Magnetic Chitosan for the Removal of Sulfamethoxazole from Tertiary Wastewaters.

Magnetic chitosan nanoparticles, synthesized by in situ precipitation, have been used as adsorbents to remove sulfamethoxazole (SMX), a sulfonamide antibiotic dangerous due to its capacity to enter ecosystems. The adsorption of SMX has been carried out in the presence of tertiary wastewaters from a depuration plant to obtain more realistic results. The effect of pH on the adsorption capacity significantly changed when carrying out the experiments in the presence of wastewater. This change has been explained while taking into account the charge properties of both the antibiotic and the magnetic chitosan. The composition of wastewaters has been characterized and discussed as regards its effect on the adsorption capacity of the magnetic chitosan. The models of Elovich and Freundlich have been selected to describe the adsorption kinetics and the adsorption isotherms, respectively. The analysis of these models has suggested that the adsorption mechanism is based on strong chemical interactions between the SMX and the magnetic chitosan, leading to the formation of an SMX multilayer.

Nano-Biochar Suspension Mediated Alterations in Growth, Physio-Biochemical Activities and Nutrient Content in Wheat (Triticum aestivum L.) at the Vegetative Stage.

Nano-biochar is a source of blackish carbonaceous material, a prerequisite for sustainable crop productivity. By using a variety of feedstock materials, nanobiochar synthesis can be employed via pyrolysis. Therefore, a project was initiated to explore the morpho-physio-biochemical alteration at the vegetative stage of wheat crops after the foliar application of nanobiochar suspension (NBS). This investigation was conducted at the Botanical Research Area of the University of Lahore in a randomized complete block design (RCBD) arrangement, with four treatments (0, 1, 3, and 5% NBS) by maintaining three replications for each treatment using the wheat variety "Zincol". Nano biochar suspension in above mentioned concentrations were foliarly applied at the end of tillering/beginning of leaf sheath elongation of wheat seedlings to assess the morphological changes (root length, shoot length, number of leaves, fresh biomass/plant, dry biomass/plant), physio-biochemical alterations (total free amino acids, total sugars, chlorophyll content, protein, phenols, flavonoids), and nutrient uptake (Na, K, Ca, Mg, N, P contents. Our findings indicate that the foliar application of 3% NBS yielded the most favorable results across all measured attributes. Furthermore, Treatment-4 (5% NBS) specifically improved certain traits, including leaf area, total soluble proteins, and leaf calcium content. Finally, all NBS resulted in a decrease in carotenoid and sodium content in wheat seedlings.

Uptake and translocation of pharmaceutically active compounds by olive tree (Olea europaea L.) irrigated with treated municipal wastewater.

Introduction: The use of treated municipal wastewater (TWW) represents a relevant opportunity for irrigation of agricultural crops in semi-arid regions to counter the increasing water scarcity. Pharmaceutically active compounds (PhACs) are often detected in treated wastewater, posing a risk to humans and the environment. PhACs can accumulate in soils and translocate into different plant tissues, reaching, in some cases, edible organs and entering the food chain. Methods: This study evaluated the uptake and translocation processes of 10 PhACs by olive trees irrigated with TWW, investigating their accumulation in different plant organs. The experiment was conducted in southern Italy, in 2-year-old plants irrigated with three different types of water: freshwater (FW), TWW spiked with 10 PhACs at a concentration of 200 µg L-1 (1× TWW), and at a triple dose (3× TWW), from July to October 2021. The concentration of PhACs in soil and plant organs was assessed, collecting samples of root, stem, shoot, leaf, fruit, and kernel at 0 (T0), 50 (T1), and 107 (T2) days of irrigation. PhACs extraction from soil and plant organs was carried out using the QuEChERS method, and their concentrations were determined by high-resolution mass spectrometry coupled with liquid chromatography. Results: Results of uptake factors (UF) showed a different behavior between compounds according to their physicochemical properties, highlighting PhACs accumulation and translocation in different plant organs (also edible part) in 1× TWW and 3× TWW compared to FW. Two PhACs, carbamazepine and fluconazole, showed interactions with the soil-plant system, translocating also in the aerial part of the plant, with a translocation factor (TF) greater than 1, which indicates high root-to-leaf translocation. Discussion: Findings highlight that only few PhACs among the selected compounds can be uptaken by woody plants and accumulated in edible parts at low concentration. No effects of PhACs exposure on plant growth have been detected. Despite the attention to be paid to the few compounds that translocate into edible organs, these results are promising for adapting wastewater irrigation in crops. Increasing knowledge about PhACs behavior in woody plants can be important for developing optimized wastewater irrigation and soil management strategies to reduce PhACs accumulation and translocation in plants.

