Next Article in Journal
Investigation of the Electrochemical Behavior of CuO-NiO-Co3O4 Nanocomposites for Enhanced Supercapacitor Applications
Previous Article in Journal
Low-Cycle Fatigue Properties of Bimetallic Steel Bar with Buckling: Energy-Based Numerical and Experimental Investigations
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Materials
Volume 17
Issue 16
10.3390/ma17163975
materials-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Review

Perspectives for Photocatalytic Decomposition of Environmental Pollutants on Photoactive Particles of Soil Minerals

by
Agnieszka Sosnowska
1,
Kinga I. Hęclik
2,
Joanna B. Kisała
2,
Monika Celuch
3 and
Dariusz Pogocki
4,*
1
Department of Landscape Architecture, Institute of Environmental Engineering, Warsaw University of Life Sciences—SGGW, Nowoursynowska 166, 02-787 Warsaw, Poland
2
Institute of Biology, College of Natural Sciences, University of Rzeszow, Rejtana 16C, 35-959 Rzeszow, Poland
3
Łukasiewicz Research Network—Warsaw Institute of Technology, Duchnicka 3, 01-796 Warsaw, Poland
4
Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warsaw, Poland
*
Author to whom correspondence should be addressed.
Materials 2024, 17(16), 3975; https://doi.org/10.3390/ma17163975 (registering DOI)
Submission received: 3 July 2024 / Revised: 5 August 2024 / Accepted: 7 August 2024 / Published: 9 August 2024
(This article belongs to the Section Catalytic Materials)
Versions Notes

Abstract

:
The literature shows that both in laboratory and in industrial conditions, the photocatalytic oxidation method copes quite well with degradation of most environmental toxins and pathogenic microorganisms. However, the effective utilization of photocatalytic processes for environmental decontamination and disinfection requires significant technological advancement in both the area of semiconductor material synthesis and its application. Here, we focused on the presence and “photocatalytic capability” of photocatalysts among soil minerals and their potential contributions to the environmental decontamination in vitro and in vivo. Reactions caused by sunlight on the soil surface are involved in its normal redox activity, taking part also in the soil decontamination. However, their importance for decontamination in vivo cannot be overstated, due to the diversity of soils on the Earth, which is caused by the environmental conditions, such as climate, parent material, relief, vegetation, etc. The sunlight-induced reactions are just a part of complicated soil chemistry processes dependent on a plethora of environmental determinates. The multiplicity of affecting factors, which we tried to sketch from the perspective of chemists and environmental scientists, makes us rather skeptical about the effectiveness of the photocatalytic decontamination in vivo. On the other hand, there is a huge potential of the soils as the alternative and probably cheaper source of useful photocatalytic materials of unique properties. In our opinion, establishing collaboration between experts from different disciplines is the most crucial opportunity, as well as a challenge, for the advancement of photocatalysis.

1. Introduction: The Basics of Photocatalysis and Strategies to Enhance Its Effectiveness

The subject of relationships between pollution and infectious disease has become a hot topic among scientists even prior to the recent COVID-19 pandemic years [1]. The pandemic itself has sparked a surge in interest in implementing measures to eliminate toxins, viruses and other pathogens from the environment. Since the advent of the photocatalysis, the method has been proposed for “self-cleaning” solutions, maintenance of clean surfaces, and depolluting applications allowing the removal of inorganic and organic pollutants present in heavily polluted environments. The decomposition and destruction of pollutants are caused by processes involving highly reactive oxidative species (ROS) generated on the surface of semiconductors when exposed to light [2,3,4,5,6,7,8,9].
For the record, the semiconductors are characterized by a filled valence band (VB) and an empty conduction band (CB) [10,11]. Thus, upon light illumination by photons of energy higher than the band gap (EBG) [12], electrons are excited and promoted into CB ( e CB − ), leaving holes ( h VB + ) in VB. The photo-generated e CB − - h VB + pairs will then migrate to the surface of photocatalyst, where, in contact with the aqueous environment and oxygen, they produce ROS [3,13]. (A less topic-oriented reader can easily find details and in-depth knowledge on semiconductors and photocatalysis in many basic books and articles, of which we will mention only a few [3,4,8,10,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31]. The basic issues related to environmental pollution and related chemistry problems can be found in many textbooks and monographs [32,33,34,35]).
It is necessary to highlight here that four essential elements for photocatalytic oxidation should be present: (i) a photocatalyst, stable under given pH and temperature conditions; (ii) sunlight; (iii) atmospheric oxygen; and (iv) humidity. The sufficiently small EBG of the photocatalyst allows the absorption of natural sunlight, whereas atmospheric oxygen and humidity allow the formation and transport of ROS out of the photocatalyst surface.
The most common photocatalysts are represented by metal oxides or sulphides such as TiO2, ZnO, ZnS, Fe2O3, and SnO2 or less frequently used but intensively tested Fe3O4, MoS2, and CdS [25,36,37,38,39,40,41,42]. The photocatalysts are natural or synthesized in laboratory conditions on a technical scale [43,44,45].
A plethora of experimental and theoretical works conducted over the last twenty years or so demonstrate the effort put into improving the efficiency of photocatalysts. The effort to obtain desired changes in the characteristics of photocatalysis usually goes in two directions: (i) utilization of a broader light absorption spectrum for enhanced quantum yield of ROS and (ii) an increase in the reducing properties of e CB − , with the goal of being able to reduce water to molecular hydrogen.
It is worth emphasizing that the manipulation of the dimensions and shape of a semiconductor particle allows change in the photocatalysts’ characteristics [10,46,47,48,49]. Another popular and quite effective way to “tune” EBG, the Fermi level (i.e., the reduction potentials of e CB − and h VB + ), the molar absorption coefficient (ε), and other characteristics of the material is by the engineering that introduces dopants and other defects (physical, including porosity, twin boundaries, and cracks, and chemical, including vacancies and interstitials) into the structure of the semiconductor [50,51,52,53,54,55,56,57,58,59]. Thus, under certain conditions, even high dielectric constant oxides like ZrO2 can be utilized to build binary oxide photocatalysts [60,61,62,63,64].
Due to the material engineering such as the incorporation of various “impurity” elements and crystal lattice defects, microstrains, and dislocations, with size and shape control, the materials could possess “the visible-light-driven photocatalytic activity” (VLD) [53,65,66,67,68,69]. (However, extended defects can provoke the recombination of e CB − - h VB + pairs, which causes reduced yield of ROS generation [22,52]).
The particles of naturally occurring minerals have unique chemical compositions that contain a main component and many other trace amounts of elements. They are formed through complex biogeochemical processes that are hardly understood and, despite many attempts, are very difficult to imitate in the laboratory conditions [70,71,72,73,74,75].
This directs interest to natural photoactive minerals, with their possible sources related to shallow deposits in the Earth’s crust and in the soil. Our focus was on the minerals found in the outer layers of the Earth’s crust and their potential contributions to the environmental decontamination in vitro and in vivo. We tried to explore these issues from the perspectives of chemists and environmental scientists, especially because we have not found attempts in the literature to describe the soil as a medium in which photocatalytic decontamination may occur.

2. Photoactalytic Activity of Earth’s Lithosphere Minerals: Natural Semiconductors Present in the Crust and Their Capabilities to Initiate Redox Reactions

Semiconducting minerals are ubiquitous on Earth, most of which are common mineral phases located near the Earth’s surface: oxides (e.g., rutile, limonite, hematite, and goethite) and sulphides (e.g., sphalerite, greenockite, and pyrite) [76]. Xu and Schoonen have reviewed about fifty kinds of semiconducting metal oxides and sulphide minerals, as shown in Table 1 [26].
The data gathered above (Table 1) can be discussed in a very simplified and condensed way: Minerals of EBG ≤ ca. 3.3 eV (380 nm) possess VLD. The oxide minerals are strong photo-oxidation catalysts in aqueous solutions but are limited in their reducing power. The majority of metal oxide semiconductors have valence band edges (EVB) in the range 1 to 3 V above the reduction potential of H 2 O (relative to the electrochemical SHE scale [77,78]), and energies for conduction band edges (ECB) are close to or less negative than the reduction potential of H 2 O . More specifically, the electron generated in CB can reduce the substance if ECB is more negative than the reduction potential of the substance (reactant) (Er) (i.e., ECB < Er). Similarly, the h VB + generated in the valence band can oxidize a substance if its reduction potential is lower than the EVB of the semiconductor (i.e., EVB > Er). One should note that none of the minerals (which are presented in Table 1), upon the light exposure, can promote electrons to CB, generating e CB − , which is able to reduce H2O and become the hydrated electron ( e aq − ) of reduction potential E aq / e aq • − ⊖ equal to −2.87 V [81]. Such electrons cannot escape into and migrate throughout the solution; thus, its reactions are limited to the immediate vicinity of the surface (see discussion in [82]). It should be noted that if ECB < 0 V, e CB − can reduce the H3O+ cation to molecular hydrogen (H2) since the reduction potential of SHE ( E H + + / H 2 ⊖ ) is by definition equal to 0 V [77,78]. On the other hand, in the majority of minerals in Table 1, the light-induced promotion of electrons to CB creates h VB + with EVB higher than E OH / OH − • ⊖ = 1.9 V [81], allowing oxidation of an -OH anion to an •OH radical. As one can see, for a much smaller number of minerals, h VB + has a reduction potential higher than E OH , H + • / H 2 O ⊖ = 2.73 V [81], allowing oxidation of H2O in a neutral or acidic solution. Please note that non-transition metal sulphides generally have both ECB and EVB of higher energies than metal oxides; therefore, h VB + here are less oxidizing, but e CB − are rarely reducing, while most transition metal sulphides are characterized by small EBG (<1 eV, ca. 1340 nm) with both the oxidizing power h VB + and the reducing power of e CB − lower than those of non-transition metal sulphides.
Additionally, one has to bear in mind that both ECB and EVB are pH-dependent since the ion balance on the mineral’s surface is affected by the pH. Thus, the oxidizing power of h VB + and the reducing power of e CB − will also depend on the pH. For semiconducting metal oxides, the ECB and EVB vary with pH, following the Nernstian relation (1) [26,83]
E CB ( orVB ) = E CB ( orVB ) ⊖ + 2.303 R T F × ( pH zpc − pH ) ,
where E CB ( orVB ) ⊖ is the potential at the pH of the zero point of charge (pHzpc), and the net adsorbed charge within the Helmholtz double layer [80] is zero. Thus, the pH has to be taken into account since its increase not only results in a lower concentration of H+, which is the major electron scavenger, but also shifts the ECB of minerals toward more negative values.

3. The Indicators of Soil Redox Activity: Redox Activity of Soil

Oxidation and reduction reactions occur instantly in soils. Soil redox abilities depend on the properties and concentration of substances contained in the so-called “soil solution”.
The indicators of soil redox activity: A straightforward indicator characterizing the oxidation and reduction ratios in soil is its reduction potential Eh, which can be calculated based on redox half-reactions with the Equation (2) [83,84,85,86]:
E h = E h ⊖ + 2.303 R T n F ( log { Ox } { Red } + m × pH ) ,
where E h ⊖ [V vs. SHE] is the reduction potential under standard conditions (all activities = 1, P H 2 = 1 atm (101,325 Pa), {H+} = 1 M), R is the universal gas constant [J mol−1 K−1], T is the temperature [K], m is the number of exchanged protons, n is the number of exchanged electrons, F is the Faraday constant [C mol−1], and {Ox}/{Red} is the ratio of the activities of oxidized to reduced species.
In addition to Eh, in the “soil chemistry”, the reader may encounter two more indicators of soil redox activity, which are less known to general chemists, i.e., rH and pe. The redox potential of soil solutions depends on the degree of saturation with molecular hydrogen (H2) and the pH of the environment. The higher H2 concentration causes the greater reduction capacity of the solution and vice versa. The rH indicator is a negative logarithm of the hydrogen pressure in the soil–“soil solution” system, which demonstrates the relationship between redox and soil pH [87].
r H ≃ E h 30 + 2 pH ,
Because many redox-active elements (mainly metals) are involved in soil redox processes, pE (or pe) equal to −log{activity of electron} (Equation (4)) seems to be a more universal redox indicator [71,76,86,88].
pE = logK − pH,
where K = { Red } / ( { Ox } × { e − } n × { H 3 O + } m ) .
Redox activity of soil: In all systems, Eh, rH, and pE are governed by the pH and the activities of oxidized {Ox} and reduced species {Red}. (For example, Eh higher than 200 mV is usually associated with the dominance of electron acceptors in the soil, e.g., O2, NO3−, MnO2, and Fe2O3.) For complex systems such as soil, where the coverage of all components in the equations can be extremely complicated, the solution is to use the professional geochemical software [89,90].
Normal limits of pH in the environment are 4 and 9, and lower are found in acid sulfate soils, while the upper end of the pH limits is associated with water in contact with carbonate rocks. Whereas the theoretical limits of Eh are determined by water instability and the release of gases, O2 upon oxidation, and H2 upon reduction. The upper limit of Eh is defined by the oxidation of H2O ( 2 H 2 O ⇌ O 2 + 4 H + + 4 e − , E ⊖ = 1.23 V), whereas its lower limit is defined by the reduction in H+ ( H 2 ⇌ 2 H + + 2 e − , E ⊖ = 0.00 V). The potentials of the above half-reaction depend on the pH and follow the Nernstian equations. (Importantly, major photoactive minerals (see above) remain stable in these pH and Eh ranges [71,84,86,91].)
From an agricultural point of view, Eh values within 200–750 mV are beneficial for normal plant development. The Eh value of 750 mV for soil is associated with full aerobiosis, at which there is already a violation of the correctness in plant nutrition, while Eh lower than 200 mV is associated with reducing processes harmful for plants. The potential Eh is mainly influenced by the soil moisture, pH, and microbiological reactions. Increasing soil moisture reduces the value of Eh, and drying has the opposite effect. Eh fluctuates depending on the hydrologic regimes [92] and the season. For instance, in the temperate climate zone (of middle latitudes 23.5° to 66.5° N/S of the equator), it is the lowest in spring and increases in summer and autumn [87].
It seems obvious that sunlight has its share of daily and seasonal fluctuations of Eh since the photochemical redox processes occur upon sunlight. Interestingly, even the effects of soil drying by sunlight are different from those by drying in the dark [71]. Although light will generally not penetrate the soil surface deeper than 2 mm, on light-exposed soil, this depth will be sufficient to create a redox interface, especially since upward diffusion may extend the effective depth of the sunlight. The redox balance in the soil is affected by exposure to sunlight. Numerous soil components are photoactive, and their chemistry will vary significantly in sunlight compared with darkness. They include Fe(III) species, polycarboxylates, humic acids, and MnO2. Probably the most prevalent reactions in soil are photoredox transformations of Fe(III) and associated organic ligands [93,94,95].
The balance of redox in soil changes under the influence of light in numerous, often competing processes. These may be reversible processes such as the Fe2+/Fe3+ redox transformations, as well as irreversible, after which reaction products such as CO2 leave the soil environment. Importantly, environmental toxins may also participate in photochemical processes, which may lead to their degradation. Examples include the degradation of aromatic and polyaromatic hydrocarbons, aryl ketones and dioxins caused by •OH radicals produced in the Haber–Weiss reaction [71,96], and photocatalytic nitrogen-oxide conversion in red soil [97,98].

