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A category of chromium (Cr)-containing fertilizers is represented by the fertilizers deriving from byproducts of tanning process. Their use is widespread because of their good agronomic response due to the high content of slow release or- ganic nitrogen (N) and carbon (C). They do not represent an environmental hazard because only the non-toxic form of Cr(III) is present. Productive processes may involve chemical, enzymatic or thermal hydrolysis. The final product is characterized by different contents of peptides and free amino acids depending on the type of hydrolysis. Legislation concerning Cr-containing fertilizers is controversial because often do not consider any scientific evidences; nevertheless, the European Union, the United States and countries as Italy, do not set the restriction to Cr(III) and generally only the presence of the toxic form, Cr(VI), is limited. Depending on its two main oxidation forms, Cr issue has been studied for many years. Several authors confirmed that Cr(VI) is carcinogenic, while Cr(III) is an essential trace element in human and animal diet. In soil Cr(III) has low mobility, whereas Cr(VI) is highly water soluble. However Cr(VI) in soil is quickly reduced to Cr(III); on the contrary oxidation of Cr(III) to Cr(VI) is rarely possible because particular conditions must occur. Only a very small fraction of Cr in soil is available to plant uptake and its translocation in edible parts is limited because it is immobilized in roots as Cr(III). Therefore risks of environmental pollution using these fertilizers are negligible; on the contrary they have positive environmental and agronomical effects. The aim of this review is to deal with the category of the organic fertilizers containing Cr derived from tannery processes focusing on its chemical, productive, legislative, environmental and agronomical aspects. Special attention is given to the ambiguous issue of Cr briefly summarizing the most important studies of the last forty years.

Tannery land plaster (TLP) is a byproduct of lime hydrolysis of leather shavings. Its use in agriculture (organic C ≈ 17%, N ≈ 6% dm) could represent an alternative to landfill or incineration, but the high Cr(III) content (≈5% dm) makes it necessary to evaluate the effect on soil biochemical properties. TLP was therefore added at the rates of 220 and 440 kg of N ha−1to 2 agricultural soils and incubated for 56 days under controlled conditions. Extractable NH4 +-N and NO3 −-N, CO2-C evolution, microbial biomass-N, protease activity, and extractable Cr were monitored. The organic N was readily mineralized (>50% in the first week) and a significant increase in microbial activity was measured, regardless of soil type and addition rate. Extractable Cr(III) quickly decreased during the incubation. The absence of a negative impact on soil biochemical properties seems to support the use of TLP in agriculture, although further investigations in long-term field experiments are suggested.

The use of organic matter from compost to promote the catalytic photodegradation of micropollutants by solar light appears to be environmentally promising. However, quantitative evaluation of the photodegradation potential of the compost is needed. Our goal was to measure the formation rate of hydroxyl radicals and singlet oxygen, two strongly oxidant species, from irradiated compost organic matter. These two reactive species were photogenerated in all of our extracts regardless of the origin of the compost or the extraction procedure; however, their formation rates increased with composting time. Two herbicides and a fungicide were successfully photodegraded when irradiated with simulated or natural solar light in the presence of the compost organic matter or compost suspensions. For reasons of simplification and ease, the use of the latter is recommended in practice.

Three blends formed by: (i) food processing waste (CP(FP)), (ii) waste water sewage sludge (CP(WW)), and (iii) their mixture (CP(FP+WW)), blended with tree pruning as bulking agent, were composted over 3 months. During composting the blends were monitored for the main physical-chemical characteristics: temperature, oxygen saturation level (O(2)%), pH, total and volatile solids, total organic carbon, and organic nitrogen (N(org)). In addition to the main parameters, the dissolved organic carbon (DOC), the inorganic nitrogen and the Oxygen Uptake Rate (OUR) were monitored. All the mixtures easily reached a peak temperature around 70°C, related to the lowest O(2)%. After 90 d, CP(FP), CP(FP+WW), and CP(WW) showed an organic matter mineralization of 43%, 35% and 33%, respectively; CP(FP) fitted an exponential model while both CP(FP+WW), and CP(WW) fitted a logistic model. During composting an OUR reduction of 79%, 78% and 73% was registered in CP(FP), CP(FP+WW), and CP(WW), respectively; the OUR successfully fitted the adopted exponential model and well reflected the stabilization process in time. The N(org) recovery at the end of the process was positive only in CP(WW) (11.6%). The DOC significantly decreased during the composting process but did not successfully fit any model. The mineral nitrogen did not follow the typical pattern with NH(4)(+) disappearance and NO(3)(-) accumulation. Strong NO(3)(-) losses were evident in all blends, while NH(4)(+) accumulations were detectable only in CP(FP), and CP(FP+WW). The NH(4)(+)/NO(3)(-) ratio did not satisfactorily reflect the composting process over time. The comparison of the first order (exponential) and logistic (sigmoidal) models applied to the OUR and OM course highlights the role of mineral nitrogen as limiting factor during composting of the more stabilized sludge.

