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Doxorubicin (Dox) is one of the most important first-line drugs used in osteosarcoma therapy. Multiple and not fully clarified mechanisms, however, determine resistance to Dox. With the aim of identifying new markers associated with Dox-resistance, we found a global up-regulation of small nucleolar RNAs (snoRNAs) in human Dox-resistant osteosarcoma cells. We investigated if and how snoRNAs are linked to resistance. After RT-PCR validation of snoRNAs up-regulated in osteosarcoma cells with different degrees of resistance to Dox, we overexpressed them in Dox-sensitive cells. We then evaluated Dox cytotoxicity and changes in genes relevant for osteosarcoma pathogenesis by PCR arrays. SNORD3A, SNORA13 and SNORA28 reduced Dox-cytotoxicity when over-expressed in Dox-sensitive cells. In these cells, GADD45A and MYC were up-regulated, TOP2A was down-regulated. The same profile was detected in cells with acquired resistance to Dox. GADD45A/MYC-silencing and TOP2A-over-expression counteracted the resistance to Dox induced by snoRNAs. We reported for the first time that snoRNAs induce resistance to Dox in human osteosarcoma, by modulating the expression of genes involved in DNA damaging sensing, DNA repair, ribosome biogenesis, and proliferation. Targeting snoRNAs or down-stream genes may open new treatment perspectives in chemoresistant osteosarcomas.

Doxorubicin is one of the most effective drugs for the first-line treatment of high-grade osteosarcoma. Several studies have demonstrated that the major cause for doxorubicin resistance in osteosarcoma is the increased expression of the drug efflux transporter ABCB1/P-glycoprotein (Pgp). We recently identified a library of H2S-releasing doxorubicins (Sdox) that were more effective than doxorubicin against resistant osteosarcoma cells. Here we investigated the molecular mechanisms of the higher efficacy of Sdox in human osteosarcoma cells with increasing resistance to doxorubicin. Differently from doxorubicin, Sdox preferentially accumulated within the endoplasmic reticulum (ER), and its accumulation was only modestly reduced in Pgp-expressing osteosarcoma cells. The increase in doxorubicin resistance was paralleled by the progressive down-regulation of genes of ER-associated protein degradation/ER-quality control (ERAD/ERQC), two processes that remove misfolded proteins and protect cell from ER stress-triggered apoptosis. Sdox, that sulfhydrated ER-associated proteins and promoted their subsequent ubiquitination, up-regulated ERAD/ERQC genes. This up-regulation, however, was insufficient to protect cells, since Sdox activated ER stress-dependent apoptotic pathways, e.g., the C/EBP-β LIP/CHOP/PUMA/caspases 12-7-3 axis. Sdox also promoted the sulfhydration of Pgp that was subsequently ubiquitinated: this process further enhanced Sdox retention and toxicity in resistant cells. Our work suggests that Sdox overcomes doxorubicin resistance in osteosarcoma cells by at least two mechanisms: it induces the degradation of Pgp following its sulfhydration and produces a huge misfolding of ER-associated proteins, triggering ER-dependent apoptosis. Sdox may represent the prototype of innovative anthracyclines, effective against doxorubicin-resistant/Pgp-expressing osteosarcoma cells by perturbing the ER functions.

Drug efflux transporters, in particular P-glycoprotein (Pgp), limit the success of chemotherapy. We previously found that synthetic doxorubicin conjugated with nitric oxide (NO)-releasing group overcomes resistance by inducing a NO-mediated inhibition of Pgp. Here we produced the first liposomal formulations of this nitrooxy-doxorubicin decorated with folic acid (FA), termed LNDF, in order to improve their active targeting against Pgp-expressing tumors. Folate was inserted onto liposomes surface using two different methods and the formulations were compared with respect to their technological features and in vitro behavior. By analyzing human and murine breast cancer cells with different expression of FA receptor (FAR) and Pgp, we demonstrated that LNDF are internalized in a FAR-dependent manner and achieve maximal anti-tumor efficacy against FAR-positive/Pgp-positive cells. Upon uptake of LNDF, nitrooxy-doxorubicin was delivered within nucleus, where it induced cell cycle arrest and DNA damages, and mitochondria, where it impaired the mitochondrial energy metabolism and triggered mitochondria-dependent apoptosis. LNDF reduced the growth of FAR-positive/Pgp-positive tumors and prevented tumor formation in mice, whereas doxorubicin and Caelyx® failed. LNDF cardiotoxicity was comparable to Caelyx®. The sensitivity to LNDF was maintained in tumors exposed to repeated cycles of the drug and in cells derived from the exposed tumors, excluding the onset of secondary resistance. By combining an innovative multitarget cargo drug, conceived to achieve high efficacy against Pgp-expressing cells, and appropriate strategies of liposome formulation and decoration, we produced a therapeutic tool that may represent a significant advancement in the treatment of FAR-positive/Pgp-positive tumors.

Purpose: The increasing need for disposal of lake-dredged material (LDM) as a consequence of intensified natural and/or anthropogenically mediated erosion processes has lead the scientific community to find new strategies for its reuse. The aim of this study is to investigate the effect of LDM use on the biochemical and functional performance of a degraded soil affected by erosion and entisolization processes. Materials and methods: As a paradigmatic case study, a hydrographic basin located in Sardinia (Italy) was investigated. Severe soil degradation processes affect this area and have resulted in intensive sheet and rill water erosion. In contrast, an increase in sedimentation has been recorded on the bottom of an artificial lake. A degraded soil, collected in this area, were treated by co-utilization of LDM, other mineral matrices (a zeolitized tuff), organic amendment (a commercial manure), and mineral fertilizer (urea, triple superphosphate, and potassium sulfate) for the growth of a pasture grass under controlled (pot) conditions. The evolution of nine different model proto-horizons (MPH) was monitored through a series of biochemical parameters and techniques (total/extracellular enzymatic activity, isoelectric focusing, and gas chromatography) to assess the potential of LDM in soil biochemical recovery. Results and discussion: On the whole, treatments containing LDM resulted in good recovery of degraded soils, as shown by a general enhancement in biochemical functionality. Application of LDM increased the more stable fraction of organic matter and its active biochemical fraction, showing the highest stable humic carbon content and humic activity. Such outcomes seem to represent a long-term beneficial effect on soil functionality. Conclusions: This study demonstrates that LDM could be a useful pedotechnomaterial (PTM) for improving the biochemical functionality of extremely degraded soils. Additionally, the use of LDM as a PTM has the ecological advantage of recycling what is often considered as a “waste material.” From a socioeconomic point of view, the reuse of LDM in pedotechnique could represent a new low-cost alternative to the complex and expensive management and disposal of this material.

