Whole crop cereals 2. Prediction of apparent digestibility and energy value from in vitro digestion techniques and near infrared reflectance spectroscopy and of chemical composition by near infrared reflectance spectroscopy

Samples of whole crop wheat (WCW, n = 134) and whole crop barley (WCB, n = 16) were collected from commercial farms in the UK over a 2-year period (2003/2004 and 2004/2005). Near infrared reflectance spectroscopy (NIRS) was compared with laboratory and in vitro digestibility measures to predict digestible organic matter in the dry matter (DOMD) and metabolisable energy (ME) contents measured in vivo using sheep. Spectral models using the mean spectra of two scans were compared with those using individual spectra (duplicate spectra). Overall NIRS accurately predicted the concentration of chemical components in whole crop cereals apart from crude protein. ammonia-nitrogen, water-soluble carbohydrates, fermentation acids and solubility values. In addition. the spectral models had higher prediction power for in vivo DOMD and ME than chemical components or in vitro digestion methods. Overall there Was a benefit from the use of duplicate spectra rather than mean spectra and this was especially so for predicting in vivo DOMD and ME where the sample population size was smaller. The spectral models derived deal equally well with WCW and WCB and Would he of considerable practical value allowing rapid determination of nutritive value of these forages before their use in diets of productive animals. (C) 2008 Elsevier B.V. All rights reserved.

Comparison of energy evaluation systems and a mechanistic model for milk production by dairy cattle offered fresh grass-based diets

Grass-based diets are of increasing social-economic importance in dairy cattle farming, but their low supply of glucogenic nutrients may limit the production of milk. Current evaluation systems that assess the energy supply and requirements are based on metabolisable energy (ME) or net energy (NE). These systems do not consider the characteristics of the energy delivering nutrients. In contrast, mechanistic models take into account the site of digestion, the type of nutrient absorbed and the type of nutrient required for production of milk constituents, and may therefore give a better prediction of supply and requirement of nutrients. The objective of the present study is to compare the ability of three energy evaluation systems, viz. the Dutch NE system, the agricultural and food research council (AFRC) ME system, and the feed into milk (FIM) ME system, and of a mechanistic model based on Dijkstra et al. [Simulation of digestion in cattle fed sugar cane: prediction of nutrient supply for milk production with locally available supplements. J. Agric. Sci., Cambridge 127, 247-60] and Mills et al. [A mechanistic model of whole-tract digestion and methanogenesis in the lactating dairy cow: model development, evaluation and application. J. Anim. Sci. 79, 1584-97] to predict the feed value of grass-based diets for milk production. The dataset for evaluation consists of 41 treatments of grass-based diets (at least 0.75 g ryegrass/g diet on DM basis). For each model, the predicted energy or nutrient supply, based on observed intake, was compared with predicted requirement based on observed performance. Assessment of the error of energy or nutrient supply relative to requirement is made by calculation of mean square prediction error (MSPE) and by concordance correlation coefficient (CCC). All energy evaluation systems predicted energy requirement to be lower (6-11%) than energy supply. The root MSPE (expressed as a proportion of the supply) was lowest for the mechanistic model (0.061), followed by the Dutch NE system (0.082), FIM ME system (0.097) and AFRCME system(0.118). For the energy evaluation systems, the error due to overall bias of prediction dominated the MSPE, whereas for the mechanistic model, proportionally 0.76 of MSPE was due to random variation. CCC analysis confirmed the higher accuracy and precision of the mechanistic model compared with energy evaluation systems. The error of prediction was positively related to grass protein content for the Dutch NE system, and was also positively related to grass DMI level for all models. In conclusion, current energy evaluation systems overestimate energy supply relative to energy requirement on grass-based diets for dairy cattle. The mechanistic model predicted glucogenic nutrients to limit performance of dairy cattle on grass-based diets, and proved to be more accurate and precise than the energy systems. The mechanistic model could be improved by allowing glucose maintenance and utilization requirements parameters to be variable. (C) 2007 Elsevier B.V. All rights reserved.