Copper Oxide Nanoparticles Induced Growth and Physio-Biochemical Changes in Maize (Zea mays L.) in Saline Soil.

Research on nanoparticles (NPs) is gaining great attention in modulating abiotic stress tolerance and improving crop productivity. Therefore, this investigation was carried out to evaluate the effects of copper oxide nanoparticles (CuO-NPs) on growth and biochemical characteristics in two maize hybrids (YH-5427 and FH-1046) grown under normal conditions or subjected to saline stress. A pot-culture experiment was carried out in the Botanical Research Area of "the University of Lahore", Lahore, Pakistan, in a completely randomized design. At two phenological stages, both maize hybrids were irrigated with the same amount of distilled water or NaCl solution (EC = 5 dS m-1) and subjected or not to foliar treatment with a suspension of CuO-NPs. The salt stress significantly reduced the photosynthetic parameters (photosynthetic rate, transpiration, stomatal conductance), while the sodium content in the shoot and root increased. The foliar spray with CuO-NPs improved the growth and photosynthetic attributes, along with the N, P, K, Ca, and Mg content in the roots and shoots. However, the maize hybrid YH-5427 responded better than the other hybrid to the saline stress when sprayed with CuO-NPs. Overall, the findings of the current investigation demonstrated that CuO-NPs can help to reduce the adverse effects of salinity stress on maize plants by improving growth and physio-biochemical attributes.

Use of constructed wetlands to prevent overloading of wastewater treatment plants.

The fluctuation in the number of people in tourist areas affects the wastewater quality and quantity. Constructed wetlands (CWs) aim to simulate physical, chemical, and biological processes occurring in natural environments for wastewater treatment and are considered a sustainable system. The current study aimed at evaluating the effectiveness of in-vessel CWs for supporting the wastewaters treatment plants in periods of overloading. Such approach can be quickly implementable, economic, and the CWs can be fast regenerated in the framework of sustainable good practices. Three pilot scale CWs were prepared in as many containers layering 10 cm of gravel, 60 cm of sand and 10 cm of gravel, and placing pieces of giant reed rhizomes in the upper layers. The bottom of each CW had a tap, and CWs were irrigated with a real municipal sewage three times a week. Before each new irrigation, the tap was opened, and the effluent collected for determining gross parameters, elemental composition, and contaminants of emerging concern (CECs). CWs significantly reduced almost all gross parameters considered and half the CECs, except for a couple of metabolites of corresponding parental compounds. With regards to the potentially toxic elements, all reduced their concentration from the influents to the effluents. The results of this study were promising and highlighted good efficiency of constructed wetlands as pre-treatment of real municipal sewage to reduce the overloading of the wastewater treatment plant.

Lead Toxicity-Mediated Growth and Metabolic Alterations at Early Seedling Stages of Maize (Zea mays L.).

To investigate the toxic effects of lead (Pb) on key metabolic activities essential for proper germination and seedling growth of maize seeds, experiments were carried out with different levels of Pb (0 to 120 mg of Pb L-1 as PbCl2) applied through growth medium to two maize hybrids H-3310S and H-6724. The research findings indicated that growth and metabolic activities were adversely affected by increased Pb contamination in growth medium; however, a slow increase in these parameters was recorded with increasing time from 0 to 120 h. Protease activity decreased with an increase in the level of Pb contamination but increased with time; consequently, a reduction in seed proteins and an increase in total free amino acids were observed with time. Similarly, α-amylase activity decreased with an increase in Pb concentration in growth medium while it increased with increasing time from 0 to 120 h; consequently, reducing and non-reducing sugars increased with time but decreased with exposure to lead. The roots of both maize hybrids had higher Pb contents than those of the shoot, which decreased the uptake of nitrogen, phosphorus, and potassium. All these nutrients are essential for optimal plant growth; therefore, the reduction in growth and biomass of maize seedlings could be due to Pb toxicity that altered metabolic processes, as sugar and amino acids are necessary for the synthesis of metabolic compounds, rapid cell division, and proper functioning of enzymes in the growing embryo, but all were dramatically reduced due to suppression of protease and α-amylase by toxicity of Pb. In general, hybrid H-3310S performed better in Pb-contaminated growth medium than H-6724.