Doxorubicin (DOXO) is one of the most effective antineoplastic agents in clinical practice. Its use is limited by acute and chronic side effects, in particular by its cardiotoxicity and by the rapid development of resistance to it. As part of a program aimed at developing new DOXO derivatives endowed with reduced cardiotoxicity, and active against DOXO-resistant tumor cells, a series of H2S-releasing DOXOs (H2S-DOXOs) were obtained by combining DOXO with appropriate H2S donor substructures. The resulting compounds were studied on H9c2 cardiomyocytes and in DOXO-sensitive U-2OS osteosarcoma cells, as well as in related cell variants with increasing degrees of DOXO-resistance. Differently from DOXO, most of the products were not toxic at 5 μM concentration on H9c2 cells. A few of them triggered high activity on the cancer cells. H2S-DOXOs 10 and 11 emerged as the most interesting members of the series. The capacity of 10 to impair Pgp transporter is also discussed.

Doxorubicin (dox) is one of the first-line drug in osteosarcoma treatment but its effectiveness is limited by the efflux pump P-glycoprotein (Pgp) and by the onset of cardiotoxicity. We previously demonstrated that synthetic doxs conjugated with a H2S-releasing moiety (Sdox) were less cardiotoxic and more effective than dox against Pgp-overexpressing osteosarcoma cells. In order to increase the active delivery to tumor cells, we produced hyaluronic acid (HA)-conjugated liposomes containing Sdox (HA-Lsdox), exploiting the abundance of the HA receptor CD44 in osteosarcoma. HA-Lsdox showed favorable drug-release profile and higher toxicity in vitro and in vivo than dox or the FDA-approved liposomal dox Caelyx® against Pgp-overexpressing osteosarcoma, displaying the same cardiotoxicity profile of Caelyx®. Differently from dox, HA-Lsdox delivered the drug within the endoplasmic reticulum (ER), inducing protein sulfhydration and ubiquitination, and activating a ER stress pro-apoptotic response mediated by CHOP. HA-Lsdox also sulfhydrated the nascent Pgp in the ER, reducing its activity. We propose HA-Lsdox as an innovative tool noteworthy to be tested in Pgp-overexpressing patients, who are frequently less responsive to standard treatments in which dox is one of the most important drugs.

This work involves a study of the interaction of humic acid (HA) with zeolitic (phillipsite+chabazite) Neapolitan yellow tuff (NYT). HA sorption isotherms were carried out on untreated as well as on Li + -, Na + -, K + -, NH 4 + -, Ca 2+ -, Mg 2+ -, or Ba 2+ -enriched samples. Except for the Li-enriched sample, Langmuir sorption curves fitted the experimental data, allowing the calculation of the maximum HA sorbable amount, Q max , and the affinity constant between the sorbate and the sorbent, k . The Q max for the untreated sample was 8512±265 mg kg −1 , with k =10.8±1.4 l kg −1 . The experimental amounts of HA taken up by the Li-enriched sample were very small (183 to 2322 mg kg −1 ) and too scattered to be consistently fitted by any significant equation. For other cation enriched-samples, the HA- Q max amounts ranged from 6583±205 mg kg −1 for the K-treated tuff to 22 029±1065 mg kg −1 for the Mg-treated tuff, whereas the k values ranged from 8.0±1.7 l kg −1 for the Na-treated tuff to 81.4±17.5 l kg −1 for the Ba-treated tuff. The tuff samples enriched by divalent cations took up HA in amounts larger than those observed for the untreated sample; the opposite was true for the monovalent cation-enriched samples. The HA sorption curves on monovalent cation-enriched tuff were scarcely different, within experimental variance, from those observed for the untreated sample. On the contrary, both the Q max and the k values calculated for the HA sorption on the divalent cation-enriched samples were widely and significantly larger than those of the untreated sample, with the highest Q max for Mg- and Ca-enriched sample, and the highest k value for the Ba-enriched one. The results demonstrate that enrichment by divalent cations enhances the ability of Neapolitan yellow tuff to take up humic acid, whereas enrichment by monovalent cations reduces it; the results also show that humic acid sorption on tuff must be regarded as a complex phenomenon, occurring as a compromise between the ability of the cations to form stable bridges with the organic matter, and, on the other hand, their specific selective sorption by the tuff.

The present study aims to assess the evolution of different proto-horizons as embryonic soils built by pedotechnologies for the reclamation and management of derelict and damaged lands, such as abandoned quarries. The model proto-horizons were assembled by utilizing coarse limestone gravel or zeolitized Phlegraean Yellow Tuff (PYT) as mineral components and commercial compost-amendments or a phosphorite-poultry manure mixture as organic matrices for growth of a pasture-grass under controlled conditions. The evolution of the model proto-horizons was followed by an evaluation of the stability and modification of the organic matter (OM) with reference to plant development. The results suggest that the natural carbonatic substrate occurring in limestone quarries was unable to sustain significant plant growth, while the PYT was suitable and efficient as a pedogenic substrate because it supported plant growth and induced a conspicuous accumulation of OM due to root activity. In particular, OM, including humic and non-humic components, greatly increased in the PYT treatment with the phosphorite-poultry manure mixture showing a concurrent trend toward humification. Conversely, an overall tendency toward degradation of OM was detected in the PYT model proto-horizon treated with commercial compost. Feasibility estimates show that quarry restoration costs appear reasonable where environmental impacts are high. © 2013 Elsevier Ltd.

