The effect of improving cow productivity, fertility, and longevity on the global warming potential of dairy systems

This study compared the environmental impact of a range of dairy production systems in terms of their global warming potential (GWP, expressed as carbon dioxide equivalents, CO₂-eq.) and associated land use, and explored the efficacy of reducing said impact. Models were developed using the unique data generated from a long-term genetic line × feeding system experiment. Holstein-Friesian cows were selected to represent the UK average for milk fat plus protein production (control line) or were selected for increased milk fat plus protein production (select line). In addition, cows received a low forage diet (50% forage) with no grazing or were on a high forage (75% forage) diet with summer grazing. A Markov chain approach was used to describe the herd structure and help estimate the GWP per year and land required per cow for the 4 alternative systems and the herd average using a partial life cycle assessment. The CO₂-eq. emissions were expressed per kilogram of energy-corrected milk (ECM) and per hectare of land use, as well as land required per kilogram of ECM. The effects of a phenotypic and genetic standard deviation unit improvement on herd feed utilization efficiency, ECM yield, calving interval length, and incidence of involuntary culling were assessed. The low forage (nongrazing) feeding system with select cows produced the lowest CO₂-eq. emissions of 1.1 kg/kg of ECM and land use of 0.65 m²/kg of ECM but the highest CO₂-eq. emissions of 16.1 t/ha of the production systems studied. Within the herd, an improvement of 1 standard deviation in feed utilization efficiency was the only trait of those studied that would significantly reduce the reliance of the farming system on bought-in synthetic fertilizer and concentrate feed, as well as reduce the average CO₂-eq. emissions and land use of the herd (both by about 6.5%, of which about 4% would be achievable through selective breeding). Within production systems, reductions in CO₂-eq. emissions per kilogram of ECM and CO₂-eq. emissions per hectare were also achievable by an improvement in feed utilization. This study allowed development of models that harness the biological trait variation in the animal to improve the environmental impact of the farming system. Genetic selection for efficient feed use for milk production according to feeding system can bring about reductions in system nutrient requirements, CO₂-eq. emissions, and land use per unit product.     

掺钴锂锰氧化物的合成机理及红外光谱与磁性研究

用TG-DTA-DTG,XRD,IR谱方法研究了掺钴锂锰氧化物LiCoxMn2-xO4的合成机理及红外光谱变化规律,并通过磁化率的测定考查了化合物中Co3+,Mn3+的价电子填充规律.结果表明蒸发Li2CO3,Co(CH3COO)2@4H2O,Mn(CH3COO)2@4H2O混合溶液之后,对其烧结制备LiCoxMn2-xO4的过程大致可分为吸附水的失去,结晶水的失去,Li2CO3,Co(CH3COO)2,Mn(CH3COO)2的分解并生成LiCoxMn2-xO4 4个阶段,烧结产物LiCoxMn2-xO4的红外光谱图形状基本相同,但吸收峰的位置随烧结温度和钴含量(摩尔分数)的不同而略有变化,但其磁化率的变化只与温度有关.     

Effect of antioxidant oxidation potential in the oxygen radical absorption capacity (ORAC) assay

The “oxygen radical absorption capacity” (ORAC) assay (Ou, B., Hampsch-Woodill, M., Prior, R.L. (2001). Development and validation of an improved oxygen radical absorbance capacity assay using fluorescein as the fluorescent probe. Journal of Agricultural and Food Chemistry 49, 4619–4626) is widely employed to determine antioxidant content of foods and uses fluorescein as a probe for oxidation by peroxyl radicals. Kinetic modeling of the ORAC assay suggests that the lag phase for loss of fluorescence results from equilibrium between antioxidant and fluorescein radicals and the value of the equilibrium constant determines the shape of the lag phase. For an efficient antioxidant this constitutes a “repair” reaction for fluoresceinyl radicals and produces a well defined lag phase. The lag phase becomes less marked with increasing oxidation potential of the antioxidant. Pulse radiolysis confirms that fluoresceinyl radicals are rapidly (k ∼ 10⁹ dm³ mol⁻¹ s⁻¹) reduced by Trolox C, a water soluble vitamin E analogue. ORAC assays of phenols with varying oxidation potentials suggest that it might be employed to obtain an estimate of the redox potential of antioxidants within food materials.     

