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Rice husk is a waste byproduct of rice production. This material has a moderate cost and is readily available, representing 20-22% of the biomass produced by rice cultivation. This study focused on the properties of rice husk in the remediation of soils contaminated by heavy metals. The effect of particle size, pH, and the presence of organic ligands on sorption efficiency was evaluated for Cd, Cu, and Mn. The continuous flow method was used to select suitable operative conditions and maximize the retention of heavy metals. Subsequently, pot experiments were carried out by growing two broadleaf plants, Lactuca sativa and Spinacia oleracea , in aliquots of soil collected in a Piedmont (Northwest Italy) site heavily contaminated by Cu, Cr, and Ni. Rice husk was added to the contaminated soil to evaluate its effectiveness in immobilizing heavy metals. The availability of Cr, Mn, Ni, Cu, Zn, Cd, and Pb in soil was studied using Tessier's sequential extraction protocol. The content of the elements was also analyzed in plants and the uptake of heavy metals was evaluated in relation to the addition of rice husk. The growth of both plants was more efficient in the presence of rice husk due to its ability to reduce the mobility of heavy metals in the soil. The simplicity, cost-effectiveness, and scalability of its employment make the use of rice husk suitable for practical applications in soil remediation.

The potential of utilizing inorganic constituents in processed animal proteins (PAPs) for species identification in animal feeds was investigated, with the aim of using these constituents to ensure the quality and authenticity of the products. This study aimed to quantify the inorganic content across various PAP species and assess whether inorganic analysis could effectively differentiate between PAP species, ultimately aiding in the identification of PAP fractions in animal feeds. Four types of PAPs, namely bovine, swine, poultry, and fish-based, were analyzed and compared to others made up of feathers of vegetal-based feed. Also, three insect-based PAPs (Cricket, Silkworm, Flour Moth) were considered in this study to evaluate the differences in terms of the nutrients present in this type of feed. Ionic chromatography (IC) was used to reveal the concentrations of NO 3 - , NO 2 , Cl - , and SO 4 2- , and inductively coupled plasma optical emission spectroscopy (ICP-OES) to detect Al, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Ni, P, Si, Sr, Ti, and Zn. The application of multivariate chemometric techniques to the experimental results allowed us to determine the identification capability of the inorganic composition to identify correlations among the variables and to reveal similarities and differences among the different species. The results show the possibility of using this component for discriminating between different PAPS; in particular, fish PAPs are high in Cd, Sr, Na, and Mg content; swine PAPs have lower metal content due to high fat; feathers and vegetal feed have similar Al, Si, and Ni, but feathers are higher in Fe and Zn; and insect PATs have nutrient levels comparable to PAPs of other origins but are very high in Zn, Cu, and K.

The chemical composition of the soluble fraction of atmospheric particulate matter (PM) and how these components can combine with each other to form different species affect the chemistry of the aqueous phase dispersed in the atmosphere: raindrops, clouds, fog, and ice particles. The study was focused on the analysis of the soluble fraction of Arctic PM 10 samples collected at Ny-Ålesund (Svalbard Islands, Norwegian Arctic) during the year 2012. The concentration values of Na + , K + , NH 4 + , Ca 2+ , Mg 2+ , Mn 2+ , Cu 2+ , Zn 2+ , Fe 3+ , Al 3+ , Cl - , NO 2 - , NO 3 - , SO 4 2- , PO 4 3- , formate, acetate, malonate, and oxalate in the water-soluble fraction of PM 10 were determined by atomic spectroscopy and ion chromatography. Speciation models were applied to define the major species that would occur in aqueous solution as a function of pH (2-10). The model highlights that (i) the main cations such as Na + , K + , Mg 2+ , and Ca 2+ occur in the form of aquoions in the whole investigated pH range; (ii) Cu 2+ , Zn 2+ , and, in particular, Fe 3+ and Al 3+ are mostly present in their hydrolytic forms; and (iii) Al 3+ , Fe 3+ , and Cu 2+ form solid hydrolytic species that precipitate at pH values slightly higher than neutrality. These latter metals show interesting interactions with oxalate and sulfate ions, too. The speciation models were also calculated considering the seasonal variability of the concentration of the components and at higher concentration levels than those found in water PM extracts, to better simulate concentrations actually found in the atmospheric aqueous phase. The results highlight the role of oxalate as the main organic ligand in solution., (© 2024. The Author(s).)

