Nitrogen processes in aquatic ecosystems

Executive summary Nature of the problem (science/management/policy) • Freshwater ecosystems play a key role in the European nitrogen (N) cycle, both as a reactive agent that transfers, stores and processes N loadings from the atmosphere and terrestrial ecosystems, and as a natural environment severely impacted by the increase of these loadings. Approaches • This chapter is a review of major processes and factors controlling N transport and transformations for running waters, standing waters, groundwaters and riparian wetlands. Key findings/state of knowledge • The major factor controlling N processes in freshwater ecosystems is the residence time of water, which varies widely both in space and in time, and which is sensitive to changes in climate, land use and management. • The effects of increased N loadings to European freshwaters include acidification in semi-natural environments, and eutrophication in more disturbed ecosystems, with associated loss of biodiversity in both cases. • An important part of the nitrogen transferred by surface waters is in the form of organic N, as dissolved organic N (DON) and particulate organic N (PON). This part is dominant in semi-natural catchments throughout Europe and remains a significant component of the total N load even in nitrate enriched rivers. • In eutrophicated standing freshwaters N can be a factor limiting or co-limiting biological production, and control of both N and phosphorus (P) loading is oft en needed in impacted areas, if ecological quality is to be restored. Major uncertainties/challenges • The importance of storage and denitrifi cation in aquifers is a major uncertainty in the global N cycle, and controls in part the response of catchments to land use or management changes. In some aquifers, the increase of N concentrations will continue for decades even if efficient mitigation measures are implemented now. • Nitrate retention by riparian wetlands has oft en been highlighted. However, their use for mitigation must be treated with caution, since their effectiveness is difficult to predict, and side effects include increased DON emissions to adjacent open waters, N2O emissions to the atmosphere, and loss of biodiversity. • In fact, the character and specific spatial origins of DON are not fully understood, and similarly the quantitative importance of indirect N2O emissions from freshwater ecosystems as a result of N leaching losses from agricultural soils is still poorly known at the regional scale. • These major uncertainties remain due to the lack of adequate monitoring (all forms of N at a relevant frequency), especially – but not only – in the southern and eastern EU countries. Recommendations (research/policy) • The great variability of transfer pathways, buffering capacity and sensitivity of the catchments and of the freshwater ecosystems calls for site specific mitigation measures rather than standard ones applied at regional to national scale. • The spatial and temporal variations of the N forms, the processes controlling the transport and transformation of N within freshwaters, require further investigation if the role of N in influencing freshwater ecosystem health is to be better understood, underpinning the implementation of the EU Water Framework Directive for European freshwaters.

Identifying and investigating pesticide application types to promote a more sustainable pesticide use: the case of smallholders in Boyacá, Colombia

The present paper investigates pesticide application types adopted by smallholder potato producers in the Department of Boyacá , Colombia. In this region, environmental, health and adverse economic effects due to pesticide mis- or over-use respectively have been observed. Firstly, pesticide application types were identified based on input-effectiveness. Secondly, their determinants of adoption were investigated. Finally suggestions were given to develop intervention options for transition towards a more sustainable pesticide use. Three application types were identified for fungicide and insecticide. The types differed in terms of input (intensity of pesticide application), effect (damage control), frequency of application, average quantity applied per application, chemical class, and productivity. Then, the determinants of different pesticide application types were investigated with a multinomial logistic regression approach and applying the integrative agent centred (IAC) framework. The area of the plot, attendance at training sessions and educational and income levels were among the most relevant determinants. The analysis suggested that better pesticide use could be fostered to reduce pesticide-related risks in the region. Intervention options were outlined, which may help in targeting this issue. They aim not only at educating farmers, but to change their social and institutional context, by involving other agents of the agricultural system (i.e. pesticide producers), facilitating new institutional settings (i.e. cooperatives) and targeting social dynamics (i.e. conformity to social norms).