Whole crop cereals 1. Effect of method of harvest and preservation on chemical composition, apparent digestibility and energy value

A total of 133 samples (53 fermented unprocessed, 19 fermented processed. 62 urea-treated processed) of whole crop wheat (WCW) and 16 samples (five fermented unprocessed, six fermented processed, five urea-treated processed) of whole crop barley (WCB) were collected from commercial farms over two consecutive years (2003/2004 and 2004/2005). Disruption of the maize grains to increase starch availability was achieved at the point of harvest by processors fitted to the forage harvesters. All samples were subjected to laboratory analysis whilst 50 of the samples (24 front Year 1, 26 front Year 2 all WCW except four WCB in Year 2) were subjected to in vivo digestibility and energy value measurements using mature wether sheep. Urea-treated WCW had higher (P<0.05) pH, and dry matter (DM) and crude protein contents and lower concentrations of fermentation products than fermented WCW. Starch was generally lower in fermented, unprocessed WCW and no effect of crop maturity at harvest (as indicated by DM content) on starch concentrations was seen. Urea-treated WCW had higher (P<0.05) in vivo digestible organic matter contents in the DM (DOMD) in Year 1 although this was not recorded in Year 2. There was a close relationship between the digestibility values of organic matter and gross energy thus aiding the use of DOMD to predict metabolisable energy (ME) content. A wide range of ME values was observed (WCW. 8.7-11.8 MJ/kg DM; WCB 7.9-11.2 MJ/kg DM) with the overall ME/DOMD ratio (ME = 0.0156 DOMD) in line With Studies in other forages. There was no evidence that a separate ME/DOMD relationship was needed for WCB which is helpful for practical application. This ratio and other parameters were affected by year of harvest (P<0.05) highlighting the influence of environmental and Other undefined factors. The variability in the composition and nutritive value of WCW and WCB highlights the need for reliable and accurate evaluation methods to be available to assess the Value of these forages before they are included in diets for dairy cows. (C) 2008 Elsevier B.V. All rights reserved.

Alternatives to linear analysis of energy balance data from lactating dairy cows

The current energy requirements system used in the United Kingdom for lactating dairy cows utilizes key parameters such as metabolizable energy intake (MEI) at maintenance (MEm), the efficiency of utilization of MEI for 1) maintenance, 2) milk production (k(l)), 3) growth (k(g)), and the efficiency of utilization of body stores for milk production (k(t)). Traditionally, these have been determined using linear regression methods to analyze energy balance data from calorimetry experiments. Many studies have highlighted a number of concerns over current energy feeding systems particularly in relation to these key parameters, and the linear models used for analyzing. Therefore, a database containing 652 dairy cow observations was assembled from calorimetry studies in the United Kingdom. Five functions for analyzing energy balance data were considered: straight line, two diminishing returns functions, (the Mitscherlich and the rectangular hyperbola), and two sigmoidal functions (the logistic and the Gompertz). Meta-analysis of the data was conducted to estimate k(g) and k(t). Values of 0.83 to 0.86 and 0.66 to 0.69 were obtained for k(g) and k(t) using all the functions (with standard errors of 0.028 and 0.027), respectively, which were considerably different from previous reports of 0.60 to 0.75 for k(g) and 0.82 to 0.84 for k(t). Using the estimated values of k(g) and k(t), the data were corrected to allow for body tissue changes. Based on the definition of k(l) as the derivative of the ratio of milk energy derived from MEI to MEI directed towards milk production, MEm and k(l) were determined. Meta-analysis of the pooled data showed that the average k(l) ranged from 0.50 to 0.58 and MEm ranged between 0.34 and 0.64 MJ/kg of BW0.75 per day. Although the constrained Mitscherlich fitted the data as good as the straight line, more observations at high energy intakes (above 2.4 MJ/kg of BW0.75 per day) are required to determine conclusively whether milk energy is related to MEI linearly or not.

