Emerging contaminants in agricultural ecosystems: impact of selected pharmaceutical on water and soil ecology and pratical implications

Pharmaceuticals are useful tools to prevent and treat human and animal diseases. Following administration, a significant fraction of pharmaceuticals is excreted unaltered into faeces and urine and may enter the aquatic ecosystem and agricultural soil through irrigation with recycled water, constituting a significant source of emerging contaminants into the environment. Understanding major factors influencing their environmental fate is consequently needed to value the risk, reduce contamination, and set up bioremediation technologies. The antiviral drug Tamiflu (oseltamivir carboxylate, OC) has received recent attention due to the potential use as a first line defence against H5N1 and H1N1 influenza viruses. Research has shown that OC is not removed during conventional wastewater treatments, thus having the potential to enter surface water bodies. A series of laboratory experiments investigated the fate and the removal of OC in surface water systems in Italy and Japan and in a municipal wastewater treatment plant. A preliminary laboratory study investigated the persistence of the active antiviral drug in water samples from an irrigation canal in northern Italy (Canale Emiliano Romagnolo). After an initial rapid decrease, OC concentration slowly decreased during the remaining incubation period. Approximately 65% of the initial OC amount remained in water at the end of the 36-day incubation period. A negligible amount of OC was lost both from sterilized water and from sterilized water/sediment samples, suggesting a significant role of microbial degradation. Stimulating microbial processes by the addition of sediments resulted in reduced OC persistence. Presence of OC (1.5 μg mL-1) did not significantly affect the metabolic potential of the water microbial population, that was estimated by glyphosate and metolachlor mineralization. In contrast, OC caused an initial transient decrease in the size of the indigenous microbial population of water samples. A second laboratory study focused on basic processes governing the environmental fate of OC in surface water from two contrasting aquatic ecosystems of northern Italy, the River Po and the Venice Lagoon. Results of this study confirmed the potential of OC to persist in surface water. However, the addition of 5% of sediments resulted in rapid OC degradation. The estimated half-life of OC in water/sediment of the River Po was 15 days. After three weeks of incubation at 20 °C, more than 8% of 14C-OC evolved as 14CO2 from water/sediment samples of the River Po and Venice Lagoon. OC was moderately retained onto coarse sediments from the two sites. In water/sediment samples of the River Po and Venice Lagoon treated with 14C-OC, more than 30% of the 14C-residues remained water-extractable after three weeks of incubation. The low affinity of OC to sediments suggests that the presence of sediments would not reduce its bioavailability to microbial degradation. Another series of laboratory experiments investigated the fate and the removal of OC in two surface water ecosystems of Japan and in the municipal wastewater treatment plant of the city of Bologna, in Northern Italy. The persistence of OC in surface water ranged from non-detectable degradation to a half-life of 53 days. After 40 days, less than 3% of radiolabeled OC evolved as 14CO2. The presence of sediments (5%) led to a significant increase of OC degradation and of mineralization rates. A more intense mineralization was observed in samples of the wastewater treatment plant when applying a long incubation period (40 days). More precisely, 76% and 37% of the initial radioactivity applied as 14C-OC was recovered as 14CO2 from samples of the biological tank and effluent water, respectively. Two bacterial strains growing on OC as sole carbon source were isolated and used for its removal from synthetic medium and environmental samples, including surface water and wastewater. Inoculation of water and wastewater samples with the two OC-degrading strains showed that mineralization of OC was significantly higher in both inoculated water and wastewater, than in uninoculated controls. Denaturing gradient gel electrophoresis and quantitative PCR analysis showed that OC would not affect the microbial population of surface water and wastewater. The capacity of the ligninolytic fungus Phanerochaete chrysosporium to degrade a wide variety of environmentally persistent xenobiotics has been largely reported in literature. In a series of laboratory experiments, the efficiency of a formulation using P. chrysosporium was evaluated for the removal of selected pharmaceuticals from wastewater samples. Addition of the fungus to samples of the wastewater treatment plant of Bologna significantly increased (P < 0.05) the removal of OC and three antibiotics, erythromycin, sulfamethoxazole, and ciprofloxacin. Similar effects were also observed in effluent water. OC was the most persistent of the four pharmaceuticals. After 30 days of incubation, approximately two times more OC was removed in bioremediated samples than in controls. The highest removal efficiency of the formulation was observed with the antibiotic ciprofloxacin. The studies included environmental aspects of soil contamination with two emerging veterinary contaminants, such as doramectin and oxibendazole, wich are common parasitic treatments in cattle farms.