4. Susceptibility of Organic Pollutants and Pathogenic Microorganisms to Oxidative- and Bio-Degradation: The Persistent Micro-Pollutants as a Main Challenge for AOPs

Here, we should emphasize that research on the decontamination of waters containing persistent organic pollutants has been the core of photocatalytic research for years (see, for example, a review [99]).
Thus, in addition to the research focused on antimicrobial nanomaterials to inhibit bacterial growth and destroy the cells, many photocatalytic disinfection studies have been performed involving bacteria, fungi, algae, and viruses [66,67,100,101,102,103,104,105,106,107,108,109,110,111,112,113,114,115,116]. On the other hand, in order to limit the spread of antibiotic-resistant bacterial strains, the photocatalytic degradation of antibiotics was also examined [117,118,119].
Numerous experimental and review papers have been published. Particularly worth recommending are the relatively recent reviews on the application of photocatalysis for toxicity reduction in real wastewaters [120] and the elimination of viruses and other pathogens from recreational waters, food packaging, hospital surfaces, etc. [121,122,123,124].
The recent reviews of Valeriani et al. [125,126] are particularly noteworthy. Both works were carried out according to a rigorous protocol of meta-analysis [127], demonstrating the most current trends in the antimicrobial effectiveness of innovative photocatalysts.
The persistent micro-pollutants as a main challenge for AOPs: With few exceptions, like perfluorinated and polyfluorinated substances (PFASs) [82,128], the ROS generation in photocatalysis very effectively induces oxidative decomposition of pollutants, which can even lead to their complete mineralization [8,15]. Therefore, one can hypothesize that the photocatalysis processes on the soil surface will take part in natural oxidative reduction processes occurring in soil [88] and as such may contribute to its decontamination. However, a complete mineralization (i.e., the formation of CO2, H2O, and NH3, exclusively) of the pollutant seems essential in many cases since degradation products have the potential to be as harmful or even more harmful toxins than the parent compounds.
The persistent micro-pollutants are frequently eliminated from the waste applying a multi-stage process where so-called advanced oxidation processes (AOPs) [2] are usually used prior to the biological stage to initially decompose the pollutants [129,130]. The micro-pollutant leftovers can appear incidentally even in the municipal waste, where the AOP pre-treatment may potentially worsen the situation due to the formation of novel toxins upon oxidation. For instance, this appears to be the case for phenylurea-derived compounds like herbicides such as Linuron, Diuron, and Metobromuron or the antimicrobial additive of personal care products such as Triclocarban [131,132,133,134,135,136,137,138,139]. The phenylurea herbicides’ production and use on beans, soybeans, tomatoes, tobacco, potatoes, flax, and sunflowers will result in their release to the environment through various waste streams. If released to the soil, the phenylurea herbicides will have moderate mobility. Volatilization of them should not be important; thus, the herbicides may be degraded on soil surfaces. Research shows that some wastewater bacteria are able to hydrolyze the urea bridge in phenylurea herbicides producing monochloroanilines and dichloroanilines [139,140,141,142]. The fate of these metabolites is not certain; however, they may slowly decompose, as well as bioaccumulate or bind to soil particles and undergo auto-oxidation [143]. This is of special importance since chloroanilines have been named “probable carcinogens” by the U.S. EPA due to their association with bladder cancer [27,28,29,144,145,146]. The environmental toxicity of Linuron and its metabolites had been partially eliminated with its replacement by Metobromuron. However, our laboratory study and computational predictions for both herbicides (Linuron and Metobromuron as well) foresees the formation of similar hazardous products upon the AOP treatment [134,147,148,149]. Among them are cyanates, e.g., isocyanatomethane (methyl isocyanate, MIC, CH3-N=C=O)—the toxin accused of causing nearly 3800 deaths in the Bhopal disaster [35,150,151]. Therefore, the suspicion that trace amounts of MIC could be formed during incomplete degradation of linuron-like pesticides ought to raise legitimate concerns.
Even when the situation is not particularly dramatic, peculiar products of the AOP reactions can avoid subsequent biodegradation. Moreover, such contamination may be significantly harmful or even destroy successive biological stages of waste decontamination [130,148,152].
It appears that the disinfection of wastewater is an easier process than the elimination of persistent organic pollutants. On the “molecular level” the processes of disinfection/hygienization of waste leads to decomposition of the natural, organic compounds, which are essential for pathogen survival and multiplication [153].
Individual molecules of proteins, lipids, sugars, and nucleic acids are relatively unstable and quite easily oxidized and hydrolyzed [154,155,156,157,158,159,160]. However, living cells are able to regenerate oxidative damage quite efficiently through enzymatic and non-enzymatic repair processes [161]. (It should be noted that this could lead to the selection of pathogens with greater resistance.) Therefore, one must keep in mind that the reduction in the pathogen population to a level corresponding to the requirements imposed by regulatory institutions (see [162]) will require an oxidation process of high intensity. It is unlikely that will be achievable in natural conditions because only a small portion of solar energy can be utilized in photocatalytic processes, which is evident from the comparison of EBG values, shown in Table 1, with the well-known spectrum of sunlight (see https://www.astm.org/g0173-03r20.html, accessed 1 July 2024).

5. Interference of Redox Processes by Soil Organic Matter: Impact of Humic Acids on the Effectiveness of Photocatalysis In Vivo and In Vitro

Soil organic matter (SOM) is one of the key elements of carbon circulation in nature [163,164]. SOM seems to be the most valuable part of the soil from an agricultural perspective but also for growth of natural vegetation cover [87,165]. It consists of mainly humified organic debris of plants and other organisms and labile organic compounds derived from exudates of soil microorganisms and plants’ roots. Numerous functions are performed by SOM in soil, starting from physical functions (the stabilization of soil structure, water retention, and thermal properties) [165,166,167,168,169]; through chemical functions (the retention of cations, buffering capacity and pH effects, chelation of metals, and interactions with xenobiotics); and ending with the biochemical functions such as a reservoir of metabolic energy, a source of macronutrients, ecosystem resilience [165,167], or even allelopathy [170]. Interestingly, the reducing environment of humic acids promotes the formation of metallic and oxide nanoparticles in both laboratory and natural conditions [75,171,172].
From the point of view of the environment decontamination, an interesting feature is the immobilization of inorganic substances as a result of the formation of complexes with inorganic cations. For example, humified organic matter and polyvalent metal cation complexes participate in the formation of micro-aggregates with clusters and silt particles, oxides, and aluminosilicates [166]. On the other hand, the immobilization of toxic-to-plants noble metals, by humic acids of peat, in the form of metal nanoparticles was observed [171,173] and confirmed in laboratory conditions [75,174,175,176]. Unfortunately, water-soluble humic acid (HA) compounds in the disinfection processes of drinking water and wastewater are considered as precursors of highly toxic, carcinogenic, and mutagenic disinfectant by-products [150,177]. The chemistry of the processes leading to the formation of toxic derivatives of HA has been previously extensively studied and described in the basic works on radical chemistry of aromatic compounds [178,179,180]. HAs are poly-aromatic compounds that have a variety of components including quinone, phenol, catechol, and sugar moieties [181,182], with significant antioxidant properties and the ability to scavenge free radicals [182,183,184,185,186,187,188,189,190,191,192,193,194,195,196,197,198,199,200,201].
The strong inhibitory effect of natural organic matter is also a major challenge for photocatalytic water purification. This organic matter can scavenge photogenerated h VB + , e CB − , and radicals and occlude ROS generation sites upon adsorption. Additionally, the quantum efficiency of photocatalysis can be reduced due to the absorption of light by organic compounds, when the light quantum has too low energy to cause dissociation of chemical bonds and its absorption causes the solution to only heat up [202]. The fact that humic acids scavenge ●OH radicals and its precursor h VB + , desired when photocatalysis is used for the degradation of humic acids, causes a decrease in the effectiveness of photocatalysis when its purpose is to degrade other pollutants [189]. A large contribution has been made to improve the quality of drinking water, thanks to the development of organic matter removal methods [203,204,205,206,207,208]. In this trend, works dedicated to increasing the photocatalysis’ efficiency counteracting the inhibitory effect of humic acids by decreasing the HA surface adsorption and mitigation of the e CB − - h VB + recombination were also created [209,210,211].

6. The Perspectives of Photocatalysis on Soils Minerals “In Vivo”: The Limits Set by Diversity of Soils and the Environmental Conditions on the Earth

Soil is a major component of the Earth’s geosystem and constitutes the outer layer of the lithosphere (the continental crust). Soil-forming factors include climate, relief, parent material (bedrock), organisms (plants, animals, fungi, and human being), and ground water; they all interact over time [212,213,214,215].
Soil consists of not only a solid phase (minerals and organic matter) but also a porous phase (gases and water). Usually, the solid phase consists of half of the soil, thus significantly affecting the physical and chemical properties.
The continental crust is characterized by a huge variability of minerals and rocks. Because they are a soil substratum, the elements derived from weathering form soil’s chemical composition. The elements found in the continental crust are divided into three groups depending on the average occurrence (Clarke number [215]). The first group consists of elements with a high Clarke number, which constitute the main mass of rocks and soils. This group includes O, Si, Al, Fe, Ca, Na, K, Mg, C, H, S, P, and Cl [216]. They determine the geochemical properties of the landscape, mainly the conditions for the migration of other elements [217]. The second group is low Clarke number elements. Their migration depends on the conditions created by the elements of the first group. The last group is rare elements, whose content in the continental crust is lower than 0.01%.
Iron as a first group element commonly occurs in the soil. The Fe content in the continental crust is between 4.1 and 5.1%, depending on whether its mass or weight share is calculated [214,218]. Iron oxides are considered to be chemical compounds with great potential in photocatalysis. Ti is similar (0.3–0.6%, second group) [219]. These two semiconductors are quite common in soils, especially containing Fe, so there is a possibility to use the topsoil in the process of photocatalysis [200,220,221].
In addition to a photocatalyst, which is stable under given pH value and temperature conditions, for oxidation to sunlight to occur, the following are also necessary: sunlight, atmospheric oxygen, and humidity. The soil surface is exposed to sunlight in the ca. 280 to 4000 nm range [222,223], so it has the ability to initiate solar energy conversion into chemical energy and therefore to control environmental pollution and decontamination [224,225].
Experimental research on the soils’ usage in the decontamination of pollutants has been carried out several times [97,200,226]. The obtained results are promising, but are there opportunities to use this phenomenon outside the laboratory? There is no clear answer to this question yet. Under natural conditions, soil, as a complex component affected by many soil-forming factors, is characterized by significant variation of physical and chemical properties and undergoes many transformations. There are a number of crucial issues that would need to be resolved for widespread photocatalytic soil usage in vivo.
The supply of solar energy and oxygen is limited to the topsoil. In most climate zones, radiation is largely absorbed by the vegetation. In woody and shrubby vegetation zones, only a small part of the radiation reaches the soil surface [227]. The Earth’s areas with sparse vegetation are a different situation; these are primarily the desert, semi-desert, and tundra zones. The supply of solar energy is much higher because of low soil shading [228,229]. In the polar climate (tundra zone), the radiation is limited with large seasonal variability, including polar nights [230]. In deserts and semi-deserts, the supply of energy is significant and is not disturbed by cloud cover. This is a consequence of low humidity and high atmospheric pressure. In these areas the soil cover is thin or not present at all. On the surface, there are different rocks and minerals (sands, clays, etc.). In the temperate climate zone, the soil surface is covered by vegetation almost all year long. Only agricultural areas before the plant growing season (usually from October until April) are not covered by vegetation. Another issue is the variability of the soil surface. Mostly, relief is not flat, so there is a variation in the supply of energy to the surface. In the Northern Hemisphere, the northern slopes are less exposed to the sunlight than the southern slopes. That affects the soil properties, such as the thickness, moisture, and nutrient content [231]. The solar radiation depends on the height of the sun above the horizon, which varies depending on the season. For example, the sun angle for Warsaw (42° N, Poland) difference between December and June is more than 45 degrees. (To obtain an overall, global picture of the solar energy supplied to the Earth’s surface, the reader can go to the handbook [222] and to the online interactive maps on the “World Bank. Global Solar Atlas” web page [230]).
The presence of Fe oxides in the soils is a fact, but their content varies both spatially and on a global scale, as in the soil profile [232,233,234]. Fe evolution in soils is controlled both by natural factors (rock weathering, pedogenic processes driven), causing Fe transformation and translocation within and from soil (eluviation illuviation and reduction oxidation processes) [235], and by human impacts (industry and agriculture) [236].
Assuming that the photocatalysis occurs only in the surface, the presence of free oxides in the topsoil (humus horizon) is negligible. Their greatest accumulation occurs in horizons, such as ferralic, nitic, or cambic, which occur deeper in soil profile [237]. Hence, soils in which Fe oxides are abundant are mainly tropical and subtropical soils, such as Ferralsols and Nitisols. In the humus horizon, the content of Fe oxides is lower due to accumulation by humus, which constitutes the sorption complex of the soil.
The diversity of soils on the Earth means that the environmental conditions, such as climate, parent material, relief, and vegetation, should be included in experiments of photocatalytic properties and deeply studied in the future. The potential of the soils is huge; they can be used as the basis of more sustainable alternatives, instead of synthetic materials for decontamination of the pollutants.