Urban textures of the Italian cities are peculiarly shaped by the local geography generating similarities among cities placed in different regions but comparable topographical districts. This suggested the following scientific question: can different topographies generate significant differences on the PM 10 chemical composition at Italian urban sites that share similar geography despite being in different regions? To investigate whether such communalities can be found and are applicable at Country-scale, we propose here a novel methodological approach. A dataset comprising season-averages of PM 10 mass concentration and chemical composition data was built, covering the decade 2005-2016 and referring to urban sites only (21 cities). Statistical analyses, estimation of missing data, identification of latent clusters and source apportionment modeling by Positive Matrix Factorization (PMF) were performed on this unique dataset. The first original result is the demonstration that a dataset with atypical time resolution can be successfully exploited as an input matrix for PMF obtaining Country-scale representative chemical profiles, whose physical consistency has been assessed by different tests of modeling performance. Secondly, this dataset can be considered a reference repository of season averages of chemical species over the Italian territory and the chemical profiles obtained by PMF for urban Italian agglomerations could contribute to emission repositories. These findings indicate that our approach is powerful, and it could be further employed with datasets typically available in the air pollution monitoring networks., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Iron, a crucial element in our environment, plays a vital role in numerous natural processes. Understanding the presence and concentration of iron in the environment is very important as it impacts various aspects of our planet's health. The on-site detection and speciation of iron are significant for several reasons. In this context, the present work aims to evaluate the applicability of voltammetry for the on-site determination of iron and its possible speciation using a portable voltammetric analyzer. Voltammetry offers the advantage of convenience and cost-effectiveness. For iron (III) determination, the modification of a glassy carbon electrode (GCE) with an antimony-bismuth film (SbBiFE) using the acetate buffer (pH = 4) as a supporting electrolyte was used. The technique adopted was Square Wave Adsoptive Cathodic Stripping Voltammetry (SW-AdCSV), and we used 1-(2-piridylazo)-2-naphthol (PAN) as the iron (III) ligand. Linearity, repeatability, detection limit, and accuracy were determined using synthetic solutions; then, a Standard Reference Material (SRM) of 1643f Trace Elements in Water (iron content: 93.44 ± 0.78 µg L -1 ) was used for validation measurements in the real matrix. the accuracy of this technique was found to be excellent since we obtained a recovery of 103.16%. The procedure was finally applied to real samples (tap, lake, and seawater), and the results obtained were compared via Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES). The amount of iron found was 207.8 ± 6.6 µg L -1 for tap water using voltammetry and 200.9 ± 1.5 µg L -1 with ICP-OES. For lake water, 171.7 ± 3.8 µg L -1 , 169.8 ± 4.1 µg L -1 , and 187.5 ± 5.7 µg L -1 were found using voltammetry in the lab both on-site and using ICP-OES, respectively. The results obtained demonstrate the excellent applicability of the proposed on-site voltammetric procedure for the determination of iron and its speciation in water.

The removal of four Contaminants of Emerging Concern, namely bisphenol A, sulfamethoxazole, diclofenac and benzotriazole; two odorous compounds, geosmin and 2-methylisoborneol, frequently detected in recirculating aquaculture systems; and Hg(II) was investigated using ZnO-based materials doped or co-doped with Ce and Cu under simulated solar radiation. Photocatalysts were synthetized via a hydrothermal route and their efficiency was assessed by changing some operational parameters in different water matrices of increasing complexity. The mixture of contaminants was successfully degraded in just 1 h, while the complete mineralization was achieved in a few hours; experiments performed in an actual aquaculture water confirmed the efficiency and broad versatility of the synthesized materials.