Uptake and accumulation of emerging contaminants in processing tomato irrigated with tertiary treated wastewater effluent: a pilot-scale study.

The reuse of treated wastewater for crop irrigation is vital in water-scarce semi-arid regions. However, concerns arise regarding emerging contaminants (ECs) that persist in treated wastewater and may accumulate in irrigated crops, potentially entering the food chain and the environment. This pilot-scale study conducted in southern Italy focused on tomato plants (Solanum lycopersicum L. cv Taylor F1) irrigated with treated wastewater to investigate EC uptake, accumulation, and translocation processes. The experiment spanned from June to September 2021 and involved three irrigation strategies: conventional water (FW), treated wastewater spiked with 10 target contaminants at the European average dose (TWWx1), and tertiary WWTP effluent spiked with the target contaminants at a triple dose (TWWx3). The results showed distinct behavior and distribution of ECs between the TWWx1 and TWWx3 strategies. In the TWWx3 strategy, clarithromycin, carbamazepine, metoprolol, fluconazole, and climbazole exhibited interactions with the soil-plant system, with varying degradation rates, soil accumulation rates, and plant accumulation rates. In contrast, naproxen, ketoprofen, diclofenac, sulfamethoxazole, and trimethoprim showed degradation. These findings imply that some ECs may be actively taken up by plants, potentially introducing them into the food chain and raising concerns for humans and the environment.

Uptake of different pharmaceuticals in soil and mycorrhizal artichokes from wastewater.

The irrigation with treated wastewater is among the main anthropogenic sources for the release of pharmaceuticals (PhACs) into the soils and their translocation into crops, with possible toxic and adverse effects on humans. The arbuscular mycorrhizal fungi (AMF) can be employed for the reduction of organic soil pollutants, even if their efficiency depends on the mycorrhizal fungi, the plant colonized, and the type and concentration of the contaminant. This study aimed to evaluate the uptake of PhACs from wastewaters of different qualities used for the irrigation of mycorrhizal artichoke plants, the presence in their edible parts and the role of the arbuscular mycorrhizal fungi. The research was carried out on artichoke plants not inoculated and inoculated with two different AMF and irrigated with treated wastewater (TW), groundwater (GW) or GW spiked with different and selected PhACs (SGW). The inocula were a crude inoculum of Septoglomus viscosum (MSE) and a commercial inoculum of Glomus intraradices and Glomus mosseae (MSY). The results of the present study showed that carbamazepine and fluconazole were found in the artichoke only with SGW irrigation. The mycorrhizal plants showed a reduction of the pharmaceutical's uptake, and within the AMF, MSE was more effective in preventing their absorption and translocation.

Advanced techniques for characterization of organic matter from anaerobically digested grapemarc distillery effluents and amended soils.

The effects of grapemarc distillery effluents on the quality of soil organic matter is extremely important to ensure the environmentally-safe and agronomically efficient use of these materials as organic amendment. In this work, the effects of the application of untreated (UG) and anaerobically digested grapemarc distillery effluents, either added with (AGM) or without mycorrhiza (AG), on soil humic acid (HA) were investigated in field plot experiments in comparison to HAs from a control soil and an inorganic fertilized soil. The humic acid-like fractions (HALs) isolated from UG, AG and soils were characterized for compositional, structural and functional properties by the use of elemental and functional group analysis, and ultraviolet/visible, Fourier transform infrared and fluorescence spectroscopies. Results obtained indicated that anaerobic digestion of effluents produced an extended mineralization with loss of organic C and stabilization of residual organic matter by increasing the content of HALs in the effluent. With respect to control soil HA, HALs isolated from UG and AG were characterized by smaller acidic functional group contents, a prevalent aliphatic character and smaller aromatic polycondensation and humification degrees. The chemical and spectroscopic characteristics of native soil HA were not substantially modified by application of UG, AG and AGM to soil, which suggests the occurred incorporation of the effluent HAL into native soil HA. In conclusion, these results showed the possibility of a beneficial and safe recycling of grapemarc distillery effluents as soil amendment.