Anthropic-accelerated erosion processes have led to an increase in reported loss of soil surface horizons worldwide. Lake-dredged materials (LDMs) have often been considered suitable for upland disposal. This study aimed to assess the potential beneficial use of LDMs in soil rebuilding strategies for Mediterranean soils affected by the loss of surface horizons with consequent erosion/entisolization processes. Different model proto-horizons (MPHs) were assembled by means of the co-utilization of LDMs, other mineral matrices, organic amendment, and mineral fertilizer for the growth of a pasture grass under controlled (pot) conditions. The evolution of nine different MPHs was monitored by means of an evaluation/comparison of several physical–chemical parameters (texture, pH, electrical conductivity, N, P, K, and cation-exchange capacity) and the stability-modification of organic matter (OM) quality in relation to plant development (dry matter production, agronomic efficiency, and plant cover). The addition of LDM resulted in statistically significant (p

The aim of this study was to evaluate differences in T helper cell sub-types and osteoclast (OCs) precursors in peripheral blood between patients affected by early rheumatoid arthritis (eRA) and healthy controls. The effect of administration of cholecalcipherol on clinical and laboratory parameters was subsequently evaluated, by a parallel, randomized double blind, placebo controlled trial. Thirty nine eRA patients and 31 age-matched controls were enrolled and compared for levels of 25OH vitamin D, T helper cell sub-types, OCs precursors including both classical and non-classical and pro-inflammatory cytokines at baseline. Eligible patients were female ≥18 years of age with a diagnosis of RA, as defined by the American College of Rheumatology 2010 criteria for

We studied the effects of amendment with zeolitized tuffs (ZT) in recovering nitrogen and phosphorus as potential plant nutrients in soils treated with wastewater (WW). The surface horizon of two contrasting soils (a sandy, alkaline Entisol, and a sandy-loam, sub-acidic Alfisol), was pedotechnically managed with different ratios of Neapolitan Yellow Tuff (NYT) and a clinoptilolite bearing tuff (ZCL). It was then exposed to repeated treatments with ‘dirty’ municipal wastewater (DMW). Results showed that the presence of ZTs had several favorable effects. As concerns the aspect connected with the investigation into the supernatant/soil solution, total N and total P decreased sharply in the supernatant as ZT content in soil/zeolite samples increased. Large quantities of nitrate were removed from the solution, most probably via bio-chemical reaction. Investigation of the soil/zeolite samples after twelve consecutive treatment cycles showed that the concentration of the essential plant macronutrients N and P increased as ZT content increased. Overall, the ZTs added directly to the poorly-resilient soils appeared to be a useful amendment in reducing the pollutants load caused by irrigation with untreated wastewater. It also played a positive role in pedotechnique strategies, improving both the natural intrinsic soil resilience and soil functionality.

A study was started aiming at assessing the pedogenic potential of zeolitized tuffs as possible substrates to soil formation, especially for soil rebuilding in degraded lands. This paper deals with Ca, Al, Mg and Fe distribution in leachates obtained by a sequence of experimental weathering cycles of Campanian Ignimbrite (yellow facies) by water (W) and Na-humate (Na-Hu). The cation amounts were Al>Ca>Mg>Fe in W and Ca>Al>Mg>Fe in Na-Hu extracts, the latter being more efficient. © 2008 Elsevier B.V. All rights reserved.

A study is in progress aiming at characterizing the chemical, chemical-physical and structural properties of organo-zeolite aggregates relevant for their use in pedological technologies for soil restoration. This paper deals with the surface and porosity properties of organo-zeolite aggregates formed by Neapolitan Yellow Tuff (N), tannic acid (T), and Ca2+ bridging ion, with different T/N ratios. T acted as a molecular plug. dramatically decreasing both the surface area and the micropore volume. © 2008 Elsevier B.V. All rights reserved. A study is in progress aiming at characterizing the chemical, chemical-physical and structural properties of organo-zeolite aggregates relevant for their use in pedological technologies for soil restoration. This paper deals with the surface and porosity properties of organo-zeolite aggregates formed by Neapolitan Yellow Tuff (N), tannic acid (T), and Ca2+ bridging ion, with different T/N ratios. T acted as a molecular plug, dramatically decreasing both the surface area and the micropore volume.

The conventional Bray 1, Egner‐Riehm, Olsen, and the innovative cation/ anion exchange resin membranes (CAERM) and iron oxide‐impregnated filter paper strips (Pi) procedures were compared as phosphorus (P) extradants from 73 represintative Portuguese soils. The soils were characterized by wide variability of their pedological, physical, and chemical properties. Eleven FAO‐UNESCO soil units, with prevailing Anthrosol, Calcisol, Cambisol, Fluvisol, Leptosol, Luvisol, and 10 different textural classes, with prevailing loamy sand, sandy loam, loam, silty loam, clay loam, silty clay loam, were recognized. The soils showed the following properties: CaCO3 0.0–50.9 g100 g‐1, organic matter 0.4–8.4 g 100 g‐1, pH‐CaCl2 3.9 to 7.9, cation exchange capacity 1.5–57.6 cmolc kg‐1 Soil‐P (mg kg‐1) ranges were: 0.2–185.9 for Bray 1, 0.6–307.7 for Egner‐Riehm, 1.0–100.5 for Olsen, 1.1–69.4 for Pi, and 0.4–48.8 for CAERM. The P extraction efficiency decreased along with the order Bray 1 > Egner‐Riehm > Olsen > Pi >...

With the purpose to set up a convenient strategy to rehabilitate degraded soils by recovering their functionality, the possibility of using zeolitized tuff as inorganic ion-exchanger components of organomineral aggregates, in place of the naturally occurring clay materials was estimated. Accordingly, after the evaluation of a suitable method for measuring the cation exchange capacity of both materials (a phillipsite-rich tuff from the surroundings of Naples, Italy, and a bentonite, from Wyoming, USA), exchange kinetics and isotherms Of Cu2+, Pb2+ and Zn2+ for Ca2+ at 25 degrees C and 0.1 total normality, were determined and the related kinetic and thermodynamic quantities computed. Comparative results demonstrate that phillipsite-rich tuffs exhibit higher cation exchange capability and selectivity performances towards noxious cations than the montmorillonite clay does, and therefore that they can be considered good substitutes of clay materials to recover and/or rebuild polluted and degraded soils.