Application of mid-infrared spectroscopy to the prediction of maturity and sensory texture attributes of cheddar cheese

The objective of this study was to determine the potential of mid-infrared spectroscopy in conjunction with partial least squares (PLS) regression to predict various quality parameters in cheddar cheese. Cheddar cheeses (n = 24) were manufactured and stored at 8 degrees C for 12 mo. Mid-infrared spectra (640 to 4000/cm) were recorded after 4, 6, 9, and 12 mo storage. At 4, 6, and 9 mo, the water-soluble nitrogen (WSN) content of the samples was determined and the samples were also evaluated for 11 sensory texture attributes using descriptive sensory analysis. The mid-infrared spectra were subjected to a number of pretreatments, and predictive models were developed for all parameters. Age was predicted using scatter-corrected, 1st derivative spectra with a root mean square error of cross-validation (RMSECV) of 1 mo, while WSN was predicted using 1st derivative spectra (RMSECV = 2.6%). The sensory texture attributes most successfully predicted were rubbery, crumbly, chewy, and massforming. These attributes were modeled using 2nd derivative spectra and had, corresponding RMSECV values in the range of 2.5 to 4.2 on a scale of 0 to 100. It was concluded that mid-infrared spectroscopy has the potential to predict age, WSN, and several sensory texture attributes of cheddar cheese..

Semi-dwarfing (Rht-B1b) improves nitrogen-use efficiency in wheat, but not at economically optimal levels of nitrogen availability

A UK field experiment compared a complete factorial combination of three backgrounds (cvs Mercia, Maris Huntsman and Maris Widgeon), three alleles at the Rht-B1 locus as Near Isogenic Lines (NILs: rht-B1a (tall), Rht-B1b (semi-dwarf), Rht-B1c (severe dwarf)) and four nitrogen (N) fertilizer application rates (0, 100, 200 and 350 kg N/ha). Linear+exponential functions were fitted to grain yield (GY) and nitrogen-use efficiency (NUE; GY/available N) responses to N rate. Averaged over N rate and background Rht-B1b conferred significantly (P<0.05) greater GY, NUE, N uptake efficiency (NUpE; N in above ground crop / available N) and N utilization efficiency (NUtEg; GY / N in above ground crop) compared with rht-B1a and Rht-B1c. However the economically optimal N rate (Nopt) for N:grain price ratios of 3.5:1 to 10:1 were also greater for Rht-B1b, and because NUE, NUpE and NUtE all declined with N rate, Rht-Blb failed to increase NUE or its components at Nopt. The adoption of semi-dwarf lines in temperate and humid regions, and the greater N rates that such adoption justifies economically, greatly increases land-use efficiency, but not necessarily, NUE.

Application of EMD as a novel technique for the study of tremor time series

This paper introduces the Hilbert Analysis (HA), which is a novel digital signal processing technique, for the investigation of tremor. The HA is formed by two complementary tools, i.e. the Empirical Mode Decomposition (EMD) and the Hilbert Spectrum (HS). In this work we show that the EMD can automatically detect and isolate tremulous and voluntary movements from experimental signals collected from 31 patients with different conditions. Our results also suggest that the tremor may be described by a new class of mathematical functions defined in the HA framework. In a further study, the HS was employed for visualization of the energy activities of signals. This tool introduces the concept of instantaneous frequency in the field of tremor. In addition, it could provide, in a time-frequency energy plot, a clear visualization of local activities of tremor energy over the time. The HA demonstrated to be very useful to perform objective measurements of any kind of tremor and can therefore be used to perform functional assessment.

Does high-frequency repetitive transcranial magnetic stimulation produce residual and/or cumulative effects within an experimental session?

A common procedure for studying the effects on cognition of repetitive transcranial magnetic stimulation (rTMS) is to deliver rTMS concurrent with task performance, and to compare task performance on these trials versus on trials without rTMS. Recent evidence that TMS can have effects on neural activity that persist longer than the experimental session itself, however, raise questions about the assumption of the transient nature of rTMS that underlies many concurrent (or "online") rTMS designs. To our knowledge, there have been no studies in the cognitive domain examining whether the application of brief trains of rTMS during specific epochs of a complex task may have effects that spill over into subsequent task epochs, and perhaps into subsequent trials. We looked for possible immediate spill-over and longer-term cumulative effects of rTMS in data from two studies of visual short-term delayed recognition. In 54 subjects, 10-Hz rTMS trains were applied to five different brain regions during the 3-s delay period of a spatial task, and in a second group of 15 subjects, electroencephalography (EEG) was recorded while 10-Hz rTMS was applied to two brain areas during the 3-s delay period of both spatial and object tasks. No evidence for immediate effects was found in the comparison of the memory probe-evoked response on trials that were vs. were not preceded by delay-period rTMS. No evidence for cumulative effects was found in analyses of behavioral performance, and of EEG signal, as a function of task block. The implications of these findings, and their relation to the broader literature on acute vs. long-lasting effects of rTMS, are considered.

