It is highly desirable but remains extremely challenging to develop a facile strategy to prepare adsorbent for dealing with heavy metal pollution in water. Here, we report a facile approach for preparing sulfydryl-functionalized graphene oxide (S-GO) by cross-linking method with an unprecedented adsorption capacity and ultrahigh selectivity for efficient Hg(II) removal. The adsorbents exhibit a prominent performance in capturing Hg(II) from wastewater with a record-high adsorption capacity of 3490 mg/g and rapid kinetics to reduce Hg(II) contaminants below the discharge standard of drinking water (2 ppb) within 60 min under a wide pH range even in the coexistent of other interfering metal ions. In addition, the adsorbents can be also easily recycled and reused multiple times with no apparent decline in removal efficiency. Considering the broad diversity, we developed also a magnetic Fe₃O₄/S-GO adsorbent by a simple chemical cross-linking reaction to achieve rapid separation of S-GO from their aqueous solution. In addition, the adsorbents were successfully applied in dealing with the practical industrial wastewater. The results indicate the potential of rationally designed sulfydryl-functionalized graphene oxide for high performance Hg(II) removal.

Pollution-tolerant lichens are recognized ecological indicators of air pollution in cities, which can also collect airborne anthropogenic particles in their tissues. Harmful (sub)micron-sized magnetites are a ubiquitous component of air particle pollution, adversely impacting human health. In this work, in situ magnetic susceptibility κᵢₛ of well-characterized ultrafine magnetite and lichen thalli were measured to quantify the amount of airborne magnetic particles (AMP) after calibration and to assess the lichen's decontamination over time. Up to 2850 magnetic measurements were carried out in twenty-nine transplanted lichens (collected in urban and clean areas) from winter 2020 to winter 2021. Before the transplants, their initial κᵢₛ values were 0.23–9.45 × 10⁻⁵ SI, representing AMP contents of 0.1–4.6 mg in lichen thalli. After lichens were transplanted to a shared site, the magnetic signals evidenced short-term increases and long-term decreases. After three, five and nine months, the AMP loss is more pronounced for transplanted lichens from polluted (e.g., AMP_5-months loss = 0.59 mg) than clean (= 0.08 mg) sites. Rainfall influenced the lichen's decontamination between seasons. In situ measurements and lichens offer a valued and time-saving methodology for biomonitoring harmful airborne particles simply and effectively.

Exposure to particulate air pollution has been associated with a variety of respiratory, cardiovascular and neurological problems, resulting in increased morbidity and mortality worldwide. Brake-wear emissions are one of the major sources of metal-rich airborne particulate pollution in roadside environments. Of potentially bioreactive metals, Fe (especially in its ferrous form, Fe²⁺) might play a specific role in both neurological and cardiovascular impairments. Here, we collected brake-wear particulate emissions using a full-scale brake dynamometer, and used a combination of magnetic measurements and electron microscopy to make quantitative evaluation of the magnetic composition and particle size of airborne emissions originating from passenger car brake systems. Our results show that the concentrations of Fe-rich magnetic grains in airborne brake-wear emissions are very high (i.e., ~100–10,000 × higher), compared to other types of particulate pollutants produced in most urban environments. From magnetic component analysis, the average magnetite mass concentration in total PM₁₀ of brake emissions is ~20.2 wt% and metallic Fe ~1.6 wt%. Most brake-wear airborne particles (>99 % of particle number concentration) are smaller than 200 nm. Using low-temperature magnetic measurements, we observed a strong superparamagnetic signal (indicative of ultrafine magnetic particles, < ~30 nm) for all of the analysed size fractions of airborne brake-wear particles. Transmission electron microscopy independently shows that even the larger size fractions of airborne brake-wear emissions dominantly comprise agglomerates of ultrafine (<100 nm) particles (UFPs). Such UFPs likely pose a threat to neuronal and cardiovascular health after inhalation and/or ingestion. The observed abundance of ultrafine magnetite particles (estimated to constitute ~7.6 wt% of PM₀.₂) might be especially hazardous to the brain, contributing both to microglial inflammatory action and excess generation of reactive oxygen species.

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.

