Contrasting effects of climate change on denitrification and nitrogen load reduction in the Po River (Northern Italy).

An increase in water temperature is one of the main factors that can potentially modify biogeochemical dynamics in lowland rivers, such as the removal and recycling of nitrogen (N). This effect of climate change on N processing deserves attention, as it may have unexpected impacts on eutrophication in the coastal zones. Intact sediment cores were collected seasonally at the closing section of the Po River, the largest Italian river and one of the main N inputs to the Mediterranean Sea. Benthic oxygen fluxes, denitrification, and dissimilatory nitrate reduction to ammonium (DNRA) rates were measured using laboratory dark incubations. Different temperature treatments were set up for each season based on historical data and future predictions. Higher water temperatures enhanced sediment oxygen demand and the extent of hypoxic conditions in the benthic compartment, favoring anaerobic metabolism. Indeed, warming water temperature stimulated nitrate (NO3-) reduction processes, although NO3- and organic matter availability were found to be the main controlling factors shaping the rates between seasons. Denitrification was the main process responsible for NO3- removal, mainly supported by NO3- diffusion from the water column into the sediments, and much more important than N recycling via DNRA. The predicted increase in the water temperature of the Po River due to climate change may exert an unexpected negative feedback on eutrophication by strongly controlling denitrification and contributing to partial buffering of N export in the lagoons and coastal areas, especially in spring.

Nitrate availability affects denitrification in Phragmites australis sediments.

Understanding relationships between an increase in nitrate (NO3 - ) loading and the corresponding effects of wetland vegetation on denitrification is essential to designing, restoring, and managing wetlands and canals to maximize their effectiveness as buffers against eutrophication. Although Phragmites australis (Cav.) Trin. ex Steud. is frequently used to remediate nitrogen (N) pollution, no information is available on how NO3 - concentration may affect plant-mediated denitrification. In the present study, denitrification was measured in outdoor vegetated and unvegetated mesocosms incubated in both summer and winter. After spiking the mesocosms with NO3 - concentrations typical of agricultural drainage water (0.7-11.2 mg N L-1 ), denitrification was quantified by the simultaneous measurement of NO3 - consumption and dinitrogen gas (N2 ) production. Although denitrification rates varied with vegetation presence and season, NO3 - availability exerted a significant positive effect on the process. Vegetated sediments were more efficient than bare sediments in adapting their mitigation potential to an increase in NO3 - , by yielding a one-order-of-magnitude increase in NO3 - removal rates, under both summer (743-6007 mg N m-2 d-1 ) and winter (43-302 mg N m-2 d-1 ) conditions along the NO3 - gradient. Denitrification was the dominant sink for water NO3 - in winter and only for vegetated sediments in summer. Nitrification likely contributed to fuel denitrification in summer unvegetated sediments. Since denitrification rates followed Michaelis-Menten kinetics, P. australis-mediated depuration may be considered optimal up to 5.0 mg N L-1 . The present outcomes provide experimentally supported evidence that restoration with P. australis can work as a cost-effective means of improving water quality in agricultural watersheds.

Effect of ebullition and groundwater temperature on estimated dinitrogen excess in contrasting agricultural environments.

Denitrification is a key microbial-mediated reaction buffering the impact of agriculturally-derived nitrate loads. Groundwater denitrification capacity is often assessed by measuring the magnitude and patterns of dinitrogen excess, although this method can be biased by dissolved gasses exsolution and ebullition. To address this issue, shallow groundwater was sampled in two field sites via nested mini-wells on a monthly basis over an entire hydrological year and analysed for dissolved gasses, nitrate and physical parameters. Both sites are located in lowland areas of the Po River basin (Italy) and are characterized by intensive agriculture. The GUA site, a freshwater paleo-river environment, with a low content of organic matter (SOM) and oxic sub-oxic groundwater. The BAN site, a reclaimed brackish swamp environment, with abundant SOM and sulphidic-methanogenic groundwater. Groundwater samples evidenced a general deficit of dinitrogen and Argon concentrations, because of ebullition induced by a total dissolved gasses pressure exceeding the hydrostatic pressure. Ebullition was recorded only during winter at the reclaimed brackish soil and was triggered by methane exsolution. While in summer both sites were affected by ebullition because of the water table drawdown. Denitrification evaluated using dinitrogen excess via dinitrogen-Argon ratio technique, was not only affected by gas exsolution, but also by groundwater temperature fluctuations. In fact, the latter induced large biases in the calculated N2 excess even in the freshwater paleo-river environment. For these reasons, dinitrogen excess estimate with standard methods resulted to be unreliable in both lowland environments and a modified method is here presented to overcome this issue.