Nanocomposites based on poly(caprolactone)-chitosan electrospun nanofibers and metallic oxide nanoparticles. Their potential use to adsorption and photocatalytic degradation of organic contaminants

Pollution of water bodies is one of the most common environmental problems today. Organic pollutants are one of the main drawbacks in this natural resource, among which the following stand out long-lived dyes, pharmaceuticals, and pesticides. This research aims at obtaining nanocomposites based on polycaprolactone-chitosan (PCL-CS) electrospun nanofibers (NFs) containing TiO2 nanoparticles (NPs) for the adsorption and photocatalytic degradation of organic pollutants, using Rhodamine B as a model. The fabricated hybrid materials were characterized by FT-IR, TGA, DSC, SEM, TEM, tensile properties, and the contact angle of water drops. The photoactivity of the NFs was investigated using a batch-type system by following UV-Vis absorbance and fluorescence of rhodamine B (RhB). For this purpose, TiO2NPs were successfully ex-situ incorporated into the polymer matrix promoting good mechanical properties and higher hydrophilicity of the material. The results showed that CS in the NFs increased the absorption and degradation of RhB by the TiO2NPs. CS attracted the pollutant molecules to the active sites vicinity of TiO2NPs, favoring initial adsorption and degradation. In other words, a bait-hook-and-destroy effect was evidenced. It also was demonstrated that the sensitization of TiO2 by organic dyes (e.g., perylene derivative) considerably improves the photocatalytic activity under visible radiation, allowing the use of low amounts of TiO2. (≈0.05 g/1 g of fiber). Hence, the current study is expected to contribute with an environmentally friendly green alternative solution.

Influence of nitrogen and soil physical characteristics on belowground carbon flux dynamics of woody plants

At ecosystem level soil respiration (Rs) represents the largest carbon (C) flux after gross primary productivity, being mainly generated by root respiration (autotrophic respiration, Ra) and soil microbial respiration (heterotrophic respiration, Rh). In the case of terrestrial ecosystems, soils contain the largest C-pool, storing twice the amount of C contained in plant biomass. Soil organic matter (SOM), representing the main C storage in soil, is decomposed by soil microbial community. This process produces CO2 which is mainly released as Rh. It is thus relevant to understand how microbial activity is influenced by environmental factors like soil temperature, soil moisture and nutrient availability, since part of the CO2 produced by Rh, directly increases atmospheric CO2 concentration and therefore affects the phenomenon of climate change. Among terrestrial ecosystems, agricultural fields have traditionally been considered as sources of atmospheric CO2. In agricultural ecosystems, in particular apple orchards, I identified the role of root density, soil temperature, soil moisture and nitrogen (N) availability on Rs and on its two components, Ra and Rh. To do so I applied different techniques to separate Rs in its two components, the ”regression technique” and the “trenching technique”. I also studied the response of Ra to different levels of N availability, distributed either in a uniform or localized way, in the case of Populus tremuloides trees. The results showed that Rs is mainly driven by soil temperature, to which it is positively correlated, that high levels of soil moisture have inhibiting effects, and that N has a negligible influence on total Rs, as well as on Ra. Further I found a negative response of Rh to high N availability, suggesting that microbial decomposition processes in the soil are inhibited by the presence of N. The contribution of Ra to Rs was of 37% on average.

Geotechnical characterization of mixed sandy and silty soils using piezocone tests: Analysis of partial drainage phenomena and rate effects on the experimental soil response

The cone penetration test (CPT), together with its recent variation (CPTU), has become the most widely used in-situ testing technique for soil profiling and geotechnical characterization. The knowledge gained over the last decades on the interpretation procedures in sands and clays is certainly wide, whilst very few contributions can be found as regards the analysis of CPT(u) data in intermediate soils. Indeed, it is widely accepted that at the standard rate of penetration (v = 20 mm/s), drained penetration occurs in sands while undrained penetration occurs in clays. However, a problem arise when the available interpretation approaches are applied to cone measurements in silts, sandy silts, silty or clayey sands, since such intermediate geomaterials are often characterized by permeability values within the range in which partial drainage is very likely to occur. Hence, the application of the available and well-established interpretation procedures, developed for ‘standard’ clays and sands, may result in invalid estimates of soil parameters. This study aims at providing a better understanding on the interpretation of CPTU data in natural sand and silt mixtures, by taking into account two main aspects, as specified below: 1)Investigating the effect of penetration rate on piezocone measurements, with the aim of identifying drainage conditions when cone penetration is performed at a standard rate. This part of the thesis has been carried out with reference to a specific CPTU database recently collected in a liquefaction-prone area (Emilia-Romagna Region, Italy). 2)Providing a better insight into the interpretation of piezocone tests in the widely studied silty sediments of the Venetian lagoon (Italy). Research has focused on the calibration and verification of some site-specific correlations, with special reference to the estimate of compressibility parameters for the assessment of long-term settlements of the Venetian coastal defences.

Water, sediment and soil physicochemical interactions in freshwater, brackish and saline systems

The physicochemical interactions between water, sediment and soil deeply influence the formation and development of the ecosystem. In this research, different freshwater, brackish and saline subaqueous environments of Northern Italy were chosen as study area to investigate the physicochemical processes which occur at the interface between water and sediments, as well as the effects of soil submergence on ecosystem development. In the freshwater system of the Reno river basin, the main purpose was to define the heavy metals hazard in water and sediments of natural and artificial water courses. Heavy metals partitioning and speciation allowed to assess the environmental risk linked to the critical action of dredging canal sediments, for the maintenance of the hydraulic safety of plain lands. In addition, some bioremediation techniques were experimented for protecting sediments from heavy metals contamination, and for giving an answer to the problem of sediments management. In the brackish system of S. Vitale park, the development of hydromorphic and subaqueous soils was investigated. The study of soil profiles highlighted the presence of a soil continuum among pedons subjected to different saturation degrees. This investigation allowed to the identification of both morphological and physicochemical indicators, which characterize the formation of subaqueous soils and describe the soil hydromorphism in transitional soil systems. In the saline system of Grado lagoon, an ecosystem approach was used to define the role of water oscillation in soil characterization and plants colonization. This study highlighted the close relationship and the mutual influence of soil submergence and aeration, tide oscillation and vegetation cover, on the soil development. In view of climate change, this study contribute to understand and suppose how soil and landscape could evolve. However, a complete evaluation of hydromorphic soil functionality will be achieved only involving physiological and biochemical expertise in these kind of studies.

Soil enzyme activities and biochemical indexes to assess soil quality in agronomic and forested ecosystems

The soil carries out a wide range of functions and it is important study the effects of land use on soil quality in order to provide most sustainable practices. Three fields trial have been considered to assess soil quality and functionality after human alteration, and to determine the power of soil enzymatic activities, biochemical indexes and mathematical model in the evaluation of soil status. The first field was characterized by conventional and organic management in which were tested also tillage effects. The second was characterized by conventional, organic and agro-ecological management. Finally, the third was a beech forest where was tested the effects of N deposition on soil organic carbon sequestration. Results highlight that both enzyme activities and biochemical indexes could be valid parameters for soil quality evaluation. Conventional management and plowing negatively affected soil quality and functionality with intensive tillage that lead to the downturn of microbial biomass and activity. Both organic and agro-ecological management revealed to be good practices for the maintenance of soil functionality with better microbial activity and metabolic efficiency. This positively affected also soil organic carbon content. At the eutrophic forest, enzyme activities and biochemical indexes positively respond to the treatments but one year of experimentation resulted to be not enough to observe variation in soil organic carbon content. Mathematical models and biochemical indicators resulted to be valid tools for assess soil quality, nonetheless it would be better including the microbial component in the mathematical model and consider more than one index if the aim of the work is to evaluate the overall soil quality and functionality. Concluding, the forest site is the richest one in terms of organic carbon, microbial biomass and activity while, the organic and the agro-ecological management seem to be the more sustainable but without taking in consideration the yield.

Sewage sludge as organic fertilizer in agriculture. A study of physico-chemical properties, agronomic efficiency and environmental safety, with a specific focus on tannery sludge

In recent decades, the use of organic fertilizers has gained increasing interest mainly for two reasons: their ability to improve soil fertility and the need to find a sustainable alternative to mineral and synthetic fertilizers. In this context, sewage sludge is a useful organic matrix that can be successfully used in agriculture, due to its chemical composition rich in organic matter, nitrogen, phosphorus and other micronutrients necessary for plant growth. This work investigated three indispensable aspects (i.e., physico-chemical properties, agronomic efficiency and environmental safety) of sewage sludge application as organic fertilizer, emphasizing the role of tannery sludge. In a comparison study with municipal sewage sludge, results showed that the targeted analyses applied (total carbon and nitrogen content, isotope ratio of carbon and nitrogen, infrared spectroscopy and thermal analysis) were able to discriminate tannery sludge from municipal ones, highlighting differences in composition due to the origin of the wastewater and the treatment processes used in the plants. Regarding agronomic efficiency, N bioavailability was tested in a selection of organic fertilizers, including tannery sludge and tannery sludge-based fertilizers. Specifically, the hot-water extractable N has proven to be a good chemical indicator, providing a rapid and reliable indication of N bioavailability in soil. Finally, the behavior of oxybenzone (an emerging organic contaminant detected in sewage sludge) in soils with different physico-chemical properties was studied. Through adsorption and desorption experiments, it was found that the mobility of oxybenzone is reduced in soils rich in organic matter. Furthermore, through spectroscopic methods (e.g., infrared spectroscopy and surface-enhanced Raman spectroscopy) the mechanisms of oxybenzone-humic acids interaction were studied, finding that H-bonds and π-π stacking were predominantly present.