The use of N-(n-butyl)thiophosphoric triamide (NBPT), as a urease inhibitor, is one of the most successful strategies utilized to increase the efficiency of urea-based fertilization. To date, NBPT has been added to the soil incorporated in fertilizers containing either urea or the inhibitor at a fixed percentage on the urea weight. The possibility of using NBPT physically separated from urea-based fertilizers could make its use more flexible. In particular, a granulated product containing NBPT could be utilized in soils treated with different urea-based fertilizers including livestock urine, the amount depending on soil characteristics and/or the urea source (e.g., mineral fertilizer, organo-mineral fertilizer, or animal slurry). In this study, a multilayer soil column device was used to investigate the influence of an experimental granular product (RV) containing NBPT and a garlic extract, combining the ability to protect NBPT by oxidation and nitrification inhibition activity, on (a) spatial variability of soil urease and nitrification activities and (b) timing of urea hydrolysis and mineral-N form accumulation (NO(2)(-), NO(3)(-), NH(4)(+)) in soil treated with urea. The results clearly demonstrated that RV can, effectively, inhibit the soil urease activity along the soil column profile up to 8-10 cm soil layer depth and that the inhibition power of RV was dependent on time and soil depth. However, nitrification activity is not significantly influenced by RV addition. In addition, the soil N transformations were clearly affected by RV; in fact, RV retarded urea hydrolysis and reduced the accumulation of NH(4)(+)-N and NO(2)(-)-N ions along the soil profile. The RV product was demonstrated to be an innovative additive able to modify some key ureic N trasformation processes correlated with the efficiency of the urea-based fertilization, in a soil column higher than 10 cm.

Peat humic acid was fractionated by tangential ultrafiltration into six nominal molecular weight (NMW) fractions, HA5-10, HA10-20, HA20-50, HA50-100, HA100-300 and HA300, which were purified by dialysis using a 0.5 kDa membrane. The absorbing and emission properties of the separated fractions were compared and their ability to generate singlet oxygen under light excitation was evaluated, using furfuryl alcohol (FFA) as a singlet oxygen scavenger. The absorbance, the emission intensity, and the apparent first order rate constants of FFA loss were normalized per mole of organic carbon (a*, IF*, and k*, respectively). The fraction absorbance decreased with NMW, except for HA300 which was less absorbing than HA100-300. The low NMW fractions and the HA300 fraction generally showed lower k* and IF* values compared to the HA50-100 and HA100-300 fractions. A plot of k* versus IF* indicates that the first order rate constant of FFA photo-oxygenation increased with the intensity of fluorescence at 380, 430, and 500 nm (R2 = 0.77-0.84). This shows that the distribution of fluorescent centers among fractions paralleled that of photosensitizing centers. Plotting k* or IF* versus a* at365 nm reveals the apparent relative quantum efficiency of the different fractions. Higher values for low NMW fractions and HA50-100 are either due higher percentages of absorbing centers able to produce singlet oxygen or exhibit fluorescence or to lower quenching processes.

Up to date, in agriculture, the urease inhibitors had been added to the soil incorporated in fertilizers containing either urea and the inhibitors, and the inhibitor concentration was calculated as a percentage on the urea weight. The possibility to use urease inhibitor physically separated from urea-based fertilizers could afford more flexibility in its use. Particularly, the granulated inhibitors, could be utilized in soils treated with different urea based fertilizers, including livestock urine, and in an amount variable as function of soil characteristics and/or urea source (e.g mineral fertilizer, organo-mineral fertilizer or animal slurry). In this study, multi-layer soil columns were used to study the effect of an experimental granular product (RV) containing an urease inhibitor (NBPT) and a garlic extract, with the capacity to protect NBPT by oxidation, on: (a) spatial variability of soil urease activity; (b) accumulation of residual urea and mineral-N forms (NO2-, NO3-, NH4+) after urea soil addition. The results have clearly demonstrated that RV had influenced the soil urease activity along the soil columns profile and the inhibition power of RV was dependent on time and soil layer depht. RV had, furthemore, delayed urea hydrolysis and reduced the soil accumulation of ammonia and nitrite ions.