Intense rainfalls trigger nitrite leaching in agricultural soils depleted in organic matter.

Nitrate and ammonium are common inorganic contaminants of anthropogenic origin in many shallow aquifers around the world, while nitrite is less common, but it is most harmful than nitrate and ammonium due to its high reactivity. This paper presents evidence of nitrite accumulation after intense rainfalls in soil samples collected in an agricultural field characterized by organic matter chronic depletion. Moreover, an intact core from the same site was also collected to perform an unsaturated column experiment (60 cm long and 20 cm outer diameter) mimicking heavy rainfalls (230 mm in 2 days). Results from the field site showed nitrite accumulation (up to 0.45 mmol/kg) at 50-70 cm depth, just below the plough layer. The column experiment showed very high initial concentrations of nitrate and nitrite in the leachate and a progressive decrease of nitrate due to denitrification. The numerical flow model was calibrated versus the observed volumetric water contents and leachate flow rates. The numerical reactive transport model was calibrated versus the leachate concentrations of six dissolved species (ammonium, nitrate, nitrite, dissolved organic carbon, chloride and bromide). The optimized model resulted to be robustly calibrated providing insights on the kinetic rates driving the production, accumulation and leakage of nitrite, showing that incomplete denitrification is the source of nitrite. As far as the authors are aware, this is the first study reporting a clear link between high nitrite leaching rates and extreme rainfall events in lowland agricultural soils depleted in organic matter. The proposed methodology could be applied to quantify nitrite cycling processes in many other agricultural areas of the world affected by extreme rainfall events.

The effect of water velocity on nitrate removal in vegetated waterways.

The extended networks of canals and ditches in agricultural landscapes provide high buffer capacity towards nitrogen (N) excess. Their N mitigation potential depends on several biotic and abiotic factors, among which water velocity is poorly explored and generally omitted from the parameterization of this remarkable ecosystem service. The present work reports new insights on the role of flow velocity in regulating N removal via denitrification in sediments colonized by Phragmites australis. Denitrification was investigated in outdoor mesocosms in the presence and absence of P. australis and over a small range of flow velocity (0-6 cm s-1) typical of low-gradient water bodies. Simultaneous measurements of NO3- consumption and N2 production based on analyses of N2:Ar by Membrane Inlet Mass Spectrometry were undertaken. Vegetated sediments were found more efficient in converting NO3- to N2 via microbial-mediated denitrification (27-233 mmol N m-2 d-1) than bare sediments (18-33 mmol N m-2 d-1). Vegetation provides multiple interfaces, i.e. in the rhizosphere and on epiphytic biofilms, that support the development and activity of bacterial communities responsible for NO3- dissipation. NO3- removal and denitrification rates exhibited one order of magnitude raise when water velocity passed from 0 to 6 cm s-1 in vegetated sediments. Indeed, in slow-flow vegetated waterways denitrification may be physically limited and the increase of water velocity enhances the rate of NO3- supply through the diffusive boundary layer, thereby promoting its consumption and loss from the system. Water velocity should be taken into account as a key factor for management and restoration actions aimed at maximizing the NO3- buffer capacity of low-flow drainage networks.

Effects of Moisture and Particle Size on Quantitative Determination of Total Organic Carbon (TOC) in Soils Using Near-Infrared Spectroscopy.