The determination of the authenticity of extra virgin olive oils (EVOOs) has become more interesting in recent years. Italy is the first country in Europe in terms of number of Protected Designation of Origin (PDO) oils, which connects consumers to a feeling of tradition and thus to higher quality standards. This work focused on the consideration of the inorganic content as a possible marker of EVOOs. Ten vegetable oils (VOs), eight Italian EVOOs and seven not Italian EVOOs were analyzed. After pretreatment by acid mineralization, Al, Ba, Ca, Cu, Fe, K, Li, Mg, Mn, Na, P, Sb, Se and Zn were determined by ICP-OES. The electrochemical properties of a selected group of EVOOs and other vegetal oils of different botanical origin were investigated by voltammetry. Carbon paste electrodes (CPEs) were prepared. The features observed in the voltammograms reflect the reactions of electroactive compounds, which are present in the oils. A chemometric treatment of the results was performed to assess the possibility to distinguish (i) the region of provenience considering the inorganic profile; and (ii) the plant species from which each oil was obtained on the basis of the current profile registered during voltammetric analysis. Inorganic composition seems to be a useful marker for the assessment of the geographical origin of an EVOO. The EVOO-CPEs voltammetry seems to have a good ability to distinguish the plant species of origin. This method could be useful to monitor the conservation status of the oils, as the redox profile is linked to the oxidative degradation state.

Lead (Pb) concentration and Pb isotope ratios have been determined in 109 snow pit samples collected at Dome C, on the East Antarctic Plateau, corresponding to the period 1971-2017. The Pb concentration was 8.2 ± 1.0 pg g -1 (mean ± 95%-confidence interval), with a decreasing trend from the early 1990s (the median Pb concentration halved from 9.0 pg g -1 in 1970-1980 to 4.4 pg g -1 in 2010-2017). The 206 Pb/ 207 Pb and 208 Pb/ 207 Pb ratios were 2.419 ± 0.003 and 1.158 ± 0.003 (mean and 95%-confidence interval), respectively. The temporal variations of Pb isotopic composition from 1970 to mid-1990s reflect the changes in the consumption of Pb-enriched gasoline in the Southern Hemisphere, whereas the subsequent increase of the Pb isotope ratios is ascribed to a shift toward the natural isotopic signature. Accordingly, the anthropogenic Pb contribution decreased from (61 ± 3)% in 1980-1990 to (49 ± 10)% in 2010-2017. The measured ratios suggest that Australia has been a significant source of anthropogenic Pb to Antarctica, even in recent times. Differences and similarities among Pb content and isotopic composition in various sites across Antarctica have been displayed by principal component analysis, indicating that the altitude and the distance from the coast significantly affect the Pb content, while the Pb isotopic signatures are not influenced by these parameters., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

It is shown here that ZVI-Fenton is a suitable technique to achieve effective degradation of ibuprofen and phenol under several operational conditions. Degradation of ibuprofen was possible in the pH interval 3-6 in both synthetic laboratory systems and actual wastewater (secondary treatment effluent), but operation at the higher pH values required higher H 2 O 2 concentration and/or higher ZVI loading. In the case of real wastewater we offset the lower degradation efficiency, caused by the occurrence of organic and inorganic interfering agents, by carrying out multiple H 2 O 2 additions. The studied wastewater sample had a buffer-capacity minimum at pH 4-5, and optimal treatment for ibuprofen degradation might take place at either pH 4 or 6. With a reagents cost in the order of 0.06-0.10 $ m -3 , the technique appears as very competitive and promising for tertiary wastewater treatment. There is a clear trade-off between savings in pH-fixing reagents and higher consumption of ZVI-Fenton reagents at the different pH values. The final choice in real application scenarios could be based on cost considerations (which favour pH 4) and/or the eventual fate of wastewater. For instance, wastewater reuse might place requirements on the salinity that is increased by the acidification/neutralization steps: in this case, operation at pH 6 is preferred. Interestingly, the ZVI-Fenton degradation of ibuprofen led to very low generation of toxic 4-isobutylacetophenone (IBAP, which is the ibuprofen by-product raising the highest concern), because of the combination of low formation yields and limited IBAP stability in the optimal reaction conditions. In addition to ibuprofen, phenol could be degraded as well by ZVI-Fenton. Interestingly, the ability of ZVI-Fenton to degrade both ibuprofen and phenol under similar conditions might open up the way to apply this technique to additional pollutants as well as to pollutant mixtures., (Copyright © 2019 Elsevier Inc. All rights reserved.)

The complete removal of biorecalcitrant xenobiotics, including most notably the pharmaceutical pollutants, by advanced oxidation processes is often difficult to be reached in urban or industrial wastewater because of the high concentration of organic and inorganic scavengers that compete with the xenobiotics for the oxidizing species. This work investigates a coupled treatment train in which wastewater effluents are pretreated with a negatively charged loose nanofiltration (NF) membrane (HydraCoRe70, made up of sulfonated polyethersulfone) to enhance the removal of xenobiotics with the thermal Fenton process. Carbamazepine (CBZ), a drug prescribed mainly for epilepsy treatment, is used here as a model xenobiotic. After optimizing the conditions for separation and degradation, the NF-Fenton approach was applied to both synthetic wastewater and real samples to assess the overall efficiency of CBZ removal. The Fenton degradation of CBZ was drastically enhanced in nanofiltered samples, thanks to the removal by the membrane of nearly all organic matter that would otherwise consume the reactive oxidizing species (e.g., the hydroxyl radical). On the basis of a preliminary treatment cost analysis, it can be concluded that the combined process is potentially applicable to the treatment of several kinds of wastewaters (e.g., industrial ones) to favor the removal of biorecalcitrant contaminants. Key cost savings of NF-Fenton concern the lower amounts of Fenton reagents needed to degrade CBZ and (even more importantly) the decreased levels of acids and bases for pH adjustment before and after the oxidative process because of the lower buffer capacity of the NF permeate compared to feed wastewater, after the removal by the NF of many inorganic ions and most organic carbon., Competing Interests: The authors declare no competing financial interest.

We have undertaken a randomized trial to confirm the ability of a class of phenolics, flavonoids, to increase urinary anti-mutagenicity in smokers. Ninety heavy smokers were recruited and randomly assigned to three groups, who were given three different diets. One diet was rich in flavonoids, but not based on supplementation ('flavonoid'), one was a normal iso-caloric diet with an adequate administration of fruit and vegetables ('normal'), and one was based on supplementation of flavonoids in the form of green tea and soy products ('supplement'). The urinary anti-mutagenicity-as inhibiting effect of the urinary extracts on the mutations induced by MeIQx-was measured in Salmonella typhimurium YG1024 in the presence of liver S9 from male Sprague-Dawley rats treated with Aroclor 1254. The amount of total phenolics in the urinary extracts was measured by use of spectrometric analysis. We found that important dietary modifications can be achieved through special recipes and instructions given by a cook during an intensive course. The intervention was focused on increasing the flavonoid intake, and it was successful in that respect. In fact, differences in flavonoid intake were appreciated mainly between the first group (normal diet) and the other two (flavonoid-rich and supplemented diet), suggesting that dietary modification can be as effective as supplementation. However, both urinary anti-mutagenicity and the amounts of urinary phenolics did not change as a consequence of the trial. These results suggest that only a small fraction of urinary phenolics is influenced by dietary changes in the intake of flavonoids, and that most urinary anti-mutagens and phenolics are metabolites of dietary flavonoids, whose formation is more affected by the activity and diversity of bacterial flora in the colon than by the quantity and type of intake. A strong correlation was found between urinary phenolics and anti-mutagenicity in all the groups involved in the trial. Such correlation was not explained by dietary variables.