7. Challenges and Future Perspectives

Our work on the review has shown the need for cooperation and information exchange between researchers involved in the photocatalysis field and environmental scientists. Personally, we learned a lot from each other during our writing sessions. In fact, the initiative for this review came from chemists involved in photocatalysis research (DP and JK). It happened under the influence of events related to the COVID-19 pandemic: The media reports were full of information about the estimated lifespan of the virus on surfaces made of various materials and the urgent need for systematic sterilization. Our experience with photocatalysis on the particles of iron oxides [38,39,40] was telling us that the wet surface of rusty steel could be photocatalytically active, and the virus’ lifespan on such a surface should be shorter than on stainless steel. We thought that the top layers of reach in iron oxide red soils should have similar properties. Thus, for example, the contaminated red soil exposed to sunlight should “purify” itself, and sunlit wasteland would be decontaminated by systematic plowing. These naive ideas were quickly dispelled during our internal discussion.
Therefore, we believe that for scientists who want to further develop photocatalytic decontamination, the main challenges may not be technical problems but rather establishing cooperation between specialists in various fields. It is unfortunate that we often use terms that are not understandable to our potential scientific partners. Without describing and understanding the basic topics, it is difficult to seize the opportunities and implement any applications. We could recommend seeking possibilities to conduct joint research and utilize local sources of natural minerals. This should help overcome the limitations and challenges of using soil minerals as photocatalysts, such as soil composition variability and the potential environmental impacts of large-scale applications.

8. Summary and Conclusions

The upper layers of the lithosphere can be a good source of unique semi-conducting materials of natural photocatalytic properties. A combination of many factors is required for the photocatalysis process to be effective. In paragraphs 4 to 6 of this work, we tried to show a realistic assessment of the conditions for effective photocatalytic decontamination in vivo and in vitro. Particular requirements such as adequate, intensive, and long-lasting sunlight; the presence of specific minerals; and moderate humidity of the soil solution mean that under natural conditions, photocatalytic processes cannot be fully effective. It cannot be ruled out that decontamination of desert and semi-desert soils can be partly attributed to photocatalysis, which can lead to the mineralization of organic matter. One can put forward the thesis that the probability that in this way, nature, without the support of technology, will cope with the pesticide residues or pathogenic microorganisms is very small. In practice, these processes call for highly advanced technical solutions. In rare circumstances, effective photocatalysis can occur spontaneously without human intervention. A forward-looking idea seems to be usage of natural photoactive minerals in new and existing technologies utilizing the photocatalytic process. The applications that are cited in [121], such as building materials using cement-based products, ceramic tiles, bituminous membranes, etc., can be good examples.
It appears that there are no negative prospects for photocatalysis development. There are also economic aspects behind the use of natural minerals: for many years to come the lower photocatalytic efficiency of natural semiconductors will be offset by their lower price.

Author Contributions

Conceptualization, D.P. and A.S.; writing—original draft preparation, D.P., A.S., J.B.K., K.I.H. and M.C.; writing—review and editing, D.P.; supervision, D.P. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Conflicts of Interest

The authors declare no conflict of interest.

Abbreviations

AllelopathyChemically mediated competition between plants
AOPsAdvanced oxidation processes
AVSAbsolute vacuum scale
CBConduction band
EBGBand-gap energy
ECBEnergy of conduction band
E Ox / Red ⊖ Standard reduction potential of the Ox/Red pair
ErReduction potential of reactant
EVBEnergy of valence band
MICisocyanatomethane (methyl isocyanate, CH3-N=C=O, CAS No. 624-83-9)
NOMNatural organic matter
PFOSsPerfluorinated organic surfactants
pHzpcThe net adsorbed charge within the Helmholtz double layer
POPsPersistent organic pollutants
SHEStandard hydrogen electrode
SRPStandard reduction potential
VBValence band