Magnetic biochars were prepared by chemical co-precipitation of Fe³⁺/Fe²⁺ onto rice straw (M-RSB) and sewage sludge (M-SSB), followed by pyrolysis treatment, which was also used to prepare the corresponding nonmagnetic biochars (RSB and SSB). The comparison of adsorption characteristics between magnetic and nonmagnetic biochars was investigated as a function of pH, contact time, and initial Cd²⁺ concentration. The adsorption of nonmagnetic biochars was better described by pseudo-second-order kinetic model, and the adsorption of RSB and SSB was better described by Langmuir and Freundlich models, respectively. Magnetization of the biochars did not change the applicability of their respective adsorption models, but reduced their adsorption capabilities. The maximum capacities were 42.48 and 4.64 mg/g for M-RSB and M-SSB, respectively, underperforming their nonmagnetic counterparts of 58.65 and 7.22 mg/g for RSB and SSB. Such a reduction was fundamentally caused by the decreases in the importance of cation-exchange and Cπ-coordination after magnetization, but the Fe-oxides contributed to the precipitation-dependent adsorption capacity for Cd²⁺ on magnetic biochars. The qualitative and quantitative characterization of adsorption mechanisms were further analyzed, in which the contribution proportions of cation-exchange after magnetization were reduced by 31.9% and 12.1% for M-RSB and M-SSB, respectively, whereas that of Cπ-coordination were reduced by 3.4% and 31.1% for M-RSB and M-SSB, respectively. These reductions suggest that for adsorbing Cd²⁺ the choice of conventional biochar was more relevant than whether the biochar was magnetized. However, magnetic biochars are easily separated from treated solutions, depending largely on initial pH. Their easy of separation suggests that magnetic biochars hold promise as more sustainable alternatives for the remediation of moderately Cd-contaminated environments, such as surface water and agriculture soil, and that magnetic biochars should be studied further.

Nitrocompounds are the major prime water contaminants. In this investigative study, toxic nitrocompounds (4-nitrophenol, 2,4-dinitrophenol, 2,4,6-trinitrophenol) were removed by using magnetic CuFe₂O₄, CoFe₂O₄, and NiFe₂O₄ material systems. The metal ferrites were synthesized through hydrothermal method and also followed with calcination process. The properties of metal ferrites were confirmed through using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and field emission scanning electron microscopy (FE-SEM) studies and results there on were presented. For the first time, the synthesized CuFe₂O₄, CoFe₂O₄, and NiFe₂O₄ material systems were used for the reduction of 4-nitrophenol (NP), 2,4-dinitrophenol (DNP), and 2,4,6-trinitrophenol (TNP) in aqueous medium. The UV–visible spectrometry was employed to monitor the removal of nitro compounds and formation of aminophenol. Among, the three catalysts, the CuFe₂O₄ displayed excellent removal activity for nitrocompounds. The CuFe₂O₄ nanoparticles completely removed the NP, DNP and TNP within 2, 5, 10 min, respectively. The NP reduction reaction follows the pseudo-first-order kinetics. Further, the investigated and proposed CuFe₂O₄, catalyst has given and demonstrated excellent kinetic rate constants 0.990, 0.317, 0.184 min⁻¹ for 4-NP, DNP and TNP respectively, which was very fast kinetic than the already published reports. Also, the aminophenol formation was confirmed for the above mentioned and select nitrocompounds. The obtained results confirm suggest that CuFe₂O₄ nanoparticles based material system could be one of the promising catalysts for nitro compounds removal process.

The presence of higher concentrations of heavy metals in water affects its quality with a concomitant adverse effect on its users thus their removal is paramount. A novel adsorbent, PN-Fe₃O₄-IDA derived from the chemical modification of peanut husk (a low-cost agricultural biomass produced in significant quantities globally) using magnetic nanoparticles (Fe₃O₄) and iminodiacetic acid was utilized for the remediation of heavy metals in aqueous solution. Analytical techniques vis-à-vis the Fourier-Transform Infrared, Scanning Electron Microscope, Brunauer–Emmett–Teller, X-ray photoelectron spectroscopy and X-ray Diffraction were applied for the characterization of PN-Fe₃O₄-IDA. Results from the characterization studies showed that PN-Fe₃O₄-IDA possessed a mesoporous structure, a heterogeneous surface and functional groups such as carboxylic acid and a tertiary nitrogen atom which enhanced its adsorption capacities as well as magnetic properties which ensured its easy removal from the solution using a magnet. The maximum uptake of Pb and Cu onto PN-Fe₃O₄-IDA was 0.36 and 0.75 mmol g⁻¹ (at 318 K) respectively with the chemisorption process being the major reaction pathway for the processes. The synthesized adsorbent exhibits significant adsorption capacity for the selected pollutants as well as some unique features which promotes its use as an adsorbent for wastewater remediation processes.