Near-Infrared Spectroscopy is a cost-effective and environmentally friendly technique that could represent an alternative to conventional soil analysis methods, including total organic carbon (TOC). Soil fertility and quality are usually measured by traditional methods that involve the use of hazardous and strong chemicals. The effects of physical soil characteristics, such as moisture content and particle size, on spectral signals could be of great interest in order to understand and optimize prediction capability and set up a robust and reliable calibration model, with the future perspective of being applied in the field. Spectra of 46 soil samples were collected. Soil samples were divided into three data sets: unprocessed, only dried and dried, ground and sieved, in order to evaluate the effects of moisture and particle size on spectral signals. Both separate and combined normalization methods including standard normal variate (SNV), multiplicative scatter correction (MSC) and normalization by closure (NCL), as well as smoothing using first and second derivatives (DV1 and DV2), were applied to a total of seven cases. Pretreatments for model optimization were designed and compared for each data set. The best combination of pretreatments was achieved by applying SNV and DV2 on partial least squares (PLS) modelling. There were no significant differences between the predictions using the three different data sets (p < 0.05). Finally, a unique database including all three data sets was built to include all the sources of sample variability that were tested and used for final prediction. External validation of TOC was carried out on 16 unknown soil samples to evaluate the predictive ability of the final combined calibration model. Hence, we demonstrate that sample preprocessing has minor influence on the quality of near infrared spectroscopy (NIR) predictions, laying the ground for a direct and fast in situ application of the method. Data can be acquired outside the laboratory since the method is simple and does not need more than a simple band ratio of the spectra.

Chlorate origin and fate in shallow groundwater below agricultural landscapes.

In agricultural lowland landscapes, intensive agricultural is accompanied by a wide use of agrochemical application, like pesticides and fertilizers. The latter often causes serious environmental threats such as N compounds leaching and surface water eutrophication; additionally, since perchlorate can be present as impurities in many fertilizers, the potential presence of perchlorates and their by-products like chlorates and chlorites in shallow groundwater could be a reason of concern. In this light, the present manuscript reports the first temporal and spatial variation of chlorates, chlorites and major anions concentrations in the shallow unconfined aquifer belonging to Ferrara province (in the Po River plain). The study was made in 56 different locations to obtain insight on groundwater chemical composition and its sediment matrix interactions. During the monitoring period from 2010 to 2011, in June 2011 a nonpoint pollution of chlorates was found in the shallow unconfined aquifer belonging to Ferrara province. Detected chlorates concentrations ranged between 0.01 and 38 mg/l with an average value of 2.9 mg/l. Chlorates were found in 49 wells out of 56 and in all types of lithology constituting the shallow aquifer. Chlorates concentrations appeared to be linked to NO3-, volatile fatty acids (VFA) and oxygen reduction potential (ORP) variations. Chlorates behaviour was related to the biodegradation of perchlorates, since perchlorates are favourable electron acceptors for the oxidation of labile dissolved organic carbon (DOC) in groundwater. Further studies must take into consideration to monitor ClO4- in pore waters and groundwater to better elucidate the mass flux of ClO4- in shallow aquifers belonging to agricultural landscapes.

Common carp Cyprinus carpio responses to sub-chronic exposure to perfluorooctanoic acid.

Perfluorooctanoic acid (PFOA) is an important and diffuse perfluorinated alkylated substance, but knowledge of the toxicological effects of this endocrine disrupter in fish is limited. Adult common carp Cyprinus carpio, L. were exposed to 200 ng/l (a concentration reported in impacted aquatic ecosystems) and 2 mg/l PFOA solutions in a flow-through system for 56 days to determine tissue accumulation and histological alterations of the primary target organs. PFOA was extracted from blood, gill, liver, muscle, kidney, gonad, and brain by an ion-pairing liquid extraction procedure and quantified using high performance liquid chromatography with electrospray ionization tandem mass spectrometry. The limit of detection (LOD) was 0.4 ng/g wet weight (ww). PFOA was not detectable in unexposed fish or in fish exposed to 200 ng/l, but was >LOD in most samples of carp exposed to 2 mg/l. Mean PFOA concentration ranged from 0.5 to 65 ng/g ww, depending on the tissue, with highest levels in the blood and liver. There were no significant differences in condition factor, hepato-somatic index, or gonado-somatic index among the fish of the three groups. Histological, histochemical, and immunohistochemical staining was performed on sections of liver and gonad. Occurrence of atretic oocytes and a paucity of spermatozoa were documented in carp treated with 2 mg/l PFOA. Exposed fish did not show gross hepatic anomalies, but there was enhancement of hepatocytes in proliferation (positive to anti-PCNA antibody) compared to controls.