Use of an inverse dispersion technique for estimating ammonia emission from surface-applied slurry

Ammonia (NH₃) emission from land application of manure is typically measured using the integrated horizontal flux (IHF) micrometeorological method. However, there are some situations in which alternative techniques (such as an inverse dispersion modelling technique) might be preferable, for example when measuring from large or irregularly shaped source areas. In this study, an inverse dispersion technique using the backward Lagrangian stochastic (bLS) model, with 2 different experimental configurations, was compared with the Integrated Horizontal Flux method (i.e. IHF), which was used as reference technique. Pig slurry was surface-applied at 125 kg N ha^?1 to bare soil on a large plot (80 × 125 m). Cumulative emissions were 19.3, 21.2 and 18.4 kg N ha^?1 from the IHF and the bLS technique (experimental configurations I and II), respectively. Mean flux within each sampling period as estimated by the two techniques compared extremely well, with a slope not significantly different from 1 and r² of 0.99. Although limited in extent, this dataset agree with a previous study in demonstrating the use of the bLS technique with longer period time-averaged concentration measurements.     

Landscape-scale spatial distribution of the Lanner Falcon (Falco biarmicus feldeggii) breeding population in Italy

Falco biarmicus feldeggii is one of the most threatened taxa in Europe. Its global population is estimated at a few hundred pairs unequally scattered in a vast and fragmented area stretching from Sicily to the Caspian Sea. Most recent counts showed that Italy hosts a large part (>25%) of the whole population. Consequently, Italian authorities promoted a national action plan. In this framework, we carried out the first national survey for the Lanner Falcon in Italy (2003-2004). Our study area covered the whole breeding range, i.e., Sicily and the Italian peninsula (n = 2909 cells 10 x 10 km). When possible, we considered also additional information from previous regional investigations (1993-2001). First, we estimated size and distribution of each breeding subpopulation. Then, we tried to identify, at landscape level, the main environmental features linked to the spatial distribution of the nesting sites. We found the Lanner Falcon in 184 cells (6.4% of the total grid map), but we estimated no more than 140-172 pairs (70-80 of which are in Sicily) in the same breeding season. Higher levels of isolation characterize the continental breeding cells whereas in Sicily cells are much more clustered. Altitude is the main factor influencing cell aggregations in Italy; nevertheless, other environmental variables, such as climate, precipitation, and vegetation may be important. Our results show that the conservation measures adopted in Italy are somewhat inadequate given the low number of breeding pairs included in protected areas (23%-28%). Many small and scattered special areas of conservation (SAC) devoted to conserve priority habitats fit the irregular spatial aggregations of Lanner Falcon sites better than several large special protection areas (SPA).     

Raptor ecotoxicology in Spain: a review on persistent environmental contaminants

Initial studies on the pressure from environmental contaminants on raptor populations in Spain date back to the 1980s, and they have been carried out from a range of viewpoints using a range of sentinel raptor species. However, there is no national monitoring scheme, and therefore the research carried out has been sporadic both spatially and temporally. The exposure to metals has not varied over time, except in the case of lead, whose concentration in eggs and tissues has diminished. In general, the concentrations of metals detected in raptor samples from Spain are generally low and not sufficient to produce toxic effects. Excepting DDT and DDE, most organochlorine-based pesticides in raptors from Spain have diminished over the last 2 decades. The concentrations of DDE found in the eggs of various species could in part explain problems in the reproductive success of raptors in Spain.     

Calibration and validation of a dynamic water model in agricultural scenarios

A dynamic aquatic model (DynA model) was previously developed to predict the fate of a chemical in aquatic scenarios characterized by daily or periodic changes in several input parameters. DynA model is here calibrated with data obtained from the literature in specific unsteady state scenarios, such as those of rice fields. The results obtained for two herbicides (cinosulfuron and pretilachlor) in rice paddy scenarios revealed the capability of the model to accurately predict water and sediment concentrations, as shown by some statistical indicators. Modelling efficiency (EF) values of 0.86-0.99 for the water compartment and of 0.77-0.84 for sediment show the good agreement between predicted and measured concentrations. An "external validation" was performed using measured data for a different herbicide (molinate) applied in a Portuguese paddy rice scenario. A sensitivity analysis for this volatile chemical revealed the influence of some climatic parameters (e.g. temperature) to the model outcomes, such as water and sediment concentrations. This confirmed the capability of DynA model as an efficient tool for the pesticide risk assessment in dynamic scenarios.     

Inter- and intra-specific variation on sensitivity of larval amphibians to nitrite

Several authors have suggested that nitrogen-based fertilizers may be contributing to the global amphibian decline. We have studied the impact of sodium nitrite on early aquatic stages of Epidalea calamita, Pelophylax perezi and Hyla meridionalis larvae from Do?ana National Park (coastal wetland) and P. perezi from Gredos Mountain (high mountain ponds), exposed during 10 to 16 days. After 8 days of exposure all P. perezi larvae from Do?ana presented 100% mortality at 5 mg l(-1)N-NO2(-) while E. calamita larvae mortality rates were significantly lower at that concentration after 15 days. However, for H. meridionalis at day 15 no deaths were registered at 5 mg l(-1)N-NO2(-) and at 20 mg l(-1)N-NO2(-) presented intermediate mortality rates. In Do?ana the 10 d LC50 of older H. meridionalis larvae was between 20 and 30 mg l(-1)N-NO2(-) whilst for P. perezi it was below 5 mg l(-1)N-NO2(-). These results indicate inter-specific variation of the sensitivity of larval amphibians to nitrite. Gredos Mountain P. perezi larvae exposed since the egg stage were highly sensitive to nitrite, with a 16 d LC50 below 0.5 mg l(-1)N-NO2(-). The same species in Do?ana had a 15 d LC50 between 5 and mg l(-1)N-NO2(-). These results suggest that there is also intra-specific variation in sensitivity of amphibian larvae to nitrite: mountain amphibian populations appear to be more sensitive to polluted environments than coastal populations. Geographic and genetic variation and evolutionary adaptation of tolerance may also be the keys to variation amongst populations of the same species.     