Due to their small dimensions, airborne particles are able to penetrate through inhalation into many human organs, from the lungs to the cardiovascular system and the brain, which can threaten our health. This work establishes a novel approach of collecting quantitative data regarding the fraction, the composition and the size distribution of combustion-emitted particulate matter through the magnetic characterization and analysis of samples received by common air pollution monitoring. To this end, SQUID magnetometry measurements were carried out for samples from urban and suburban areas in Thessaloniki, the second largest city of Greece, taking into consideration the seasonal and weekly variation of airborne particles levels as determined by occurring traffic and meteorological conditions. The level of estimated magnetically-responding atmospheric particulate matter was at least 0.5 % wt. of the collected samples, mostly being present in the form of ultrafine particles with nuclei sizes of approximately 14 nm and their aggregates. The estimated quantities of magnetic particulate matter show maximum values during autumn months (0.8 % wt.) when increased commuting takes place, appearing higher in the city center by up to 50% than those in suburban areas. In combination with high-resolution transmission electron imaging and elemental analysis, it was found that Fe₃O₄ and similar ferrites, some of them attached to heavy metals (Co, Cr), are the dominant magnetic contributors arising from anthropogenic high-temperature processes, e.g. due to traffic emissions. Importantly, nasal cytologic samples collected from residents of both central and suburban areas showed same pattern in what concerns magnetic behavior, thus verifying the critical role of nanosized magnetic particles in the assessment of air pollution threats. Despite the inherent statistical limitations of our study, such findings also indicate the potential transmission of infectious pathogens by means of pollution-derived nanoparticles into the respiratory system of the human body.

The environmental-friendly photocatalytic process with a magnetic catalyst CoFe₂O₄/TiO₂ mediated by solar light for ibuprofen (IBP) degradation in pure water, wastewater effluent and artificial seawater was investigated systematically. The study aims to reveal the efficiency, the mechanism and toxicity evolution during IBP degradation. Hydroxyl radicals and photo-hole (h⁺) were found to contribute to the IBP decay. The presence of SO₄²⁻ showed no significant effect, while NO₃⁻ accelerated the photodegradation, and other anions including HCO₃⁻, Cl⁻, F⁻, and Br⁻ showed significant inhibition. The removal efficiency was significantly elevated with the addition of peroxymonosulfate (PMS) or persulfate (PS) ([Oxidant]₀:[IBP]₀ = 0.4–4), with reaction rate of 5.3–13.1 and 1.3–2.9 times as high as the control group, respectively. However, the reaction was slowed down with the introduction of H₂O₂. A mathematic model was employed to describe the effect of ferrate, high concentration or stepwise addition of ferrate was suggested to play a positive role in IBP photodegradation. Thirteen transformation products were identified and five of them were newly reported. The degradation pathways including hydroxylation, the benzene ring opening and the oxidation of carbon were proposed. IBP can be efficiently removed when spiked in wastewater and seawater despite the decreased degradation rate by 41% and 56%, respectively. Compared to the IBP removal, mineralization was relatively lower. The adverse effect of the parent compound IBP to the green algae Chlorella vulgaris was gradually eliminated with the decomposition of IBP. The transformation product C178a which possibly posed toxicity to rotifers Brachionus calyciflorus can also be efficiently removed, indicating that the photocatalysis process is effective in IBP removal, mineralization and toxicity elimination.

Children in urban environments are exposed to potential harmful elements (PHEs) through variable exposure media. Playing activities in outdoor playgrounds have been considered of high concern due to children's exposure to sand-bound PHEs through unintentional or intentional sand ingestion. Furthermore, the affinity of magnetic particles with dust-bound PHEs in playgrounds has been reported. In this study, playground sands (PG sands) from public playgrounds in the city of Thessaloniki, N. Greece were sampled and the levels, the contamination degree, oral bioaccessibility and exposure assessment of PHEs were evaluated. In addition, low-cost and fast magnetic measurements (i.e. mass specific magnetic susceptibility, χₗf) were explored as potential pollution and health risk proxies. Mineralogically, siliceous PG sands dominated, while morphologically angular magnetic particles and Fe-rich “spherules” of anthropogenic origin were revealed and verified by enhanced χₗf values. The average total elemental contents exhibited a descending order of Mn > Ba > Cr > Zn > Ni > Pb > Cu > Co > As > Sn > Bi > Cd, however only Cd, Bi, Pb, Cr, As and Zn were presented anthropogenically enhanced. Notable increase on PHEs levels and finer sand fractions were observed with continuous sand use. Anthropogenically derived elements (i.e. Cd and Pb with high Igₑₒ values) exhibited higher bioaccessible fractions in PG sands and considered easily soluble in gastric fluids through ingestion. However, increased risks were found for specific PHEs (especially Pb) only in a worst case exposure scenario of an intentional sand ingestion (pica disorder). Statistical analysis results revealed a linkage of anthropogenic components with sand-bound magnetic particles. Moreover, the recorded high affinity of Pb contents (in an enhanced magnetized sub-set of PG sands) and bioaccessible Cd fractions with χₗf provide a preliminary indication on the successful applicability of low-cost and fast magnetic measurements in high impacted playground environments.