Geophysical field zoning for nitrogen fertilization in durum wheat (Triticum durum Desf.).

The current social context requires an increase in food production, improvement of its quality characteristics and greater environmental sustainability in the management of agricultural systems. Technological innovation plays a great role in making agriculture more efficient and sustainable. One of the main aims of precision farming (PF) is optimizing yield and its quality, while minimizing environmental impacts and improving the efficient use of resources. Variable rate techniques (VRT) are amongst the main management options for PF, and they require spatial information. This work incorporates maps of soil properties from low induction electromagnetic measurements into nitrogen (N) balance calculations for a field application of VRT nitrogen fertilization of (Triticum durum Desf., var. Tirex). The trial was conducted in 2018-19 at Genzano di Lucania (PZ, Italy) geologically located on the clayey hillsides of the Bradanica pit and the Sant'Arcangelo basin. Three soil homogeneous areas were detected through low induction electromagnetic measurements and used as uniform management zones. The amount of nitrogen fertilizer to be applied by VRT was calculated on the base of estimated crop nitrogen uptake and soil characteristics of each homogeneous area. Crop response to VRT was compared to uniform nitrogen application (UA) on the whole field. The application of VRT resulted in a reduction of 25% nitrogen fertilizer with the same level of yield respect to UA. Grain protein content, as well as gluten content and N content, were significantly higher in VRT than in UA. As a consequence of lower nitrogen input and higher levels of N removal, VRT reached a higher nitrogen use efficiency than UA, and this indicates a lower environmental impact and a higher economic profitability.

Reuse of Wasted Bread as Soil Amendment: Bioprocessing, Effects on Alkaline Soil and Escarole (Cichorium endivia) Production.

In an era characterized by land degradation, climate change, and a growing population, ensuring high-yield productions with limited resources is of utmost importance. In this context, the use of novel soil amendments and the exploitation of plant growth-promoting microorganisms potential are considered promising tools for developing a more sustainable primary production. This study aimed at investigating the potential of bread, which represents a large portion of the global food waste, to be used as an organic soil amendment. A bioprocessed wasted bread, obtained by an enzymatic treatment coupled with fermentation, together with unprocessed wasted bread were used as amendments in a pot trial. An integrated analytical plan aimed at assessing (i) the modification of the physicochemical properties of a typical Mediterranean alkaline agricultural soil, and (ii) the plant growth-promoting effect on escarole (Cichorium endivia var. Cuartana), used as indicator crop, was carried out. Compared to the unamended soils, the use of biomasses raised the soil organic carbon content (up to 37%) and total nitrogen content (up to 40%). Moreover, the lower pH and the higher organic acid content, especially in bioprocessed wasted bread, determined a major availability of Mn, Fe, and Cu in amended soils. The escaroles from pots amended with raw and bioprocessed bread had a number of leaves, 1.7- and 1.4-fold higher than plants cultivated on unamended pots, respectively, showing no apparent phytotoxicity and thus confirming the possible re-utilization of such residual biomasses as agriculture amendments.

Effects of different pioneer and exotic species on the changes of degraded soils.