A study was performed to evaluate the suitability of zeolitized tuffs to restore degraded soils. Ca-saturated Neapolitan yellow tuff or clinoptilolite-rich tuff from Turkey were mixed with organic matter either as humic matter (tannic acid, humic acids) or non-humic matter (polygalacturonic acid). Organic matter was strongly stabilized in clinoptilolite-rich tuff aggregates based on humic matter, whereas it was more easily oxidized in models with nonhumic matter. Cation exchange capacity (CEC) was determined according to Ba/Mg-TEA method and by ammonium acetate procedure. The former method underestimated the CEC of the zeolitized tuffs, but was able to detect the contribution of organic matter to the CEC of aggregates. The latter method provided consistent CEC values for the zeolitized tuffs, but underestimated the exchange activity of the organic components of aggregates. CEC of aggregates including tannic acid was practically nil. Binding tannic acid to zeolite via Cabridges, results evidently in occlusion of zeolite pores. © 2007 Elsevier B.V. All rights reserved. A study was performed to evaluate the suitability of zeolitized tuffs to restore degraded soils. Ca-saturated Neapolitan yellow tuff or clinoptilolite-rich tuff from Turkey were mixed with organic matter either as humic matter (tannic acid, humic acids) or non-humic matter (polygalacturonic acid). Organic matter was strongly stabilized in clinoptilolite-rich tuff aggregates based on humic matter, whereas it was more easily oxidized in models with non-humic matter. Cation exchange capacity (CEC) was determined according to Ba/Mg-TEA method and by ammonium acetate procedure. The former method underestimated the CEC of the zeolitized tuffs, but was able to detect the contribution of organic matter to the CEC of aggregates. The latter method provided consistent CEC values for the zeolitized tuffs, but underestimated the exchange activity of the organic components of aggregates. CEC of aggregates including tannic acid was practically nil. Binding tannic acid to zeolite via Ca-bridges, results evidently in occlusion of zeolite pores.

A study aiming at evaluating the technical and economic suitability of zeolitized tuffs as mineral substrate for soil re-building in pedotechnique strategies was carried out. The chemical and physical-chemical properties of aggregates ped models, obtained by interaction between tannic acid, i.e., an organic matrix precursor of humic substances, and a zeolitized material, namely Neapolitan Yellow Tuff, using Ca ions as "bridge", were investigated. Ped models were characterized according to chemical and physical standard methods for soil analysis, color analysis by visual interpretation and by spectro-radiometry, as well as by FT-IR spectrometry. The results suggest that the interaction between zeolite, Ca ions and tannic acid leads to the formation of stable aggregates with peculiar chemical and chemical-physical properties. © 2005 Elsevier B. V. All rights reserved. A study aiming at evaluating the technical and economic suitability of zeolitized tuffs as mineral substrate for soil re-building in pedotechnique strategies was carried out. The chemical and physical-chemical properties of aggregates ped models, obtained by interaction between tannic acid, i.e., an organic matrix precursor of humic substances, and a zeolitized material, namely Neapolitan Yellow Tuff, using Ca ions as "bridge", were investigated. Ped models were characterized according to chemical and physical standard methods for soil analysis, color analysis by visual interpretation and by spectro-radiometry, as well as by FT-IR spectrometry. The results suggest that the interaction between zeolite, Ca ions and tannic acid leads to the formation of stable aggregates with peculiar chemical and chemical-physical properties. © 2005 Elsevier B. V. All rights reserved.

Toxic metal release in simple leaching tests has been studied in this paper to assess waste behaviour in realistic landfilling scenarios. The waste is a galvanic sludge, raw or cement stabilized. Six different leachants were taken into account: distilled water, CO2-saturated solution, Olsen solution, Mehlich No. 3 solution, acid or alkaline soil circulating solution. Dynamic leaching tests of different duration were used for raw and stabilized waste. The results have shown that, with the exception of Mehlich No. 3 solution, when the waste comes into contact with waters of composition similar to that of the solutions studied, the potential environmental contamination should not be of concern.

A field experiment was carried out on maize (Zea mays, L.) to study the effects of different fertilizer management on nitrogen status in soil and plant response. Three different fertilizers, mineral (MN), mineral plus buffalo manure (MN + BM) and organo-mineral with peat (OMP), were added at the usual (140, 61 and 116 kg ha−1) and the reduced (70, 31 and 58 kg ha−1) rates of N, P and K. respectively. Soil samples were analyzed for N by both the Kjeldahl method and the electro-ultrafiltration technique (EUF). The soil Kjeldahl-N concentrations were scarcely affected by the different fertilizer treatments, while the EUF-N concentrations were closely correlated with the amounts of N added. The EUF also discriminated between the NO3-N and the sum of the ammonium and the easily extractable organic N forms (EUF-Norg + NH4). The largest proportions of EUF-Norg + NH4 were found in the untreated plots and in the plots treated with buffalo manure. The different fertilizer treatments significantly affected grain yield, which ranged from a minimum of 6.3 t ha−1 from the untreated plots, to a maximum of 11.9 t ha−1 from those supplied with 140 kg N, 61 kg P and 116 kg K ha−1 by OMP fertilizer. The highest agronomic efficiency index for N was exhibited in the OMP treatment at the reduced rate. The grain yield was closely correlated with the total extractable EUF-N, but different relationships were found between the rate of N added, the level of EUF-NO,-N in soil and grain yield for the different fertilizer treatments.

Primary hyperparathyroidism (PHPT) is a common cause of bone loss that is modeled by continuous PTH (cPTH) infusion. Here we show that the inflammatory cytokine IL-17A is upregulated by PHPT in humans and cPTH in mice. In humans, IL-17A is normalized by parathyroidectomy. In mice, treatment with anti-IL-17A antibody and silencing of IL-17A receptor IL-17RA prevent cPTH-induced osteocytic and osteoblastic RANKL production and bone loss. Mechanistically, cPTH stimulates conventional T cell production of TNFα (TNF), which increases the differentiation of IL-17A-producing Th17 cells via TNF receptor 1 (TNFR1) signaling in CD4(+) cells. Moreover, cPTH enhances the sensitivity of naive CD4(+) cells to TNF via GαS/cAMP/Ca(2+) signaling. Accordingly, conditional deletion of GαS in CD4(+) cells and treatment with the calcium channel blocker diltiazem prevents Th17 cell expansion and blocks cPTH-induced bone loss. Neutralization of IL-17A and calcium channel blockers may thus represent novel therapeutic strategies for hyperparathyroidism.

The present work is part of a study focused on the use of organo-zeolite conditioner to remediate soil polluted by toxic elements. The Neapolitan yellow tuff (NYT) was utilized as a component of an organo-mineral sorbent/exchanger soil conditioner with pellet manure (NYT/PM) to reduce the mobility of Cd and Pb and recover plant performance in heavily polluted soils from illegal dumps near Santa Maria La Fossa (Lower Volturno river basin, Campania Region, southern Italy). Pot experiments were performed by adding the NYT/PM mixture (1:1, w/w) to polluted soil at the rates of 0%, 25%, 50% or 75% (w/w). Wheat (Triticum aestivum) was used as the test plant. The addition of organo-zeolite. NYT/PM mixture significantly reduced the DTPA (diethylene-triamine-pentaacetic acid)-extractable Cd and Pb from 1.01 and 97.5 mg kg-1 in the polluted soil, to 0.14 and 11.6 mg kg-1, respectively, in the soil amended with 75% NYT/PM. The best plant response was observed in amended soil systems treated with 25% NYT/PM, whereas larger additions induced plant toxicities due to increased soil salinity.

A phosphate (P) availability index “F” (F) is proposed as a parameter to evaluate the fraction of P added to soil which remains actually available after a given time. A quick test to measure the F is also discussed. Twenty soils from the typical Mediterranean pedoclimatic environments, with contrasting chemical and physical properties, were utilized in this investigation. Three different soil+P incubation periods, i.e., 16 and 48 hours and 60 days were considered. After equilibrium, the available P was extracted by both Olsen (Olsen-P) and M3 (M3-P) reactants. The F were given by the values of the b slopes of the respective linear regressions: extracted-P = a + b added-P, obtained by the various soil+P equilibrium procedures and the two P extraction methods. The F were compared among them as well as with the classical Sorption Index (SI) parameter. The F obtained after 16 and 48 hours or 60 days by Olsen-P measurements (F-Olsen) ranged from 0.25 to 0.75, 0.19 to 0.56, and 0.17 to 0.56, with mean values of 0.55, 0.38, and 0.36, respectively. The corresponding F by M3-P (F-M3) showed ranges from 0.19 to 0.89, 0.11 to 0.85, and 0.07 to 0.78, with mean values of 0.54, 0.40, and 0.41. The SI ranged from 4.7 to 65.7, with a mean value of 21.7. We found that both the F and the SI parameters were consistently correlated to some soil properties effective in soil-P adsorption phenomena, with special reference to the cation exchange capacity (CEC). However, the F-Olsen and the F-M3 indexes calculated after 48 hours were strictly correlated, and practically coincident, to those calculated after 60 days, but not with the respective SI. Differently, the F-M3 after 16 hours showed the best correlations with both the other F values after 48 hours (r = 0.938) and 60 days (r = 0.955) and the SI (r = 0.861), thus providing a reliable index for the P availability evaluation.© 1995, Taylor & Francis Group, LLC. All rights reserved.

An investigation was undertaken aiming to evaluate the suitability of zeolitized tuffs as an anthropogeomorphic material for soil re-building in degraded and desertified areas. Four artificial soil proto-horizons were prepared utilizing fine limestone gravel or Neapolitan yellow tuff as inorganic components, and sewage sludge or pellet manure as organic parent materials. The proto-horizons evolution was followed by analyzing leachates periodically collected over 80 days. After 80 days, the body of proto-horizons was also analyzed. Our results showed that the release of C- and N- compounds in the leachates was strictly dependent on the nature of the parent organic material. The presence of Neapolitan yellow tuff in the proto-horizon bodies clearly favored an advantageous evolution and stabilization of parent organic matrices, in optimizing the carbon to nitrogen ratios by increasing the C/N values, and by protecting the organic matter against a disproportionate degradation. Our findings led to conclude that the zeolitized tuff is a promising material in pedotechnique strategies for soil reconstruction and fight against desertification; on the contrary, the organic matter appeared to be excessively demolished in the presence of limestone gravel.

Two zeolitized tuffs (ZTs), viz . a Neapolitan yellow tuff (NYT) and a clinoptilolite-bearing tuff (ZCL), were tested as pedotechnical materials to improve soil resilience against the impact of treatment by a `dirty' municipal sewage system (DSW). Soils (surface horizon) were a sandy, alkaline Entisol (Typic Xeropsamment), and a sandy-loam, sub-acidic Alfisol (Ultic Palexeralf). Results showed that the presence of ZTs resulted in several favourable effects. Electrical conductivity (EC) decreased and pH was buffered. Ammonium was selectively taken up from the DSW, making the zeolitized tuffs almost saturated by \batchmode \documentclass[fleqn,10pt,legalpaper]{article} \usepackage{amssymb} \usepackage{amsfonts} \usepackage{amsmath} \pagestyle{empty} \begin{document} \(\mathrm{NH}_{4}^{+}\) \end{document}, by exchanging both beneficial cations, such as K+ and Ca2+, thus improving their potential availability to plants, and undesirable cations such as Na+, thereby hindering the exchangeable sodium percentage (ESP) increase and concurrent soil salinization-alkalinization. At the same time, \batchmode \documentclass[fleqn,10pt,legalpaper]{article} \usepackage{amssymb} \usepackage{amsfonts} \usepackage{amsmath} \pagestyle{empty} \begin{document} \(\mathrm{NH}_{4}^{+}\) \end{document} was stored as a potentially slow-release nitrogen fertilizer. The mobility of Pb, Cu and Zn dropped off to a large extent. NYT produced the best effects, and the Entisol gained the greatest benefit from treatments.

The multiple-element extractant Mehlich 3 (M3) has not been tested extensively in Europe. In this Land, soil-P test recommendations are based, since decades, on the evaluation of the Olsen-extractable P, and the optimal soil-P levels have been established to range between 1.5 and 3.0 mg of Olsen-P per 100 g of soil. A research programme was started in order to assess the suitability of M3 as routine soil-P test in European laboratories. As a first approach, we develop conversion equations from Olsen-P to M3-P, in order to assess the agreement and the consistency of the measurements under a wide range of chemical and physical soil properties. To this aim, 120 samples with drastically contrasting features were selected within 206 soils collected from all the regions of South Italy. Soil-P ranges were 0.07–60.53 for M3, and 0.08–21.47 mg/100 g for Olsen. The results showed that M3-P was a P extractant more efficient than Olsen. The amounts of M3-P were, on the average, twice as large as the Olsen-P ones, with mean values of 5.70 and 2.75 mg/100g respectively. The soil properties exerted a great influence, as well as showed a contrasting effect, on the extraction efficiency of each method. For neutral-alkaline calcareous soils, the average M3-P/Olsen-P ratio increased to 2.52, and the efficiency of M3 poorly varied according to soil pH and CaC03content. On the contrary, in CaC03-free acidic soils, the M3-P/Olsen-P ratio decreased to 1.63. In particular, anomalous ratio values less than 1.0 were observed for acidic soils with high content of organo-mineral complexes with active amorphous A1 (Al-Oxa>7.5 g/kg). The Olsen-P values could be converted into M3-P values by simple linear equations; however, the conversions were more significant if equations by distinct multiple regressions were used either for calcareous (R2 = 0.798*) or for CaC03-free (R2 = 0.769*) soils. The soil properties, which significantly affected the regressions M3-P versus Olsen-P as accessory variables, were Fe-Oxa and Sand for calcareous soils, and pH-KCl, CEC, and Sand for CaC03-free soils. The ranges of the optimal soil M3-P levels, as estimated by converting the Olsen-P critical values adopted in Italy, were, on the average, 3.0–6.0 mg/100 g. Such limits should be shifted to 3.7–7.7 for calcareous soils, and to 2.7–4.9 for CaC03-free soils. Field calibrations would give more information to establish the proper values according to either the soil properties and plant requirements. The results encourage the introduction of M3 as routine soil-P test in our Countries. One must take into account, however, that some soil properties, in particular the CaC03content, migth be considered for a more precise comparative evaluation with existing laboratory data. © 1992, Taylor & Francis Group, LLC. All rights reserved.

iPTH increases WNT10b in T cells Our results show a marked increase in WNT10b expression in lymphoid cells during treatment with iPTH, whereas calcium and vitamin D alone has no effect; the increase is maximum after 6 months of treatment. We show that iPTH increases WNT10b production mainly by T cells. cPTH does not affect WNT10b expression In patients affected by primary hyperparatiroidism there was no significant difference in baseline expression as respect to osteoporotic, non-treated patients and surgical intervention does not modify WNT10b expression, data not shown.

Within a research program aimed to utilize natural zeolites for pedotechnical purposes, such as to rebuild degraded soils, to improve soil fertility and to remove soil pollutants, the adsorption process of humic acids (HAs) on untreated Neapolitan Yellow Tuff and on Ca2+-enriched samples was investigated in the temperature range 1-45°C. Experimental data showed a negligible temperature effect indicating that ΔH ≈ 0. Moreover, Scatchard-like plots suggested the occurrence of more than one adsorption sites for both samples. A good fit of the adsorption isotherms was obtained by two-site Langmuir equation. For both sites the HAs affinity was not modified by Ca2+-enrichment and ΔS° was >0. The adsorption of HAs on tuff is an entropy-driven process. © 2007 Springer Science+Business Media, LLC.

An experimental pedology research program was started aiming at modeling the potential pedogenization of zeolitized tuffs. The present study deals with a medium-term weathering of Phlegraean Yellow Tuff (PYT, with phillipsite>chabazite) and Red Tuff with Black Scoriae (RTBS, with chabazite>phillipsite) under discontinuous treatment by water (W) and by humic acids (HA). Significant amounts of cations, increasing in the sequence Al

A two‐step digestion with hydrogen peroxide (H2O2)/boiling sulfuric acid (H2SO4) ("peroxy treatment") in the absence of heavy metals catalysts is proposed as an alternative to the copper (Cu)/selenium (Se) catalyzed digestion process for the routine determination of soil Kjeldahl‐nitrogen (N). Sixty‐eight samples from pedotypes representative of the Mediterranean environment, with contrasting features and use, were chosen in order to ensure the largest variability of total N and organic carbon (C) contents. The average soil N content was 0.223 g/100g for the H2O2 treatment, and 0.196 g/100g for the Cu/Se one, with significant difference between the means and with limits ranging from 0.042 to 0.678 and from 0.025 to 0.696 g/100g for H2O2‐N and Cu/Se‐N, respectively. The amounts of soil N determined by the contrasted procedures were strictly dependent on the respective organic C contents, and they correlated each other by the highly significant linear regression: Cu/Se‐N = ‐0.017 + 0.955/H2O2‐N, R2...