Evaluation and management of the impact of land use change on the nitrogen and phosphorus load delivered to surface waters: the export coefficient modelling approach

A manageable, relatively inexpensive model was constructed to predict the loss of nitrogen and phosphorus from a complex catchment to its drainage system. The model used an export coefficient approach, calculating the total nitrogen (N) and total phosphorus (P) load delivered annually to a water body as the sum of the individual loads exported from each nutrient source in its catchment. The export coefficient modelling approach permits scaling up from plot-scale experiments to the catchment scale, allowing application of findings from field experimental studies at a suitable scale for catchment management. The catchment of the River Windrush, a tributary of the River Thames, UK, was selected as the initial study site. The Windrush model predicted nitrogen and phosphorus loading within 2% of observed total nitrogen load and 0.5% of observed total phosphorus load in 1989. The export coefficient modelling approach was then validated by application in a second research basin, the catchment of Slapton Ley, south Devon, which has markedly different catchment hydrology and land use. The Slapton model was calibrated within 2% of observed total nitrogen load and 2.5% of observed total phosphorus load in 1986. Both models proved sensitive to the impact of temporal changes in land use and management on water quality in both catchments, and were therefore used to evaluate the potential impact of proposed pollution control strategies on the nutrient loading delivered to the River Windrush and Slapton Ley

Steady state and dynamic modelling of nitrogen in the River Kennet: impacts of land use change since the 1930s

Steady state and dynamic models have been developed and applied to the River Kennet system. Annual nitrogen exports from the land surface to the river have been estimated based on land use from the 1930s and the 1990s. Long term modelled trends indicate that there has been a large increase in nitrogen transport into the river system driven by increased fertiliser application associated with increased cereal production, increased population and increased livestock levels. The dynamic model INCA Integrated Nitrogen in Catchments. has been applied to simulate the day-to-day transport of N from the terrestrial ecosystem to the riverine environment. This process-based model generates spatial and temporal data and reproduces the observed instream concentrations. Applying the model to current land use and 1930s land use indicates that there has been a major shift in the short term dynamics since the 1930s, with increased river and groundwater concentrations caused by both non-point source pollution from agriculture and point source discharges. �

The prediction of nutrients into estuaries and their subsequent behaviour: application to the Tamar and comparison with the Tweed, U.K.

Some of the techniques used to model nitrogen (N) and phosphorus (P) discharges from a terrestrial catchment to an estuary are discussed and applied to the River Tamar and Tamar Estuary system in Southwest England, U.K. Data are presented for dissolved inorganic nutrient concentrations in the Tamar Estuary and compared with those from the contrasting, low turbidity and rapidly flushed Tweed Estuary in Northeast England. In the Tamar catchment, simulations showed that effluent nitrate loads for typical freshwater flows contributed less than 1% of the total N load. The effect of effluent inputs on ammonium loads was more significant (∼10%). Cattle, sheep and permanent grassland dominated the N catchment export, with diffuse-source N export greatly dominating that due to point sources. Cattle, sheep, permanent grassland and cereal crops generated the greatest rates of diffuse-source P export. This reflected the higher rates of P fertiliser applications to arable land and the susceptibility of bare, arable land to P export in wetter winter months. N and P export to the Tamar Estuary from human sewage was insignificant. Non-conservative behaviour of phosphate was particularly marked in the Tamar Estuary. Silicate concentrations were slightly less than conservative levels, whereas nitrate was essentially conservative. The coastal sea acted as a sink for these terrestrially derived nutrients. A pronounced sag in dissolved oxygen that was associated with strong nitrite and ammonium peaks occurred in the turbidity maximum region of the Tamar Estuary. Nutrient behaviour within the Tweed was very different. The low turbidity and rapid flushing ensured that nutrients there were essentially conservative, so that flushing of nutrients to the coastal zone from the river occurred with little estuarine modification.

