High rates of nitrogen cycling in volcanic soils from Chilean grasslands

There are over one million hectares of pasture in Chile, and 80% and 50% of the country's milk and meat comes from 72% of this area, situated in the lake region of southern Chile. The soils are volcanic and a major characteristic is that they have very high organic matter (OM) contents with the potential to support plant growth with only moderate levels of added nitrogen (N). To understand better the potential fertility of these soils in order to maximise production and minimise losses of N, we undertook studies using the stable isotope of N ((15)N) to resolve the rates of the main internal N cycling processes in three soils representing the two main volcanic soil types: Osorno and Chiloé (Andisol) and Cudico (Ultisol). We also assessed the longer-term potential of these soils to sustain N release using anaerobic incubation. Gross rates (μg N g(-1) day(-1)) of mineralisation were 27.9, 27.1 and 15.5 and rates of immobilisation were 5.9, 12.0 and 6.3 for Osorno, Chiloé and Cudico, respectively, implying high rates of net mineralisation in these soils. This was confirmed by anaerobic incubation which gave potential seasonal net mineralisation indices of 1225, 1059 and 450 kg N ha(-1) in the top 10 cm soil layers of the three soils. However, plant production may still benefit from added N, as the release of N from organic sources may not be closely synchronised with crop demand. The low rates of nitrification that we found with these acidic soils suggest that the more mobile N (viz. nitrate-N) would be in limited supply and plants would have to compete for the less mobile ammonium-N with the soil microbial biomass. Nitrogen was mineralised in appreciable amounts even down to 60 cm depth, so that leaching could become significant, particularly if the soils were limed, which could enhance nitrification and N mobility through the soil profile.     

Development and characterization of non-treated and chemically modified olive pomace biosorbents to remove Ce(III) ions from aqueous solutions

Journal of Radioanalytical and Nuclear Chemistry - In this study, low-cost olive pomace, which is a waste of olive mill, was chemically modified using different acids, characterized, and utilized...     

Applicability of an In-Vitro Digestion Model to Assess the Bioaccessibility of Phenolic Compounds from Olive-Related Products

The Mediterranean diet includes virgin olive oil (VOO) as the main fat and olives as snacks. In addition to providing nutritional and organoleptic properties, VOO and the fruits (olives) contain an extensive number of bioactive compounds, mainly phenolic compounds, which are considered to be powerful antioxidants. Furthermore, olive byproducts, such as olive leaves, olive pomace, and olive mill wastewater, considered also as rich sources of phenolic compounds, are now valorized due to being mainly applied in the pharmaceutical and nutraceutical industries. The digestive system must physically and chemically break down these ingested olive-related products to release their phenolic compounds, which will be further metabolized to be used by the human organism. The first purpose of this review is to provide an overview of the current status of in-vitro static digestion models for olive-related products. In this sense, the in-vitro gastrointestinal digestion methods are widely used with the following aims: (i) to study how phenolic compounds are released from their matrices and to identify structural changes of phenolic compounds after the digestion of olive fruits and oils and (ii) to support the functional value of olive leaves and byproducts generated in the olive industry by assessing their health properties before and after the gastrointestinal process. The second purpose of this review is to survey and discuss all the results available to date.     

Nitrogen-15 in NO3- characterises differently reactive soil organic N pools

Intercropping with legumes is known to increase the plant-available nitrogen (N) in soil, but can also increase leaching of NO3- to the groundwater. To minimise NO3- leaching risks, knowledge of the N-release processes is essential, including an estimate of the contribution of legumes to total NO3- concentrations in soil. Our objectives were to answer the questions: (1) whether the presence of legume roots increases N mineralisation, and (2) whether the proportion of legume-derived N in NO3- could be calculated with the help of natural abundance 15N in NO3-. We sampled soil monoliths of a Medicago x varia Martyn monoculture in August 2004 and set up three treatments: 'disturbance' (sieved to <2 mm), 'disturbance-roots' (sieved to <2 mm and visible roots removed), and 'control' (left untreated). During an incubation period of 70 days, an N-free nutrient solution was leached through the samples weekly. In the leachates we measured total N, total organic carbon, NO3-, and NH4+ concentrations. Six of the 13 sampling dates were chosen for N isotope analysis in NO3-. Nitrate was separated as AgNO3. During the incubation, 3 to 6% of the initial total mass of total N (192 to 274 mg N) in soil was mineralised. Nitrogen mineralisation followed zero-order kinetics independent of treatments. Mineralisation rates decreased in the order control (day 70: 3.7 microg NO3-N (mg Ninitial)-1)>disturbance-roots (2.6 microg NO3-N (mg Ninitial)-1)>disturbance (1.9 microg NO3-N (mg Ninitial)-1), indicating that mineralisation of legume roots did not play a major role in N mineralisation. The delta15N values jumped from ca. 3 per thousand to ca. 8 per thousand after 2 weeks of incubation, which we attributed to the contribution of two N pools. An exponential two-pool model could not be fitted to the data. Legume-derived soil organic matter, SOM (pool 1), was mineralised at the same rate as SOM accumulated before establishment of the legumes (pool 2). Fresh legume roots did not contribute significantly to N mineralisation.     

氮肥管理对夏玉米土壤CH4和N2O排放的影响

通过设置四个不同的氮肥管理措施, 即氮肥施用量300 kg N/ha (N300)和250 kg N/ha (N250)、改进的施肥模式(Optimized)以及施用缓释肥(SRU), 研究华北平原夏玉米生长季土壤与大气之间CH₄和N₂O的交换通量及相应措施的减排潜力. 结果表明, 在2008年整个夏玉米生长季, 土壤都是大气CH₄的净吸收库和N₂O的排放源. 夏玉米生长季土壤氧化吸收的CH₄总量从大到小依次为Optimized > N250 > SRU > N300, 对应的吸收总量依次为624.16、590.07、487.89以及316.02 g CH₄-C/ha, 各处理间氧化吸收的CH₄总量无显著差异. 与N300和N250这两个处理相比, 依据夏玉米对氮肥的需肥规律以及玉米根层土壤速效氮的供给能力而确定氮肥施用量, 同时再平衡施用磷肥和钾肥的改进施肥模式能够显著降低夏玉米生长季N₂O的排放. 施用聚乙烯包膜的尿素也能够显著降低夏玉米季N₂O的排放. 夏玉米生长季土壤排放的N₂O总量从大到小依次为N300 > N250 > Optimized > SRU, 对应的排放总量依次为3462.18、2340.07、1680.00以及911.91 g N2O-N/ha, 相应的N₂O排放系数分别为1.15%、0.94%、0.91%以及0.30%.     

Olive Tree in Circular Economy as a Source of Secondary Metabolites Active for Human and Animal Health Beyond Oxidative Stress and Inflammation

Extra-virgin olive oil (EVOO) contains many bioactive compounds with multiple biological activities that make it one of the most important functional foods. Both the constituents of the lipid fraction and that of the unsaponifiable fraction show a clear action in reducing oxidative stress by acting on various body components, at concentrations established by the European Food Safety Authority’s claims. In addition to the main product obtained by the mechanical pressing of the fruit, i.e., the EVOO, the residual by-products of the process also contain significant amounts of antioxidant molecules, thus potentially making the Olea europea L. an excellent example of the circular economy. In fact, the olive mill wastewaters, the leaves, the pomace, and the pits discharged from the EVOO production process are partially recycled in the nutraceutical and cosmeceutical fields also because of their antioxidant effect. This work presents an overview of the biological activities of these by-products, as shown by in vitro and in vivo assays, and also from clinical trials, as well as their main formulations currently available on the market.     

Use of labelled nitrogen to measure gross and net rates of mineralization and microbial activity in permanent pastures following fertilizer applications at different time intervals

Measurements of some of the main internal N-cycling processes in soil were obtained by labelling the inorganic N pool with the stable isotope of nitrogen ((15)N). The (15)N mean pool dilution technique, combined with other field measurements, enabled gross and net N-mineralization rates to be resolved in grassland soils, which had previously either received fertilizer N (F), or had remained unfertilized (U) for many years. The two soils were subdivided into plots that received N at different time intervals (over 3 weeks), prior to (15)N measurements being made. By this novel approach, possible 'priming' effects over time were investigated to try to overcome some of the temporal problems of isotopic labelling of soil N (native plus fertilizer) and to identify possible changes in a range of primary N-transformation processes. The results suggested that an overall stimulation of microbially mediated processes occurred with all N treatments, but there were inconsistencies associated with the release of N, both in the timing and the degree to which different processes responded to the application of fertilizer N. The rates of these processes were, however, within the range of previously reported data and the (15)N measurements were not adversely affected by the differences in N pools created by the treatments. Thus, the mean pool dilution technique was shown to be applicable to agricultural soils, under conditions relevant to grass swards receiving fertilizer. For example, between the U and F treatments, the size of inorganic N pools increased by five-fold and gross rates of mineralization reached 3.5 and 4.8 microg N g(-1) (dry soil) d(-1), respectively, but did not vary greatly with the timing of N applications. A correlation (r(2) = 0.57) was found between soil respiration (which is relatively simple to measure) and net mineralization (which is more time consuming), suggesting that the former might be used as an indicator of the latter. Although this relationship was stronger in previously unfertilized soils, the similarities found with fertilized soils suggest that this approach could be used to obtain information of wider agronomic value and would, therefore, warrant further work under a range of soil conditions.     

Comparison of polyphenol extractions from olive pomace and solid fraction of olive mill waste water

The solid fraction of olive mill waste water (OMWW) was separated from OMWW and then the solutes in the solid fraction of OMWW were extracted with ethanol. The detection of polyphenols in the ethanol extract showed the presence of polyphenols in the solid fraction of OMWW. Effects of solvent-to-solid ratio, extraction and agitation time on the extraction of polyphenols from the solid fraction of OMWW were examined and the maximum amount of polyphenol was extracted from the solid fraction of OMWW with a solvent-to-solid ratio of 15 at 70?min of extraction and 10?min of agitation time. Percent yields and purities of the polyphenols extracted from solid fraction of OMWW were higher than those of the polyphenols extracted from olive pomace with ethanol at 70?min of extraction and 10?min of agitation time with solvent-to-solid ratio of 15.     

Cell protection from Ca2+-overloading by bioactive molecules extracted from olive pomace

We are reporting in the present study that molecules extracted from olive pomace prevent cell death induced by Ca²⁺-overloading in different cell types. Exposure of cells to these molecules counteracts the Ca²⁺-induced cell damages by reducing the activation of the Ca²⁺-dependent protease calpain, acting possibly through the modification of the permeability to Ca²⁺ of the plasma membrane. The purification step by RP-HPLC suggests that effective compound(s), differing from the main biophenols known to be present in the olive pomace extract, could be responsible for this effect. Our observations suggest that bioactive molecules present in the olive pomace could be potential candidates for therapeutic applications in pathologies characterised by alterations of intracellular Ca²⁺ homeostasis.     

13C nuclear magnetic resonance spectroscopy to determine olive oil grades

¹³C nuclear magnetic resonance spectroscopy was used in a first attempt to differentiate olive oil samples by grades. High resolution ¹³C NMR Distortionless Enhancement by Polarization Transfer (DEPT) spectra of 137 olive oil samples from the four grades, extra virgin olive oils, olive oils, olive pomace oils and lampante olive oils, were measured. The data relative to the resonance intensities (variables) of the unsaturated carbons of oleate (C-9 and C-10) and linoleate (L-9, L-10 and L-12) chains attached at the 1,3- and 2-positions of triacylglycerols were analyzed by linear discriminant analysis. The 1,3- and 2- carbons of the glycerol moiety of triacylglycerols along with the C-2, C-16 and C-18 resonance intensities of saturated, oleate and linoleate chains were also analyzed by linear discriminant analysis. The three discriminanting functions, which were calculated by using a stepwise variable selection algorithm, classified in the true group by cross-validation procedure, respectively, 76.9, 70.0, 94.4 and 100% of the extra virgin, olive oil, olive pomace oil and lampante olive oil grades.     

Effect of olive pomace extracts on hyperlipidaemia

In this study, we have examined the hypolipidemic effect of olive pomace extracts. Identification and quantitation of maslinic acid and oleanolic acid as the potentially effective components of the pomace extracts were carried out by high performance liquid chromatography methods. Hyperlipidaemia was induced in male Sprague Dawley rats by feeding them with a high cholesterol diet for 30 days. The olive pomace extracts were supplemented (200 mg kg?1 body wt day?1) for 15 days. The levels of serum total cholesterol, triglyceride, high density lipoprotein-cholesterol, low density lipoprotein-cholesterol, aspartate aminotransferase and alanine aminotransferase increased in rats with hyperlipidaemia. Treatment with the olive pomace extracts significantly modulated the abnormalities induced by hyperlipidaemia. Lipid accumulation was decreased in histological findings. This study provides the possibility of utilising the olive pomaces for the prevention and treatment of hyperlipidaemia.     

Use of a novel nitrification inhibitor to reduce nitrous oxide emission from (15)N-labelled dairy slurry injected into soil

Recent recommendations for environmentally sound use of liquid animal manure often include injection of slurry into soil. Two of the most important undesired side effects, ammonia (NH(3)) volatilisation and odour emissions, are usually significantly reduced by slurry injection. On the other hand, because of the higher amount of nitrogen (N) remaining in soil, the risk of nitrate (NO(3)(-)) leaching and nitrous oxide (N(2)O) emissions is increased. Thus, the reduction of local effects caused by NH(3) deposition, e.g. N enrichment and soil acidification, may be at the cost of large-scale effects such as ozone depletion and global warming as a result of emitted N(2)O. In this context, nitrification inhibitors can contribute significantly to a reduction in NO(3)(-) leaching and N(2)O production. A field experiment was carried out at IGER, North Wyke, which aimed to evaluate the effect of the new nitrification inhibitor 3,4-dimethylpyrazole phosphate (DMPP/ENTEC). For this experiment, (15)N enriched dairy slurry was used and the isotopic label in soil N as well as in N(2)O were studied. After slurry injection into the grassland soil in August 2000, the major emissions of N(2)O occurred during the first ten days. As expected, high N(2)O emission rates and (15)N content of the emissions were concentrated on the slurry injection slots, showing a steep decrease towards the untreated centre-point between slurry injection slots. The nitrification inhibitor DMPP proved to be very efficient in reducing N(2)O emissions. At a rate of 2 kg DMPP ha(-1), the total amount of N(2)O emitted was reduced by 32%, when compared with slurry injection without DMPP. The isotopic label of the emitted N(2)O showed that during the 22-day experimental period, emissions from the slurry N pool were strongly reduced by DMPP from 0.93 kg N(2)O-N ha(-1) (-DMPP) to 0.50 kg N(2)O-N ha(-1) (+DMPP), while only a minor effect on emissions from the soil N pool was observed (0.69 to 0.60 kg N(2)O-N ha(-1); -DMPP, +DMPP, respectively).     

The Valorisation of Olive Mill Wastewater from Slovenian Istria by Fe3O4 Particles to Recover Polyphenolic Compounds for the Chemical Specialties Sector

Olive oil production using three-phase decanter systems creates olive oil and two by-products: olive mill wastewater (OMWW) and pomace. These by-products contain the highest share of polyphenolic compounds that are known to be associated with beneficial effects on human health. Therefore, they are an attractive source of phenolic compounds for further industrial use in the cosmetic, pharmaceutical and food industries. The use of these phenolics is limited due to difficulties in recovery, high reactivity, complexity of the OMWW matrix and different physiochemical properties of phenolic compounds. This research, focused on OMWW, was performed in two phases. First, different polyphenol extraction methods were compared to obtain the method that yields the highest polyphenol concentration. Twenty-five phenolic compounds and their isomers were determined. Acidifying OMWW, followed by five minutes of ultrasonication, resulted in the highest measured polyphenol content of 27 mg/L. Second, the collection of polyphenolic compounds from OMWW via adsorption on unmodified iron (II, III) oxide particles was investigated. Although low yields were obtained for removed polyphenolic compounds in one removal cycle, the process has a high capability to be repeated.     

Nitrogen and phosphorus co-doped carbocatalyst for efficient organic pollutant removal through persulfate-based advanced oxidation processes

Carbocatalysts doped with heteroatoms such as nitrogen or sulphur have been reported to be useful in persulfate-based advanced oxidation processes for organic pollutant removal. However, there is limited research on the effect of doping with phosphorus atoms on degradation performance. In this work, a new nitrogen and phosphorus-doped carbocatalyst (N, P-HC) was designed using hydrothermal carbonization followed by pyrolysis at 700 °C, with olive pomace as a carbon source, to degrade organic pollutants in the presence of peroxydisulfate (PDS). Experimental results showed that N, P-HC, with its large specific surface area (871.73 m².g⁻¹), high content of N-pyridinic and N-pyrrolic groups, and the presence of P-O-C and O-P-C bonds, exhibited high degradation performance (98% degradation of Rhodamine B (RhB) in 40 min, with an apparent rate constant (k_app) of 0.055 min⁻¹ and an excellent turnover frequency (TOF) of 0.275 min⁻¹). Quenching study and EPR analysis revealed that singlet oxygen generation (¹O₂) and direct electron transfer were the main reaction pathways for the non-radical pathway in the degradation of RhB. The improved catalytic efficiency in the N, P-HC/PDS/RhB system can be attributed to the synergistic effect between N and P atoms in the graphitic structure of the carbocatalyst, its high surface area, and the presence of oxygenated functional groups on the surface of the N, P-HC. The used N, P-HC carbocatalyst can also be efficiently recovered by heat treatment at 500 °C. Overall, this study presents a simple and environmentally friendly method for synthesizing a high-performance N, P co-doped olive pomace-based carbocatalyst for water decontamination through PS-AOPs processes.     

A 15N-aided artificial atmosphere gas flow technique for online determination of soil N2 release using the zeolite Köstrolith SX6

N2 is one of the major gaseous nitrogen compounds released by soils due to N-transformation processes. Since it is also the major constituent of the earth's atmosphere (78.08% vol.), the determination of soil N2 release is still one of the main methodological challenges with respect to a complete evaluation of the gaseous N-loss of soils. Commonly used approaches are based either on a C2H2 inhibition technique, an artificial atmosphere or a 15N-tracer technique, and are designed either as closed systems (non-steady state) or gas flow systems (steady state). The intention of this work has been to upgrade the current gas flow technique using an artificial atmosphere for a 15N-aided determination of the soil N2 release simultaneously with N2O. A 15N-aided artificial atmosphere gas flow approach has been developed, which allows a simultaneous online determination of N2 as well as N2O fluxes from an open soil system (steady state). Fluxes of both gases can be determined continuously over long incubation periods and with high sampling frequency. The N2 selective molecular sieve K?strolith SX6 was tested successfully for the first time for dinitrogen collection. The presented paper mainly focuses on N2 flux determination. For validation purposes soil aggregates of a Haplic Phaeozem were incubated under aerobic (21 and 6 vol.% O2) and anaerobic conditions. Significant amounts of N2 were released only during anaerobic incubation (0.4 and 640.2 pmol N2 h(-1) g(-1) dry soil). However, some N2 formation also occurred during aerobic incubation. It was also found that, during ongoing denitrification, introduced [NO3]- will be more strongly delivered to microorganisms than the original soil [NO3]-.     

Novel Processes for the Extraction of Phenolic Compounds from Olive Pomace and Their Protection by Encapsulation

Olive pomace, the solid by-product derived from olive oil production consists of a high concentration of bioactive compounds with antioxidant activity, such as phenolic compounds, and their recovery by applying innovative techniques is a great opportunity and challenge for the olive oil industry. This study aimed to point out a new approach for the integrated valorization of olive pomace by extracting the phenolic compounds and protecting them by encapsulation or incorporation in nanoemulsions. Innovative assisted extraction methods were evaluated such as microwave (MAE), homogenization (HAE), ultrasound (UAE), and high hydrostatic pressure (HHPAE) using various solvent systems including ethanol, methanol, and natural deep eutectic solvents (NADESs). The best extraction efficiency of phenolic compounds was achieved by using NADES as extraction solvent and in particular the mixture choline chloride-caffeic acid (CCA) and choline chloride-lactic acid (CLA); by HAE at 60 °C/12,000 rpm and UAE at 60 °C, the total phenolic content (TPC) of extracts was 34.08 mg gallic acid (GA)/g dw and 20.14 mg GA/g dw for CCA, and by MAE at 60 °C and HHPAE at 600 MPa/10 min, the TPC was 29.57 mg GA/g dw and 25.96 mg GA/g dw for CLA. HAE proved to be the best method for the extraction of phenolic compounds from olive pomace. Microencapsulation and nanoemulsion formulations were also reviewed for the protection of the phenolic compounds extracted from olive pomace. Both encapsulation techniques exhibited satisfactory results in terms of encapsulation stability. Thus, they can be proposed as an excellent technique to incorporate phenolic compounds into food products in order to enhance both their antioxidative stability and nutritional value.     

Natural source compatibilizers for olive waste/recycled polypropylene matrix composites

A simple, environmentally friendly process was developed for surface hydrophobization of cellulose-rich waste to improve their compatibility with recycled polypropylene (rPP), helping reduce costs while recycling environmentally problematic waste such as solid olive waste (also called olive pomace). In this study, an improvement of the interfacial bonding strength between the hydrophilic waste particles and the hydrophobic matrix was achieved by surface hydrophobization of the waste using a ring-opening polymerization reaction of epoxidized soy-bean oil (ESBO) with SnCl₂ as a catalyst. The treatment on cellulose based filter paper led to a contact angle of 128°. The composite containing treated olive pomace has shown an increase in the elongation of 92% and an increase in the stress at yield of 15%, indicating improved compatibility.     

Solid phase microextraction-gas chromatographic-mass spectrometric determination of nitrous oxide evolution to measure denitrification in estuarine soils and sediments

A SPME-GC-MS method was developed to quantify nitrous oxide (N(2)O) to evaluate denitrification rates. There is a need for this sensitive and definitive N(2)O detection method to accurately measure the soil and sediment ability to convert anthropogenic mineral nitrogen loads to N(2) through denitrification hence decreasing estuarine waterway pollution loading. This method is applied to measure denitrification, which is a major pathway for inorganic nitrogen removal, by incorporating the acetylene (C(2)H(2)) block method on anaerobic assays. Currently, denitrification is largely measured using GCs fitted with TCD or ECD detectors. With a mean R(2) value of 0.996, the calibration curve spanned over three orders of magnitude (4.1-2030 nM) with a limit of detection (LOD) of 4.1 nM N(2)O (18 ppb) and a limit of quantification (LOQ) of 16 nM N(2)O (72 ppb). This detection method was valid with less than 15% relative standard deviation (RSD) and error for middle and high quality control (QC) points and less than 20% for low QC points on three experimental days. Measuring N(2)O using SPME-GC-MS technology allows for confidence in identification, high sensitivity, reproducibility, and short run times.     

Contribution of nitrification and denitrification to nitrous oxide emissions from soils after application of biogas waste and other fertilizers

The attribution of nitrous oxide (N₂O) emission to organic and inorganic N fertilizers requires understanding of how these inputs affect the two biological processes, i.e. denitrification and nitrification. Contradictory findings have been reported when the effects of organic and inorganic fertilizers on nitrous oxide emission were compared. Here we aimed to contribute to the understanding of such variation using ¹⁵N‐labelling techniques. We determined the processes producing N₂O, and tested the effects of soil moisture, N rates, and the availability of organic matter. In a pot experiment, we compared soil treated with biogas waste (BGW) and mineral ammonium sulphate (Min‐N) applied at four rates under two soil moisture regimes. We also tested biogas waste, conventional cattle slurry and mineral N fertilizer in a grassland field experiment. During the first 37 days after application we observed N₂O emissions of 5.6 kg N₂O‐N ha^?1 from soils supplied with biogas waste at a rate of 360 kg N ha^?1. Fluxes were ca. 5‐fold higher at 85% than at 65% water holding capacity (WHC). The effects of fertilizer types and N rates on N₂O emission were significant only when the soil moisture was high. Organic fertilizer treated soils showed much higher N₂O emissions than those receiving mineral fertilizer in both, pot and field experiment. Over all the treatments the percentage of the applied N emitted as N₂O was 2.56% in BGW but only 0.68% in Min‐N. In the pot experiment isotope labelling indicated that 65–95% of the N₂O was derived from denitrification for all fertilizer types. However, the ratio of denitrification/nitrification derived N₂O was lower at 65% than at 85% WHC. We speculate that the application of organic matter in conjunction with ammonium nitrogen first leads to a decrease in denitrification‐derived N₂O emission compared with soil receiving mineral fertilizer. However, at later stages when denitrification becomes C‐limited, higher N₂O emissions are induced when the soil moisture is high. Copyright © 2009 John Wiley & Sons, Ltd.     

NMR studies of coupled low- and high-barrier hydrogen bonds in pyridoxal-5'-phosphate model systems in polar solution

The 1H and 15N NMR spectra of several 15N-labeled pyridoxal-5'-phosphate model systems have been measured at low temperature in various aprotic and protic solvents of different polarity, i.e., dichloromethane-d2, acetonitrile-d3, tetrahydrofuran-d8, freon mixture CDF3/CDClF2, and methanol. In particular, the 15N-labeled 5'-triisopropyl-silyl ether of N-(pyridoxylidene)-tolylamine (1a), N-(pyridoxylidene)-methylamine (2a), and the Schiff base with 15N-2-methylaspartic acid (3a) and their complexes with proton donors such as triphenylmethanol, phenol, and carboxylic acids of increasing strength were studied. With the use of hydrogen bond correlation techniques, the 1H/15N chemical shift and scalar coupling data could be associated with the geometries of the intermolecular O1H1N1 (pyridine nitrogen) and the intramolecular O2H2N2 (Schiff base) hydrogen bonds. Whereas O1H1N1 is characterized by a series of asymmetric low-barrier hydrogen bonds, the proton in O2H2N2 faces a barrier for proton transfer of medium height. When the substituent on the Schiff base nitrogen is an aromatic ring, the shift of the proton in O1H1N1 from oxygen to nitrogen has little effect on the position of the proton in the O2H2N2 hydrogen bond. By contrast, when the substituent on the Schiff base nitrogen is a methyl group, a proton shift from O to N in O1H1N1 drives the tautomeric equilibrium in O2H2N2 from the neutral O2-H2...N2 to the zwitterionic O2-...H2-N(2+) form. This coupling is lost in aqueous solution where the intramolecular O2H2N2 hydrogen bond is broken by solute-solvent interactions. However, in methanol, which mimics hydrogen bonds to the Schiff base in the enzyme active site, the coupling is preserved. Therefore, the reactivity of Schiff base intermediates in pyridoxal-5'-phosphate enzymes can likely be tuned to the requirements of the reaction being catalyzed by differential protonation of the pyridine nitrogen.