An investigation was carried out to elucidate the role of Al or Fe poorly-ordered oxyhydroxides in determining the surface properties of soil ped models formed by interaction with bentonite clay (C) and polyphenol (pp) in acidic milieu, with emphasis on phosphorus (P) sorption/desorption phenomena. P was chosen because of its important involvement on pedogenic processes as well as on soil fertility. P was added to models (Pa) at the rate of 10 mg·g-1. Pa was then extracted from the models at different aggregation states (suspended, freeze dried, air-dried, re-suspended), by using the electro-ultrafiltration technique (EUF-P). The cumulative amount EUF-P extracted after 40 min, representing the loosely-bound immediately-exchangeable P (Pi) and the maximum desorbable EUF-P, representing the slowly released P (Pm) were considered. The models were analyzed for their Cation Exchange Capacity (CEC), Specific Surface Area (SSA), Specific Cationic Surface Charge (SCSC), Titratable Acidity (TA) to pH = 7.0 or pH = 8.0 by KOH or by Ca(OH)2, and Phosphorus Sorption Coefficient (PSC). The C-Fe-pp model was characterized by an elevated surface reactivity, showing values of CEC (1777 μeq·g-1), SSA (483.2 m2·g-1), SCSC (3.678 μeq·m-2), TA (from 572 to 804 μeq·g-1) and PSC (92.4%), which were considerably larger than the respective determined for the C-Al-pp model (CEC= 1173 μeq·g-1, SSA = 420.0 m2·g-1, SCSC = 2.793 μeq·m-2, TA from 36 to 176 μeq·g-1, and PSC = 76.8%). Contrastingly, both the amounts EUF Pi and Pm desorbable from the same C-Fe-pp model were much larger than the respective determined for the C-Al-pp model. With reference to the aggregation state of the prepared materials, Pi decreased on the average as suspended > freeze-dried > air-dried ≥ resuspended. The desiccation via air-drying definitively stabilized the P pool, especially in the C-Al-pp model. Such stabilization was irreversible, since both Pi and Pm for C-Al-pp, and Pi for C-Fe-pp, did not substantially change in the re-suspended materials. With regard to kinetics aspects, the EUF-P desorption from C-Al-pp always followed a 2nd reaction order, while that from C-Fe-pp followed zero or 1st reaction order from suspended and freeze-dried, or from air-dried and re-suspended materials, respectively. The achieved data clearly demonstrated that the different interactions of bentonite clay and polyphenol with Al- or Fehydrolytic products led to the formation of aggregates with peculiar surface properties and physical-chemical behavior, with distinct mechanisms controlling the interactions of P with C-Al-pp or C-Fe-pp in both sorption and desorption phenomena. An investigation was carried out to elucidate the role of Al or Fe poorly-ordered oxyhydroxides in determining the surface properties of soil ped models formed by interaction with bentonite clay (C) and polyphenol (pp) in acidic milieu, with emphasis on phosphorus (P) sorption/desorption phenomena. P was chosen because of its important involvement on pedogenic processes as well as on soil fertility. P was added to models (Pa) at the rate of 10 mg·g-1. Pa was then extracted from the models at different aggregation states (suspended, freeze dried, air-dried, re-suspended), by using the electro-ultrafiltration technique (EUF-P). The cumulative amount EUF-P extracted after 40 min, representing the loosely-bound immediately-exchangeable P (Pi) and the maximum desorbable EUF-P, representing the slowly released P (Pm) were considered. The models were analyzed for their Cation Exchange Capacity (CEC), Specific Surface Area (SSA), Specific Cationic Surface Charge (SCSC), Titratable Acidity (TA) to pH = 7.0 or pH = 8.0 by KOH or by Ca(OH)2, and Phosphorus Sorption Coefficient (PSC). The C-Fe-pp model was characterized by an elevated surface reactivity, showing values of CEC (1777 μeq·g-1), SSA (483.2 m2·g-1), SCSC (3.678 μeq·m-2), TA (from 572 to 804 μeq·g-1) and PSC (92.4%), which were considerably larger than the respective determined for the C-Al-pp model (CEC= 1173 μeq·g-1, SSA = 420.0 m2·g-1, SCSC = 2.793 μeq·m-2, TA from 36 to 176 μeq·g-1, and PSC = 76.8%). Contrastingly, both the amounts EUF Pi and Pm desorbable from the same C-Fe-pp model were much larger than the respective determined for the C-Al-pp model. With reference to the aggregation state of the prepared materials, Pi decreased on the average as suspended > freeze-dried > air-dried ≥ resuspended. The desiccation via air-drying definitively stabilized the P pool, especially in the C-Al-pp model. Such stabilization was irreversible, since both Pi and Pm for C-Al-pp, and Pi for C-Fe-pp, did not substantially change in the re-suspended materials. With regard to kinetics aspects, the EUF-P desorption from C-Al-pp always followed a 2nd reaction order, while that from C-Fe-pp followed zero or 1st reaction order from suspended and freeze-dried, or from air-dried and re-suspended materials, respectively. The achieved data clearly demonstrated that the different interactions of bentonite clay and polyphenol with Al- or Fehydrolytic products led to the formation of aggregates with peculiar surface properties and physical-chemical behavior, with distinct mechanisms controlling the interactions of P with C-Al-pp or C-Fe-pp in both sorption and desorption phenomena.

A modeling approach was applied to understand and clarify the composite phenomena of the organo-mineral complexing and the ped formation in soil. The properties of conglomerates formed at pH 5.5 by montmorillonitic clay (C), synthetic Al- or Fe-oxyhydroxides, and polyphenol (pp) as humic material were studied. Investigational methods included SEM, FT-IR spectroscopy, X-ray diffraction, particle-size distribution, mechanical stability against ultrasonic dispersion and chemical stability to mild and strong reactants and to oxidative treatments. The models showed distinct morphological, mineralogical, mechanical, chemical and physico-chemical features. By SEM studies, the C-Al-pp model exhibited an irregularly rugged surface, while the C-Fe-pp showed evidence of spheroidal outgrowths. FT-IR spectroscopy provided clues for the effective interaction among the organic and inorganic components of conglomerates. X-ray diffraction patterns showed that Al- and, by a lesser extent, Fe- hydrolytic products partly entered the clay layers, thus expanding the basal period. The presence of broad and weak diffusion bands also suggested the formation of poorly-ordered Al- and Fe-oxy-hydroxides. The presence of Al- led to the prevailingly formation of small massive packets (

The soil availability index, 'F', showed to be a suitable tool to assess the fraction of phosphorus (P) added to soil remaining available after a given time. However, the classical F determination methods are laborious and time-consuming; so we devised more quick and simple procedure. This paper deals with the reliability of Olsen, Mehlich 3 (M3), and the innovative 'iron-impregnated paper-strip' (Pi) methods to evaluate the F index by short- term, double-point soil+P equilibration procedures. Representative Italian Alfisol were examined: they were characterized by from low to high P Sorption Index (SI) values (4.6 to 35.4, mean 22.0) and from low to sufficient available Olsen-P contents (2.0 to 33.0 ppm, mean 11.3). The samples were supplied with 0 or 50 mg P per kg soil (P0 or P50, respectively), and then incubated for 2 or 24 hours (short term soil+P incubation periods), or 90 days (long-term period). At the balance, the available P was extracted by the compared methods and the respective F indexes were calculated in relation to the different amounts of available P extracted from P50 and P0 samples. For both P0 and P50 samples, and after the different incubation periods, all the compared methods provided consistent and homogeneous extractable-P values (p

Phosphate sorption and desorption in soils are markedly influenced by iron oxides, although little is known on how the common iron oxides differ in their behaviour towards added phosphate. In this study, we investigated phosphate sorption and desorption in the clay fractions of 12 Terre Rosse that ranged widely in Fe oxide content, had very low contents of oxalate-extractable Fe oxides and different hematite/goethite ratios. Phosphate sorption at an equilibrium concentration of 1 mg P 1−1 was correlated with the goethite but not with the hematite content of the clay fractions. When phosphate was desorbed by electro-ultrafiltration, the difference in desorption half-time between untreated and deferrified clays was positively correlated with the goethite but not with the hematite content. These results suggest that goethite is more active than hematite in phosphate sorption and retention by soils. Einflus von Goethit und Hamatit auf die Phosphat-Sorption und -Desorption in Terre Rosse In Boden werden Phosphat-Sorption und -Desorption von den Eisenoxiden beeinflust; der spezifische Einflus der verschiedenen Eisenoxide ist jedoch kaum bekannt. Es wurden P-Sorption und -Desorption der Tonfraktionen von 12 Terre Rosse mit sehr verschiedenen Gehalten an Goethit und Hamatit und geringem oxalat-loslichen Fe untersucht. Bei einer Gleichgewichtskonzentration von 1 mg P 1−1 war die P-Sorption mit dem Goethitgehalt, nicht dagegen mit dem Hamatitgehalt, korreliert. Die Zeit bei der durch Elektro-Ultrafiltration die Halfte des sorbierten P desorbiert wurde, war ebenfalls mit dem Goethitgehalt korreliert. Es wird gefolgert, das Goethit die P-Sorption und -Desorption dieser Boden starker beeinflust als Hamatit.

The effect of two levels of K and P applications on an Italian vertisol was investigated adding known quantites of KC1 and Na2HPO4 solutions, respectively. The extractions were carried out using electro‐ultrafiltration (EUF) at a constant electric field and different temperatures. The EUF data were compared with the NH4OAC extracted K and Olsen‐P values. We found that both the soluble K fraction, extracted by moderate EUF conditions, and the reserve K fraction, extracted by stronger EUF conditions, did not increase significantly with fertilization treatments. On the contrary, in the case of P the first moderate extraction assessed the different “fertilization”; levels better than the successive, more powerful procedure.

‐ An investigation on the desorption rates of potassium and phosphorus from an Italian vertisol was carried out using electro‐ultrafiltration system (EUF). Desorption rate parameters as maximum desorbable quantity, half‐time and rate constant were determined, when possible, using different extraction procedures. The buffer power of this soil and the effects of K and P applications on kinetics factors were evaluated. Potassium release from soil was described by either zero or second order reaction kinetics, depending on selected EUF procedure. The effects of K applications were almost always negligible. P desorption was better described in all cases by zero order reaction kinetics. A set of equations was reported to characterize the soil with respect to the kinetics of nutrient releases.

The adsorption of paraquat (1,1‐dimethyl 4,4'‐dipyridylium dichloride) by a soil and two soil aggregate models containing tannic acid as the source of organic matter was studied. The isotherms obtained fit the Langmuir adsorption equation. The values of maximum adsorption found for the aggregates were higher than the cation exchange capacity indicating the existence of specific interactions as well as cation exchange. This is attributed, in agreement with the results of other studies, to the low Donnan potential of the water‐paraquat‐colloids of the soils system, owing to the sparingly ionized tannic acid. A study was also made of the adsorption of paraquat by the soil and the aggregates after removing the organic matter by oxidation. In all cases, a reduction in adsorption was observed. The values of the Langmuir K constants, of the sorptivity indices and of the mean equilibrium concentrations, indicate that the interaction mechanisms involved in the adsorption of the herbicide by the natural and oxidize...

Hydroxy-aluminum-tannate-montomorillonite complexes, which were prepared at pH 4.5 by different addition sequences of hydroxy-Al, tannic acid and montomorillonite showed distinct differences in titratable acidity both before and after drying. Titratable acidity of the complexes depended on the feed rate of the base and on the presence and nature of neutral salts (KCl or CaCl2). The organo-mineral complexes showed acidity values in CaCl2 substantially higher than those determined in KCl or in water (in the order listed), probably because many weak acidic groups released H+ ions by complexation (tannate molecules) or adsorption (OH-Al-ions) of Ca2+ ions. The hydroxy-Al-tannate-montmorillonite complexes, which were washed differently (dialyzed or ultrafiltered) and dried (freeze-dried or air-dried) also showed remarkably different titratable acidity. All the complexes usually showed much lower acidity values when air-dried than when freeze-dried. After sonification the titratable acidity values of all the complexes increased, but some air-dried samples, even after four sonification treatments, showed titratable acidity lower than that of the same freeze-dried complexes before sonification. Key words: Organo-mineral complexes, aluminum, titratable acidity, potentiometric titrations

Stability and infectivity of cucumber mosaic virus, strain D (CMV-D), associations with kaolinite and montmorillonite were determined, as affected by: i) nature of clay minerals; ii) nature of clay saturating cations; iii) exposure to dissociating salt solutions (2 M LiCl). Infectivity experiments carried out with sediments following centrifugation of the virus-clay mixtures (sd fractions), showed that, in absence of LiCl, the highest values were obtained with kaolinite, in the order Li+= K+ > NH4+= Mg++ > Na+ > Ca++ clay saturating cations, ranging between 91 and 30 % of the untreated control, whereas comparable montmorillonite fractions gave infectivity values with all cations about 10–15 % of the control. In presence of 2 M LiCl, montmorillonite preserved infectivity of the same fraction (Lsd fraction), which, in the case of Li+- or Ca++ -saturated samples, was higher when compared with the corresponding sd values, thus revealing for these cations an amplifying effect on infection. This did not occur with kaolinite which, however, gave a Lsd fraction more infectious than the other clay. The results confirmed that clay minerals preserve infectivity of virus preparations exposed to critical conditions, thus providing an explanation for the persistence in soil of infectivity of viruses which are normally not soil-borne. Under appropriate soil conditions these viruses may form complexes with clay minerals thus retaining an infectivity which may be enhanced by addition of cations as those contained in fertilizers.

A study was carried out on the influence of the sequence of addition of montmorillonite, hydroxy-A1 ions, and tannic acid ((A1) = 0.015 M; 6 mmole A1/g of clay; tannic acid/A1 molar ratio = 0.1) on the nature of organo-clay complexes formed at pH 4.5. A negligible amount of tannate was held on the clay surfaces in the absence of A1, whereas in the presence of A1, hydroxy-Al-tannate species were easily adsorbed on clay surfaces. Their distribution on the external surface and in the interlayer space of montmorillonite, however, was a consequence of how the components reacted with each other. The complexes showed broad X-ray powder diffraction peaks at 15.6 to 19.2 A at room temperature. They also showed different behavior to preheating, ethylene glycol solvation, and chemical treatments. Whereas tannic acid showed two prominent exothermic peaks at 390 ~ and 510~ all hydroxy-Al-tannate-mont- morinonite complexes showed a broad exotherm at about 400~ Some complexes showed, in addition, a small inflection between 350 ~ and 420~ The complexes also showed distinct differences in cation-exchange capacity, carbon content, extractable AI, titratable acidity, and mode of aggregation after drying.