An inhibitor of urease activity effectively reduces ammonia emissions from soil treated with urea under Mediterranean conditions

Urea is an important source of ammonia (NH₃) emissions to the atmosphere from agricultural soils. Abatement strategies are necessary in order to achieve NH₃ emission targets by reducing those emissions. In this context, a field experiment was carried out on a sunflower crop in spring 2006 with the aim of evaluating the effect of the N-(n-butyl) thiophosphoric triamide (NBPT) in the mitigation of volatilized NH₃ from a urea-fertilised soil. Ammonia emission was quantified, using the integrated horizontal flux (IHF) method, following application of urea with and without the urease inhibitor NBPT. Urea and a mixture of urea and NBPT (0.14%, w/w) were surface-applied at a rate of 170 kg N ha⁻¹ to circular plots (diameter 40 m). The soil was irrigated with 10 mm of water just after the application of urea to dissolve and incorporate it into the upper layer of soil. Over the duration of the measurement period (36 days) three peaks of NH₃ were observed. The first peak was associated with hydrolysis of urea after irrigation and the others with the increase of ammonia in soil solution after changes in atmospheric variables such as wind speed and rainfall. The total NH₃ emission during the whole experiment was 17.3 ± 0.5 kg NH₃–N ha⁻¹ in the case of urea treated soils and 10.0 ± 2.2 kg NH₃–N ha⁻¹ where NBPT was included with the urea (10.1 and 5.9%, respectively, of the applied urea–N). The lower NH₃ emissions from plots fertilised with urea + NBPT, compared with urea alone, were associated with a reduction in urease activity during the first 9 days after inhibitor application. This reduction in enzymatic activity promoted a decrease in the exchangeable NH₄⁺ pool.     

Persistent organic pollutants, brominated flame retardants and synthetic musks in fish from remote alpine lakes in Switzerland

Remote alpine lakes do not receive any direct aquatic inputs from anthropogenic activities. Therefore, these ecosystems may receive persistent organic compounds (POPs) by direct atmospheric deposition, only. Consequently, fish dwelling in these ecosystems represent an excellent indicator for the long-term atmospheric input of bioaccumulating and persistent contaminants. In the present study, fish from seven remote alpine lakes, located between 2062 and 2637 m above sea level in south eastern Switzerland (Grisons), were investigated. Lipid-based fish tissue concentrations of pesticides including dichlorodiphenyltrichloroethane (DDT) and its transformation products (2,4'-DDT, 4,4'-DDT, 2,4'-dichlorodiphenyldichloroethane (DDD), 4,4'-DDD, 2,4'-dichlorodiphenyldichloroethene (DDE), 4,4'-DDE), as well as dieldrin, heptachlor exo-epoxide (HPEX), hexachlorobenzene (HCB), hexachlorocyclohexanes (HCH), polychlorinated biphenyls (PCB), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F), and polybrominated diphenyl ethers (PBDE) were measured. In addition, seven synthetic musk compounds (Crysolide (ADBI), Phantolide (AHMI), Fixolide (AHTN), Traseolide (ATII), Galaxolide (HHCB), musk ketone (MK), and musk xylene (MX)) were determined. Concentrations of PCB, PCDD/F, and PBDE were in the same range as in fish from the major lakes situated in the Swiss plateau, indicating mainly atmospheric input of these persistent compounds. In contrast, concentrations of synthetic musks which are used as fragrances in laundry detergents and cosmetic products were distinctly lower than concentrations in fish from Swiss plateau lakes which receive inputs from waste water treatment plants.     

Fenton's pre-treatment of mature landfill leachate

The aim of this study was to check the effectiveness of the Fenton's reagent (Fe2+ + H2O2 + H+) for the pre-treatment of a municipal landfill leachate with the objective of improving its overall biodegradability, evaluated in terms of BOD5/COD ratio, up to a value compatible with biological treatment. The leachate came from a municipal sanitary landfill located in southern Italy and the average values of its main parameters were: pH=8.2; COD=10,540 mgl(-1); BOD5=2,300 mgl(-1); TOC=3,900 mgl(-1); NH4-N=5210 mgl(-1); conductivity=45,350 microScm(-1); alkalinity=21,470 mgl(-1) CaCO3. The effect of initial pH value on the pre-treatment effectiveness was evaluated by titrating the amount of acidic by-products formed. The extent of leachate oxidation was monitored and controlled by both pH and redox potential measurements. The best operational conditions for achieving the desired goal (i.e., BOD5/COD> or =0.5) resulted: Fe2+=275 mgl(-1); H2O2=3,300 mgl(-1); initial pH=3; reaction time=2 h. At the end of the Fenton's pre-treatment, in order to permit a subsequent biological treatment, residual ferric ions were removed increasing the pH up to 8.5 by adding 3 gl(-1) of Ca(OH)2 and 3 mgl(-1) of a cationic polyelectrolyte, the latter as an aid to coagulation. This final step also resulted in a further modest removal of residual COD due to co-precipitation phenomena.