Standards development of global warming gas species: methane, nitrous oxide, trichlorofluoromethane, and dichlorodifluoromethane

Environmental scientists from federal agencies, such as the National Oceanic and Atmospheric Administration (NOAA), and academia have long suspected that increasing anthropogenic inputs of various trace gases into the atmosphere can cause changes in the earth's climate and protective ozone layer. Nitrous oxide and methane, cited in the Kyoto Protocol, as well astrichlorofluoromethane (CFC-11) and dichlorodifluoromethane (CFC-12), cited in the Montreal Protocol, are all greenhouse gases and are implicated in the destruction of the stratospheric ozone layer. The lack of national standards prompted research to determine the feasibility of preparing accurate and stable standards containing these four compounds. Development of these standards would support the measurement of these species by those in the atmospheric research community not having their own source of standards. A suite of eight primary gas standards containing methane, nitrous oxide, CFC-11, and CFC-12 in a balance of air were prepared gravimetrically to bracket the ambient atmospheric concentrations. The combined uncertainties (uc) were calculated from error propagation analysis that included the weighing data from the gravimetric preparation and other sources of error such as the purity analysis of the compounds and air matrix. The expanded uncertainties (U) for the gravimetric standards were < 0.5% as calculated from the equation U = kuc, where the coverage factor k is equal to 2 for a 95% confidence interval. Analyses of the suite of standards by gas chromatography with flame-ionization and electron capture detection resulted in average absolute residuals of < 0.25% from regression models. The NIST suite of eight gravimetric standards was used to determine the concentrations in two standardsfrom NOAA. Those analyses resulted in bias across the two laboratories of < or = 2.1%.     

Atmospheric trends and radiative forcings of CF4 and C2F6 inferred from firn air

The atmospheric histories of two potent greenhouse gases, tetrafluoromethane (CF4) and hexafluoroethane (C2F6), have been reconstructed for the 20th century based on firn air measurements from both hemispheres. The reconstructed atmospheric trends show that the mixing ratios of both CF4 and C2F6 have increased during the 20th century by factors of approximately 2 and approximately 10, respectively. Initially, the increasing mixing ratios coincided with the rise in primary aluminum production. However, a slower atmospheric growth rate for CF4 appears to be evident during the 1990s, which supports recent aluminum industry reports of reduced CF4 emissions. This work illustrates the changing relationship between CF4 and C2F6 that is likely to be largely the result of both reduced emissions from the aluminum industry and faster growing emissions of C2F6 from the semiconductor industry. Measurements of C2F6 in the older firn air indicate a natural background mixing ratio of <0.3 parts per trillion (ppt), demonstrating that natural sources of this gas are negligible. However, CF4 was deduced to have a preindustrial mixing ratio of 34 -1 ppt (-50% of contemporary levels). This is in good agreement with the previous work of Harnisch et al. (18) and provides independent confirmation of their results. As a result of the large global warming potentials of CF4 and C2F6, these results have important implications for radiative forcing calculations. The radiative forcings of CF4 and C2F6 are shown to have increased over the past 50 years to values in 2001 of 4.1 x 10(-3) Wm(-2) and 7.5 x 10(-4) Wm(-2), respectively, relative to preindustrial concentrations. These forcings are small compared to present day forcings due to the major greenhouse gases but, if the current trends continue, they will continue to increase since both gases have essentially infinite lifetimes. There is, therefore, a large incentive to reduce perfluorocarbon emissions such that through the implementation of the Kyoto Protocol, the atmospheric growth rates may decline in the future.     

Degradation of the adsorbent Tenax TA by nitrogen oxides,ozone, hydrogen peroxide,OH radical,and limonene oxidation products

The degradation of the adsorbent Tenax TA was studied qualitatively by sampling oxidants common in indoor air followed by thermal desorption and gas chromatography. A total of 25 degradation products were identified. Several degradation products not reported previously were identified: 9 for nitrogen dioxide; 11 for ozone; 2 for hydrogen peroxide; 12 for hydroxyl radical; 1 for ozone-limonene mixtures, but none for nitrogen oxide. Whereas ozone shows a complex degradation of the adsorbent, hydrogen peroxide and limonene--ozone mixtures show few products. Nitrogen dioxide and the hydroxyl radical behave almost identically and produce 2,6-diphenyl-p-benzoquinone as the major degradation product. Reactant specific degradation products were identified for ozone (11) and nitrogen dioxide (1).     