References

  1. Erickson, B.E. Linking Pollution and Infectious Disease. Chemicals and Pathogens Interact to Weaken the Immune System, Reduce Vaccine Efficacy, and Increase Pathogen Virulence. Chem. Eng. News 2019, 97, 11. [Google Scholar]
  2. Csay, T.; Homlok, R.; Ille, E.; Takas, E.; Wojnarovits, L. The Chemical Background of Advanced Oxidation Processes. Isr. J. Chem. 2014, 54, 233–241. [Google Scholar] [CrossRef]
  3. Nosaka, Y.; Nosaka, A.Y. Generation and Detection of Reactive Oxygen Species in Photocatalysis. Chem. Rev. 2017, 117, 11302–11336. [Google Scholar] [CrossRef] [PubMed]
  4. Hassaan, M.A.; El-Nemr, M.A.; Elkatory, M.R.; Ragab, S.; Niculescu, V.-C.; El Nemr, A. Principles of Photocatalysts and Their Different Applications: A Review. Top. Curr. Chem. 2023, 381, 31. [Google Scholar] [CrossRef]
  5. Yang, X.; Wang, D. Photocatalysis: From Fundamental Principles to Materials and Applications. ACS Appl. Energy Mater. 2018, 1, 6657–6693. [Google Scholar] [CrossRef]
  6. Nosaka, Y.; Nosaka, A. Introduction to Photocatalysis: From Basic Science to Applications; The Royal Society of Chemistry: London, UK, 2016; ISBN 978-1-78262-320-5. [Google Scholar]
  7. Schneider, J.; Matsuoka, M.; Takeuchi, M.; Zhang, J.; Horiuchi, Y.; Anpo, M.; Bahnemann, D.W. Understanding TiO2 Photocatalysis: Mechanisms and Materials. Chem. Rev. 2014, 114, 9919. [Google Scholar] [CrossRef] [PubMed]
  8. Kisch, H. Semiconductor Photocatalysis-Mechanistic and Synthetic Aspects. Angew. Chem. Int. Ed. 2013, 52, 812–847. [Google Scholar] [CrossRef] [PubMed]
  9. Hakki, A.; Schneider, J.; Bahnemann, D. Understanding the Chemistry of Photocatalytic Processes. In Photocatalysis: Fundamentals and Perspectives; Schneider, J., Bahnemann, D., Ye, J., Li Puma, G., Dionysiou, D.D., Schneider, J., Bahnemann, D., Ye, J., Li Puma, G., Dionysiou, D.D., Eds.; The Royal Society of Chemistry: London, UK, 2016; pp. 29–50. ISBN 978-1-78262-041-9. [Google Scholar]
  10. Pizzini, S. Physical Chemistry of Semiconductor Materials and Processes; Wiley: New York, NY, USA, 2015; ISBN 978-1-118-51457-3. [Google Scholar]
  11. Grosso, G.; Parravicini, G.P. Solid State Physics, 2nd ed.; Elsevier: Amsterdam, The Netherlands; Academic Press: Cambridge, MA, USA, 2014; ISBN 0-12-385030-4. [Google Scholar]
  12. Bredas, J.-L. Mind the Gap! Mater. Horiz. 2014, 1, 17–19. [Google Scholar] [CrossRef]
  13. Wardman, P. Factors Important in the Use of Fluorescent or Luminescent Probes and Other Chemical Reagents to Measure Oxidative and Radical Stress. Biomolecules 2023, 13, 1041. [Google Scholar] [CrossRef]
  14. Zhu, S.; Wang, D. Photocatalysis: Basic Principles, Diverse Forms of Implementations and Emerging Scientific Opportunities. Adv. Energy Mater. 2017, 7, 1700841. [Google Scholar] [CrossRef]
  15. Paz, Y. Specificity in Photocatalysis. In Photocatalysis: Fundamentals and Perspectives; The Royal Society of Chemistry: London, UK, 2016; pp. 80–109. ISBN 978-1-78262-041-9. [Google Scholar]
  16. Gamage, J.; Zhang, Z. Applications of Photocatalytic Disinfection. Int. J. Photoenergy 2010, 2010, 764870. [Google Scholar] [CrossRef]
  17. Lee, S.K.; Mills, A.; O’Rourke, C. Action Spectra in Semiconductor Photocatalysis. Chem. Soc. Rev. 2017, 46, 4877–4894. [Google Scholar] [CrossRef] [PubMed]
  18. Ohtani, B. Photocatalysis A to Z—What We Know and What We Do Not Know in a Scientific Sense. J. Photochem. Photobiol. C 2010, 11, 157–178. [Google Scholar] [CrossRef]
  19. Parrino, F.; Loddo, V.; Augugliaro, V.; Camera-Roda, G.; Palmisano, G.; Palmisano, L.; Yurdakal, S. Heterogeneous Photocatalysis: Guidelines on Experimental Setup, Catalyst Characterization, Interpretation, and Assessment of Reactivity. Catal. Rev. 2019, 61, 163–213. [Google Scholar] [CrossRef]
  20. Doni, E.; Girlanda, R. Electronic Energy Bands. In Electronic Structure and Electronic Transitions in Layered Materials; Grasso, V., Ed.; Springer: Dordrecht, The Netherlands, 1986; pp. 1–171. ISBN 978-94-009-4542-5. [Google Scholar]
  21. Serpone, N.; Emeline, A.V. Semiconductor Photocatalysis—Past, Present, and Future Outlook. J. Phys. Chem. Lett. 2012, 3, 673–677. [Google Scholar] [CrossRef] [PubMed]
  22. Bassani, F.; Parravicini, G.P.; Ballinger, R.A.; Birman, J.L. Electronic States and Optical Transitions in Solids. Phys. Today 1976, 29, 58–59. [Google Scholar] [CrossRef]
  23. Morrison, S.R. The Chemical Physics of Surfaces; eBook; Springer: New York, NY, USA, 2012; ISBN 978-1-4615-8007-2. [Google Scholar]
  24. Sidorova, T.; Danilyuk, A.L. Electron Tunneling to the Surface States at Photocatalysis. Mater. Phys. Mech. 2019, 41, 15–18. [Google Scholar] [CrossRef]
  25. Khan, M.M.; Adil, S.F.; Al-Mayouf, A. Metal Oxides as Photocatalysts. J. Saudi Chem. Soc. 2015, 19, 462–464. [Google Scholar] [CrossRef]
  26. Xu, Y.; Schoonen, M.A.A. The Absolute Energy Positions of Conduction and Valence Bands of Selected Semiconducting Minerals. Am. Mineral. 2000, 85, 543–556. [Google Scholar] [CrossRef]
  27. Mohamed, H.H.; Bahnemann, D.W. The Role of Electron Transfer in Photocatalysis: Fact and Fictions. Appl. Catal. B 2012, 128, 91–104. [Google Scholar] [CrossRef]
  28. Mills, A.; Le Hunte, S. An Overview of Semiconductor Photocatalysis. J. Photochem. Photobiol. A 1997, 108, 1–35. [Google Scholar] [CrossRef]
  29. Emeline, A.V.; Ryabchuk, V.K.; Serpone, N. Dogmas and Misconceptions in Heterogeneous Photocatalysis. Some Enlight. Reflect. J. Phys. Chem. B 2005, 109, 18515–18521. [Google Scholar] [CrossRef]
  30. Wu, Y.; Wark, M. New Concepts in Photocatalysis. In Photocatalysis: Fundamentals and Perspectives; Schneider, J., Bahnemann, D., Ye, J., Li Puma, G., Dionysiou, D.D., Schneider, J., Bahnemann, D., Ye, J., Li Puma, G., Dionysiou, D.D., Eds.; The Royal Society of Chemistry: London, UK, 2016; pp. 129–161. ISBN 978-1-78262-041-9. [Google Scholar]
  31. Antoniadou, M.; Balis, N.; Falaras, P. Novel Semiconductors for Energy Production via Electrochemical Processes. SVOA-MST 2020, 4, 76–79. [Google Scholar]
  32. Liu, D.H.F.; Liptak, B.G. Environmental Engineers’ Handbook, 2nd ed.; CRC Press: Boca Raton, FL, USA, 1998. [Google Scholar]
  33. Asmus, K.D. Pollution and Environmental Protection: Chemical Aspects and Related Considerations; Umweltverschmutzung Und Umweltschutz: Chemische Aspekte Und Hintergründe; Zanieczyszczenie i Ochrona Środowiska: Uwarunkowania Chemiczne i Środowiskowe; Wydawnictwo Naukowe Uniwersytetu im Adama Mickiewicza: Poznań, Poland, 2005. [Google Scholar]
  34. Manahan, S.E. Fundamentals of Environmental Chemistry, 11th ed.; CRC Press: Boca Raton, FL, USA, 2022; ISBN 978-1-00-309623-8. [Google Scholar]
  35. Dragović, N.; Vulević, T. Soil Degradation Processes, Causes, and Assessment Approaches. In Life on Land; Leal Filho, W., Azul, A.M., Brandli, L., Lange Salvia, A., Wall, T., Eds.; Springer International Publishing: Cham, Germany, 2020; pp. 1–12. ISBN 978-3-319-71065-5. [Google Scholar]
  36. Fujishima, A.; Rao, T.N.; Tryk, D.A. Titanium Dioxide Photocatalysis. J. Photoch. Photobiol. C 2000, 1, 1–21. [Google Scholar] [CrossRef]
  37. Zhang, S.; Ou, X.; Xiang, Q.; Carabineiro, S.A.C.; Fan, J.; Lv, K. Research Progress in Metal Sulfides for Photocatalysis: From Activity to Stability. Chemosphere 2022, 303, 135085. [Google Scholar] [CrossRef] [PubMed]
  38. Kisała, J.; Tomaszewska, A.; Pogocki, D. 4,4′-Isopropylidenebis(2,6-Dibromophenol) Photocatalytic Debromination on Nano- and Micro-Particles Fe3O4 Surface. J. Photocat. 2020, 1, 61–66. [Google Scholar] [CrossRef]
  39. Kisała, J.; Vasile, B.S.; Ficai, A.; Ficai, D.; Wojnarowska-Nowak, R.; Szreder, T. Reductive Photodegradation of 4,4′-Isopropylidenebis(2,6-Dibromophenol) on Fe3O4 Surface. Materials 2023, 16, 4380. [Google Scholar] [CrossRef] [PubMed]
  40. Kisała, J.; Tomaszewska, A.; Kolek, P. Non-Stoichiometric Magnetite as Catalyst for the Photocatalytic Degradation of Phenol and 2,6-Dibromo-4-Methylphenol—A New Approach in Water Treatment. Beilstein J. Nanotechnol. 2022, 13, 1531–1540. [Google Scholar] [CrossRef] [PubMed]
  41. Giannakis, S.; Liu, S.; Carratalà, A.; Rtimi, S.; Talebi Amiri, M.; Bensimon, M.; Pulgarin, C. Iron Oxide-Mediated Semiconductor Photocatalysis vs. Heterogeneous Photo-Fenton Treatment of Viruses in Wastewater. Impact of the Oxide Particle Size. J. Hazard. Mater. 2017, 339, 223–231. [Google Scholar] [CrossRef]
  42. Cao, Y.; Zhu, C.; Wang, T.T.; Jiang, D.; Ye, S. CdS-Based Photocatalysts for Solar Water Splitting. J. Photocat. 2021, 2, 201–222. [Google Scholar] [CrossRef]
  43. Li, Y.; Ding, C.; Liu, Y.; Li, Y.; Lu, A.; Wang, C.; Ding, H. Visible Light Photocatalysis of Natural Semiconducting Minerals. In Advances in Photocatalytic Disinfection; An, T., Zhao, H., Wong, P.K., Eds.; Springer: Berlin/Heidelberg, Germany, 2017; pp. 17–39. ISBN 978-3-662-53496-0. [Google Scholar]
  44. Xia, D.; Wang, W.; Wong, P.K. Visible-Light-Driven Photocatalytic Treatment by Environmental Minerals. In Advances in Photocatalytic Disinfection; An, T., Zhao, H., Wong, P.K., Eds.; Springer: Berlin/Heidelberg, Germany, 2017; pp. 41–61. ISBN 978-3-662-53496-0. [Google Scholar]
  45. Baig, N.; Kammakakam, I.; Falath, W. Nanomaterials: A Review of Synthesis Methods, Properties, Recent Progress, and Challenges. Mater. Adv. 2021, 2, 1821–1871. [Google Scholar] [CrossRef]
  46. Tahir, M.B.; Sohaib, M.; Sagir, M.; Rafique, M. Role of Nanotechnology in Photocatalysis. In Encyclopedia of Smart Materials; Olabi, A.-G., Ed.; Elsevier: Oxford, UK, 2022; pp. 578–589. ISBN 978-0-12-815733-6. [Google Scholar]
  47. Trindade, T.; O’Brien, P.; Pickett, N.L. Nanocrystalline Semiconductors:  Synthesis, Properties, and Perspectives. Chem. Mater. 2001, 13, 3843–3858. [Google Scholar] [CrossRef]
  48. Pileni, M.P. Semiconductor Nanocrystals. In Nanoscale Materials in Chemistry; John Wiley & Sons Ltd.: New York, NY, USA, 2001; pp. 61–84. ISBN 978-0-471-22062-6. [Google Scholar]
  49. Chanéac, C.; Jolivet, J.-P. Influence of Iron Oxide Structure and Size on Redox Reactivity. In Redox-Reactive Minerals: Properties, Reactions and Applications in Clean Technologies; Ahmed, I.A.M., Hudson-Edwards, K.A., Eds.; European Mineralogical Union: London, UK, 2017; Volume 17, pp. 5–27. ISBN 978-0-903056-57-1. [Google Scholar]
  50. Koenraad, P.M.; Flatté, M.E. Single Dopants in Semiconductors. Nat. Mater. 2011, 10, 91–100. [Google Scholar] [CrossRef]
  51. Kisała, J.; Hörner, G.; Barylyak, A.; Pogocki, D.; Bobitski, Y. Photocatalytic Degradation of 4,4′-Isopropylidenebis (2,6-Dibromophenol) on Sulfur-Doped Nano TiO2. Materials 2022, 15, 361. [Google Scholar] [CrossRef]
  52. McCluskey, M.D.; Haller, E.E. Dopants and Defects in Semiconductors, 2nd ed.; CRC Press: Boca Raton, FL, USA, 2021; ISBN 978-0-367-78143-9. [Google Scholar]
  53. Etacheri, V.; Di Valentin, C.; Schneider, J.; Bahnemann, D.; Pillai, S.C. Visible-Light Activation of TiO2 Photocatalysts: Advances in Theory and Experiments. J. Photochem. Photobiol. C Photochem. Rev. 2015, 25, 1–29. [Google Scholar] [CrossRef]
  54. Goclon, J.; Bankiewicz, B.; Pogocki, D.; Kolek, P.; Kisala, J.B.; Winkler, K. Structural Modification and Band Gap Engineering of Carbon Nano-Onions via Sulphur Doping: Theoretical DFT Study. Appl. Surf. Sci. 2023, 613, 156046. [Google Scholar] [CrossRef]
  55. McCluskey, M.D.; Janotti, A. Defects in Semiconductors. J. Appl. Phys. 2020, 127, 190401. [Google Scholar] [CrossRef]