Humic-like acids (HLA) were extracted from compost at the beginning and after 70, 130 and 730 days of maturation in order to be investigated for their ability to induce the transformation of 2,4,6-trimethylphenol under irradiation at 365 nm. The rate of 2,4,6-trimethylphenol phototransformation in the presence of HLA (25 mg l(-1)) varied within HLA 0HLA70 approximately HLA 130 approximately HLA 730. The changes of photoinductive capacity paralleled the changes of HLAs absorptivity indicating that the formation of photoinductive constituents is related to that of the colored moieties. The polyacrylamide gel electrophoresis analysis showed that intensity of all humic electrophoretic fractions significantly increased during the first 70 days of maturation but did not undergo significant changes for longer composting times. These data confirm the changes of HLS during composting.

A new method was developed for the simultaneous determination of the intrinsic carbon and nitrogen mineralization capacity of organic matter (OM) sources by means of an aerobic incubation in suspension. The proposed method is based on determination of the oxygen consumption, monitored indirectly via pressure measurement, and on determination of nitrogen mineralization, through the periodical measurement of NH 4 + -N, in a liquid suspension of the samples. The suspension is standardized in terms of nutrient composition and pH, and well-controlled incubation conditions that can be enforced as desired. This method rules out the effect of soil conditions and thus reflects the intrinsic properties of the OM. The method is faster and more reproducible than soil incubation tests that are currently used. In such a system, it is important that nitrification is inhibited to avoid oxygen consumption by nitrifiers and prevent the production of gaseous nitrogen compounds. Two nitrification inhibitors, N -allylthiourea and 2-ethynylpyridine, were tested at different concentrations for three reference samples, soil, bark and manure. Both inhibitors completely suppress NO 3 − formation without suppressing the heterotrophic microbial activity, thus allowing the correct determination of the oxygen uptake rate (OUR). When nitrification inhibitors were added, nitrous oxide could not be detected anymore in the gas phase of the system, which confirms that nitrification was inhibited and indicates that denitrification and nitrifier denitrification activity was negligible. N mineralization rates were determined by frequent sampling from the liquid phase of the system without disturbing the pressure measurement during the incubation and subsequent determination of NH 4 + -N. The method presented allows for the reliable and relatively easy and cheap, simultaneous determination of carbon and nitrogen mineralization rates for a wide range of OM sources.

Chromium (Cr) is a unique element in soil, because of (i) essentiality to human and animal life and non-essentiality for the vegetable kingdom and (ii) its possible presence in two main oxidation forms, trivalent (CrIII) and hexavalent (CrVI), which show opposite properties. The two forms have completely different effects on living organisms: the first (CrIII) is apparently useful or harmless at reasonable concentrations, while the second (CrVI) is extremely toxic. In addition, CrIII is not mobile in soil, therefore the risks of leaching are negligible, while CrVI, mainly present in the forms of chromates (CrO2− 4 ) and dichromates (Cr2O2− 7 ), is generally mobile and often is part of crystalline minerals (ophiolites, serpentines). Chromium-rich soils are common in many countries, where Cr minerals are diffuse and its content in natural soils (i.e. serpentine soils) may easily exceed 10,000 mg/kg. Conversion of CrIII to CrVI has been shown in some particular soils: rich in manganese (Mn) oxides, poor in organic matter and high redox potential. On the contrary, the reverse transformation of CrVI to CrIII is very common and easier, so that it is difficult to find hexavalent chromium forms in soil solution or in leaching waters. Chromium shows a soil-plant transfer factor (F) (“F” indicates the amount of metals that passes from the soil to the plants) very low (normally less than 5), so that Cr belongs to the less mobile elements of the soil-system. The main barrier to the income of Cr in plants is represented by the roots. CrIII is fixed on the roots and the amount that cross the cellular wall is negligible. The problem of Cr enrichment in soil has been often discussed not only in relation to the discharge of tannery wastes, but also to the possibility of Cr presence in soil amendments, mainly organics, and to the existence of excellent organic fertilizers produced from leather residues or wastes. Environmental or safety issues are often cited fearing the use of such fertilizers, generally without scientific support. As a matter of fact, the United States Environmental Protection Agency has withdrawn any limit to the presence of Cr in biosolids. The main aim of this session is to discuss updated positions of this problem, gathering the contribution of scientists who have devoted their study to chromium in recent years.

The agronomic performance and the mineral composition and trace element content in Begonia semperflorens “Bellavista F1”, Mimulus “Magic × hybridus”, Salvia splendens “maestro”, and Tagete patula × erecta “Zenith Lemon Yellow”, were tested by growing the plants on substrates of white peat and 25–50–75–100% green waste and sewage sludge (80% + 20% v/v) compost (CP). A commercial peat medium of black and white peat (2:1 v/v) was used as control. At flowering, the agronomic parameters were compared by ANOVA and plant nutritional status was compared by vector analysis. Substrate-species interactions (P < 0.001) were evident for all measured parameters. In the 25% CP medium all the species showed an increase or preservation of the studied agronomic parameters. Begonia grown in 25% CP, showed the highest dry weight (DW) and number of flowers. Other treatments were comparable to the control. Mimulus and Salvia showed the highest DW in the 25–50% CP. Mimulus, after a DW increase up to 50% CP, showed the steepest reduction as the CP increased further. Tagete showed no differences in DW up to 50% CP, or in flower number up to 25% CP, compared to the control. The additional increases of CP in the medium showed a DW decrease similar to that of Salvia. Vector analysis showed the use of compost mainly induced a decrease of P concentration in tissues, except for Begonia which remained unchanged. Plant tissues showed a general P reduction due to a dilution effect in the low compost mixtures (25–50%) and a deficiency in the higher CP mixtures. In contrast, an increase of Mg in the aboveground tissues of all species was detectable as compost usage increased, with the exception of Salvia which suffered a Mg deficiency. Vector analysis also highlighted a Ni and partial Fe deficiency in Tagete and Salvia.

Olive pulp (OP) and its effluents produced after digestion processes were characterised and their suitability as soil amendment materials were investigated. Results showed that OP and its effluent for hydrogen (EH2) and methane production (ECH4) contain high amount of organic matter, remarkable concentration of nutrients and negligible content of heavy metals. Decreasing concentrations of low molecular weight phenols (monomeric phenols) and increasing amount of humic-like materials were found passing from OP to EH2 and ECH4. The effects on both wheat seed germination and seedlings growth were also investigated. Addition of OP at the highest doses delayed both seed germination and seedling growth. These effects decreased when the OP and its effluents were incorporated into the soil. On the contrary an enhancement of seedlings growth was detected by addition of EH2 and ECH4. Enhancement effects also were found out by addition of lower OP concentrations. The phytotoxic effects decreased when the products were incorporated into the soil.

Three blends formed by: agro-industrial waste, wastewater sewage sludge, and their mixture, blended with tree pruning as bulking agent, were composted over a 3-month period. During the composting process the blends were monitored for the main physical and chemical characteristics. Electrofocusing (EF) was carried out on the extracted organic matter. The EF profiles were analyzed by principal component analysis (PCA) in order to assess the suitability of EF to evaluate the stabilisation level during the composting process. Throughout the process, the blends showed a general shifting of focused bands, from low to high pH, even though the compost origin affected the EF profiles. If the EF profile is analyzed by dividing it into pH regions, the interpretation of the results can be affected by the origin of compost. A good clustering of compost samples depending on the process time was obtained by analyzing the whole profile by PCA. Analysis of EF results with PCA represents a useful analytical technique to study the evolution and the stabilisation of composted organic matter.

To use compost appropriately in agriculture it is extremely important to estimate the stabilization level of the organic matter. In this work, two different piles of compost were studied by means of (i) humification parameters (degree of humification––DH, humification rate––HR, humification index––HI) prior to and after enzymatic hydrolysis of the extracted organic carbon, (ii) watersoluble organic carbon (WSOC) and (iii) water-soluble nitrogen. A significant relationship between composting time, WSOC and humification parameters after enzymatic hydrolysis (DHenz ;H R enz ;H I enz) was found. � 2003 Elsevier Ltd. All rights reserved.

Humic acids extracted from peats (P), brown coals (BC) and lignites (L), were characterized using different (chemical, 1H-nuclear magnetic resonance spectroscopy and differential thermal analysis) techniques. Fourteen variables were obtained from these analyses and only five were selected because uncorrelated in multiple partial correlation. The chosen variables were C concentration, aliphatic and aromatic components and the heat of reaction of the second exothermic peak. The multivariate discriminant analysis was performed on these variables and a discriminant function was obtained which was able to efficiently separate the P, BC and L. This function enables simple predictions on samples of unknown origin. The straightforward method proposed and the results obtained are discussed. © 2003 Elsevier Science Ltd. All rights reserved.