Temperature effects on the removal of potential HFC replacements, CF3CH2CH2OH and CF3(CH2)2CH2OH, initiated by OH radicals

The gas-phase kinetic coefficients of OH radicals with two primary fluorinated alcohols, CF(3)CH(2)CH(2)OH (k(1)) and CF(3)(CH(2))(2)CH(2)OH (k(2)), potential replacements of hydrofluorocarbons (HFCs), are reported here as a function of temperature (T = 263-358 K) for the first time. k(1) and k(2) (together referred as k(i)) were measured under pseudo-first-order conditions with respect to the initial OH concentration using the pulsed laser photolysis/laser induced fluorescence technique. The observed temperature dependence of k(i) (in cm(3) molecule(-1) s(-1)) is described by the following Arrhenius expressions: k(1)(T) = (2.82 ± 1.28) × 10(-12) exp{-(302 ± 139)/T} cm(3) molecule(-1) s(-1) and k(2)(T) = (1.20 ± 0.73) × 10(-11) exp{-(425 ± 188)/T} cm(3) molecule(-1) s(-1).The uncertainties in the Arrhenius parameters are at a 95% confidence level (± 2σ). Uncertainties in k(i)(T) include both statistical and systematic errors. Activation energies were (2.5 ± 1.2) kJ/mol and (3.6 ± 1.6) kJ/mol for the OH-reaction with CF(3)CH(2)CH(2)OH and CF(3)(CH(2))(2)CH(2)OH, respectively. The global lifetime (τ) at 275 K for CF(3)CH(2)CH(2)OH and CF(3)(CH(2))(2)CH(2)OH due to the OH-reaction was estimated to be ca. 2 weeks and 5 days, respectively. The reported Arrhenius parameters can be used in 3D models that take into account the geographical region and season of emissions for estimating a matrix of instantaneous lifetimes. As a consequence of the substitution of the -CH(3) group by a -CH(2)OH group in HFCs, such as CF(3)CH(2)CH(3) and CF(3)(CH(2))(2)CH(3), the tropospheric lifetime with respect to the OH reaction is significantly shorter and, since their radiative forcing is similar, global warming potentials of CF(3)CH(2)CH(2)OH and CF(3)(CH(2))(2)CH(2)OH are negligible. Therefore, CF(3)CH(2)CH(2)OH and CF(3)(CH(2))(2)CH(2)OH seem to be suitable alternatives to HFCs.     

Kinetic and mechanistic study of the atmospheric oxidation by OH radicals of allyl acetate

Acetates are emitted into the atmosphere by several anthropic and natural sources. To better evaluate the environmental impact of these compounds, OH-induced oxidation kinetic and mechanism of allyl acetate (CH3C(O)OCH2-CH=CH2) have been investigated at room temperature and atmospheric pressure using three environmental chambers: an indoor Teflon-film bag (LISA, Créteil), an indoor Pyrex photoreactor (LISA, Créteil), and the outdoor Smog chamber EUPHORE (Valencia). Rate constant of the reaction of allyl acetate with OH radicals was determined by relative rate technique in the indoor Teflon-film bag. It is (30.6 +/- 3.1) x 10(-12) cm3 molecule-1 s-1. Mechanistic experiments were performed in the indoor photoreactor and in the outdoor Smog chamber EUPHORE. The main oxidation products observed by FTIR in both chambers were acetoxyacetaldehyde and formaldehyde. From these data, a mechanism was developed to describe the OH-induced oxidation of this acetate in the presence of NOx. Finally, atmospheric impact of allyl acetate emissions was evaluated using kinetic and mechanistic results.     

