Biochar modification by metals and metal oxides is considered a practical approach for enhancing the adsorption capacity of anionic compounds such as phosphate (P). This study obtained paper mill sludge (PMS) biochar (PMSB) via a one-step process by pyrolyzing PMS waste containing ferric salt to remove anionic P from water. The ferric salt in the sludge was transformed into ferric oxide and zero-valent-iron (Fe⁰) in N₂ atmosphere at pyrolysis temperatures ranging from 300 to 800 °C. The maximum adsorption (Qₘ) of the PMSBs for P ranged from 9.75 to 25.19 mg P/g. Adsorption is a spontaneous and endothermic process, which implies chemisorption. PMSB obtained at 800 °C (PMSB800) exhibited the best performance for P removal. Fe⁰ in PMSB800 plays a vital role in P removal via adsorption and coprecipitation, such as forming the ≡Fe–O–P ternary complex. Furthermore, the possible chemical precipitation of P by CaO decomposed from calcite (CaCO₃; an additive of paper production that remains in PMS) may also contribute to the removal of P by PMSB800. Moreover, PMSBs can be easily separated magnetically from water after application and adsorption. This study achieved a waste-to-wealth strategy by turning waste PMS into a metal/metal oxide-embedded biochar with excellent P removal capability and simple magnetic separation properties via a one-step pyrolysis process.

At present, the simultaneous removal of organic dyes and heavy metals in complex wastewater has raised considerable concern, owing to their striking differences in physicochemical properties. Adsorption, as one of the few removal methods, has attracted extensive attention and gained popularity. Herein, a versatile EDTA and chitosan bi-functionalized magnetic bamboo biochar adsorbent (ECMBB) was synthesized for coinstantaneous adsorption of methyl orange (MO) and heavy metals (Cd(II) and Zn(II)). In this case, the as-synthesized ECMBB composites inherited favorable anionic MO removal performance from bamboo biochar (BB) obtained at 700 °C through electrostatic attraction, hydrogen bonding and π-π interaction, also enhanced the binding of cationic metals by introducing amino groups of chitosan and carboxyl groups of EDTA. In the unitary system, the removal of MO, Cd(II) and Zn(II) by three as-prepared adsorbents can be well illuminated by pseudo-second-order kinetic model and Langmuir isotherm theory. The saturated capture amounts of ECMBB at 25 °C are 305.4 mg g⁻¹ for MO, 63.2 mg g⁻¹ for Cd(II) and 50.8 mg g⁻¹ for Zn(II), which, under the same conditions, are 1.3, 2.6 and 2.5 times those of chitosan-modified magnetic bamboo biochar (CMBB) and 1.9, 6.1 and 5.4 times those of magnetic bamboo biochar (MBB), respectively. Remarkably, in MO-metal binary system, coexisting MO visibly enhanced the adsorption of Cd(II) and Zn(II), while coexisting heavy metals had no significant impact on MO adsorption. Furthermore, ECMBB exhibited no significant loss in adsorption efficiency even after eight adsorption-desorption experiments. This study lays the foundation for fabricating desired integrative biochar adsorbents in the simultaneous purification of organic and metallic pollutants from complex wastewater.

Novel magnetic microcomposites consisting of graphene oxide and iron oxide was synthesized to immobilize metabolically versatile Paracoccus sp. MKU1 and Leucobacter sp. AA7 and tested for the simultaneous adsorption and enhanced biological detoxification of hexavalent chromium (Cr(VI)) from tannery wastewater. This study reports highest chromium adsorption of 272.6 mg/g and 179.3 mg/g with complete reduction of Cr(VI) to Cr(III) by the microcomposites of AA7 and MKU1 from wastewater in a bioreactor (10 L) at large-scale for first time in ex situ. Furthermore, both the microcomposites displayed an enhanced detoxification of tannery wastewater by reducing various physicochemical conditions such as ammonia, nitrate, TDS, fluoride, CaCO₃, Ca, Mg, NO₃ and SO₂ under the permissible limits. Use of electromagnetic device for magnetic microcomposites recovery from bioreactor yielded a maximum of 88% and 80.6% recovery for AA7 and MKU1, respectively. The rate of chromium recuperation achieved following desorption from the microcomposites of AA7 and MKU1 was 90.71% and 93.97%, respectively. Thus, the multifarious benefits including adsorption, metabolic detoxification, recovery, and recuperation by single functional microcomposites seems to be an intriguing and profitable approach for practicing in real-time operations to effectively remove heavy metals from the contaminated wastewater for environmental protection.

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.

Size and magnetic separation of incineration bottom ash (IBA) are common for ferrous metals recovery, however, their influences on the mineral phase and the element redistribution, and subsequently the induced variation of metal leaching potential herein remain limited understanding. The lack of research in this field may misunderstand IBA performances, cause confused results for comparison among various studies, and potentially lead to biased conclusions. We herein quantitatively investigate the effects of size and magnetic separation on the IBA based on element distribution, leaching behavior, morphology, and mineralogy with statistical analysis. For preparation, sieving was performed with the original IBA (to obtain 7 size-fractions termed as OR1-7, respectively), followed by magnetic separation of each, to further yield magnetic fractions (MF1-7) to discriminate nonmagnetic fractions (NF1-7). In this study, we show that size and magnetic separation may pose significant yet different impacts on different fractions, which would affect their leaching potential concerning their respective downstream applications.