Effect of energy and protein supplementation on phosphorus utilization in lactating dairy cows

Two experiments were undertaken in which grass silage was used in conjunction with a series of different concentrate types designed to examine the effect of carbohydrate source, protein level and degradability on total dietary phosphorus (P) utilization with emphasis on P pollution. Twelve Holstein-Friesian dairy cows in early to mid-lactation were used in an incomplete changeover design with four periods consisting of 4 weeks each. Phosphorus intake ranged from 54 to 80 g/day and faecal P represented the principal route by which ingested P was disposed of by cows, with insignificant amounts being voided in urine. A positive linear relationship between faecal P and P intake was established. In Experiment 1, P utilization was affected by dietary carbohydrate type, with an associated output of 3.3 g faecal P/g milk P produced for all treatments except those utilizing low degradable starch and low protein supplements, where a mean value of 2.8 g faecal P/g milk P was observed. In Experiment 2, where two protein levels and three protein degradabilities were examined, the efficiency of P utilization for milk P production was not affected by either level or degradability of crude protein (CP) but a significant reduction in faecal P excretion due to lower protein and P intake was observed. In general, P utilization in Experiment 2 was substantially improved compared to the Experiment 1, with an associated output of 1.8 g faecal P/g milk P produced. The improved utilization of P in Experiment 2 could be due to lower P content of the diets offered and higher dry matter (DM) intake. For dairy cows weighing 600 kg, consuming 17-18 kg DM/day and producing about 25 kg milk, P excretion in faeces and hence P pollution to the environment might be minimized without compromising lactational performance by formulating diets to supply about 68 g P/day, which is close to recent published recommended requirements for P.

Evaluation of NRC, UC Davis and ADAS approaches to estimate the metabolizable energy values of feeds at maintenance energy intake from equations utilizing chemical assays and in vitro determinations

Feed samples received by commercial analytical laboratories are often undefined or mixed varieties of forages, originate from various agronomic or geographical areas of the world, are mixtures (e.g., total mixed rations) and are often described incompletely or not at all. Six unified single equation approaches to predict the metabolizable energy (ME) value of feeds determined in sheep fed at maintenance ME intake were evaluated utilizing 78 individual feeds representing 17 different forages, grains, protein meals and by-product feedstuffs. The predictive approaches evaluated were two each from National Research Council [National Research Council (NRC), Nutrient Requirements of Dairy Cattle, seventh revised ed. National Academy Press, Washington, DC, USA, 2001], University of California at Davis (UC Davis) and ADAS (Stratford, UK). Slopes and intercepts for the two ADAS approaches that utilized in vitro digestibility of organic matter and either measured gross energy (GE), or a prediction of GE from component assays, and one UC Davis approach, based upon in vitro gas production and some component assays, differed from both unity and zero, respectively, while this was not the case for the two NRC and one UC Davis approach. However, within these latter three approaches, the goodness of fit (r(2)) increased from the NRC approach utilizing lignin (0.61) to the NRC approach utilizing 48 h in vitro digestion of neutral detergent fibre (NDF:0.72) and to the UC Davis approach utilizing a 30 h in vitro digestion of NDF (0.84). The reason for the difference between the precision of the NRC procedures was the failure of assayed lignin values to accurately predict 48 h in vitro digestion of NDF. However, differences among the six predictive approaches in the number of supporting assays, and their costs, as well as that the NRC approach is actually three related equations requiring categorical description of feeds (making them unsuitable for mixed feeds) while the ADAS and UC Davis approaches are single equations, suggests that the procedure of choice will vary dependent Upon local conditions, specific objectives and the feedstuffs to be evaluated. In contrast to the evaluation of the procedures among feedstuffs, no procedure was able to consistently discriminate the ME values of individual feeds within feedstuffs determined in vivo, suggesting that the quest for an accurate and precise ME predictive approach among and within feeds, may remain to be identified. (C) 2004 Elsevier B.V. All rights reserved.