  56. Zhu, G.; Yin, H.; Yang, C.; Cui, H.; Wang, Z.; Xu, J.; Lin, T.; Huang, F. Black Titania for Superior Photocatalytic Hydrogen Production and Photoelectrochemical Water Splitting. ChemCatChem 2015, 7, 2614–2619. [Google Scholar] [CrossRef]
  57. Wang, J.; Hasegawa, T.; Asakura, Y.; Yin, S. Recent Advances in Ternary Metal Oxides Modified by N Atom for Photocatalysis. Catalysts 2022, 12, 1568. [Google Scholar] [CrossRef]
  58. Guo, N.; Liu, H.; Fu, Y.; Hu, J. Preparation of Fe2O3 Nanoparticles Doped with In2O3 and Photocatalytic Degradation Property for Rhodamine B. Optik 2020, 201, 163537. [Google Scholar] [CrossRef]
  59. Chen, P.; Liu, H.; Cui, W.; Lee, S.C.; Wang, L.; Dong, F. Bi-Based Photocatalysts for Light-Driven Environmental and Energy Applications: Structural Tuning, Reaction Mechanisms, and Challenges. EcoMat 2020, 2, e12047. [Google Scholar] [CrossRef]
  60. Robertson, J. High Dielectric Constant Oxides. Eur. Phys. J. Appl. Phys. 2004, 28, 265–291. [Google Scholar] [CrossRef]
  61. Neppolian, B.; Wang, Q.; Yamashita, H.; Choi, H. Synthesis and Characterization of ZrO2–TiO2 Binary Oxide Semiconductor Nanoparticles: Application and Interparticle Electron Transfer Process. Appl. Catal. A-Gen. 2007, 333, 264–271. [Google Scholar] [CrossRef]
  62. He, H.; Liao, A.; Guo, W.; Luo, W.; Zhou, Y.; Zou, Z. State-of-the-Art Progress in the Use of Ternary Metal Oxides as Photoelectrode Materials for Water Splitting and Organic Synthesis. Nano Today 2019, 28, 100763. [Google Scholar] [CrossRef]
  63. Ibrahim, M.M. Photocatalytic Activity of Nanostructured ZnO–ZrO2 Binary Oxide Using Fluorometric Method. Spectrochim. Acta A Mol. Biomol. Spectrosc. 2015, 145, 487–492. [Google Scholar] [CrossRef]
  64. Siwińska-Ciesielczyk, K.; Świgoń, D.; Rychtowski, P.; Moszyński, D.; Zgoła-Grześkowiak, A.; Jesionowski, T. The Performance of Multicomponent Oxide Systems Based on TiO2, ZrO2 and SiO2 in the Photocatalytic Degradation of Rhodamine B: Mechanism and Kinetic Studies. Colloids Surf. A Physicochem. Eng. Asp. 2020, 586, 124272. [Google Scholar] [CrossRef]
  65. Zhang, C.; Li, Y.; Shuai, D.; Shen, Y.; Wang, D. Progress and Challenges in Photocatalytic Disinfection of Waterborne Viruses: A Review to Fill Current Knowledge Gaps. Chem. Eng. J. 2019, 355, 399–415. [Google Scholar] [CrossRef]
  66. Yang, Y.; Chen, H.; Lu, J. Inactivation of Algae by Visible-Light-Driven Modified Photocatalysts: A Review. Sci. Total Environ. 2023, 858, 159640. [Google Scholar] [CrossRef] [PubMed]
  67. Wang, D.; Chen, J.; Gao, X.; Ao, Y.; Wang, P. Maximizing the Utilization of Photo-Generated Electrons and Holes of g-C3N4 Photocatalyst for Harmful Algae Inactivation. Chem. Eng. J. 2022, 431, 134105. [Google Scholar] [CrossRef]
  68. Singh, M.; Goyal, M.; Devlal, K. Size and Shape Effects on the Band Gap of Semiconductor Compound Nanomaterials. J. Taibah Univ. Sci. 2018, 12, 470–475. [Google Scholar] [CrossRef]
  69. Singh, M.; Taele, B.; Goyal, M. Modeling of Size and Shape Dependent Band Gap, Dielectric Constant and Phonon Frequency of Semiconductor Nanosolids. Chin. J. Phys. 2021, 70, 26–36. [Google Scholar] [CrossRef]
  70. Matocha, C.J.; Scheckel, K.G.; Sparks, D.L. Kinetics and Mechanisms of Soil Biogeochemical Processes. In Chemical Processes in Soils; SSSA Book Series; The Soil Science Society of America, Inc.: Madison, WI, USA, 2005; pp. 309–342. ISBN 978-0-89118-892-6. [Google Scholar]
  71. Bartlett, R.J.; Ross, D.S. Chemistry of Redox Processes in Soils. In Chemical Processes in Soils; SSSA Book Series; The Soil Science Society of America, Inc.: Madison, WI, USA, 2005; pp. 461–487. ISBN 978-0-89118-892-6. [Google Scholar]
  72. Kaempf, N.; Scheinost, A.C.; Schulze, D.G. Oxide Minerals in Soils. In Handbook of Soil Sciences: Properties and Processes, Part III: Soil Mineralogy; Huang, P.M., Li, Y., Sumner, M.E., Eds.; CRC Press: Boca Raton, FL, USA, 2012; pp. 22-1–22-34. [Google Scholar]
  73. Kisała, J.; Pogocki, D. The Green-Synthesis of Nanoparticles-Promise of a New Civilizational Breakthrough. Nat. Prod. Ind. J. 2018, 12, 1–6. [Google Scholar]
  74. Kisała, J.; Hęclik, K.B.; Maslowska, A.; Celuch, M.; Pogocki, D. Natural Environments for Nanoparticles Synthesis of Metal, Metal Oxides, Core-Shell and Bimetallic Systems. Stud. Nat. Prod. Chem. 2017, 52, 18–84. [Google Scholar] [CrossRef]
  75. Hęclik, K.I.; Hęclik, K.; Zarzyka, I. Metal-Humus Acid Nanoparticles—Synthesis, Characterization and Molecular Modeling. Pol. J. Environ. Stud. 2021, 30, 3587–3599. [Google Scholar] [CrossRef]
  76. Chesworth, W. Encyclopedia of Soil Science, 1st ed.; Springer: Dordrecht, The Netherlands, 2007; ISBN 978-1-4020-3994-2. [Google Scholar]
  77. Trasatti, S. The Absolute Electrode Potential: An Explanatory Note (Recommendations 1986). Pure Appl. Chem. 1986, 58, 955–966. [Google Scholar] [CrossRef]
  78. Fletcher, S. Electrochemical Potentials from First Principles. J. Solid State Electrochem. 2020, 24, 3029–3038. [Google Scholar] [CrossRef]
  79. Helmholtz, H. Ueber Einige Gesetze Der Vertheilung Elektrischer Ströme in Körperlichen Leitern Mit Anwendung Auf Die Thierisch-Elektrischen Versuche [On Some Laws of the Distribution of Electrical Currents in Physical Conductors, with Application to Animal-Electrical Experiments]. Ann. Phys. 1853, 165, 211–233. [Google Scholar] [CrossRef]
  80. Sposito, G. On Points of Zero Charge. Environ. Sci. Technol. 1998, 32, 2815–2819. [Google Scholar] [CrossRef]
  81. Wardman, P. Reduction Potentials of One-Electron Couples Involving Free Radicals in Aqueous Solution. J. Phys. Chem. Ref. Data 1989, 18, 1637–1755. [Google Scholar] [CrossRef]
  82. Kisała, J.; Goclon, J.; Pogocki, D. Reductive Dehalogenation—Challenges of Perfluorinated Organics. J. Photocat. 2021, 2, 244–251. [Google Scholar] [CrossRef]
  83. Atkins, P.W.; de Paula, J. Physical Chemistry; NW. H. Freeman & Co.: New York, NY, USA, 2002; Volume 7. [Google Scholar]
  84. DeLaune, R.D.; Reddy, K.R. Redox Potential. In Encyclopedia of Soils in the Environment; Academic Press: Cambridge, MA, USA; Elsevier Inc.: Cambridge, MA, USA, 2004; Volume 4, pp. 366–371. ISBN 978-008054795-4. [Google Scholar]
  85. Patrick, W.; Gambrell, R.; Faulkner, S. Redox Measurements of Soils. Methods Soil Anal. Part 3 Chem. Methods 1996, 5, 1255–1273. [Google Scholar]
  86. Strawn, D.G.; Bohn, H.L.; O’Connor, G.A. Redox Reactions in Soils. In Soil Chemistry; John Wiley & Sons Ltd.: New York, NY, USA, 2020; pp. 119–149. ISBN 978-1-119-51525-8. [Google Scholar]
  87. Uggla, H. Gleboznawstwo Rolnicze [Agricultural Soil Science], 4th ed.; PWN: Warszawa, Poland, 1983; ISBN 83-1-03604-4. [Google Scholar]
  88. James, B.; Brose, D. Oxidation-Reduction Phenomena. In Handbook of Soil Sciences: Properties and Processes, Part III: Soil Mineralogy; Huang, P.M., Li, Y., Sumner, M.E., Eds.; CRC Press, Taylor & Francis Group: Boca Raton, FL, USA, 2012; pp. 14-1–14-13. ISBN 978-1-4398-0305-9. [Google Scholar]
  89. Allison, J.D.; Brown, D.S. MINTEQA2/PRODEFA2—A Geochemical Speciation Model and Interactive Preprocessor. In Chemical Equilibrium and Reaction Models; SSSA Special Publications; The Soil Science Society of America, Inc.: Madison, WI, USA, 1995; pp. 241–252. ISBN 978-0-89118-937-4. [Google Scholar]
  90. Gustafsson, J.P. Visual MINTEQ 4. Available online: https://vminteq.com/ (accessed on 1 July 2024).
  91. Krauskopf, K.B. Introduction to Geochemistry, 2nd ed.; McGraw-Hill: New York, NY, USA, 1979. [Google Scholar]
  92. Zhang, Z.; Furman, A. Soil Redox Dynamics under Dynamic Hydrologic Regimes—A Review. Sci. Total Environ. 2021, 763, 143026. [Google Scholar] [CrossRef] [PubMed]
  93. Faust, B.C.; Zepp, R.G. Photochemistry of Aqueous Iron (III) -Polycarboxylate Complexes: Roles in the Chemistry of Atmospheric and Surface Waters. Environ. Sci. Technol. 1993, 27, 2517–2522. [Google Scholar] [CrossRef]
  94. Chen, J.; Browne, W.R. Photochemistry of Iron Complexes. Coord. Chem. Rev. 2018, 374, 15–35. [Google Scholar] [CrossRef]
  95. Rabani, J.; Mamane, H.; Pousty, D.; Bolton, J.R. Practical Chemical Actinometry—A Review. Photochem. Photobiol. 2021, 97, 873–902. [Google Scholar] [CrossRef] [PubMed]
  96. Koppenol, W.H. A Resurrection of the Haber–Weiss Reaction. Nat. Commun. 2022, 13, 396. [Google Scholar] [CrossRef] [PubMed]
  97. Gan, Y.; Abdellatif, H.R.S.; Zhang, J.; Wan, Y.; Zeng, Q.; Chen, J.; Ni, J.; Zhang, Y.; E, S.; Ni, C. Photocatalytic Nitrogen-Oxide Conversion in Red Soil. J. Clean. Prod. 2021, 326, 129377. [Google Scholar] [CrossRef]
  98. Gan, J.; Zhu, Y.; Wilen, C.; Pittenger, D.; Crowley, D. Effect of Planting Covers on Herbicide Persistence in Landscape Soils. Environ. Sci. Technol. 2003, 37, 2775–2779. [Google Scholar] [CrossRef]
  99. Guan, S.-H.; Zhao, K.-F.; Tong, Q.; Rao, Q.-X.; Cheng, L.; Song, W.; Zhang, Q.-C.; Wang, X.-L.; Song, W.-G. A Review of Photocatalytic Materials Application on Nonylphenol Degradation. Environ. Chall. 2021, 4, 100172. [Google Scholar] [CrossRef]
  100. He, J.; Kumar, A.; Khan, M.; Lo, I.M.C. Critical Review of Photocatalytic Disinfection of Bacteria: From Noble Metals- and Carbon Nanomaterials-TiO(2) Composites to Challenges of Water Characteristics and Strategic Solutions. Sci. Total Environ. 2021, 758, 143953. [Google Scholar] [CrossRef]
  101. Puri, N.; Gupta, A. Water Remediation Using Titanium and Zinc Oxide Nanomaterials through Disinfection and Photo Catalysis Process: A Review. Environ. Res. 2023, 227, 115786. [Google Scholar] [CrossRef]
  102. Hoai, P.T.T.; Huong, N.T.M. Latest Avenues on Titanium Oxide-Based Nanomaterials to Mitigate the Pollutants and Antibacterial: Recent Insights, Challenges, and Future Perspectives. Chemosphere 2023, 324, 138372. [Google Scholar] [CrossRef]
  103. Birben, N.C.; Tomruk, A.; Bekbolet, M. The Role of Visible Light Active TiO(2) Specimens on the Solar Photocatalytic Disinfection of E. Coli. Environ. Sci. Pollut. Res. Int. 2017, 24, 12618–12627. [Google Scholar] [CrossRef]
  104. Zuarez-Chamba, M.; Rajendran, S.; Herrera-Robledo, M.; Priya, A.K.; Navas-Cárdenas, C. Bi-Based Photocatalysts for Bacterial Inactivation in Water: Inactivation Mechanisms, Challenges, and Strategies to Improve the Photocatalytic Activity. Environ. Res. 2022, 209, 112834. [Google Scholar] [CrossRef] [PubMed]
  105. Kumar, A.; Hasija, V.; Sudhaik, A.; Raizada, P.; Nguyen, V.-H.; Le, Q.V.; Singh, P.; Nguyen, D.C.; Thakur, S.; Hussain, C.M. The Practicality and Prospects for Disinfection Control by Photocatalysis during and Post-Pandemic: A Critical Review. Environ. Res. 2022, 209, 112814. [Google Scholar] [CrossRef]
  106. Choi, S.-Y.; Cho, B. Extermination of Influenza Virus H1N1 by a New Visible-Light-Induced Photocatalyst under Fluorescent Light. Virus Res. 2018, 248, 71–73. [Google Scholar] [CrossRef]
  107. Laxma Reddy, P.V.; Kavitha, B.; Kumar Reddy, P.A.; Kim, K.-H. TiO(2)-Based Photocatalytic Disinfection of Microbes in Aqueous Media: A Review. Environ. Res. 2017, 154, 296–303. [Google Scholar] [CrossRef]
  108. Nasir, A.M.; Awang, N.; Hubadillah, S.K.; Jaafar, J.; Othman, M.H.D.; Wan Salleh, W.N.; Ismail, A.F. A Review on the Potential of Photocatalysis in Combatting SARS-CoV-2 in Wastewater. J. Water Process Eng. 2021, 42, 102111. [Google Scholar] [CrossRef]
  109. Kumar, A.; Soni, V.; Singh, P.; Parwaz Khan, A.A.; Nazim, M.; Mohapatra, S.; Saini, V.; Raizada, P.; Hussain, C.M.; Shaban, M.; et al. Green Aspects of Photocatalysts during Corona Pandemic: A Promising Role for the Deactivation of COVID-19 Virus. RSC Adv. 2022, 12, 13609–13627. [Google Scholar] [CrossRef]