Soil magnetic susceptibility (MS) is an important parameter in pollution studies owing to its relationship with atmospheric deposition, and the concomitance of technogenic magnetic particles (TMPs) with potentially toxic elements (PTEs), Fe and Mn. In this study, we performed a detailed soil study under tree canopies for a forest area with high historical TMP-bearing industrial dust deposition. The technogenic sources of magnetic signals in topsoil were analyzed via scanning electron microscope electron dispersive spectroscopy (SEM/EDS), while the minor role of geogenic sources was obtained from soil profile analysis. To our knowledge, this is the first study to show soil TMP distribution in three dimensional (3D) space. In addition, using the data from 275 soil cores and 8250 individual measurements, 3D maps of MS for four tree species were plotted. There is a noticeable difference between coniferous (spruce and pine) and deciduous (beech and oak) species regarding depth of maximum concentration of magnetic particles in the topsoil. For beech and oak, maximum MS values were measured at 3 cm depth; pine and spruce, maximum MS values were measured at 5 cm depth. However, no significant differences were found among tree species in terms of mean MS or PTE contents. This suggests that there is little different among tree species in terms of dust capture over their life span. Significant correlations between MS and other parameters (PTEs and organic matter contents) present new possibilities for spatial 3D analysis of topsoil horizons.

Between 9 March and 18 May 2020, strict lockdown measures were adopted in Italy for containing the COVID-19 pandemic: in Rome, despite vehicular traffic on average was more than halved, it was not observed a evident decrease of the airborne particulate matter (PM) concentrations, as assessed by air quality data. In this study, daily PM₁₀ filters were collected from selected automated stations operated in Rome by the regional network of air quality monitoring: their magnetic properties – including magnetic susceptibility, hysteresis parameters and FORC (first order reversal curves) diagrams - were compared during and after the lockdown, for outlining the impact of the COVID-19 measures on airborne particulate matter. In urban traffic sites, the PM₁₀ concentrations did not significantly change after the end of the lockdown, when vehicular traffic promptly returned to its usual levels; conversely, the average volume and mass magnetic susceptibilities approximately doubled, and the linear correlation between volume magnetic susceptibility and PM₁₀ concentration became significant, pointing out the link between PM₁₀ concentrations and the increasing levels of traffic-related magnetic emissions. Magnetite-like minerals, attributed to non-exhaust brakes emissions, dominated the magnetic fraction of PM₁₀ near urban traffic sites, with natural magnetic components emerging in background sites and during exogenous dusts atmospheric events. Magnetic susceptibility constituted a fast and sensitive proxy of vehicular particulate emissions: the magnetic properties can play a relevant role in the source apportionment of PM₁₀, especially when unsignificant variations in its concentration levels may mask important changes in the traffic-related magnetic fraction. As a further hint, increasing attention should be drawn to the reduction of brake wear emissions, that are overcoming by far fuel exhausts as the main particulate pollutant in traffic contexts.

Air pollution represents one of the major concerns worldwide, fueled by the increasing urbanization and related PM production worsening air quality in open air as well as in confined environments. In the present work, exposure to atmospheric metal pollution was investigated in 20 paired indoor (I)-outdoor (O) sites located in two urban areas of Italy and Belgium, by chemical (ICP-MS) and magnetic (saturation isothermal remanent magnetization, SIRM) analyses of Hypnum cupressiforme moss exposed in bags. After 12 weeks, the elemental profiles of the moss material exposed in the two countries largely overlapped, except for some elements which specifically accumulated in Belgium (Ag, As, Cd, Mo, Pb and Sb) and in Italy (Ca, Mg, Co, Cr, Sr, Ti and U). Element concentrations were higher in moss exposed outdoors, with the Italian sites mostly showing a terrigenous footprint, and the Belgian sites mostly affected by elements of environmental concern (e.g., As, Pb, Sb). The Indoor/Outdoor ratios (mostly lower than 0.75) indicated indoor pollution as strongly affected by outdoor pollution, although specific elements could be of indoor origin or magnified in indoor environments (e.g., Al, Ag, Cd and Co). In line with the chemical analysis, the SIRM signal was significantly higher in outdoor than indoor moss material. A positive, significant correlation was observed between SIRM and several accumulated elements indicating SIRM analysis as a powerful tool to predict the level of metal pollution. Moss bags were confirmed as a useful and versatile tool to highlight metal contamination even in confined environments, an essential prerogative in the perspective of the evaluation of the total exposure risk for humans to these pollutants.

Hexavalent chromium (Cr(VI)) has significantly threatened the environmental health because of its distinct toxicity. A novel magnetic core-shell structured NZVI@ZD composite was designed for simultaneous adsorption and reduction of Cr(VI). NZVI@ZD was synthesized by carbonization of the as-prepared core-shell structure NZVI@zeolitic imidazole framework-67 (ZIF-67). After carbonization, the original ZIF-67 shell shape was preserved well with marginal parts developing to graphitized carbon. Both cobalt (Co) and NZVI nanoparticles were finely dispersed in the porous ZIF-67 derivative (ZD). NZVI@ZD exhibited excellent removal performance for Cr(VI), owing to its high specific surface area and large pore size favorable for Cr(VI) adsorption and diffusion. The maximum adsorption capacity of NZVI@ZD for Cr(VI) was surprisingly as high as 226.5 mg g⁻¹, surpassing the pristine ZIF-67 (29.35 mg g⁻¹) and NZVI@ZIF-67 (36.53 mg g⁻¹). Zeta potential and X-ray photoelectron spectroscopy (XPS) spectra revealed that electrostatic attraction, reduction and precipitation might be involved in the Cr(VI) removal process by NZVI@ZD, resulting in the conversion of the adsorbed Cr(VI) to Cr(III) of lower toxicity and an eventual immobilization on the NZVI@ZD. The magnetic core-shell structured NZVI@ZD possessed superior adsorptive reactivity for Cr(VI) to most other traditional or newly reported materials, thus should be deemed highly efficient for Cr(VI)-contaminated wastewater treatment.