Energy substitutability in transition agriculture: estimates and implications for Hungary

Subsidised energy prices in pre-transition Hungary had led to excessive energy intensity in the agricultural sector. Transition has resulted in steep input price increases. In this study, Allen and Morishima elasticities of substitution are estimated to study the effects of these price changes on energy use, chemical input use, capital formation and employment. Panel data methods, Generalised Method of Moments (GMM) and instrument exogeneity tests are used to specify and estimate technology and substitution elasticities. Results indicate that indirect price policy may be effective in controlling energy consumption. The sustained increases in energy and chemical input prices have worked together to restrict energy and chemical input use, and the substitutability between energy, capital and labour has prevented the capital shrinkage and agricultural unemployment situations from being worse. The Hungarian push towards lower energy intensity may be best pursued through sustained energy price increases rather than capital subsidies. (C) 2003 Elsevier B.V. All rights reserved.

Do all tannins have similar nutritional effects? A comparison of three Brazilian fodder legumes

Three tropical legumes, namely Leucaena leucocephala, Sesbania sesban and Cajanus cajan, were subjected to chemical analysis plus in vitro, in situ and in vivo evaluations. Three different assays were used to determine total tannins: adsorption to polyvinyl pyrrolidine (PVPP-tannins), radial diffusion (RD-tannins) and protein precipitation capacity (BSA-tannins). Total phenols, total tannins and condensed tannins were highest for Sesbania. RD-tannins were correlated with total phenols (r(2) = 0.93), PVPP-tannins (r(2) = 0.92) and condensed tannins (r(2) = 0.99). The protein precipitation capacity of Sesbania, Leucaena and Cajanus were 25.9, 6.13 and 4.05 mu g BSA/g DM, respectively. Gas production at 24h was negatively correlated with total phenols (r(2) = 0.99), PVPP-tannins (r(2) = 0.99) and condensed tannins (r(2) = 0.91). The RD-, PVPP-tannins and the response to polyethylene glycol (PEG) in the gas production assay appeared to be useful as a first screen for tannins. In situ degradability did not reflect any adverse effects of tannins. However, in vivo experiments showed that the apparent DM digestibility of Sesbania and Leucaena was lower than the basal diet. The apparent protein digestibility was lower for all legumes compared to the basal diet. Most treatments caused a negative nitrogen balance. The problems associated with browse feeding were not only related to tannin contents, other factors such as inherently poor digestibility and low energy intake may also have lead to the poor animal performance on these diets. We propose, given the limitations of current tannin assays, that it is not possible to predict beneficial or harmful nutritional effects from total tannin concentrations per se. (C) 2004 Elsevier B.V. All rights reserved.

Limit-feeding a high-energy diet to meet energy requirements in the dry period alters plasma metabolite concentrations but does not affect intake or milk production in early lactation

Limit-feeding dry cows a high-energy diet may enable adequate energy intake to be sustained as parturition approaches, thus reducing the extent of negative energy balance after parturition. Our objective was to evaluate the effect of dry period feeding strategy on plasma concentrations of hormones and metabolites that reflect energy status. Multiparous Holstein cows (n = 18) were dried off 45 d before expected parturition, paired by expected calving date, parity, and previous lactation milk yield, and randomly assigned to 1 of 2 dry-period diets formulated to meet nutrient requirements at ad libitum or limited intakes. All cows were fed the same diet for ad libitum intake after parturition. Prepartum dry matter intake (DMI) for limit-fed cows was 9.4 kg/d vs. 13.7 kg/d for cows fed ad libitum. During the dry period, limit-fed cows consumed enough feed to meet calculated energy requirements, and ad libitum-fed cows were in positive calculated net energy for lactation (NEL) balance (0.02 vs. 6.37 Mcal/d, respectively). After parturition, milk yield, milk protein concentration, DMI, body condition score, and body weight were not affected by the prepartum treatments. Cows limit fed during the dry period had a less-negative calculated energy balance during wk 1 postpartum. Milk fat concentration and yield were greater for the ad libitum treatment during wk 1 but were lower in wk 2 and 3 postpartum. Plasma insulin and glucose concentrations decreased after calving. Plasma insulin concentration was greater in ad libitum-fed cows on d -2 relative to calving, but did not differ by dietary treatment at other times. Plasma glucose concentrations were lower before and after parturition for cows limit-fed during the dry period. Plasma nonesterified fatty acid concentrations peaked after parturition on d 1 and 4 for the limit-fed and ad libitum treatments, respectively, and were greater for limit-fed cows on d -18, -9, -5, and -2. Plasma tumor necrosis factor-alpha concentrations did not differ by treatment in either the pre- or postpartum period, but tended to decrease after parturition. Apart from a reduction in body energy loss in the first week after calving, limit feeding a higher NEL diet during the dry period had little effect on intake and milk production during the first month of lactation.