  110. Arun, J.; Nachiappan, S.; Rangarajan, G.; Alagappan, R.P.; Gopinath, K.P.; Lichtfouse, E. Synthesis and Application of Titanium Dioxide Photocatalysis for Energy, Decontamination and Viral Disinfection: A Review. Environ. Chem. Lett. 2023, 21, 339–362. [Google Scholar] [CrossRef]
  111. Bono, N.; Ponti, F.; Punta, C.; Candiani, G. Effect of UV Irradiation and TiO(2)-Photocatalysis on Airborne Bacteria and Viruses: An Overview. Materials 2021, 14, 1075. [Google Scholar] [CrossRef] [PubMed]
  112. Zheng, X.; Shen, Z.-P.; Cheng, C.; Shi, L.; Cheng, R.; Yuan, D.-H. Photocatalytic Disinfection Performance in Virus and Virus/Bacteria System by Cu-TiO(2) Nanofibers under Visible Light. Environ. Pollut. 2018, 237, 452–459. [Google Scholar] [CrossRef]
  113. Porcu, S.; Maloccu, S.; Corona, A.; Hazra, M.; David, T.C.; Chiriu, D.; Carbonaro, C.M.; Tramontano, E.; Ricci, P.C. Visible Light-Mediated Inactivation of H1N1 Virus Using Polymer-Based Heterojunction Photocatalyst. Polymers 2023, 15, 2536. [Google Scholar] [CrossRef]
  114. Zhou, Z.; Li, B.; Liu, X.; Li, Z.; Zhu, S.; Liang, Y.; Cui, Z.; Wu, S. Recent Progress in Photocatalytic Antibacterial. ACS Appl. Bio. Mater. 2021, 4, 3909–3936. [Google Scholar] [CrossRef] [PubMed]
  115. Poormohammadi, A.; Bashirian, S.; Rahmani, A.R.; Azarian, G.; Mehri, F. Are Photocatalytic Processes Effective for Removal of Airborne Viruses from Indoor Air? A Narrative Review. Environ. Sci. Pollut. Res. Int. 2021, 28, 43007–43020. [Google Scholar] [CrossRef]
  116. Valeriani, F.; Carraturo, F.; Lofrano, G.; Volpini, V.; Izzo, M.G.; Bruno, A.; Guida, M.; Romano Spica, V. Algae in Recreational Waters: An Overview within a One Health Perspective. Water 2024, 16, 946. [Google Scholar] [CrossRef]
  117. Zheng, X.; Xu, S.; Wang, Y.; Sun, X.; Gao, Y.; Gao, B. Enhanced Degradation of Ciprofloxacin by Graphitized Mesoporous Carbon (GMC)-TiO(2) Nanocomposite: Strong Synergy of Adsorption-Photocatalysis and Antibiotics Degradation Mechanism. J. Colloid. Interface Sci. 2018, 527, 202–213. [Google Scholar] [CrossRef] [PubMed]
  118. Ashraf, A.; Liu, G.; Yousaf, B.; Arif, M.; Ahmed, R.; Irshad, S.; Cheema, A.I.; Rashid, A.; Gulzaman, H. Recent Trends in Advanced Oxidation Process-Based Degradation of Erythromycin: Pollution Status, Eco-Toxicity and Degradation Mechanism in Aquatic Ecosystems. Sci. Total Environ. 2021, 772, 145389. [Google Scholar] [CrossRef] [PubMed]
  119. Alegbeleye, O.; Daramola, O.B.; Adetunji, A.T.; Ore, O.T.; Ayantunji, Y.J.; Omole, R.K.; Ajagbe, D.; Adekoya, S.O. Efficient Removal of Antibiotics from Water Resources Is a Public Health Priority: A Critical Assessment of the Efficacy of Some Remediation Strategies for Antibiotics in Water. Environ. Sci. Pollut. Res. Int. 2022, 29, 56948–57020. [Google Scholar] [CrossRef]
  120. Rueda-Marquez, J.J.; Levchuk, I.; Fernández Ibañez, P.; Sillanpää, M. A Critical Review on Application of Photocatalysis for Toxicity Reduction of Real Wastewaters. J. Clean. Prod. 2020, 258, 120694. [Google Scholar] [CrossRef]
  121. Guerrini, G.L. Photocatalysis and Virus. From Theory to Applications. J. Photocat. 2021, 2, 25–34. [Google Scholar] [CrossRef]
  122. Margarucci, L.M.; Romano Spica, V.; Gianfranceschi, G.; Valeriani, F. Untouchability of Natural Spa Waters: Perspectives for Treatments within a Personalized Water Safety Plan. Environ. Int. 2019, 133, 105095. [Google Scholar] [CrossRef] [PubMed]
  123. Margarucci, L.M.; Gianfranceschi, G.; Romano Spica, V.; D’Ermo, G.; Refi, C.; Podico, M.; Vitali, M.; Romano, F.; Valeriani, F. Photocatalytic Treatments for Personal Protective Equipment: Experimental Microbiological Investigations and Perspectives for the Enhancement of Antimicrobial Activity by Micrometric TiO(2). Int. J. Environ. Res. Public Health 2021, 18, 8662. [Google Scholar] [CrossRef]
  124. Margarucci, L.M.; Romano Spica, V.; Protano, C.; Gianfranceschi, G.; Giuliano, M.; Di Onofrio, V.; Mucci, N.; Valeriani, F.; Vitali, M.; Romano, F. Potential Antimicrobial Effects of Photocatalytic Nanothecnologies in Hospital Settings. Ann. Ig. 2019, 31, 461–473. [Google Scholar] [CrossRef] [PubMed]
  125. Lofrano, G.; Ubaldi, F.; Albarano, L.; Carotenuto, M.; Vaiano, V.; Valeriani, F.; Libralato, G.; Gianfranceschi, G.; Fratoddi, I.; Meric, S.; et al. Antimicrobial Effectiveness of Innovative Photocatalysts: A Review. Nanomaterials 2022, 12, 2831. [Google Scholar] [CrossRef]
  126. Ubaldi, F.; Valeriani, F.; Volpini, V.; Lofrano, G.; Romano Spica, V. Antimicrobial Activity of Photocatalytic Coatings on Surfaces: A Systematic Review and Meta-Analysis. Coatings 2024, 14, 92. [Google Scholar] [CrossRef]
  127. Page, M.J.; McKenzie, J.E.; Bossuyt, P.M.; Boutron, I.; Hoffmann, T.C.; Mulrow, C.D.; Shamseer, L.; Tetzlaff, J.M.; Akl, E.A.; Brennan, S.E.; et al. The PRISMA 2020 Statement: An Updated Guideline for Reporting Systematic Reviews. BMJ 2021, 372, n71. [Google Scholar] [CrossRef]
  128. Szreder, T.; Kisała, J.; Bojanowska-Czajka, A.; Kasperkowiak, M.; Pogocki, D.; Bobrowski, K.; Trojanowicz, M. High Energy Radiation—Induced Cooperative Reductive/Oxidative Mechanism of Perfluorooctanoate Anion (PFOA) Decomposition in Aqueous Solution. Chemosphere 2022, 295, 133920. [Google Scholar] [CrossRef] [PubMed]
  129. Chemlal, R.; Azzouz, L.; Kernani, R.; Abdi, N.; Lounici, H.; Grib, H.; Mameri, N.; Drouiche, N. Combination of Advanced Oxidation and Biological Processes for the Landfill Leachate Treatment. Ecol. Eng. 2014, 73, 281–289. [Google Scholar] [CrossRef]
  130. Jurczyk, Ł.; Koc-Jurczyk, J. Quantitative Dynamics of Ammonia-Oxidizers during Biological Stabilization of Municipal Landfill Leachate Pretreated by Fenton’s Reagent at Neutral pH. Waste Manag. 2017, 63, 310–326. [Google Scholar] [CrossRef] [PubMed]
  131. Rao, Y.F.; Chu, W. Linuron Decomposition in Aqueous Semiconductor Suspension under Visible Light Irradiation with and without H2O2. Chem. Eng. J. 2010, 158, 181–187. [Google Scholar] [CrossRef]
  132. Guzzella, L.; Capri, E.; Di Corcia, A.; Barra Caracciolo, A.; Giuliano, G. Fate of Diuron and Linuron in a Field Lysimeter Experiment. J. Environ. Qual. 2006, 35, 312–323. [Google Scholar] [CrossRef] [PubMed]
  133. Mendoza-Huzair, H.L. Chemical Reactivity of Isoproturon, Diuron, Linuron, and Chlorotoluron Herbicides in Aqueous Phase: A Theoretical Quantum Study Employing Global and Local Reactivity Descriptors. J. Chem. 2015, 2015, 751527. [Google Scholar] [CrossRef]
  134. Kisała, J.; Kumienga, P.; Balawejder, M.; Hęclik, K.I.; Celuch, M.; Kosno, L.; Pogocki, D.; Pasternakiewicz, R.; Wite, B.A. Stawarz Linuron Contaminated Water Detoxification by Ozonolysis and Fenton Reaction: Xenobiotics: Soil, Food and Human Health Interactions; Wydawnictwo Uniwersytetu Rzeszowskiego: Rzeszow, Poland, 2012. [Google Scholar]
  135. Katsumata, H.; Kaneco, S.; Suzuki, T.; Ohta, K.; Yobiko, Y. Degradation of Linuron in Aqueous Solution by the Photo-Fenton Reaction. Chem. Eng. J. 2005, 108, 269–276. [Google Scholar] [CrossRef]
  136. Sniegowski, K.; Mertens, J.; Diels, J.; Smolders, E.; Springael, D. Inverse Modeling of Pesticide Degradation and Pesticide-Degrading Population Size Dynamics in a Bioremediation System: Parameterizing the Monod Model. Chemosphere 2009, 75, 726–731. [Google Scholar] [CrossRef]
  137. U.S. EPA High Production Volume (HPV) Challenge. Available online: https://hero.epa.gov/hero/index.cfm/reference/details/reference_id/1060798 (accessed on 1 July 2024).
  138. Wallnofer, P. The Decomposition of Urea Herbicides by Bacillus Sphaericus, Isolated from Soil. Weed Res. 1969, 9, 333–339. [Google Scholar] [CrossRef]
  139. Miller, T.R.; Colquhoun, D.R.; Halden, R.U. Identification of Wastewater Bacteria Involved in the Degradation of Triclocarban and Its Non-Chlorinated Congener. J. Hazard. Mater. 2010, 183, 766–772. [Google Scholar] [CrossRef]
  140. Di Corcia, A.; Costantino, A.; Crescenzi, C.; Samperi, R. Quantification of Phenylurea Herbicides and Their Free and Humic Acid-Associated Metabolites in Natural Waters. J. Chrom. A 1999, 852, 465–474. [Google Scholar] [CrossRef]
  141. Gledhill, W.E. Biodegradation of 3,4,4’-Trichlorocarbanilide, TCCT, in Sewage and Activated Sludge. Water Res. 1975, 9, 649–654. [Google Scholar] [CrossRef]
  142. Kor-Bicakci, G.; Abbott, T.; Ubay-Cokgor, E.; Eskicioglu, C. Occurrence and Fate of Antimicrobial Triclocarban and Its Transformation Products in Municipal Sludge during Advanced Anaerobic Digestion Using Microwave Pretreatment. Sci. Total Environ. 2020, 705, 135862. [Google Scholar] [CrossRef]
  143. Cloos, P.; Moreale, A.; Broers, C.; Badot, C. Adsorption and Oxidation of Aniline and P-Chloroanilne by Montmorillonite. Clay Miner. 1979, 14, 307–321. [Google Scholar] [CrossRef]
  144. Liu, C.S.; Liou, S.H.; Loh, C.H.; Yu, Y.C.; Uang, S.N.; Shih, T.S.; Chen, H.I. Occupational Bladder Cancer in a 4,4’-Methylenebis(2-Chloroaniline) (MBOCA)-Exposed Worker. Environ. Health Perspect. 2005, 113, 771–774. [Google Scholar] [CrossRef] [PubMed]
  145. National Toxicology Program NIH. Report on Carcinogens; DIANE Publishing Company: Collingdale, PA, USA, 2011; Volume 12, ISBN 978-1-4379-8736-2. [Google Scholar]
  146. Office of Pesticide Programs. Chemicals Evaluated for Carcinogenic Potential; Annual Cancer Report 2016; U.S. Environmental Protection Agency: Washington, DC, USA, 2016; pp. 1–37.
  147. Celuch, M.; Bojanowska-Czajka, A.; Pogocki, D.; Kisala, J.; Kulisa, K.; Mirkowski, J. Wolnorodnikowa Degradacja Wybranych Pestycydów. In Free Radical Degradation of Selected Pesticides; Wydawnictwo Naukowe Uniwersytetu im Adama Mickiewicza: Poznań, Poland, 2013. [Google Scholar]
  148. Kisała, J.; Jurczyk, Ł.; Celuch, M.; Pogocki, D. Ozonoliza roztworu wodnego linuronu—badania toksycznooci produktów ubocznych. In Ozonolysis of Linuron Aqueous Solution–Toxicological Studies of By-Products; Wydawnictwo Naukowe Uniwersytetu im Adama Mickiewicza: Poznań, Poland, 2012. [Google Scholar]
  149. Kisała, J.; Kumięga, P.; Balawejder, M.; Hęclik, K.; Pogocki, D. Linuron Contaminated Water Detoxification by Ozonlysis and Fenton Reaction; Wydawnictwo Uniwersytetu Rzeszowskiego: Rzeszow, Poland, 2011. [Google Scholar]
  150. Murbach, T.S.; Glávits, R.; Endres, J.R.; Clewell, A.E.; Hirka, G.; Vértesi, A.; Béres, E.; Pasics Szakonyiné, I. A Toxicological Evaluation of a Fulvic and Humic Acids Preparation. Toxicol. Rep. 2020, 7, 1242–1254. [Google Scholar] [CrossRef] [PubMed]
  151. Broughton, E. The Bhopal disaster and its aftermath: A review. Environ. Health 2005, 4, 6. [Google Scholar] [CrossRef] [PubMed]
  152. Dejonghe, W.; Berteloot, E.; Goris, J.; Boon, N.; Crul, K.; Maertens, S.; Ho, M.; De Vos, P.; Verstraete, W.; Top, E.M. Synergistic Degradation of Linuron by a Bacterial Consortium and Isolation of a Single Linuron-Degrading Variovorax Strain. Appl. Environ. Microbiol. 2003, 69, 1532–1541. [Google Scholar] [CrossRef]
  153. Irving, W.; Boswell, T.; Ala’Alden, D. Instant Notes Medical Microbiology. In BIOS Instant Notes; Taylor & Francis: Nottingham, UK, 2005; ISBN 978-1-85996-254-1. [Google Scholar]
  154. Halliwell, B.; Gutteridge, J.M. Free Radicals in Biology and Medicine; Oxford University Press: Oxford, UK, 1999; Volume 3. [Google Scholar]
  155. Connors, K.A.; Amidon, G.L.; Stella, V.J. Chemical Stability of Pharmaceuticals: A Handbook for Pharmacists; Wiley-Interscience publication: Wiley, WA, USA, 1986; ISBN 978-0-471-87955-8. [Google Scholar]