Mononuclear palladium and heterodinuclear palladium–ruthenium complexes of semicarbazone ligands: synthesis, characterization, and application in C–C cross-coupling reactions

Reaction of salicylaldehyde semicarbazone (L-1), 2-hydroxyacetophenone semicarbazone (L-2), and 2-hydroxynaphthaldehyde semicarbazone (L-3) with [Pd(PPh3)(2)Cl-2] in ethanol in the presence of a base (NEt3) affords a family of yellow complexes (1a, 1b and 1c, respectively). In these complexes the semicarbazone ligands are coordinated to palladium in a rather unusual tridentate ONN-mode, and a PPh3 also remains coordinated to the metal center. Crystal structures of the 1b and 1c complexes have been determined, and structure of 1a has been optimized by a DFT method. In these complexes two potential donor sites of the coordinated semicarbazone, viz. the hydrazinic nitrogen and carbonylic oxygen, remain unutilized. Further reaction of these palladium complexes (1a, 1b and 1c) with [Ru(PPh3)(2)(CO)(2)Cl-2] yields a family of orange complexes (2a, 2b and 2c, respectively). In these heterodinuclear (Pd-Ru) complexes, the hydrazinic nitrogen (via dissociation of the N-H proton) and the carbonylic oxygen from the palladium-containing fragment bind to the ruthenium center by displacing a chloride and a carbonyl. Crystal structures of 2a and 2c have been determined, and the structure of 2b has been optimized by a DFT method. All the complexes show characteristic H-1 NMR spectra and, intense absorptions in the visible and ultraviolet region. Cyclic voltammetry on all the complexes shows an irreversible oxidation of the coordinated semicarbazone within 0.86-0.93 V vs. SCE, and an irreversible reduction of the same ligand within -0.96 to -1.14 V vs. SCE. Both the mononuclear (1a, 1b and 1c) and heterodinuclear (2a, 2b and 2c) complexes are found to efficiently catalyze Suzuki, Heck and Sonogashira type C-C coupling reactions utilizing a variety of aryl bromides and aryl chlorides. The Pd-Ru complexes (2a, 2b and 2c) are found to be better catalysts than the Pd complexes (1a, 1b and 1c) for Suzuki and Heck coupling reactions.

Sparse shape representation using the Laplace-Beltrami eigenfunctions and its application to modeling subcortical structures

We present a new sparse shape modeling framework on the Laplace-Beltrami (LB) eigenfunctions. Traditionally, the LB-eigenfunctions are used as a basis for intrinsically representing surface shapes by forming a Fourier series expansion. To reduce high frequency noise, only the first few terms are used in the expansion and higher frequency terms are simply thrown away. However, some lower frequency terms may not necessarily contribute significantly in reconstructing the surfaces. Motivated by this idea, we propose to filter out only the significant eigenfunctions by imposing l1-penalty. The new sparse framework can further avoid additional surface-based smoothing often used in the field. The proposed approach is applied in investigating the influence of age (38-79 years) and gender on amygdala and hippocampus shapes in the normal population. In addition, we show how the emotional response is related to the anatomy of the subcortical structures.

Cyclic prefixed OQAM-OFDM and its application to single-carrier FDMA

Single-carrier frequency division multiple access (SC-FDMA) has appeared to be a promising technique for high data rate uplink communications. Aimed at SC-FDMA applications, a cyclic prefixed version of the offset quadrature amplitude modulation based OFDM (OQAM-OFDM) is first proposed in this paper. We show that cyclic prefixed OQAMOFDM CP-OQAM-OFDM) can be realized within the framework of the standard OFDM system, and perfect recovery condition in the ideal channel is derived. We then apply CP-OQAMOFDM to SC-FDMA transmission in frequency selective fading channels. Signal model and joint widely linear minimum mean square error (WLMMSE) equalization using a prior information with low complexity are developed. Compared with the existing DFTS-OFDM based SC-FDMA, the proposed SC-FDMA can significantly reduce envelope fluctuation (EF) of the transmitted signal while maintaining the bandwidth efficiency. The inherent structure of CP-OQAM-OFDM enables low-complexity joint equalization in the frequency domain to combat both the multiple access interference and the intersymbol interference. The joint WLMMSE equalization using a prior information guarantees optimal MMSE performance and supports Turbo receiver for improved bit error rate (BER) performance. Simulation resultsconfirm the effectiveness of the proposed SC-FDMA in termsof EF (including peak-to-average power ratio, instantaneous-toaverage power ratio and cubic metric) and BER performances.