Atmospheric chemistry of N-methyl perfluorobutane sulfonamidoethanol, C4F9SO2N(CH3)CH2CH2OH: kinetics and mechanism of reaction with OH

Relative rate methods were used to measure the gas-phase reaction of N-methyl perfluorobutane sulfonamidoethanol (NMeFBSE) with OH radicals, giving k(OH + NMeFBSE) = (5.8 +/- 0.8) x 10(-12) cm3 molecule(-1) s(-1) in 750 Torr of air diluent at 296 K. The atmospheric lifetime of NMeFBSE is determined by reaction with OH radicals and is approximately 2 days. Degradation products were identified by in situ FTIR spectroscopy and offline GC-MS and LC-MS/MS analysis. The primary carbonyl product C4F9SO2N(CH3)CH2CHO, N-methyl perfluorobutane sulfonamide (C4F9SO2NH(CH3)), perfluorobutanoic acid (C3F7C(O)OH), perfluoropropanoic acid (C2F5C(O)OH), trifluoroacetic acid (CF3C(O)OH), carbonyl fluoride (COF2), and perfluorobutane sulfonic acid (C4F9SO3H) were identified as products. A mechanism involving the addition of OH to the sulfone double bond was proposed to explain the production of perfluorobutane sulfonic acid and perfluorinated carboxylic acids in yields of 1 and 10%, respectively. The gas-phase N-dealkylation product, N-methyl perfluorobutane sulfonamide (NMeFBSA), has an atmospheric lifetime (>20 days) which is much longer than that of the parent compound, NMeFBSE. Accordingly,the production of NMeFBSA exposes a mechanism by which NMeFBSE may contribute to the burden of perfluorinated contamination in remote locations despite its relatively short atmospheric lifetime. Using the atmospheric fate of NMeFBSE as a guide, it appears that anthropogenic production of N-methyl perfluorooctane sulfonamidoethanol (NMeFOSE) contributes to the ubiquity of perfluoroalkyl sulfonate and carboxylate compounds in the environment.     

Black carbon from the Mississippi River: quantities,sources, and potential implications for the global carbon cycle

Black carbon (BC) may be a major component of riverine carbon exported to the ocean, but its flux from large rivers is unknown. Furthermore, the global distribution of BC between natural and anthropogenic sources remains uncertain. We have determined BC concentrations in suspended sediments of the Mississippi River, the 7th largest river in the world in terms of sediment and water discharge, during high flow and low flow in 1999. The 1999 annual flux of BC from the Mississippi River was 5 x 10(-4) petagrams (1 Pg = 10(15) g = 1 gigaton). We also applied a principal components analysis to particulate-phase high molecular weight polycyclic aromatic hydrocarbon isomer ratios in Mississippi River suspended sediments. In doing so, we determined that approximately 27% of the BC discharged from the Mississippi River in 1999 originated from fossil fuel combustion (coal and smelter-derived combustion), implicating fluvial BC as an important source of anthropogenic BC contamination into the ocean. Using our value for BC flux and the annual estimate for BC burial in ocean sediments, we calculate that, in 1999, the Mississippi River discharged approximately 5% of the BC buried annually in the ocean. These results have important implications, not only for the global carbon cycle but also for the fluvial discharge of particulate organic contaminants into the world's oceans.     

基于双积分球技术的植物油热氧化过程吸收与散射特性变化规律的研究

植物油在运输储藏、销售等过程中,容易被储藏环境、储藏方式影响,导致植物油氧化劣变,产生醛酮和羧酸类有害化合物。本研究采用自主搭建的双积分球系统结合逆向倍增算法(IAD),实现植物油吸收系数(μ_a)与约化散射系数(μ′_s)的高精度检测。采用该技术对植物油的热氧化的吸收与散射特性变化规律进行研究。结果表明,植物油的热稳定性与其种类相关。基于特征波长建立植物油热氧化μ_a和μ′_s模型的稳定性和精度有所提高。偏最小二乘判别(PLSDA)模型的总正确率能够达到95%。通过偏最小二乘回归(PLSR)算法,建立植物油过氧化值含量预测模型。结果表明基于特征波长,建立μ_a和μ′_s的PLSR模型相对分析偏差(RPD)均大于3,表明基于吸收与散射特性的植物油热氧化定量预测模型精度较高,能够满足定量预测要求。     

Dicarbonyl products of the OH radical-initiated reactions of naphthalene and the Cl- and C2-alkylnaphthalenes

Naphthalene and the C1- and C2-alkylnaphthalenes are the most abundant polycyclic aromatic hydrocarbons (PAHs) in urban atmospheres. Their major atmospheric loss process is by gas-phase reaction with hydroxyl (OH) radicals. In this study, we have used in situ direct air sampling atmospheric pressure ionization mass spectrometry (API-MS) as well as gas chromatography-mass spectrometry (GC/MS) techniques to investigate the products of the gas-phase reactions of OH radicals with naphthalene, naphthalene-ds, 1- and 2-methylnaphthalene (MN), 1- and 2-MN-dio, 1- and 2-ethylnaphthalene (EN), and the 10 isomeric dimethylnaphthalenes (DMNs). The major reaction products are ring-opened dicarbonyls that are 32 mass units higher in molecular weight than the parent compound, one or more ring-opened dicarbonyls of lower molecular weight resulting from loss of two P-carbons and associated alkyl groups, and ring-containing compounds that may be epoxides. Phthalic anhydride and alkyl-substituted phthalic anhydrides were observed as second generation products. The position of alkyl-substitution on the naphthalene ring is a key factor determining the ring cleavage site and the isomeric product distribution.     

The water absorption of sapwood and heartwood of Scots pine and Norway spruce heat-treated at 170 °C, 190 °C, 210 °C and 230 °C

Heat-treatment changes the chemical and physical properties of wood. Wood polymers are degraded, dimensional stability is enhanced, equilibrium moisture content is lowered, colour darkens and biological durability is increased. The properties of heat-treated wood have been researched considerably, but the differences between sapwood and heartwood have not been reported separately. In this research, water absorption differences between sapwood and heartwood of Scots pine and Norway spruce heat-treated at temperatures 170 °C, 190 °C, 210 °C and 230 °C were investigated. The results were compared to industrially kiln-dried reference samples. Water absorption was determined with a floating test based on the EN 927-5 standard. The heartwood of both wood species absorbed less water than sapwood. Heat-treatment evidently decreased the water absorption of spruce and pine heartwood. The higher the heat-treating temperature, the lower the amount of absorbed moisture. However, a very interesting exception was pine sapwood, whose water absorption actually increased with heat-treatment after the three lowest heat-treatment temperatures compared to the reference material. Water absorption did not decrease until the heat-treatment temperature was 230 °C.     

Studies on the structure and oxidation properties of extracted cooked cured meat pigment by four spectra

The structure and oxidation properties of cooked cured meat pigment (CCMP) were investigated by comparing the change in spectra of CCMP before and after oxidisation. CCMP was extracted using petroleum ether/acetone/ethyl acetate step by step from precooked cured beef. The extracted sample was oxidised by being exposed to air with normal lighting or adding 1.5 ppm H₂O₂, respectively. The structure of CCMP was identified as a pentacoordinate mononitrosylheme complex by electron paramagnetic resonance (EPR), HPLC/ESI-HR-MS, Raman and FT–IR spectra. The changed EPR spectra of CCMP in acetone oxidised under different conditions suggested a new proposal that the NO⁻ group might not detach itself from iron porphyrin during oxidation in air with normal lighting, but changed in conjugated structure, and the structure tended to axial symmetry by analysis of the changes in g factor. This hypothesis was further supported by the results of the HPLC/ESI-HR-MS and Raman spectrum.     

Atmospheric chemistry of perfluoroalkanesulfonamides: kinetic and product studies of the OH radical and Cl atom initiated oxidation of N-ethyl perfluorobutanesulfonamide

Perfluorooctanesulfonamides [C8F17SO2N(R1)(R2)] are present in the atmosphere and may, via atmospheric transport and oxidation, contribute to perfluorocarboxylates (PFCA) and perfluorooctanesulfonate (PFOS) pollution in remote locations. Smog chamber experiments with the perfluorobutanesulfonyl analogue N-ethyl perfluorobutanesulfonamide [NEtFBSA; C4F9SO2N(H)CH2CH3] were performed to assess this possibility. By use of relative rate methods, rate constants for reactions of NEtFBSA with chlorine atoms (296 K) and OH radicals (301 K) were determined to be kCL) = (8.37 +/- 1.44) x 10(-12) and kOH = (3.74 +/- 0.77) x 10(-13) cm3 molecule(-1) s(-1), indicating OH reactions will be dominant in the troposphere. Simple modeling exercises suggestthat reaction with OH radicals will dominate removal of perfluoroalkanesulfonamides from the gas phase (wet and dry deposition will not be important) and that the atmospheric lifetime of NEtFBSA in the gas phase will be 20-50 days, thus allowing substantial long-range atmospheric transport. Liquid chromatography/tandem mass spectrometry (LC/MS/MS) analysis showed that the primary products of chlorine atom initiated oxidation were the ketone C4F9SO2N(H)COCH3; aldehyde 1, C4F9SO2N(H)CH2CHO; and a product identified as C4F9SO2N(C2H5O)- by high-resolution MS but whose structure remains tentative. Another reaction product, aldehyde 2, C4F9SO2N(H)CHO, was also observed and was presumed to be a secondary oxidation product of aldehyde 1. Perfluorobutanesulfonate was not detected above the level of the blank in any sample; however, three perfluoroalkanecarboxylates (C3F7CO2-, C2F5CO2-, and CF3CO2-) were detected in all samples. Taken together, results suggest a plausible route by which perfluorooctanesulfonamides may serve as atmospheric sources of PFCAs, including perfluorooctanoic acid.     

核桃油自氧化及其抗氧化的实验研究

以过氧化值(P0V)为指标研究了温度、时间对核桃油自氧化过程的影响及添加抗氧化剂对核桃油抗氧化性能的影响。结果表明,温度、时间对核桃油的氧化过程有高度显著的影响。TBHQ对核桃油具有较好的抗氧化性能,抗坏血酸和柠檬酸对TBHQ均表现出较强的协同抗氧化效应,且抗坏血酸的协同抗氧化性优于柠檬酸。使用0.015％TBHQ+0.01％柠檬酸或0.015％TBHQ+0.01％抗坏血酸为核桃油的抗氧化剂,可使核桃油在15℃下的贮藏期从2.9个月分别延长至29.8个月和38.9个月。     

普洱茶茶多酚及清除·OH能力的研究

采用光谱法测定普洱茶中茶多酚的含量。方法的回收率为94%～105%,变异系数小于1.00%。用邻菲罗啉—Cu —H2O2化学发光体系,结合流动注射技术研究普洱茶清除·OH的能力。实验结果表明,普洱茶中茶多酚的含量和清除·OH的能力,随着贮藏时间延长、贮藏温度提高而下降。     

Identification of the intermediates of in vivo oxidation of 1 ,4-dioxane by monooxygenase-containing bacteria

1,4-dioxane is a probable human carcinogen and an emerging water contaminant. Monooxygenase-expressing bacteria have been shown to degrade dioxane via growth-supporting as well as cometabolic mechanisms. In this study, the intermediates of dioxane degradation by monooxygenase-expressing bacteria were determined by triple quadrupole-mass spectrometry and Fourier transform ion cyclotron resonance-mass spectrometry. The major intermediates were identified as 2-hydroxyethoxyacetic acid (HEAA), ethylene glycol, glycolate, and oxalate. Studies with uniformly labeled 14C dioxane showed that over 50% of the dioxane was mineralized to CO2 by CB1190, while 5% became biomass-associated after 48 h. Volatile organic acids and non-volatiles, respectively, accounted for 20 and 11% of the radiolabeled carbon. Although strains cometabolizing dioxane exhibited limited transformation capacities, nearly half of the initial dioxane was recovered as CO2. On the basis of these analytical results, we propose a pathway for dioxane oxidation by monooxygenase-expressing cells in which dioxane is first converted to 2-hydroxy-1,4-dioxane, which is spontaneously oxidized to HEAA. During a second monooxygenation step, HEAA is further hydroxylated, resulting in a mixture of dihydroxyethoxyacetic acids with a hydroxyl group at the ortho or para position. After cleavage of the second ether bond, small organic molecules such as ethylene glycol, glycolate, glyoxalate, and oxalate are progressively formed, which are then mineralized to CO2 via common cellular metabolic pathways. Bioremediation of dioxane via this pathway is not expected to cause an accumulation of toxic compounds in the environment.