Soil degradation resulting from deforestation contributes to a dramatic decline in soil quality whose restoration must go through reforestation with pioneer species. We investigated the effects of cypress and black locust, pioneer but exotic species, on soil chemical properties and microbial and enzymatic activities of two marginal soils. The sampling sites were Lama Giulia and Locone lake in the Murge plateau of the Apulia Region, Italy. The soils at Lama Giulia presented a silty loam texture, while at Locone Lake site were sandy, and most likely due to the different texture, the former exhibited higher organic C, N, P and micronutrients contents than Locone Lake under black locust reforestation, despite the latter was reforested earlier. In addition, the higher microbial entropy and turnover of Locone Lake's soils suggested a less conservative soil state than Lama Giulia's soils. The effects of black locust reforestation at Lama Giulia on almost all soil parameters considered did not differ from those of the corresponding pasture, confirming the more conservative soil state in that site and suggesting that the time of reforestation was not enough to get differences between the reforested and not reforested soil. The soils reforested with cypress showed the significantly highest SOC, N, dissolved organic C and microbial biomass C content. In addition, it presented also the numerically largest dehydrogenase, phosphatase and ß-glucosidase activities, soluble carbohydrates, and phenolic compounds content. These results may be ascribed to the longer litter deposition occurred in cypress soils.

Influence of crop rotation, tillage and fertilization on chemical and spectroscopic characteristics of humic acids.

The changes in soil organic matter composition induced by anthropogenic factors is a topic of great interest for the soil scientists. The objective of this work was to identify possible structural changes in humic molecules caused by a 2-year rotation of durum wheat with faba bean, lasted for a decade, and conducted with different agricultural practices in a Mediterranean soil. Humic acids (HA) were extracted at three depths (0-30, 30-60 and 60-90 cm) from a Mediterranean soil subjected to different tillage (no tillage, minimum tillage and conventional tillage), crops (faba bean and wheat), and fertilization. The changes in HA quality were assessed by several chemical (ash, yield and elemental analysis) and spectroscopic techniques (solid-state 13C nuclear magnetic resonance, Fourier transform infrared and fluorescence). The results suggest that the different agronomic practices strongly affected the quality of HA. Smaller but more aromatic molecules were observed with depth, while the fertilization induced the formation of simpler and less aromatic molecules due to the enhanced decomposition processes. Under no tillage, more stable humic molecules were observed due to the less soil aeration, while under conventional tillage larger and more aromatic molecules were obtained. Compared to wheat, more aromatic and more oxidized but less complex molecules were observed after faba bean crop. The inorganic fertilization accelerates the decomposition of organic substances rather than their stabilization. At the end of each crop cycle, humic matter of different quality was isolated and this confirms the importance of the rotation practice to guarantee a diversification of the soil organic matter with time. Finally, no tillage induces the formation of more stable humic matter.

Effect of hydrolyzed protein-based mulching coatings on the soil properties and productivity in a tunnel greenhouse crop system.

Polymeric protein-based biocomposites were used in this work as water dispersions to generate, in situ, biobased mulching coatings by spray technique, as alternative to low density polyethylene films for soil mulching. At the end of their lifetime, these biodegradable coatings degrade in soil thank to the microbial community that mineralizes them. Protein hydrolysates (PH) were derived from waste products of the leather industry, while poly(ethylene glycol) diglycidyl ether (PEG) and epoxidized soybean oil (ESO) were used to make the biodegradable spray coatings. A study under greenhouse condition was carried out using seedling test plots in order to investigate the performance of the spray coatings and their possible influence on some aspects of leaf growth, functionality and nutritional quality of lettuce (Lactuca sativa L., Mortarella selection Romanella variety Duende) and on soil properties. The biodegradable coatings showed the same good agronomic performances comparable with the ones of a commercial low density polyethylene mulching film, maintaining the mulching effect for the requested cultivation period and ensuring at the same time a similar rate of plant growth and dry matter accumulation. The research showed that 2 months after the tillage carried out at the end of the cultivation the amount of coating residues present in the soil was <5% of the initial weight of the biodegradable coatings. At the end of the field test, the soil mulched with the polyethylene film recorded an electrical conductivity value lower with respect to the soil mulched with the sprayed coatings, which release nutrients in the soil during their decomposition.

Minimum tillage and organic fertilization for the sustainable management of Brassica carinata A. (Braun) in the Mediterranean environment.

In recent years, the massive exploitation of agricultural land intended to meet growing food demand has led to a reduction in soil fertility through the depletion of nutrients and organic matter. To implement sustainable agriculture, it is necessary to reduce soil tillage and use residual biomasses that are easily available in the region as soil amendments. Furthermore, it is important to test these residual biomasses in order to exclude a possible increase of heavy metals in soils due to the incorporation of the aforementioned biomasses. The current study aimed to evaluate the effects on soil fertility and health following the application of organic fertilizers combined with different soil tillage practices and the agronomic response of Brassica carinata A. (Braun). The soil tillage treatments consisted of conventional (CT) and minimum tillage (MT), whereas the fertilization treatments were mineral fertilizer (Nmin), municipal solid waste compost (Ncomp), mixed compost and mineral fertilizer (Nmix), and sewage sludge (Nss). These treatments were compared with an unfertilized control (N0). The Ncomp and Nss treatments enhanced soil fertility, increasing the organic carbon and available phosphorus concentrations compared with N0 and Nmin, whereas no significant difference was showed between the soil tillage treatments in terms of soil fertility. In addition, Nss did not show any significant difference compared to Nmin in terms of crop biomass, whereas this parameter appeared higher in CT compared with MT. A principal component analysis showed that the concentrations of toxic elements applied by the organic amendments did not change the dynamic equilibrium of the soil-plant system. Over the short term, the replacement of CT and Nmin with MT and Nss can be achieved, thus guaranteeing the sustainable cultivation of Brassica, without significant changes in heavy metal concentration in soil.

Evolution of the fulvic acid fractions during co-composting of olive oil mill wastewater sludge and tree cuttings.

Fulvic acids (FAs) were isolated by a conventional procedure from two mixtures of the sludge residue obtained from olive oil mill wastewater (OMW) evaporated in open-air pond and tree cuttings (TC) at different stages of the co-composting process. The FAs were analyzed for elemental (C, H, N, S, O) and acidic functional group (carboxylic and phenolic) composition, and by ultraviolet/visible, Fourier transform infrared and fluorescence spectroscopies. At the initial stage of composting, FAs from the OMW sludge-TC mixtures were characterized by a prevalent aliphatic character, large contents of C, S-containing groups, proteinaceous materials and polysaccharide components, extended molecular heterogeneity, small O and acidic functional group contents, and small degrees of aromatic ring polycondensation, polymerization and humification. As composting proceeded, C, H and S contents, C/N ratio, and aliphaticity decreased, whereas N, O, COOH and phenolic OH contents, C/H and O/C ratios, and aromaticity increased. These results suggested that, with increasing the composting time, the chemical and structural properties of the FA components of the two OMW sludge-TC mixtures approached the characteristics typical of native soil FAs. Thus, co-composting of OMW sludge mixed with TC may represent a suitable treatment for enhancing the quality of organic matter in these materials when used as soil amendments.

Olive pomace amendment in Mediterranean conditions: effect on soil and humic acid properties and wheat (Triticum turgidum L.) yield.

The effects of the addition of either crude or exhausted olive pomace at two rates (10 and 20 t ha(-)(1)) on soil and soil humic acid (HA) properties and durum wheat (Triticum turgidum L.) yield were investigated in open-field Mediterranean conditions. Soil amendment with olive pomaces produced a significant increase of total organic, total extractable, humified and nonhumified C forms, and available K contents. With respect to control soil HA, humic-like acids isolated from crude and exhausted olive pomaces were characterized by larger phenolic OH group contents, smaller carboxyl group contents, a prevalent aliphatic character, extended molecular heterogeneity, and smaller aromatic polycondensation and humification degrees. In general, application of olive pomaces to soil produced a number of modifications in soil HAs, including the increase of O and acidic functional group contents, C/N ratio, and aliphaticity and the decrease of C/H ratio and N and C contents. Wheat grain yield increased significantly as an effect of olive pomace amendment. In particular, the increases were related to kernel weight, kernel number per square meter, and soil organic matter content. Possibly, the enhanced amount of soil organic matter in olive-pomace-amended soils relieved wheat of drought stress from anthesis to maturity by promoting a good soil structure, thereby reducing water loss by evaporation.

Changes in the ascorbate system in the response of pumpkin (Cucurbita pepo L.) roots to aluminium stress.