Determination of the optical properties of plastic films used as cladding materials in novel energy efficient greenhouses

Greenhouse cladding materials are a major component in the design of energy efficient greenhouses. The optical properties of cladding materials determine a major part of the overall performance of a greenhouse both in terms of the energy balance of the greenhouse and on crop behavior. Various film plastic greenhouse-cladding materials were measured under laboratory conditions using a spectroradiometer equipped with an integrating sphere. Films were measured over a range of angles of incidence and the effect of increasing distance between double films was also measured. PAR transmission remained nearly constant for angles of incidence increased up to 30 degrees but fell rapidly thereafter as the angles of incidence increased up to 90 degrees. Increasing distance between double films did not significantly affect PAR transmission in all films examined. These results are discussed in relation to the design criteria for an energy efficient greenhouse.

A study by high energy transfer inelastic neutron scattering spectroscopy of the mineral fraction of ox femur bone

We have used high energy transfer (HET) inelastic neutron scattering spectroscopy to measure the vibrational modes in the spectra of hydroxyapatite, bone and brushite to confirm our earlier work that only a fraction of the hydroxyl groups in bone mineral are substituted. The HET spectra are better observed due to the higher scattering cross section of hydrogen compared with the other elements in the calcium phosphate compounds. (C) 2003 Elsevier Science B.V. All rights reserved.

An investigation of the germylene addition reaction, GeH2+C2H2: Time-resolved gas-phase kinetic studies and quantum chemical calculations of the reaction energy surface

Time resolved studies of germylene, GeH2, generated by laser flash photolysis of 3,4-dimethylgermacyclopentene-3, have been carried out to obtain rate constants for its bimolecular reaction with acetylene, C2H2. The reaction was studied in the gas-phase over the pressure range 1-100 Tort, with SF6 as bath gas, at 5 temperatures in the range 297-553 K. The reaction showed a very slight pressure dependence at higher temperatures. The high pressure rate constants (obtained by extrapolation at the three higher temperatures) gave the Arrhenius equation: log(k(infinity)/cm(3) molecule(-1) s(-1)) (-10.94 +/- 0.05) + (6.10 +/- 0.36 kJ mol(-1))/RTln10. These Arrhenius parameters are consistent with a fast reaction occurring at approximately 30% of the collision rate at 298 K. Quantum chemical calculations (both DFT and ab initio G2//B3LYP and G2//QCISD) of the GeC2H4 potential energy surface (PES), show that GeH2 + C2H2 react initially to form germirene which can isomerise to vinylgermylene with a relatively low barrier. RRKM modelling, based on a loose association transition state, but assuming vinylgermylene is the end product (used in combination with a weak collisional deactivation model) predicts a strong pressure dependence using the calculated energies, in conflict with the experimental evidence. The detailed GeC2H4 PES shows considerable complexity with ten other accessible stable minima (B3LYP level), the three most stable of which are all germylenes. Routes through this complex surface were examined in detail. The only product combination which appears capable of satisfying the (P-3) + C2H4.C2H4 was confirmed as a product by GC observed lack of a strong pressure dependence is Ge(P-3) + C2H4. C2H4 was confirmed as a product by GC analysis. Although the formation of these products are shown to be possible by singlet-triplet curve crossing during dissociation of 1-germiranylidene (1-germacyclopropylidene), it seems more likely (on thermochernical grounds) that the triplet biradical, (GeCH2CH2.)-Ge-., is the immediate product precursor. Comparisons are made with the reaction of SiH2 with C2H2.