  156. Manning, M.C.; Patel, K.; Borchardt, R.T. Stability of Protein Pharmaceuticals. Pharm. Res. 1989, 6, 903–918. [Google Scholar] [CrossRef]
  157. Pogocki, D.; Schoneich, C. Chemical Stability of Nucleic Acid-Derived Drugs. J. Pharm. Sci. 2000, 89, 443–456. [Google Scholar] [CrossRef]
  158. Manning, M.C.; Chou, D.K.; Murphy, B.M.; Payne, R.W.; Katayama, D.S. Stability of Protein Pharmaceuticals: An Update. Pharm. Res. 2010, 27, 544–575. [Google Scholar] [CrossRef]
  159. Torosantucci, R.; Schöneich, C.; Jiskoot, W. Oxidation of Therapeutic Proteins and Peptides: Structural and Biological Consequences. Pharm. Res. 2014, 31, 541–553. [Google Scholar] [CrossRef]
  160. Valgimigli, L. Lipid Peroxidation and Antioxidant Protection. Biomolecules 2023, 13, 1291. [Google Scholar] [CrossRef]
  161. Jaganjac, M.; Milkovic, L.; Zarkovic, N.; Zarkovic, K. Oxidative Stress and Regeneration. Free Radic. Biol. Med. 2022, 181, 154–165. [Google Scholar] [CrossRef] [PubMed]
  162. U.S. Environmental Protection Agency. National Primary Drinking Water Regulation Table; USEPA: Washington, DC, USA, 2009.
  163. Horwath, W.R. Carbon Cycling and Formation of Soil Organic Matter. In Encyclopedia of Soil Science; Springer: Dordrecht, The Netherlands, 2007; pp. 91–97. ISBN 978-1-4020-3994-2. [Google Scholar]
  164. Lehmann, J.; Kleber, M. The Contentious Nature of Soil Organic Matter. Nature 2015, 528, 60–68. [Google Scholar] [CrossRef] [PubMed]
  165. Baldock, J.; Nelson, P. Soil Organic Matter. In Handbook of Soil Science; CRC Press: Boca Raton, FL, USA; pp. B25–B84.
  166. Ghezzehei, T.A. Soil Structure. In Handbook of Soil Sciences: Properties and Processes, Part I: Soil Physics; Huang, P.M., Li, Y., Sumner, M.E., Eds.; CRC Press, Taylor & Francis Group: Boca Raton, FL, USA, 2012; pp. 2-1–2-17. [Google Scholar]
  167. Baldock, J.A.; Brose, K. Soil Organic Matter. In Handbook of Soil Sciences: Properties and Processes, Part II: Soil Chemistry; Huang, P.M., Li, Y., Sumner, M.E., Eds.; CRC Press, Taylor & Francis Group: Boca Raton, FL, USA, 2012; pp. 11-1–11-52. ISBN 978-1-4398-0305-9. [Google Scholar]
  168. Smejkalova, D.; Piccolo, A. Aggregation and Disaggregation of Humic Supramolecular Assemblies by NMR Diffusion Ordered Spectroscopy (DOSY-NMR). Environ. Sci. Technol. 2008, 42, 699–706. [Google Scholar] [CrossRef]
  169. Piccolo, A. The Supramolecular Structure of Humic Substances: A Novel Understanding of Humus Chemistry and Implications in Soil Science. In Advances in Agronomy; Academic Press: Cambridge, MA, USA, 2002; Volume 75, pp. 57–134. ISBN 0065-2113. [Google Scholar]
  170. Mushtaq, W.; Siddiqui, M.B.; Hakeem, K.R. History of Allelopathy. In Allelopathy: Potential for Green Agriculture; Mushtaq, W., Siddiqui, M.B., Hakeem, K.R., Eds.; Springer International Publishing: Cham, Switzerland, 2020; pp. 5–24. ISBN 978-3-030-40807-7. [Google Scholar]
  171. Radomskii, S.M.; Radomskaya, V.I.; Moiseenko, N.V.; Moiseenko, V.G. Nanoparticles of Noble Metals in Peat of the Upper and Middle Amur Region. Dokl. Earth Sci. 2009, 426, 620–622. [Google Scholar] [CrossRef]
  172. Tao, Z.; Zhou, Q.; Zheng, T.; Mo, F.; Ouyang, S. Iron Oxide Nanoparticles in the Soil Environment: Adsorption, Transformation, and Environmental Risk. J. Hazard. Mater. 2023, 459, 132107. [Google Scholar] [CrossRef] [PubMed]
  173. Baron, S.; Lavoie, M.; Ploquin, A.; Carignan, J.; Pulido, M.; De Beaulieu, J.L. Record of Metal Workshops in Peat Deposits: History and Environmental Impact on the Mont Lozere Massif, France. Environ. Sci. Technol. 2005, 39, 5131–5140. [Google Scholar] [CrossRef] [PubMed]
  174. Gondar, D.; Iglesias, A.; Lopez, R.; Fiol, S.; Antelo, J.M.; Arce, F. Copper Binding by Peat Fulvic and Humic Acids Extracted from Two Horizons of an Ombrotrophic Peat Bog. Chemosphere 2006, 63, 82–88. [Google Scholar] [CrossRef] [PubMed]
  175. Akaighe, N.; MacCuspie, R.I.; Navarro, D.A.; Aga, D.S.; Banerjee, S.; Sohn, M.; Sharma, V.K. Humic Acid-Induced Silver Nanoparticle Formation Under Environmentally Relevant Conditions. Environ. Sci. Technol. 2011, 45, 3895–3901. [Google Scholar] [CrossRef] [PubMed]
  176. Sal’nikov, D.S.; Pogorelova, A.S.; Makarov, S.V.; Vashurina, I.Y. Silver Ion Reduction with Peat Fulvic Acids. Russ. J. Appl. Chem. 2009, 82, 545–548. [Google Scholar] [CrossRef]
  177. Singer, P.C. Humic Substances as Precursors for Potentially Harmful Disinfection By-Products. Water Sci. Technol. 1999, 40, 25–30. [Google Scholar] [CrossRef]
  178. Neta, P.; Steenken, S. Radiation Chemistry of Phenols. In The Chemistry of Phenols; Patai Series; The Chemistry of Functional Groups; John Wiley & Sons, Ltd.: New York, NY, USA, 2003; pp. 1097–1104. ISBN 0-471-49737-1. [Google Scholar]
  179. Rappoport, Z. The Chemistry of Phenols; Patai’s Chemistry of Functional Groups; Wiley: New York, NY, USA, 2003; Volume 2, ISBN 978-0-471-49737-0. [Google Scholar]
  180. Steenken, S.; Neta, P. One-Electron Redox Potentials of Phenols–Hydroxyphenols and Aminophenols and Related Compounds of Biological Interest. J. Phys. Chem. 1982, 86, 3661. [Google Scholar] [CrossRef]
  181. Matthiessen, A.; Senesi, N.; Miano, T.M. Humic Substances in the Global Environment and Implications on Human Health; Elsevier: Amsterdam, The Netherlands, 1994. [Google Scholar]
  182. de Melo, B.A.G.; Motta, F.L.; Santana, M.H.A. Humic Acids: Structural Properties and Multiple Functionalities for Novel Technological Developments. Mater. Sci. Eng. C 2016, 62, 967–974. [Google Scholar] [CrossRef] [PubMed]
  183. Aeschbacher, M.; Graf, C.; Schwarzenbach, R.P.; Sander, M. Antioxidant Properties of Humic Substances. Environ. Sci. Technol. 2012, 46, 4916–4925. [Google Scholar] [CrossRef]
  184. Aeschbacher, M.; Vergari, D.; Schwarzenbach, R.P.; Sander, M. Electrochemical Analysis of Proton and Electron Transfer Equilibria of the Reducible Moieties in Humic Acids. Environ. Sci. Technol. 2011, 45, 8385. [Google Scholar] [CrossRef] [PubMed]
  185. Aeschbacher, M.; Sander, M.; Schwarzenbach, R.P. Novel Electrochemical Approach to Assess the Redox Properties of Humic Substances. Environ. Sci. Technol. 2010, 44, 87. [Google Scholar] [CrossRef] [PubMed]
  186. Bauer, M.; Heitmann, T.; Macalady, D.L.; Blodau, C. Electron Transfer Capacities and Reaction Kinetics of Peat Dissolved Organic Matter. Environ. Sci. Technol. 2007, 41, 139–145. [Google Scholar] [CrossRef]
  187. Bravo, C.; Toniolo, R.; Pellegrini, E.; Millo, C.; Covelli, S.; Contin, M.; Martin-Neto, L.; De Nobili, M. Electron Donating Properties of Humic Acids in Saltmarsh Soils Reflect Soil Geochemical Characteristics. Geoderma 2022, 419, 115872. [Google Scholar] [CrossRef]
  188. Bravo, C.; De Nobili, M.; Gambi, A.; Martin-Neto, L.; Nascimento, O.R.; Toniolo, R. Kinetics of Electron Transfer Reactions by Humic Substances: Implications for Their Biogeochemical Roles and Determination of Their Electron Donating Capacity. Chemosphere 2022, 286, 131755. [Google Scholar] [CrossRef]
  189. Derakhshani, E.; Naghizadeh, A.; Arab-Zozani, M.; Farkhondeh, T. A Systematic Review of Photocatalytic Degradation of Humic Acid in Aqueous Solution Using Nanoparticles. Rev. Environ. Health 2023, 38, 577–587. [Google Scholar] [CrossRef]
  190. Fukushima, M.; Shigematsu, S.; Nagao, S. Influence of Humic Acid Type on the Oxidation Products of Pentachlorophenol Using Hybrid Catalysts Prepared by Introducing Iron(III)-5,10,15,20-Tetrakis(p-Hydroxyphenyl) Porphyrin into Hydroquinone-Derived Humic Acids. Chemosphere 2010, 78, 1155–1159. [Google Scholar] [CrossRef]
  191. Gara, P.M.; Bosio, G.N.; Gonzalez, M.C.; Russo, N.; Del Carmen, M.M.; Diez, R.P.; Martire, D.O. A Combined Theoretical and Experimental Study on the Oxidation of Fulvic Acid by the Sulfate Radical Anion. Photochem. Photobiol. Sci. 2009, 8, 992–997. [Google Scholar] [CrossRef]
  192. Helburn, R.S.; Maccarthy, P. Determination of Some Redox Properties of Humic Acid by Alkaline Ferricyanide Titration. Anal. Chim. Acta 1994, 295, 263. [Google Scholar] [CrossRef]
  193. Li, X.; Fang, J.; Liu, G.; Zhang, S.; Pan, B.; Ma, J. Kinetics and Efficiency of the Hydrated Electron-Induced Dehalogenation by the Sulfite/UV Process. Water Res. 2014, 62, 220–228. [Google Scholar] [CrossRef] [PubMed]
  194. Lovley, D.R.; Coates, J.D.; Blunt-Harris, E.L.; Phillips, E.J.P.; Woodward, J.C. Humic Substances as Electron Acceptors for Microbial Respiration. Nature 1996, 382, 445. [Google Scholar] [CrossRef]
  195. Matthiessen, A. Determining the Redox Capacity of Humic Substances as a Function of pH. Vom Wasser 1995, 84, 229. [Google Scholar]
  196. Maurer, F.; Christl, I.; Kretzschmar, R. Reduction and Reoxidation of Humic Acid: Influence on Spectroscopic Properties and Proton Binding. Environ. Sci. Technol. 2010, 44, 5787. [Google Scholar] [CrossRef] [PubMed]
  197. Page, S.E.; Sander, M.; Arnold, W.A.; McNeill, K. Hydroxyl Radical Formation upon Oxidation of Reduced Humic Acids by Oxygen in the Dark. Environ. Sci. Technol. 2012, 46, 1590. [Google Scholar] [CrossRef] [PubMed]
  198. Peretyazhko, T.; Sposito, G. Reducing Capacity of Terrestrial Humic Acids. Geoderma 2006, 137, 140. [Google Scholar] [CrossRef]
  199. Struyk, Z.; Sposito, G. Redox Properties of Standard Humic Acids. Geoderma 2001, 102, 329–346. [Google Scholar] [CrossRef]
  200. Zhang, L.; Li, P.; Gong, Z.; Li, X. Photocatalytic Degradation of Polycyclic Aromatic Hydrocarbons on Soil Surfaces Using TiO2 under UV Light. J. Hazard. Mater. 2008, 158, 478–484. [Google Scholar] [CrossRef]
  201. Piotrowska, D.; Dlugosz, A.; Witkiewicz, K.; Pajak, J. The Research on Antioxidative Properties of TOLPA Peat Preparation and Its Fractions. Acta Pol. Pharm. 2000, 57, 127–129. [Google Scholar] [PubMed]
  202. Schalk, O.; Tapavicza, E. Photochemistry. In ACS in Focus; American Chemical Society: Washington, DC, USA, 2020. [Google Scholar]
  203. Matilainen, A.; Vepsäläinen, M.; Sillanpää, M. Natural Organic Matter Removal by Coagulation during Drinking Water Treatment: A Review. Adv. Colloid Interface Sci. 2010, 159, 189–197. [Google Scholar] [CrossRef] [PubMed]
  204. Sillanpää, M.; Matilainen, A. Chapter 3—NOM Removal by Coagulation. In Natural Organic Matter in Water; Sillanpää, M., Ed.; Butterworth-Heinemann: Oxford, UK, 2015; pp. 55–80. ISBN 978-0-12-801503-2. [Google Scholar]
  205. Sillanpää, M.; Särkkä, H.; Vepsäläinen, M. Chapter 4—NOM Removal by Electrochemical Methods. In Natural Organic Matter in Water; Sillanpää, M., Ed.; Butterworth-Heinemann: Oxford, UK, 2015; pp. 81–111. ISBN 978-0-12-801503-2. [Google Scholar]
  206. Sillanpää, M.; Metsämuuronen, S.; Mänttäri, M. Chapter 5—Membranes. In Natural Organic Matter in Water; Sillanpää, M., Ed.; Butterworth-Heinemann: Oxford, UK, 2015; pp. 113–157. ISBN 978-0-12-801503-2. [Google Scholar]
  207. Sillanpää, M.; Matilainen, A. Chapter 6—NOM Removal by Advanced Oxidation Processes. In Natural Organic Matter in Water; Sillanpää, M., Ed.; Butterworth-Heinemann: Oxford, UK, 2015; pp. 159–211. ISBN 978-0-12-801503-2. [Google Scholar]
  208. Oskoei, V.; Dehghani, M.H.; Nazmara, S.; Heibati, B.; Asif, M.; Tyagi, I.; Agarwal, S.; Gupta, V.K. Removal of Humic Acid from Aqueous Solution Using UV/ZnO Nano-Photocatalysis and Adsorption. J. Mol. Liq. 2016, 213, 374–380. [Google Scholar] [CrossRef]
