Manganese: From Soil to Human Health-A Comprehensive Overview of Its Biological and Environmental Significance.

Background: Manganese is an essential micronutrient that plays a pivotal role in environmental systems, plant physiology, and human health. This review comprehensively examines the manganese cycle in the environment, its absorption and transport mechanisms in plants, and the implications of manganese exposure to human health. Objectives: The objectives of this review are to (i) analyze the environmental cycling of manganese and its bioavailability, (ii) evaluate the role of manganese in plant metabolism and disease resistance, and (iii) assess the impact of manganese toxicity and deficiency on human health. Conclusion: This review highlights that while manganese is crucial for photosynthesis, enzyme activation, and resistance to plant diseases, both its deficiency and toxicity can have severe consequences. In plants, manganese deficiency can lead to impaired growth and reduced crop yields, while toxicity, particularly in acidic soils, can inhibit photosynthesis and stunt development. In humans, manganese is necessary for various physiological processes, but overexposure, especially in occupational settings, can result in neurodegenerative conditions such as manganism. The conclusion emphasizes the importance of managing manganese levels in agriculture and industry to optimize its benefits while minimizing health risks. A multidisciplinary approach is advocated to enhance agricultural productivity and ensure public health safety.

Phosphorus Availability and Balance with Long-Term Sewage Sludge and Nitrogen Fertilization in Chernozem Soil under Maize Monoculture.

A continuous long-term field experiment with maize monoculture was conducted to evaluate the P availability and balance, DM yield, P uptake, and P sorption parameters in chernozem soil after 27 years. A total of 2 doses of nitrogen (120 and 240 kg ha-1) were applied as mineral nitrogen (N120 and N240) and sewage sludge (SS120 and SS240) and compared with unfertilized control (Con). The aboveground biomass (DM) yields significantly increased in the order of Con < SS120 < SS240 < N120 < N240 treatments and the maximum P uptake was recorded for both N240 and SS240 (25.1 kg P ha-1) according to the nutrient application gradient. The N120 and N240 treatments positively influenced the DM yield but negatively influenced the P balance (-648 and -678 kg P ha-1 27 years-1), gradually bringing a risk of P deficiency in the soil. On the other hand, applications of SS120 and SS240 positively influenced the P availability and pseudototal (PAR) content in the soil, which resulted in a buildup of legacy P or an increase in P saturation greater than the environmental threshold value. Aluminum was found to be a major controlling sorption factor for P in our chernozem soil.

Plant Nutrition-New Methods Based on the Lessons of History: A Review.

As with new technologies, plant nutrition has taken a big step forward in the last two decades. The main objective of this review is to briefly summarise the main pathways in modern plant nutrition and attract potential researchers and publishers to this area. First, this review highlights the importance of long-term field experiments, which provide us with valuable information about the effects of different applied strategies. The second part is dedicated to the new analytical technologies (tomography, spectrometry, and chromatography), intensively studied environments (rhizosphere, soil microbial communities, and enzymatic activity), nutrient relationship indexes, and the general importance of proper data evaluation. The third section is dedicated to the strategies of plant nutrition, i.e., (i) plant breeding, (ii) precision farming, (iii) fertiliser placement, (iv) biostimulants, (v) waste materials as a source of nutrients, and (vi) nanotechnologies. Finally, the increasing environmental risks related to plant nutrition, including biotic and abiotic stress, mainly the threat of soil salinity, are mentioned. In the 21st century, fertiliser application trends should be shifted to local application, precise farming, and nanotechnology; amended with ecofriendly organic fertilisers to ensure sustainable agricultural practices; and supported by new, highly effective crop varieties. To optimise agriculture, only the combination of the mentioned modern strategies supported by a proper analysis based on long-term observations seems to be a suitable pathway.

Soil microbial communities following 20 years of fertilization and crop rotation practices in the Czech Republic.

BACKGROUND: Although fertilization and crop rotation practices are commonly used worldwide in agriculture to maximize crop yields, their long-term effect on the structures of soil microorganisms is still poorly understood. This study investigated the long-term impact of fertilization and crop rotation on soil microbial diversity and the microbial community structure in four different locations with three soil types. Since 1996, manure (MF; 330 kg N/ha), sewage sludge (SF; 330 and SF3x; 990 kg N/ha), and NPK (NPK; 330 kg N/ha) fertilizers were periodically applied to the soils classified as chernozem, luvisol and cambisol, which are among the most abundant or fertile soils used for agricultural purposes in the world. In these soils, potato (Solanum tuberosum L.), winter wheat (Triticum aestivum L.), and spring barley (Hordeum vulgare L.) were rotated every three years. RESULTS: Soil chemistry, which was significantly associated with location, fertilization, crop rotation, and the interaction of fertilization and location, was the dominant driver of soil microbial communities, both prokaryotic and fungal. A direct effect of long-term crop rotation and fertilization on the structure of their communities was confirmed, although there was no evidence of their influence on microbial diversity. Fungal and bacterial communities responded differently to fertilization treatments; prokaryotic communities were only significantly different from the control soil (CF) in soils treated with MF and SF3x, while fungal communities differed across all treatments. Indicator genera were identified for different treatments. These taxa were either specific for their decomposition activities or fungal plant pathogens. Sequential rotation of the three crops restricted the growth of several of the indicator plant pathogens. CONCLUSIONS: Long-term fertilization and crop rotation significantly altered microbial community structure in the soil. While fertilization affected soil microorganisms mainly through changes in nutrient profile, crop rotations lead to the attraction and repulsion of specific plant pathogens. Such changes in soil microbial communities need to be considered when planning soil management.

Soil Organic Matter Degradation in Long-Term Maize Cultivation and Insufficient Organic Fertilization.

Soil organic matter carbon (CSOM) compounds degradation was observed in long-term field experiments with silage maize monoculture. Over a period of 26 years, the content of carbon in topsoil decreased by 22% in control unfertilized plots compared to 25% and 26% in treatments fertilized annually with mineral nitrogen. With annual wheat straw application (together with mineral N), the content of CSOM decreased by 8%. Contrary to that, the annual application of farmyard manure resulted in a CSOM increase of 16%. The ratio of carbon produced by maize related to total topsoil CSOM content ranged between 8.1-11.8%. In plots with mineral N fertilization, this ratio was always higher than in the unfertilized control plots. With the weaker soil extraction agent (CaCl2), the ratio of carbon produced by maize was determined to be 17.9-20.7%. With stronger extraction agent (pyrophosphate) it was only 10.2-14.6%. This shows that maize produced mostly unstable carbon compounds. Mineral N application resulted in stronger mineralization of original and stable organic matter compared to the unfertilized control. However, the increase of maize-produced carbon content in fertilized plots did not compensate for the decrease of "old" organic matter. As a result, a tendency to decrease total CSOM content in plots with mineral N applied was observed.

Microbial Communities in Soils and Endosphere of Solanum tuberosum L. and their Response to Long-Term Fertilization.

An understanding of how fertilization influences endophytes is crucial for sustainable agriculture, since the manipulation of the plant microbiome could affect plant fitness and productivity. This study was focused on the response of microbial communities in the soil and tubers to the regular application of manure (MF; 330 kg N/ha), sewage sludge (SF; 330 and SF3x; 990 kg N/ha), and chemical fertilizer (NPK; 330-90-300 kg N-P-K/ha). Unfertilized soil was used as a control (CF), and the experiment was set up at two distinct sites. All fertilization treatments significantly altered the prokaryotic and fungal communities in soil, whereas the influence of fertilization on the community of endophytes differed for each site. At the site with cambisol, prokaryotic and fungal endophytes were significantly shifted by MF and SF3 treatments. At the site with chernozem, neither the prokaryotic nor fungal endophytic communities were significantly associated with fertilization treatments. Fertilization significantly increased the relative abundance of the plant-beneficial bacteria Stenotrophomonas, Sphingomonas and the arbuscular mycorrhizal fungi. In tubers, the relative abundance of Fusarium was lower in MF-treated soil compared to CF. Although fertilization treatments clearly influenced the soil and endophytic community structure, we did not find any indication of human pathogens being transmitted into tubers via organic fertilizers.

The response of soil nematode Caenorhabditis elegans on the sewage sludge-derived micropollutants.

Sewage sludge application to soil is of great interest, due to required organic matter and the wide spectra of nutrients it provides. However, the presence of unpredictable content of emerging contaminants may turn this valuable raw material into a hazardous substance. In this study, three selected sewage sludges derived micropollutants from different origins; that is, one each under persistent organic pollutants (POPs), pharmaceuticals and personal care products (PPCPs) were considered. The effect of each micropollutant on the feeding activity of free-living soil nematode Caenorhabditis elegans was analysed. The analysis was performed in model soil solution using a larval feeding inhibition assay. The results showed no significant effects from selected POP-2,2',4,4',5-pentabromodiphenyl either and pharmaceutical-chlortetracycline on the feeding activity of tested nematodes. On the contrary, feeding activity was inhibited by PPCP-galaxolide (HHCB) with an effective concentration of 12.2 ±â€¯2.2 mg.l-1. The calculated risk quotient for galaxolide (RQ = 0.14) demonstrated a medium ecological risk to the nematodes. Based on our findings, concentrations of micropollutants in sewage sludge treated soil pose negligible risk to feeding activity of soil nematode. However, the potential impact of musk compounds on free-living soil biota requires detailed evaluation in further research.

Fractionation of sulfur (S) in beech (Fagus sylvatica) forest soils in relation to distance from the stem base as useful tool for modeling S biogeochemistry.

The investigation of the fractionation of S compounds in forest soils is a powerful tool for interpreting S dynamics and S biogeochemistry in forest ecosystems. Beech stands on high pH (nutrient-rich) sites on Flysch and on low pH (nutrient-poor) sites on Molasse were selected for testing the influence of stemflow, which represents a high input of water and dissolved elements to the soil, on spatial patterns of sulfur (S) fractions. Soil cores were taken at six distances from a beech stem per site at 55 cm uphill and at 27, 55, 100, 150 and 300 cm downhill from the stem. The cores were divided into the mineral soil horizons 0-3, 3-10, 10-20, 20-30 and 30-50 cm. Soil samples were characterized for pH, Corg, pedogenic Al and Fe oxides and S fractions. Sequential extraction by NH4Cl, NH4H2PO4 and HCl yielded readily available sulfate-S (RAS), adsorbed sulfate-S (AS) and HCl-soluble sulfate-S (HCS). Organic sulfur (OS) was estimated as the difference between total sulfur (ToS) and inorganic sulfur (RAS + AS + HCS). Organic sulfur was further divided into ester sulfate-S (ES, HI-reduction) and carbon bonded sulfur (CS). On Flysch, RAS represented 3-6%, AS 2-12%, HCS 0-8% and OS 81-95% of ToS. On Molasse, RAS amounted 1-6%, AS 1-60%, HCS 0-8% and OS 37-95% of ToS. Spatial S distribution patterns with respect to the distance from the tree stem base could be clearly observed at all investigated sites. The presented data is a contribution to current reports on negative input-output S budgets of forest watersheds, suggesting that mineralization of OS on nutrient rich soils and desorption of historic AS on nutrient-poor soils are the dominant S sources, which have to be considered in future modeling of sulfur.

Agent Orange footprint still visible in rural areas of central Vietnam.

Levels of polychlorinated dioxins/furans (PCDD/PCDF) in selected environmental samples (soils, sediments, fish, and farm animals) were analyzed from the area of Phong My commune (Thua Thien-Hue province, Vietnam). This area was affected by Agent Orange spraying during the Vietnam war (1968-1971). Whereas PCDD/PCDF content in soil and sediment samples is relatively low and ranges between 0.05 and 5.1 pg WHO-TEQ/g for soils and between 0.7 and 6.4 pg WHO-TEQ/g for sediments, the PCDD/PCDF content in poultry muscle and liver in most cases exceeded the maximum permissible limit of dioxin content per unit fat mass. In some cases of soil and sediments samples, 2,3,7,8-TCDD represented more than 90% of the total PCDD/PCDF, which indicates Agent Orange as the main source.

The Rengen Grassland experiment: bryophytes biomass and element concentrations after 65 years of fertilizer application.

The Rengen Grassland Experiment in Germany, established in 1941, consists of the following fertilizer treatments applied under a two cut management: control, Ca, CaN, CaNP, CaNP-KCl, and CaNP-K(2)SO(4). The aim of this study was (1) to identify effects of fertilizer application on biomass and species composition of bryophytes and (2) to investigate the impact of fertilizer application on macro- (N, P, K, Ca, Mg), micro- (Cu, Fe, Mn, Zn), and toxic (As, Cd, Cr, Pb, Ni) element concentrations in bryophyte biomass. In June 2006, Rhytidiadelphus squarrosus was the only bryophyte species recorded in the control. In treatment Ca, R. squarrosus was the dominant bryophyte species whereas Brachythecium rutabulum occurred sporadically only in a single plot of that treatment. The latter was the only bryophyte species collected in CaN, CaNP, CaNP-KCl, and CaNP-K(2)SO(4) treatments. Dry matter accumulation of bryophytes was highest in the control (180 g m(-2)) followed by Ca (46 g m(-2)), CaNP (25 g m(-2)), CaNP-KCl (15 g m(-2)), CaNP-K(2)SO(4) (9 g m(-2)), and CaN (2 g m(-2)) treatments. A negative correlation between biomass production of bryophytes and dry matter production of vascular plants was revealed up to a threshold value of 400 g m(-2). Above this limit, biomass production of bryophytes remained obviously unaffected by further increase in biomass production of vascular plants. A significant effect of treatment on As, Cd, Cr, Fe, Mn, Ni, Pb, P, Ca, Mg, K, and N concentrations was revealed. Concentrations of these elements were a function of amount of elements supplied with fertilizers. Bryophytes seem to be promising bio-indicators not only for airborne deposition of toxic element but also for fertilizer introduced as well.

Interactions of EDDS with Fe- and Al-(hydr)oxides.

The efficiency of EDDS ([S,S]-ethylenediaminedisuccinate) in metal (phyto) extraction has been discussed in many recent papers. This study demonstrated that the presence of Fe- and Al-(hydr)oxides in soils influences the speciation of EDDS and thus can decrease the extraction of the targeted metallic contaminants (e.g., Pb, Cu, Zn). Above all, amorphous and poorly crystalline oxides (e.g., ferrihydrite) seem to significantly control dissolved Fe and Al concentrations in soils in the presence of metal-EDDS complexes and especially uncomplexed EDDS. Metals released from these minerals compete for the chelating agent and the extraction efficiency of the targeted metals is lowered. The formation of stable Cu-EDDS complexes, which are preferentially formed in soils with high Cu concentrations, results into a lower dissolution of ferrihydrite and goethite compared to free EDDS and Al-EDDS. Information about the contents of amorphous and poorly crystalline oxides in the treated soils would thus be beneficial for choosing efficient EDDS dosages.

Retention of copper originating from different fungicides in contrasting soil types.

This work described the retention of Cu from two different commonly used pesticides, the Bordeaux mixture (CuSO(4)+Ca(OH)(2)) and Cu-oxychloride (3Cu(OH)(2).CuCl(2)), and from Cu(NO(3))(2) in contrasting soil types (Leptosol, Chernozem, Cambisol). Thermodynamic modeling showed that Cu speciation was similar in all fungicide solutions. However, the retention of Cu differed with the fungicide used (maximum retention from the Bordeaux mixture) which indicates that different retention processes occurred in the studied soils. The suggested mechanisms include: specific and non-specific adsorption (especially on soil organic matter), precipitation of newly formed phases, such as CuO, Cu(OH)(2), Cu(2)(OH)(3)NO(3), CuCO(3)/Cu(2)(OH)(2)CO(3) and in the case of the Bordeaux mixture, precipitation of various Cu-hydroxysulfates. These phases were identified by the speciation model. The retention of fungicide-derived Cu in the studied soil types followed well the Freundlich isotherm and was directly controlled by the chemical form of Cu. This fact should be taken into account for both environmental and practical applications.

Glutamate kinase as a potential biomarker of heavy metal stress in plants.

Changes of glutamate kinase activity (GKA) in plants under cadmium and zinc chronic stress reported here reveal a regulatory role of this enzyme in plant heavy metal stress adaptation and indicate its potential use as a stress biomarker. Results of the first experimental series confirmed the toxic effects of cadmium and zinc at tested levels (30, 60, 90 mg Cd kg(-1) and 250, 500, 750 mg Zn kg(-1) soil) for spinach. A significant decrease of GKA in plants grown on contaminated treatments was found. Changes of GKA of plants grown on the highest contaminated treatments in the second series of experiments showed a similar course as a curve of plant stress response indicating the process of plant adaptation to chronic stresses--the decline of GKA in period of damage of cell activities, increase of its activity in period of maximum resistance and its following decrease in period of the plant metabolism depletion.

Determination of certain micro and macroelements in plant stimulants and their infusions.

The quantitative analysis of Al, B, Cu, Fe, Mn, P and Zn by inductively coupled plasma optical emission spectrometry (ICP-OES) and Ca, K and Mg by atomic absorption spectrometry (AAS) has been carried out in both the raw material and infusions from 31 samples of traditional plant stimulants (tea and coffee) and mate, rooibos, honeybush and chamomile. The results were discussed with respect to differences to the beverage quality and their role in the human diet. The levels of elements not significantly differ between tea types (black, green, oolong, white), and between Arabica and Robusta coffee. In comparison with tea, coffee was found to be a poor source of elements with the exception of Ca and Fe. High levels of B, Ca, Cu, Mn, Mg and Zn were found in mate (mainly green type) and of B, Ca, Cu, Fe and P in chamomile, whereas the amounts of all elements in rooibos and honeybush infusions were low (except of Ca). Apart from tea, other stimulants appeared to not represent important sources of potentially harmful amounts of Al for the human diet.

Comparison of mild extraction procedures for determination of plant-available arsenic compounds in soil.

In this work three mild extraction agents for determination of plant-available fractions of elements in soil were evaluated for arsenic speciation in soil samples. Pepper (Capsicum annum, L.) var. California Wonder was cultivated in pots, and aqueous solutions of arsenite, arsenate, methylarsonic acid, and dimethylarsinic acid, at a concentration of 15 mg As kg(-1) soil, were added at the beginning of the experiment. Control pots (untreated) were also included. Deionized water, 0.01 mol L(-1) CaCl2, and 0.05 mol L(-1) (NH4)2SO4 were used to extract the plant-available fraction of the arsenic compounds in soil samples collected during the vegetation period of the plants. Whereas in control samples the extractable arsenic fraction did not exceed 1% of total arsenic content, soil amendment by arsenic compounds resulted in extraction of larger amounts, which varied between 1.4 and 8.1% of total arsenic content, depending on soil treatment and on the extracting agent applied. Among arsenic compounds determined by HPLC-ICPMS arsenate was predominant, followed by small amounts of arsenite, methylarsonic acid, and dimethylarsinic acid, depending on the individual soil treatment. In all the experiments in which methylarsonic acid was added to the soil methylarsonous acid was detected in the extracts, suggesting that the soil bacteria are capable of reducing methylarsonic acid before a further methylation occurs. No significant differences were observed between analytical data obtained by using different extraction procedures.

Development of a procedure for the sequential extraction of substances binding trace elements in plant biomass.

This work investigates how the amounts of some important substances in a plant, and their behaviour inside the plant, depend on the levels of stress placed on the plant. To this end, model plant spinach (Spinacia oleracea L.) was cultivated on soil treated with sewage sludge. The sewage sludge contained various trace elements (As, Cd, Cu, Zn), and the uptake of these trace elements placed the plant under stress. Following this, a sequential extraction procedure was employed to determine the levels and distributions of trace elements within the most important groups of compounds present in the spinach plants. Since the usual five-step sequential extraction procedure provides only general information on the distributions of elements within individual groups of organic compounds, due to the wide range of organic compounds within the individual fractions, this scheme was extended and improved through the addition of two solvent extraction steps-a butanol step (between the ethyl acetate and methanol solvent steps) and an H(2)O step (after the methanol+H(2)O solvent step). The distributions and levels of the trace elements within the main groups of compounds in spinach biomass was investigated using this new seven step sequential extraction (water free solvents: petroleum ether (A) --> ethyl acetate (B) --> butanol (C) --> methanol (D) --> water solvents: methanol+H(2)O (1+1; v/v) (E) --> H(2)O (F) --> methanol+H(2)O+HCl (49.3+49.3+1.4; v/v/v) (G)). The isolated fractions were characterized using IR spectroscopy and the trace element contents were determined in the individual fractions. Lipophilic compounds with low contents of Cd, Cu and Zn were separated in the first two fractions (A, B). Compounds with higher As contents (11.5-12.8% of total content) were also extracted in the second fraction, B. These two fractions formed the smallest portion of the isolated fractions. Low molecular compounds from secondary metabolism and polar lipids were separated in the third (C) and fourth (D) fractions, and high molecular compounds (mainly polypeptides and proteins) separated in the fifth and sixth fractions (E, F). The addition of the H(2)O solvent step was particularly useful for separating compounds that have a significant impact on trace element bounds. The methanol fraction was dominant for all treatments, and a significant decrease in the spinach biomass separated in this fraction was observed when the soil was treated with sewage sludge. Most of the As (35.5-38.8% of total content), Cu (45.0-51.6%) and Zn (39.8-47.2%) was also determined in this fraction. The G fraction (obtained after acid hydrolysis) contained polar compounds. Most of the Cd was also found in this fraction, as was a significant amount of Zn. Non-extractable residues formed the last fraction (polysaccharides, proteins).