Effects of nitrogen and sulfur fertilization on free amino acids, sugars, and acrylamide-forming potential in potato

Nitrogen (N) fertilizer is used routinely in potato (Solanum tuberosum) cultivation to maximize yield. However, it also affects sugar and free amino acid concentrations in potato tubers, and this has potential implications for food quality and safety because free amino acids and reducing sugars participate in the Maillard reaction during high-temperature cooking and processing. This results in the formation of color, aroma, and flavor compounds, but also some undesirable contaminants, including acrylamide, which forms when the amino acid that participates in the final stages of the reaction is asparagine. Another mineral, sulfur (S), also has profound effects on tuber composition. In this study, 13 varieties of potato were grown in a field trial in 2010 and treated with different combinations of N and S. Potatoes were analyzed immediately after harvest to show the effect of N and S fertilization on concentrations of free asparagine, other free amino acids, sugars, and acrylamide-forming potential. The study showed that N application can affect acrylamide-forming potential in potatoes but that the effect is type- (French fry, chipping, and boiling) and variety-dependent, with most varieties showing an increase in acrylamide formation in response to increased N but two showing a decrease. S application reduced glucose concentrations and mitigated the effect of high N application on the acrylamide-forming potential of some of the French fry-type potatoes.

A universal agro-hydrological model for water and nitrogen cycles in the soil-crop system SMCR_N: critical update and further validation

Agro-hydrological models have widely been used for optimizing resources use and minimizing environmental consequences in agriculture. SMCRN is a recently developed sophisticated model which simulates crop response to nitrogen fertilizer for a wide range of crops, and the associated leaching of nitrate from arable soils. In this paper, we describe the improvements of this model by replacing the existing approximate hydrological cascade algorithm with a new simple and explicit algorithm for the basic soil water flow equation, which not only enhanced the model performance in hydrological simulation, but also was essential to extend the model application to the situations where the capillary flow is important. As a result, the updated SMCRN model could be used for more accurate study of water dynamics in the soil-crop system. The success of the model update was demonstrated by the simulated results that the updated model consistently out-performed the original model in drainage simulations and in predicting time course soil water content in different layers in the soil-wheat system. Tests of the updated SMCRN model against data from 4 field crop experiments showed that crop nitrogen offtakes and soil mineral nitrogen in the top 90 cm were in a good agreement with the measured values, indicating that the model could make more reliable predictions of nitrogen fate in the crop-soil system, and thus provides a useful platform to assess the impacts of nitrogen fertilizer on crop yield and nitrogen leaching from different production systems. (C) 2010 Elsevier B.V. All rights reserved.

The water quality of the River Enborne, UK: observations from high-frequency Monitoring in a rural, lowland river system

This paper reports the results of a 2-year study of water quality in the River Enborne, a rural river in lowland England. Concentrations of nitrogen and phosphorus species and other chemical determinands were monitored both at high-frequency (hourly), using automated in situ instrumentation, and by manual weekly sampling and laboratory analysis. The catchment land use is largely agricultural, with a population density of 123 persons km−2. The river water is largely derived from calcareous groundwater, and there are high nitrogen and phosphorus concentrations. Agricultural fertiliser is the dominant source of annual loads of both nitrogen and phosphorus. However, the data show that sewage effluent discharges have a disproportionate effect on the river nitrogen and phosphorus dynamics. At least 38% of the catchment population use septic tank systems, but the effects are hard to quantify as only 6% are officially registered, and the characteristics of the others are unknown. Only 4% of the phosphorus input and 9% of the nitrogen input is exported from the catchment by the river, highlighting the importance of catchment process understanding in predicting nutrient concentrations. High-frequency monitoring will be a key to developing this vital process understanding.