  209. Long, M.; Brame, J.; Qin, F.; Bao, J.; Li, Q.; Alvarez, P.J.J. Phosphate Changes Effect of Humic Acids on TiO2 Photocatalysis: From Inhibition to Mitigation of Electron–Hole Recombination. Environ. Sci. Technol. 2017, 51, 514–521. [Google Scholar] [CrossRef]
  210. Ren, M.; Drosos, M.; Frimmel, F.H. Inhibitory Effect of NOM in Photocatalysis Process: Explanation and Resolution. Chem. Eng. J. 2018, 334, 968–975. [Google Scholar] [CrossRef]
  211. Zheng, L.; Yu, X.; Long, M.; Li, Q. Humic Acid-Mediated Visible-Light Degradation of Phenol on Phosphate-Modified and Nafion-Modified TiO2 Surfaces. Chin. J. Catal. 2017, 38, 2076–2084. [Google Scholar] [CrossRef]
  212. Gray, J.M.; Humphreys, G.S.; Deckers, J.A. Distribution Patterns of World Reference Base Soil Groups Relative to Soil Forming Factors. Geoderma 2011, 160, 373–383. [Google Scholar] [CrossRef]
  213. Bockheim, J.G.; Gennadiyev, A.N.; Hartemink, A.E.; Brevik, E.C. Soil-Forming Factors and Soil Taxonomy. Geoderma 2014, 226–227, 231–237. [Google Scholar] [CrossRef]
  214. Rudnick, R.L.; Gao, S. 4.1—Composition of the Continental Crust. In Treatise on Geochemistry, 2nd ed.; Holland, H.D., Turekian, K.K., Eds.; Elsevier: Oxford, UK, 2014; pp. 1–51. ISBN 978-0-08-098300-4. [Google Scholar]
  215. Clark, F.W. The Relative Abundance of the Chemical Elements. Bull. Phil. Soc. Washington. 1892, 11, 131–142. [Google Scholar]
  216. Perelman, A. Geochemia Krajobrazu [Landscape Geochemistry]; PWN: Warszawa, Poland, 1971. [Google Scholar]
  217. Pokojska, U.; Bednarek, R. Geochemia Krajobrazu [Landscape Geochemistry]; Wydawnictwo Naukowe Uniwersytetu Mikołaja Kopernika: Toruń, Poland, 2012; ISBN 978-83-231-2965-3. [Google Scholar]
  218. Clarke, F.W.; Washington, H.S. The Composition of the Earth’s Crust; Department of the Interior, U.S. Geological Survey Office: Washington, DC, USA, 1924; Volume 127, pp. 1–117.
  219. Clarke, F.W. The Data of Geochemistry. In Bulletin, 5th ed.; U.S. Geological Survey Office: Washington, DC, USA, 1924; p. 841. [Google Scholar]
  220. Barroso, M.; Pendlebury, S.R.; Cowan, A.J.; Durrant, J.R. Charge Carrier Trapping, Recombination and Transfer in Hematite (α-Fe2O3) Water Splitting Photoanodes. Chem. Sci. 2013, 4, 2724–2734. [Google Scholar] [CrossRef]
  221. Lu, A.; Li, Y.; Ding, H.; Xu, X.; Li, Y.; Ren, G.; Liang, J.; Liu, Y.; Hong, H.; Chen, N.; et al. Photoelectric Conversion on Earth’s Surface via Widespread Fe- and Mn-Mineral Coatings. Proc. Natl. Acad. Sci. USA 2019, 116, 9741–9746. [Google Scholar] [CrossRef]
  222. Section 10—Solar. In Handbook of Energy; Cleveland, C.J.; Morris, C. (Eds.) Elsevier: Amsterdam, The Netherlands, 2013; pp. 405–450. ISBN 978-0-08-046405-3. [Google Scholar]
  223. ASTM Subcommittee on Radiometry, Standard Tables for Reference Solar Spectral Irradiances: Direct Normal and Hemispherical on 37° Tilted Surface. 2012. Available online: https://cdn.standards.iteh.ai/samples/26795/a2e98d8ad97444ce9554a4c295fba45c/ASTM-G173-03.pdf (accessed on 1 July 2024).
  224. Barrón, V.; Méndez, J.M.; Balbuena, J.; Cruz-Yusta, M.; Sánchez, L.; Giménez, C.; Sacristán, D.; González-Guzmán, A.; Sánchez-Rodríguez, A.R.; Skiba, U.M.; et al. Photochemical Emission and Fixation of NOX Gases in Soils. Sci. Total Environ. 2020, 702, 134982. [Google Scholar] [CrossRef] [PubMed]
  225. Shen, C.; Gu, X.; Yang, B.; Zhang, D.; Wang, Z.; Shu, Z.; Dick, J.; Lu, A. Mineralogical Characteristics and Photocatalytic Properties of Natural Sphalerite from China. J. Environ. Sci. 2020, 89, 156–166. [Google Scholar] [CrossRef]
  226. Sánchez-Rodríguez, A.R.; Gómez-Álvarez, E.; Méndez, J.M.; Skiba, U.M.; Jones, D.L.; Chadwick, D.R.; del Campillo, M.C.; Fernandes, R.B.A.; Kleffmann, J.; Barrón, V. Photocatalytic Fixation of NOx in Soils. Chemosphere 2023, 338, 139576. [Google Scholar] [CrossRef] [PubMed]
  227. Beringer, J.; Chapin, F.S.; Thompson, C.C.; McGuire, A.D. Surface Energy Exchanges along a Tundra-Forest Transition and Feedbacks to Climate. Agric. For. Meteorol. 2005, 131, 143–161. [Google Scholar] [CrossRef]
  228. Juszak, I.; Eugster, W.; Heijmans, M.M.P.D.; Schaepman-Strub, G. Contrasting Radiation and Soil Heat Fluxes in Arctic Shrub \hack\newlineand Wet Sedge Tundra. Biogeosciences 2016, 13, 4049–4064. [Google Scholar] [CrossRef]
  229. Dedkov, V.P.; Danzhalova, E.V.; Tkachenko, S.N.; Khadbaatar, S.; Ariunbold, E.; Gunin, P.D.; Bazha, S.N. The Influence of Vegetation on Reflected Solar Radiation in Arid and Extra-Arid Zone of Mongolian Gobi. Geogr. Environ. Sustain. 2020, 13, 72–80. [Google Scholar] [CrossRef]
  230. World Bank. Global Solar Atlas. 2017. Available online: https://globalsolaratlas.info (accessed on 11 September 2023).
  231. Jakšić, S.; Ninkov, J.; Milić, S.; Vasin, J.; Živanov, M.; Jakšić, D.; Komlen, V. Influence of Slope Gradient and Aspect on Soil Organic Carbon Content in the Region of Niš, Serbia. Sustainability 2021, 13, 8332. [Google Scholar] [CrossRef]
  232. Bech, J.; Tume, P.; Longan, L.; Reverter, F.; Bech, J.; Tume, L.; Tempio, M. Concentration of Cd, Cu, Pb, Zn, Al, and Fe in Soils of Manresa, NE Spain. Environ. Monit. Assess. 2008, 145, 257–266. [Google Scholar] [CrossRef]
  233. Fekiacova, Z.; Pichat, S.; Cornu, S.; Balesdent, J. Inferences from the Vertical Distribution of Fe Isotopic Compositions on Pedogenetic Processes in Soils. Geoderma 2013, 209–210, 110–118. [Google Scholar] [CrossRef]
  234. Zhang, Q.; Han, G. Contribution of Natural and Agricultural Activities on Fe Dynamics: Insights from Fe Isotope in Soils under Different Land-Use Types. Agric. Ecosyst. Environ. 2023, 358, 108705. [Google Scholar] [CrossRef]
  235. Wang, K.; Jia, R.; Li, L.; Jiang, R.; Qu, D. Community Structure of Anaeromyxobacter in Fe (III) Reducing Enriched Cultures of Paddy Soils. J. Soils Sediments 2020, 20, 1621–1631. [Google Scholar] [CrossRef]
  236. Garnier, J.; Garnier, J.-M.; Vieira, C.L.; Akerman, A.; Chmeleff, J.; Ruiz, R.I.; Poitrasson, F. Iron Isotope Fingerprints of Redox and Biogeochemical Cycling in the Soil-Water-Rice Plant System of a Paddy Field. Sci. Total Environ. 2017, 574, 1622–1632. [Google Scholar] [CrossRef] [PubMed]
  237. IUSS Working Group 2015 World Reference Base for Soil Resources 2014. In International Soil Classification System for Naming Soils and Creating Legends for Soil Maps; World Soil Resources Reports; FAO: Rome, Italy, 2015; pp. 1–203.
Table 1. The EBG, E VB ⊖ , and E CB ⊖ energy positions at the zero point of charge (pHzpc) a for oxides and sulphides based on the Xu and Schoonen [26] data. The E VB ⊖ and E CB ⊖ values were recalculated to the electrochemical scale E (vs. SHE) = −E(AVS) − 4.44 V [77,78].
Table 1. The EBG, E VB ⊖ , and E CB ⊖ energy positions at the zero point of charge (pHzpc) a for oxides and sulphides based on the Xu and Schoonen [26] data. The E VB ⊖ and E CB ⊖ values were recalculated to the electrochemical scale E (vs. SHE) = −E(AVS) − 4.44 V [77,78].
Mineral/OxideEBG/eV
(nm)		 E VB ⊖ /V E CB ⊖ /VpHzpcMineral/SulphideEBG/eV
(nm)		 E VB ⊖ /V E CB ⊖ /VpHzpc
Ag2O00.250.2511.2Ag2S (Argentite)0.92 (1348)1.020.062
AlTiO33.6 (345)2.8−0.88.23AgAsS2 (Trechmannite)1.95 (635)2.020.072
BaTiO33.3 (375)3.440.149AgSbS2 (Miargyrite)00.070.072
Bi2O3 (Bismite)2.8 (443)3.190.396.2As2S3 (Orpiment)2.5 (496)2.640.142
CdO (Monteponite)2.2 (564)2.370.1711.6CdS (Greenockite)2.4 (517)2.26−0.462
CdFe2O42.3 (539)2.540.247.22Ce2S30−0.85−0.852
Ce2O32.4 (517)1.96−0.448.85CoS00.730.732
CoO2.6 (477)2.55−0.057.59CoS2 (Catterite)01.051.051.5
CoTiO32.25 (551)2.450.27.41CoAsS (Cobaltite)00.520.522
Cr2O3 (Eskolaite)3.5 (554)2.99−0.518.1CuS (Covellite)00.830.832
CuO (Tenorite)1.7 (729)2.220.529.5Cu2S (Chalcocite)1.1 (1127)1.102
Cu2O (Cuprite)2.2 (564)1.98−0.228.53CuS2 (Villamaninite)01.131.132
CuTiO32.99 (415)2.87−0.127.29Cu3AsS4 (Enargite)1.28 (969)1.590.312
FeO (Wustite)2.4 (517)2.29−0.118CuFeS2 (Chalcopyrite)0.35 (3542)0.880.531.8
Fe2O3 (Hematite)2.2 (564)2.540.348.6Cu5FeS4 (Bornite)00.110.112
Fe3O4 (Magnetite)0.1 (12,398)1.391.296.5CuInS21.5 (827)2.62−0.382
FeOOH (Goethite)2.6 (477)3.240.649.7CuIn5S81.26 (984)0.91−0.352
FeTiO3 (Ilmenite)2.8 (443)2.65−0.156.3Dy2S32.85 (435)1.77−1.082
Ga2O3 (β-Ga2O3)4.8 (258)3.31−1.498.47FeS (Pyrrhotite)0.1 (12,398)0.630.533
HgO (Montroydite)1.9 (653)2.590.697.3FeS2 (Pyrite)0.95 (1305)1.430.481.4
Hg2Nb2O71.8 (689)2.670.876.25Fe3S4 (Greigite)00.740.742
Hg2Ta2O71.8 (689)2.70.96.17FeAsS (Arsenopyrite) 00.570.571.5
In2O3 (India)2.8 (443)2.24−0.568.64Gd2S32.55 (486)1.68−0.872
KNbO33.3 (376)2.5−0.88.62HfS21.13 (1097)1.40.272
KTaO33.5 (354)2.63−0.878.55HgS (Cinnabarite)00.080.082
La2O35.5 (225)3.59−1.9110.4HgSb4S81.68 (738)2.050.372
LaTi2O70−0.54−0.547.06In2S30−0.74−0.742
LiNbO33.5 (354)2.83−0.678.02La2S30−1.19−1.192
LiTaO30−0.89−0.897.94MnS (Alabandite)3 (413)1.87−1.132
MgTiO3 (Geikielite)3.7 (335)3.01−0.697.81MnS2 (Hauerite)00.550.552
MnO (Manganosite)3.6 (345)2.65−0.958.61MoS2 (Molybdenite)1.17 (1060)1.460.292
MnO2 (Pyrolusite)0.25 (4959)1.641.394.6Nd2S32.7 (459)1.56−1.142
MnTiO30−0.4−0.47.83NiS (Polydymite)00.590.592
Nb2O5 (Niobia)3.4 (367)3.550.156.06NiS2 (Vaesite) 00.950.950.6
Nd2O34.7 (264)3.13−1.578.81OsS2 (Erlichmanite)00.30.32
NiO (Bunsenite)3.5 (354)3.06−0.4410.3PbS (Galena)0.37 (3351)3.370.31.4
NiTiO32.18 (569)2.440.267.34Pb10Ag3Sb11S281.39 (982)1.540.152
PbO (Massicot)2.8 (443)2.38−0.428.29Pb2As2S51.39 (982)1.660.272
PbFe12O192.3 (539)2.560.267.17PbCuSbS31.23 (1008)1.40.172
PdO00.850.857.34Pb5Sn3Sb2S140.65 (1907)1.160.512
Pr2O33.9 (318)2.7−1.28.87Pr2S32.4 (517)1.39−1.012
Sb2O3 (Valentinite)3 (413)3.380.385.98PtS20.95 (1305)2.041.092
Sm2O34.4 (282)3.03−1.378.69Rh2S31.5 (827)1.670.172
SnO (Romarchite)4.2 (295)3.35−0.857.59RuS2 (Laurite)1.38 (898)1.830.452
SnO2 (Cassiterite)3.5 (354)3.560.064.3Sb2S3 (Antimonite)1.72 (721)20.282
SrTiO3 (Tausonite)3.4 (365)2.2−1.28.6Sm2S32.6 (477)1.55−1.052
Ta2O5 (Tantite)0−0.11−0.112.9SnS (Herzenbergite)1.01 (1228)1.230.222
Tb2O33.8 (326)2.8−18.5SnS2 (Berndtite)0002
TiO2 (Anatase)3.2 (387)2.97−0.235.8Tb2S32.5 (496)1.57−0.932
Tl2O3 (Avicennite)1.6 (775)1.710.118.47TiS200.320.322
V2O5 (Karelianite)2.8 (443)3.050.266.54TlAsS2 (Lorandite)1.8 (689)1.52−0.282
WO3 (Tungstinite, Meymacite, Hydrotungstite)2.7 (459)3.50.80.43WS2 (Tungstenite)1.35 (918)1.770.422
Yb2O34.9 (253)3.48−1.428.15ZnS (Sphalerite)3.6 (345)2.62−0.981.7
YFeO32.6 (476)2.46−0.147.81ZnS22.7 (459)2.47−0.232
ZnO (Zincite)3.2 (247)2.95−0.258.8Zn3In2S62.81 (441)1.98−0.852
ZnTiO30−0.17−0.177.31ZrS21.82 (681)1.67−0.152
ZrO2 (Baddeleyite)5 (248)3.97−1.036.7--------------------
a pHzpc for which the net adsorbed charge within the Helmholtz double layer [79,80] is equal to zero.
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Sosnowska, A.; Hęclik, K.I.; Kisała, J.B.; Celuch, M.; Pogocki, D. Perspectives for Photocatalytic Decomposition of Environmental Pollutants on Photoactive Particles of Soil Minerals. Materials 2024, 17, 3975. https://doi.org/10.3390/ma17163975

AMA Style

Sosnowska A, Hęclik KI, Kisała JB, Celuch M, Pogocki D. Perspectives for Photocatalytic Decomposition of Environmental Pollutants on Photoactive Particles of Soil Minerals. Materials. 2024; 17(16):3975. https://doi.org/10.3390/ma17163975

Chicago/Turabian Style

Sosnowska, Agnieszka, Kinga I. Hęclik, Joanna B. Kisała, Monika Celuch, and Dariusz Pogocki. 2024. "Perspectives for Photocatalytic Decomposition of Environmental Pollutants on Photoactive Particles of Soil Minerals" Materials 17, no. 16: 3975. https://doi.org/10.3390/ma17163975

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop