Investigation of isomeric transformations of chlorogenic acid in buffers and biological matrixes by ultraperformance liquid chromatography coupled with hybrid quadrupole/ion mobility/orthogonal acceleration time-of-flight mass spectrometry

Ultraperformance liquid chromatography coupled with hybrid quadrupole/ion mobility/orthogonal acceleration time-of-flight (oa-TOF) mass spectrometry (UPLC-IM-MS) was used to study the isomeric transformations of trans-5-caffeoylquinic acid, an extremely active compound present in multiple vegetables, fruits, and beverages. The UPLC/oa-TOF MS results proved that in phosphate buffer (pH 7.4), plasma, or urine sample, trans-5-caffeoylquinic acid first isomerizes to trans-4-caffeoylquinic acid and then to trans-3-caffeoylquinic acid by intramolecular acyl migration. When exposed to UV light, trans-3-, -4-, and -5-caffeoylquinic acids undergo cis/trans isomerization to form cis isomers. The isomerization was solely dependent on the pH of the matrix, as well as the incubation temperature, and was independent of metabolic enzymes. UPLC-IM-MS results revealed that a reversible cis/trans isomerization of caffeoylquinic acids could also be induced by the electric field in an electrospray source. Thus, understanding the possible role of electric field-induced isomerization of caffeoylquinic acids may help lessen the confusion between gas phase phenomena and liquid state chemistry when applying IM-MS analysis. The comprehensive understanding of caffeoylquinic acid isomerization transformations is crucial for the appropriate handling of samples and interpretation of experimental data.     

IT—Information Technology and the Human Interface: A Review of the Environmental Effects of Different Livestock Manure Storage Systems, and a Suggested Procedure for Assigning Environmental Ratings

There are concerns over a range of adverse environmental effects resulting from the storage of livestock manures on farms. The objectives of this study were to examine all the likely environmental effects of different storage methods, and to recommend which were the most desirable options.Literature reviews were undertaken to identify the likely environmental consequences of each commonly used storage method, in terms of water pollution risks, odour and ammonia emissions, greenhouse gas emissions and survival of microorganisms during storage. Planning and landscape aspects were considered and the most feasible options for abatement of ammonia emissions were identified. An ‘environmental rating’ for different storage systems was then devised, with the aim of obtaining a balance between water pollution, aerial emissions and other concerns.The environmental rating exercise favoured the more sophisticated and hence most expensive storage methods. No large differences emerged between ratings for slurry systems and solid systems when ease of adding ammonia control measures was excluded. For pigs, slurry systems appear to have a slight advantage, because of the greater ammonia emissions from the solid pig manure. The use of such a rating system could be developed further as more data become available. Whilst the method indicates the relative desirability of systems at a national scale it could be adapted to take account of local considerations or those of individual farm sites.     

How do hedgerows influence soil organic carbon stock in livestock‐grazed pasture?

Hedgerows have the potential to influence ecosystem function in livestock‐grazed pasture. Despite this, they are often ignored when quantifying farmland ecosystem service delivery. In this study, we assess the contribution of hedgerows to the ecosystem function of carbon (C) storage, with a particular emphasis on soil organic carbon (SOC). We measured SOC stock (kg C m^?2), on an equivalent soil mass basis, at 0–0.15 m depth in pasture adjacent to 38 hedgerows (biotic) and 16 stone walls or fences (abiotic controls) across ten farms in the county of Conwy, Wales, UK. Pasture SOC stock (~7 kg C m^?2) was similar adjacent to biotic and abiotic field boundaries, positively associated with soil moisture and negatively with soil bulk density (BD). For biotic boundaries, two further variables were significantly associated with SOC stock, distance from hedgerow (decrease in SOC stock) and slope orientation (upslope SOC stock greater than downslope). For pasture adjacent to hedgerows, a model combining the aforementioned variables (BD, soil moisture, distance from hedgerow, slope orientation) explained 78% of variation in SOC stock. This study demonstrates that whilst hedgerows do have subtle positive effects on SOC stock in adjacent pasture, SOC storage adjacent to field boundaries is influenced more by soil moisture content and BD than field boundary type.     

The effect of crop residue incorporation date on soil inorganic nitrogen, nitrate leaching and nitrogen mineralization

 Delaying cultivation and incorporation of arable crop residues may delay the release of NO₃ ^– and hence reduce leaching. The objective of this study was to investigate the effect of timing of cultivation on the mineralization and leaching of NO₃ ^– from an arable crop residue. Overwinter N leaching and periodic measurements of soil inorganic N were combined to estimate net N mineralized after ploughing a crop residue into a free-draining loamy sand soil in central England on six dates from June 1994 to January 1995. The crop residue was whole green barley with approximately 2% N. N leaching in the two following winters was increased by the addition of crop residues. Early residue application also tended to increase N leached in the first winter, largely as a consequence of relatively large losses early in the drainage period. Thus, early incorporation of crop residues presents a greater leaching risk. The amount of N leached in the second (drier) winter was similar for all dates of incorporation. At the end of the first winter, inorganic N derived from the crop residue was greatest for earlier additions: June (40% N applied) > September (30% N applied) > August (20% N applied) > October (19% N applied) > November (11% N applied) > January (3% N applied). However, at the end of the experiment, there was no evidence that the residues which had mineralized least by the end of the first winter had, to any significant degree, caught up, and this was confirmed by the parameters of the equation for first-order decomposition in thermal time. These results indicate that the effect of temperature, particularly in the early stages of residue mineralization, is complex and interacts with other soil processes in terms of the fate of the N mineralized. Received: 19 July 1999     

Race specific resistance against Phytophthora infestans in potato is controlled by more genetic factors than only R-genes

Summary For RFLP mapping of R-genes, determining resistance to specific races of Phytophthora infestans in tetraploid potato, it is necessary to develop well segregating populations at the 2x level. During mapping studies, evidence was obtained that more genetic factor(s) are involved in the expression of R-genes than conventionally believed. Two experiments are described in which such an additional genetic factor was suppressing or enhancing the expression of unknown R _nand R _ifactors. R _nand R _iappeared to be present in the investigated plant material, containing R4 and R10, or in one of the susceptible crossing parents. In a third experiment, the expression and the segregation of the well known R1 gene was influenced by an additional genetic factor. In that case there were indications for a dominant suppressor. This was established by the selection of susceptible plants carrying a RFLP allele of probe GP21 closely linked to R1. In three of the four F₁ populations, resulting from crosses between such susceptible plants and susceptible tester plants, resistnat progenies were found. The resistance appeared to be R1-specific. This clearly indicates that in three of the four investigated susceptible plants, the R1 gene was still present but not expressed.     

Reverse phase liquid chromatographic determination of aspartame in beverages and beverage mixes

A method is described for determining the artificial sweetener aspartame in beverages and beverage mixes by liquid chromatography. Aspartame is separated on a microC18 column, using a mobile phase of acetic acid, water, and isopropyl alcohol at pH 3.0 and UV detection at 254 nm. Beverages are filtered through 0.45 micron filters and injected directly into the chromatograph. Aspartame is eluted in approximately 7 min. Detection of aspartame is confirmed by a UV scan of the trapped peak. Aspartame is quantitated in the presence of other beverage additives such as saccharin, caffeine, sodium benzoate, artificial colors, and artificial flavors. Results are presented for spiked soda beverages, beverages from fruit-flavored mixes, instant tea, reconstituted presweetened drink mixes, and a powdered tabletop sweetener.     

Interactions between physical and biotic factors influence CO2 flux in Antarctic dry valley soils

Soil carbon dioxide (CO₂) flux is an integrative measure of ecosystem functioning representing both biotic and physical controls over carbon (C) balance. In the McMurdo Dry Valleys of Antarctica, soil CO₂ fluxes (approximately −0.1-0.15 μmol m⁻² s⁻¹) are generally low, and negative fluxes (uptake of CO₂) are sometimes observed. A combination of biological respiration and physical mechanisms, driven by temperature and mediated by soil moisture and mineralogy, determine CO₂ flux and, therefore, soil organic C balance. The physical factors important to CO₂ flux are being altered with climate variability in many ecosystems including arid forms such as the Antarctic terrestrial ecosystems, making it critical to understand how climate factors interact with biotic drivers to control soil CO₂ fluxes and C balances. We measured soil CO₂ flux in experimental field manipulations, microcosm incubations and across natural environmental gradients of soil moisture to estimate biotic soil respiration and abiotic sources of CO₂ flux in soils over a range of physical and biotic conditions. We determined that temperature fluctuations were the most important factor influencing diel variation in CO₂ flux. Variation within these diel CO₂ cycles was explained by differences in soil moisture. Increased temperature (as opposed to temperature fluctuations) had little or no effect on CO₂ flux if moisture was not also increased. We conclude that CO₂ flux in dry valley soils is driven primarily by physical factors such as soil temperature and moisture, indicating that future climate change may alter the dry valley soil C cycle. Negative CO₂ fluxes in arid soils have recently been identified as potential net C sinks. We demonstrate the potential for arid polar soils to take up CO₂, driven largely by abiotic factors associated with climate change. The low levels of CO₂ absorption into soils we observed may not constitute a significant sink of atmospheric CO₂, but will influence the interpretation of CO₂ flux for the dry valley soil C cycle and possibly other arid environments where biotic controls over C cycling are secondary to physical drivers.     

Development of buffer methods and evaluation of pedotransfer functions to estimate pH buffer capacity of highly weathered soils

The pH buffer capacity of a soil (pHBC) determines the amount of lime required to raise the pH of the soil layer from its initial acid condition to an optimal pH for plant growth and the time available under current net acid addition rate (NAAR) until the soil layer acidifies to a critical pH leading to likely production losses. Accurate values of pHBC can also be used to calculate NAAR from observed changes in soil pH. In spite of its importance, there is a critical shortage of pHBC data, likely due to the long period of time needed for its direct measurement. This work aimed to develop quick, simple and reliable methods of pHBC measurement and to test these methods against a slow (7‐day) titration used as benchmark. The method developed here calculates pHBC directly from the pH buffer capacity of the buffer solution and the increase in soil pH and corresponding decrease in pH of the buffer solution following mixing and equilibration. The pHBC values calculated using Adams and Evans or modified Woodruff buffers were in accord with those measured by slow titration. Buffer methods are easily deployed in commercial and research laboratories as well as in the field. The advantage of using buffer solutions to calculate pHBC instead of lime requirement is the broad application of this soil property. The pHBC of a soil is an intrinsic property that would not be expected to need remeasurement over periods of less than decades. Recurring lime requirement can be calculated from the soil's pHBC, initial and target pH values. A large proportion of the variability in pHBC was explained by the soil organic carbon content. This relationship between pHBC and soil organic carbon content allowed us to develop local pedotransfer functions to estimate pHBC for different regions of Australia.     

Indicators of Cotton Nitrogen Status

ABSTRACT

Nitrogen (N) deficiency limits cotton yields, while too much N causes excessive vegetative growth hurting yields, wastes expensive inputs, and causes environmental pollution. Diagnostic indicators are needed to assess cotton N status so that yields can be optimized as efficiently as possible. This study evaluated selected tools for predicting cotton responses to N fertilizer application. Petiole nitrate (NO₃)-N (PNN) concentration was found to correlate with cotton N status and a good indicator of potential for response to N application. Critical PNN concentrations for irrigated cotton in subtropical South Texas at first bloom, and 10, 20 and 30 d later were determined to be 15.0, 9.0, 4.5, and 2.0 g kg^{? 1}, respectively. These critical PNN levels are higher than in more humid areas of the traditional southern US Cotton Belt, probably due to the effects of the subtropical climate. Cotton plants in this area tend to be less vegetative, possibly due to shorter growing season day lengths, and therefore need to be “pushed” slightly harder with greater N fertilization. Leaf total N concentrations were found to be less responsive to changes in applied N than were PNN levels. Although leaf N tended to be more stable over time, there was no consistent pattern between years. Leaf N values of 35 g kg^{? 1} or less appear to represent a deficiency at any time, and optimum levels may be slightly higher. Nodes above white flower showed very small responses to N fertilization and the differences occurred late in the bloom period. Chlorophyll meter readings showed a good relationship with N fertilizer application within a given sampling date, but much greater variability occurred between dates and due to other factors. The most effective indicator of cotton N status was found to be PNN, and to a lesser extent leaf N, but none of other parameters could be recommended for purposes of making inferences as to N status of cotton.     

Assessing daily egestion rates in earthworms: using fungal spores as a natural soil marker to estimate gut transit time

Earthworms have an important role in ‘bioturbation’—the mixing of soil due to biological processes. Quantification of earthworm bioturbation relies on estimating earthworm egestion rates which in turn depend on two parameters: the gut content of the worms and the gut transit time (GTT). Gut content can be determined relatively easily, but determining GTT is problematic. The present study aimed at estimating daily soil egestion rates of Aporrectodea caliginosa and Lumbricus terrestris, refining the most common approach for estimating GTT by using fungal spores as natural markers in ingested soil. This approach avoids the use of artificial markers that may adversely affect the earthworms. Gut transit time was estimated by tracking the passage of marked soil through the gut by the appearance of the spores in the egested faeces. Gut transit time was estimated to be 9.6?±?0.3 h for A. caliginosa and 11.6?±?0.5 h for L. terrestris. Gut content averaged 465?±?40(± standard error (SE))?mg dw g^?1 dw worm for A. caliginosa and 265?±?80 mg dw g^?1 dw worm for L. terrestris. From these values, daily egestion rates of 1.16 and 0.66 g dw faeces g^?1 dw worm d^?1 were calculated for A. caliginosa and L. terrestris, respectively. Both values compare well to literature values for each species. The presented method for GTT estimation is inexpensive, rapid and easy to evaluate, with spores being a good alternative to existing markers.