The involvement of the ascorbate (AsA) system in the response of pumpkin (Cucurbita pepo L.) roots to aluminium stress was studied. The treatment of 5-day-old pumpkin seedlings with 50 microM aluminium sulphate resulted in approximately 60% inhibition of root growth within 48-60 h of treatment, while aluminium accumulated in the roots reaching a maximum within 48h. During the same period, the hydrogen peroxide content of the roots was strongly enhanced. The increased level of hydrogen peroxide was matched by both increased ascorbate peroxidase (APX) (EC 1.11.1.11) activity and ascorbate free radical reductase (AFRR) (EC 1.1.5.4) activity, while dehydroascorbate reductase (DHAR) (EC 1.8.5.1) and glutathione reductase (GR) (EC 1.6.4.2) did not change. The levels of AsA in the roots were also increased by the Al treatment. It was concluded that an oxidative burst is probably involved in the toxicity of Al in pumpkin roots and that plants react to the enhanced production of reactive oxygen species by expressing higher levels of scavenging systems such as the AsA-APX system.

Proton binding by humic and fulvic acids from pig slurry and amended soils.

The knowledge of acid-base characteristics of humic acid (HA) and fulvic acid (FA) fractions of organic amendments and amended soils is of considerable importance for assessing their agronomic efficacy and environmental impact. In this work, the acid-base properties of HAs and FAs isolated from pig slurry, soils amended with either 90 or 150 m(3) ha(-1) yr(-1) of pig slurry for 3 yr, and the corresponding nonamended control soil were investigated by using a current potentiometric titration method. The nonideal competitive adsorption (NICA) model that describes proton binding by two classes of binding sites (carboxylic- and phenolic-type groups) was successfully fit to titration data. With respect to the control soil HA and FA, pig-slurry HA and FA were generally characterized by smaller carboxylic-type group contents, slightly smaller phenolic-type group contents, larger affinities for proton binding by the carboxylic-type groups, and much smaller, in the case of the HA fraction, or similar, in the case of the FA fraction, affinities for proton binding by the phenolic-type groups. Amendment with pig slurry determined a number of modifications in soil HAs and FAs, including decrease of acidic functional group contents, and slight increase of the proton affinity of the carboxylic-type groups. Further, a slight decrease of the affinities for proton binding by the phenolic-type groups of HAs was observed. These effects can have a large impact on the biological availability, mobilization, and transport of macro- and micronutrients, toxic metal ions, and xenobiotic organic cations in pig slurry-amended soils.

Effects of pig slurry application on soils and soil humic acids.

The effect of three annually consecutive additions of pig slurry at two rates (90 and 150 m3 x ha(-1) x year(-1) on soils and soil humic acids (HAs) was investigated in a field experiment under semiarid conditions. Soils and pig slurries were analyzed by standard methods. The HAs were isolated from soils and pig slurry by a conventional procedure based on alkaline extraction, acidic precipitation to pH 1, purification by repeated alkaline dissolutions and acidic precipitations, water washing, dialysis, and final freeze-drying. The HAs obtained were analyzed for elemental (C, H, N, S, and O) and acidic functional group (carboxylic and phenolic) composition, and by UV-vis, FT-IR, fluorescence, and ESR spectroscopies. With respect to the control soil, the pig slurry amended soils had greater pH and electrical conductivity, slightly larger total N content, and smaller values of C/N ratio. A decrease of total organic C was observed only in soils amended for 2 and 3 years at the higher slurry rate. With respect to control soil HA, pig slurry HA was characterized by larger contents of S- and N-containing groups, smaller acidic functional group and organic free radical contents, a prevalent aliphatic character, extended molecular heterogeneity, and smaller aromatic polycondensation and humification degrees. Amendment with pig slurry HA determines a number of modifications in soil HAs, including increase of C, S, and COOH contents, C/N ratios, and aliphaticity and decrease of extraction yields and N, O, phenolic OH, and organic free radical contents. These effects are generally more evident after the first year of slurry application and tend to disappear with increasing number of treatments. Most probably, over the years the slightly humified slurry HA is mineralized through extended microbial oxidation, whereas only the most recalcitrant components, such as S-containing, phenolic, and aliphatic structures, are partially accumulated by incorporation into soil HA.