and further provided information on morphology and composition of the micro/nano-plastic particles. This work is promising as it demonstrates that a wide range of recyclable nanostructures, in-laboratory built or commercial, can provide ultra-trace capability for quantification for both soluble polymers and insoluble plastics in air, water and soil. It may thereby produce key missing information to determine the fate of micro/nanoplastics in the environment, and their impacts on human health.

The rapid determination of the bioaccessibility of polycyclic aromatic hydrocarbons (PAHs) in soils is challenging due to their slow desorption rates and the insufficient extraction efficiency of the available methods. Herein, magnetic poly(β-cyclodextrin) microparticles (Fe₃O₄@PCD) were combined with hydroxypropyl-β-cyclodextrin (HPCD) or methanol (MeOH) as solubilizing agents to develop a rapid and effective method for the bioaccessibility measurement of PAHs. Fe₃O₄@PCD was first validated for the rapid and quantitative adsorption of PAHs from MeOH and HPCD solutions. The solubilizing agents were then coupled with Fe₃O₄@PCD to extract PAHs from soil-water slurries, affording higher extractable fractions than the corresponding solution extraction and comparable to or higher than single Fe₃O₄@PCD or Tenax extraction. The desorption rates of labile PAHs could be markedly accelerated in this process, which were 1.3–12.0 times faster than those of single Fe₃O₄@PCD extraction. Moreover, a low HPCD concentration was sufficient to achieve a strong acceleration of the desorption rate without excessive extraction of the slow desorption fraction. Finally, a comparison with a bioaccumulation assay revealed that the combination of Fe₃O₄@PCD with HPCD could accurately predict the PAH concentration accumulated in earthworms in three field soil samples, indicating that the method is a time-saving and efficient procedure to measure the bioaccessibility of PAHs.

Atmospheric semi-volatile organic compounds (SVOCs) are complex in their chemical and toxicological characteristics with sources from both primary combustion emissions and secondary oxygenated aerosol formation processes. In this study, thermal desorption of PM₂.₅ in association with online measurement of reactive oxygen species (ROS) was carried out to study the role of SVOCs in its gas-particle partitioning. The mass concentrations of PM₂.₅, black carbon (BC) and p-PAHs downstream of a thermodenuder were measured online at different temperature settings (25, 50, 100, and 200 °C) to characterize PM physico-chemical properties. While the mass concentrations of PM₂.₅ and p-PAHs reduced to ∼34% at 200 °C compared to that in ambient temperature, BC mass concentration has decreased by 30% at the highest temperature. Furthermore, the submicron particle size distribution showed reduced particle number concentration in Aitken mode at 200 °C heating. The ROS, measured by Particle-into-Nitroxide-Quencher, also showed reduction and followed a similar trend with PM measurements, where the total ROS decreased by 12%, 31%, and 53% at 50 °C, 100 °C, and 200 °C, respectively, compared to the ambient sample. When a HEPA filter was included in the upstream of samples, 39% of gas phase ROS reduction was observed at 200 °C. This provided a good estimate of the contribution of SVOCs in ROS production in PM₂.₅, where decreased SVOCs concentration at 200 °C increased the percentage of particle surface area. This concludes that the surface chemistry of these organic coatings on the particles is important for assessing the health impacts of PM.

The well-known toxicity of conventional chemical oil spill dispersants demands the development of alternative and environmentally friendly dispersant formulations. Therefore, in the present study we have developed a pair of less toxic and green dispersants by combining lactonic sophorolipid (LS) biosurfactant individually with choline myristate and choline oleate ionic liquid surfactants. The aggregation behavior of resulted surfactant blends and their dispersion effectiveness was investigated using the baffled flask test. The introduction of long hydrophobic alkyl chain with unsaturation (attached to choline cation) provided synergistic interactions between the binary surfactant mixtures. The maximum dispersion effectiveness was found to be 78.23% for 80:20 (w/w) lactonic sophorolipid-choline myristate blends, and 81.15% for 70:30 (w/w) lactonic sophorolipid-choline oleate blends at the dispersant-to-oil ratio of 1:25 (v/v). The high dispersion effectiveness of lactonic sophorolipid-choline oleate between two developed blends is attributed to the stronger synergistic interactions between surfactants and slower desorption rate of blend from oil-water interface. The distribution of dispersed oil droplets at several DOR were evaluated and it was observed that oil droplets become smaller with increasing DOR. In addition, the acute toxicity analysis of developed formulations against zebra fish (Danio rerio) confirmed their non-toxic behavior with LC₅₀ values higher than 400 ppm after 96 h. Overall, the proposed new blends/formulations could effectively substitute the toxic and unsafe chemical dispersants.

Though many studies pertaining to soil bioremediation have been performed to study the microbial kinetics in shake flasks, the process efficiency in column tests is seldom. In the present study, soil columns tests were carried out to study the biodegradation of soil contaminated with a high concentration of diesel (≈19.5 g/kg) petroleum hydrocarbons expressed as C₁₀–C₅₀. Experiments were done with crude enzymatic cocktail produced by the hydrocarbonoclastic bacterium, Alcanivorax borkumensis. A. borkumensis was grown on a media with 3% (v/v) motor oil as the sole carbon and energy source. The effects of the enzyme concentration, treatment time and oxidant on the bioremediation efficiency of C₁₀–C₅₀ were investigated. A batch test was also carried out in parallel to investigate the stability of the enzymes and the effect of the biosurfactants on the desorption and the bioconversion of C₁₀–C₅₀. Batch tests indicated that the biosurfactants significantly affected the desorption and alkane hydroxylase and lipase enzymes, maintained their catalytic activity during the 20-day test, with a half-life of 7.44 days and 8.84 days, respectively. The crude enzyme cocktail, with 40 U/mL of lipase and 10 U/mL of alkane hydroxylase, showed the highest conversion of 57.36% after 12 weeks of treatment with a degradation rate of 0.0218 day⁻¹. The results show that the soil column tests can be used to optimize operating conditions for hydrocarbon degradation and to assess the performance of the overall bioremediation process.

Phosphogypsum (PG) is disposed worldwide in large stacks usually placed in coastal zones, as in the case of Huelva (SW of Spain), where around 100 Mt of PG are stored on the salt marshes of the Tinto River estuary covering a surface of about 1000 ha. This management generates the weathering of PG, and due to its high acidity (pH ≈ 2) and pollutant load can provoke significant emissions into their surroundings. In this work were evaluated by laboratory experiments the effects of pH increase in the behaviour of heavy metals and natural radionuclides during the mixing of phosphogypsum leachates with seawater.The acidic phosphogypsum leachates showed concentrations of heavy metals from two to three orders of magnitude higher than natural continental waters, and natural radionuclides (U-isotopes and ²¹⁰Po) from four to five orders of magnitude higher than unperturbed aquatic systems. Major elements and some heavy metals as Mn, Ni, Cd, As, Sb and Co showed a conservative behaviour during the neutralisation of the leachates with seawater, remaining in the liquid phase, while other ones as Al, Fe, Cr, Zn, Cu, Pb precipitated and/or were adsorbed onto the solid phase. The U-isotopes and ²¹⁰Po showed a clear non-conservative behaviour probably due to coprecipitation/adsorption processes onto the formed precipitates, but while ²¹⁰Po reached a total removal at pH ≈ 7, U- isotopes after a total removal at pH ≈ 5 returned into the liquid phase due to redissolution/desorption processes at near neutral pH.The formed precipitates, mainly composed by iron phosphates particles, showed heavy metal and natural radionuclide concentrations from one to three orders of magnitude higher than unperturbed soils. All these facts demonstrate the serious environmental impact produced by the PG stacks into their surroundings and the urgency of effective restoration measures.

Contamination of waters and soils with microplastics (MPs) is an emerging environmental issue worldwide. MPs constitute a cocktail of various additives and polymers besides adsorbing toxic heavy metals from the environment. This co-occurrence of MPs with heavy metals poses a threat to the health of organisms and is poorly understood. Ingestion of MPs contaminated with heavy metals may also result in subsequent transfer of heavy metals up in the food chain. MPs surfaces play a crucial role in the adsorption of heavy metals. Aged/biofouled MPs facilitate greater adsorption of metals and certain microplastic (MP) polymers adsorb some metals more specifically. External factors involved in the process of adsorption/accumulation of heavy metals are the solution pH, salinity, and the concentration of relevant heavy metals in the media. Desorption greatly depends upon pH of the external solution. This is more concerning as the guts/digestive systems of organisms have low pH which could enhance the desorption of toxic metals and making them accumulate in their bodies. The aim of this article is to discuss the abundance, distribution, adsorption, and desorption behavior of MPs for heavy metals, and their combined toxic effects on flora and fauna based on the limited research on this topic in the literature. There is an overarching need to understand the interactions of MPs with heavy metals in different ecosystems so that the extent of ecotoxic effects they pose could be assessed which would help in the environmental regulation of these pollutants.

Polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) emission is one of main concerns for the secondary pollution of municipal solid waste incinerators (MSWI). For timely response to emission, 1,2,4-trichlorobenzene (1,2,4-TrClBz) as dioxin indicator can be monitored via online measurement techniques. In this study, multi-walled carbon nanotubes (MWCNTs) were investigated for their suitability as a 1,2,4-TrClBz sorbent for MSWI stack gas analysis. The tests include, batch adsorption, continuous adsorption-desorption of 1,2,4-TrClBz via thermal desorption coupled with gas chromatography (TD-GC-ECD), temperature and concentration stability of MWCNTs, and adsorption performance of the system. Thermogravimetric/derivative thermogravimetric (TGA/DTG) analysis reveals that MWCNTs has higher capacity in terms of weight loss (14.34%) to adsorb 1,2,4-TrClBz compared to Tenax TA (9.46%) and also shows fast desorption of adsorbate at temperature of 87 °C compared to Tenax TA (130 °C). Interestingly, carbon nanotubes and Tenax TA gave almost similar adsorption-desorption response, and from TD-GC-ECD analysis it was found that with increasing mass flow of 1,2,4-TrClBz (7.42 × 10⁻⁶ - 44.52 × 10⁻⁶ mg ml⁻¹) through sorbent traps, average peak areas increased from 2.86 ± 0.02 to 13.54 ± 0.26 for MWCNTs and 2.89 ± 0.02 to 13.38 ± 0.12 for Tenax TA, respectively. The stability of MWCNTs for temperature was 400 °C and for concentration of 1,2,4-TrClBz was 50 ppbv. However, regeneration of sorbent at 100 ppbv (1,2,4-TrClBz) was not possible. TD-GC-ECD system showed high adsorption performance with 3.86% and 3.59% relative standard deviation at 250 °C and 300 °C, respectively. Further Fourier Transform Infrared Spectroscopy (FTIR) analysis confirmed that adsorbate can be fully desorbed at 300 °C.

This study explored biochar (BC) amendment effects on microcystin-LR (MCLR) concentration-dependent sorption and sequential desorption (SDE) by diverse soils to assess MCLR-trapping by BC-amended soils. Soil properties varied with rising BC dose and aging time. As aging proceeded, BC-amended soils shared a generally similar ‘firstly increase and then decrease’ trend of MCLR sorption and ‘firstly decrease and then increase’ trend of desorption at most cases. It appeared that MCLR sorption by BC-amended soils was most positively correlated with mesoporosity and surface basic functionality. BC-amendment increased MCLR-trapping for most soils, especially 4% BC at 3 month-aging maximized trapping ratio of GZ, SY and SX to 86.59%–95.43%, 80.01%–87.20% and 78.73%–90.85%, respectively, at 50–500 μg/L MCLR by largely increasing sorption and decreasing desorption. BC-amendment best matched GZ soil because MCLR-trapping of BC-amended GZ exceeded other amended soils at the same BC dose and aging time, but failed to obviously increase MCLR-trapping of HS soil at most cases, except only case with 2% BC at 3 month-aging. Site energy distribution verified that maximally enhanced MCLR-trapping of most soils was due to greatly enhanced sorption affinity during sorption and 1st desorption cycle, making closer MCLR-binding that more resistant to desorption. Contrarily, BC-amendment did not enhance sorption affinity of HS along sorption-SDE to compromise MCLR-trapping increase at most cases. This study validated 3 months as suitable BC-aging time to maximize MCLR-trapping in diverse soils, and elucidated influencing factors and mechanisms from view of site energy distribution, which shed novel insights on MCLR sorption-desorption by BC-amended soils, and guided to optimize BC-amendment strategy for efficient MCLR-immobilization and eco-risk elimination in diverse soils.

Thermal desorption is widely adopted for the remediation of organic compounds, yet is generally considered a non-green-sustainable manner owing to its energy-intensive nature and potential to deteriorate soil reuse. Here, lube oil-contaminated soils were remediated at 200–500 °C in nitrogen atmosphere, upon which removal behaviors of lube oil and physicochemical properties of soils were explored. Illumina 16S ribosomal RNA (rRNA) and 18S rRNA amplicon sequencing were employed to determine the relative abundances and diversities of bacteria and fungi in soils, respectively. The results indicated that, after heating at 350 °C for 60 min, 93% of the lube oil was reduced, with the residual lube oil concentration lower than the Chinese risk intervention values (GB 36600–2018). The weakly-alkaline, multi-phosphorus and char-rich soils after indirect thermal desorption could provide a nutrient source and favorable habitat space for living organisms, and the decomposition of minerals in soils is more conducive to the survival of organisms. Microbial species in soils after heating at 350 °C became extinct, however, microbial species after 3 days of recolonization were enough to carry out DNA extraction when these soils were exposed to natural grass land. Though the microbial richness and diversity in heated soils after 3 days of recolonization were still little lower than those in contaminated soils, Firmicutes (29.41%) and Basidiomycota (9.33%) became dominant at phyla level, while Planomicrobium (16.37%), Massilia (10.09%), Jeotgalibaca (7.91%) and Psychrobacter (6.84%) were dominant at general level, whose ecological function was more conducive to nutrient cycling and ecological resiliency. Overall, this innovative research provides a new perspective: low temperature indirect thermal desorption may also achieve a sustainable remediation, due to its energy-saving (low temperature), favorable physicochemical properties and the rapid recolonization capacity of microbial communities in heated soils.