Gas phase kinetic and quantum chemical studies of the reactions of silylene with the methylsilanes. Absolute rate constants, temperature dependences, RRKM modelling and potential energy surfaces

Time resolved studies of silylene, SiH2, generated by the 193 nm laser. ash photolysis of phenylsilane, have been carried out to obtain rate coefficients for its bimolecular reactions with methyl-, dimethyl- and trimethyl-silanes in the gas phase. The reactions were studied over the pressure range 3 - 100 Torr with SF6 as bath gas and at five temperatures in the range 300 - 625 K. Only slight pressure dependences were found for SiH2 + MeSiH3 ( 485 and 602 K) and for SiH2 + Me2SiH2 ( 600 K). The high pressure rate constants gave the following Arrhenius parameters: [GRAPHICS] These are consistent with fast, near to collision-controlled, association processes. RRKM modelling calculations are consistent with the observed pressure dependences ( and also the lack of them for SiH2 + Me3SiH). Ab initio calculations at both second order perturbation theory (MP2) and coupled cluster (CCSD(T)) levels, showed the presence of weakly-bound complexes along the reaction pathways. In the case of SiH2 + MeSiH3 two complexes, with different geometries, were obtained consistent with earlier studies of SiH2 + SiH4. These complexes were stabilised by methyl substitution in the substrate silane, but all had exceedingly low barriers to rearrangement to product disilanes. Although methyl groups in the substrate silane enhance the intrinsic SiH2 insertion rates, it is doubtful whether the intermediate complexes have a significant effect on the kinetics. A further calculation on the reaction MeSiH + SiH4 shows that the methyl substitution in the silylene should have a much more significant kinetic effect ( as observed in other studies).

Rovibrational energy levels of hydrogen peroxide, studied by MULTIMODE with a reaction path Hamiltonian

Recently. Carter and Handy [J. Chem. Phys. 113 (2000) 987] have introduced the theory of the reaction path Hamiltonian (RPH) [J. Chem. Phys. 72 (1980) 99] into the variational scheme MULTIMODE, for the calculation of the J = 0 vibrational levels of polyatomic molecules, which have a single large-amplitude motion. In this theory the reaction path coordinate s becomes the fourth dimension of the moment-of-inertia tensor, and must be treated separately from the remaining 3N - 7 normal coordinates in the MULTIMODE program. In the modified program, complete integration is performed over s, and the M-mode MULTIMODE coupling approximation for the evaluation of the matrix elements applies only to the 3N - 7 normal coordinates. In this paper the new algorithm is extended to the calculation of rotational-vibration energy levels (i.e. J > 0) with the RPH, following from our analogous implementation for rigid molecules [Theoret. Chem. Acc. 100 (1998) 191]. The full theory is given, and all extra terms have been included to give the exact kinetic energy operator. In order to validate the new code, we report studies on hydrogen peroxide (H2O2), where the reaction path is equivalent to torsional motion. H2O2 has previously been studied variationally using a valence coordinate Hamiltonian; complete agreement for calculated rovibrational levels is obtained between the previous results and those from the new code, using the identical potential surface. MULTIMODE is now able to calculate rovibrational levels for polyatomic molecules which have one large-amplitude motion. (C) 2003 Elsevier B.V. All rights reserved.

Rovibrational energy levels for the electronic ground state of A1OH

The vibrational-rotational energy levels of aluminum monohydroxide in its electronic ground state, (A) over tilde (1)A' AlOH, have been predicted using the variational method. The potential energy surface of the (X) over tilde (1)A' ground state of AlOH was determined employing the ab initio coupled cluster method with single, double, and perturbative triple excitations [CCSD(T)] and the correlation-consistent polarized valence quadruple zeta (cc-pVQZ) basis set. Low-lying J= 0 and J= 1 vibrational levels are reported. These are analyzed in terms of the quasilinearity of the molecule. Coriolis effects are shown to be significant. We hope that our predictions will be of value in the future when assigning rovibrational transitions in spectroscopic studies. (c) 2006 Elsevier B.V. All rights reserved.