Derivative spectrophotometric determination of some corticosteroids in combinations with other drugs

Three 2-component mixtures, namely, dexamethazone-chlorpheniramine maleate, prednisolone-chlorpheniramine maleate, and prednisolone-salicylic acid, have been assayed using their first (D1) and second (D2) derivative spectra in methanol, delta absorption (delta A), and second derivative of delta A (delta D2) spectra in methanol-methanolic HCl. In the first 2 mixtures, chlorpheniramine maleate was determined by measuring its delta D2 value at 278 nm, while dexamethazone and prednisolone were analyzed by measuring their D1 values at 248 nm. Prednisolone and salicylic acid were analyzed in combination by using their respective D2 spectral responses at 272 and 314 nm. The results obtained are reasonably reproducible with a relative standard deviation less than 2%. The method has been successfully applied to the analysis of these drugs in their pharmaceutical formulations.     

Fluorometric and spectrophotometric determination of pirbuterol hydrochloride in authentic and dosage forms

Pirbuterol hydrochloride has been assayed in alkaline medium by using a fluorometric method to measure fluorescence intensity at 372 nm with excitation at 310 nm and by the delta A method at 242 nm. The linearity ranges are 0.5-4 micrograms/mL and 10-50 micrograms/mL, respectively. An authentic pirbuterol HCl sample was analyzed by nonaqueous potentiometric titration using 0.1N perchloric acid, and the results were compared with those for fluorometric and delta A methods. The mean percent recoveries for the authentic sample were 98.72 +/- 1.13 and 99.24 +/- 0.85, respectively. When applied to commercial capsules containing 10 mg and 15 mg each, the fluorometric method gave mean percent recoveries of 101.11 +/- 1.05 and 98.12 +/- 0.93; the delta A method gave mean percent recoveries of 100.57 +/- 0.83 and 97.80 +/- 0.75, respectively.     

Specific natural isotope profile studied by isotope ratio mass spectrometry (SNIP-IRMS): (13)C/(12)C ratios of fructose, glucose, and sucrose for improved detection of sugar addition to pineapple juices and concentrates

The delta(13)C values of fructose, glucose, and sucrose have been determined in authentic pineapple juices. The sugar fraction is separated from the organic acids by an anionic exchange process. Then the individual components (fructose, glucose, and sucrose) are isolated on a preparative HPLC device using a NH(2)-type column. It is demonstrated that no significant isotope fractionation occurs when close to 100% of material is recovered and when the hydrolysis of sucrose is avoided. The control of the recovery rates and of the sucrose hydrolysis rate after purification is recommended for a reliable interpretation of the results. Correlations between the delta(13)C values of fructose (delta(13)Cf), glucose (delta(13)Cg), and sucrose (delta(13)Csu) can be characterized by systematic differences between these values. For the set of measurements on authentic pineapple juices and concentrates, the mean and the standard deviation of the differences are delta(13)Cf - delta(13)Cg = -0.6 +/- 0.6 per thousand, delta(13)Cf - delta(13)Csu = -1.3 +/- 0. 6 per thousand, and delta(13)Cf - delta(13)Csu = -0.7 +/- 0.5 per thousand. The determinations of the (13)C content of fructose, glucose, and sucrose enable a refinement of the detection of added sugars in fruit juices, re-enforcing the SNIP-IRMS method.     

Nitrogen isotope relationships between crops and fertilizer: implications for using nitrogen isotope analysis as an indicator of agricultural regime

The effect of fertilizer type, amount of fertilizer applied, growing medium, and water type on the nitrogen-15 content of carrots, tomatoes, and lettuces has been investigated. Crops grown using synthetic nitrogen fertilizer were isotopically lighter than those grown using pelleted chicken manure. For example, for equivalent amounts of nitrogen applied, carrots grown with ammonium nitrate fertilizer had delta15N values between 3 per thousand and 4 per thousand lower than those grown using pelleted chicken manure. Plants grown in peat-based compost were generally found to be isotopically lighter than those grown in composted bark based compost. Results suggest that nitrate content and the delta15N of the nitrate in irrigation water may also influence crop delta15N. Wider implications of using crop delta15N more generally as an indicator of whether synthetic nitrogen fertilizers have been applied to a crop and the possible application and limitations of using crop delta15N as an indicator of agricultural regime (organic/conventional) are discussed.     

Carbon and hydrogen stable isotope ratios of carotenoids and beta-carotene-based dietary supplements

Considering the increasing nutritional and commercial importance of carotenoids, there is an interest in developing a reliable method for authenticity assessment of these compounds. Applying isotope ratio mass spectrometry using elemental analysis in the "combustion" (C) and "pyrolysis" (P) modes (EA-C/P-IRMS), the delta (13)C V-PDB and delta (2)H V-SMOW values of selected carotenoids and alpha/beta-carotene-based commercial dietary supplements were determined in comparison to those of synthetic and "natural" references. The delta (13)C V-PDB and delta (2)H V-SMOW values of synthetic beta-carotene samples ( n = 4), ranging from -25.3 per thousand to -26.4 per thousand and from -144 per thousand to -155 per thousand, respectively, differed clearly from the data determined for carotenoids from various natural sources, including C 3 plant material ( n = 9; delta (13)C V-PDB ranging from -28.5 per thousand to -32.8 per thousand and delta (2)H V-SMOW from -180 per thousand to -275 per thousand) and microalgae Dunaliella salina ( n = 1; delta (13)C V-PDB value of -15.6 per thousand and delta (2)H V-SMOW value of -191 per thousand). From five commercial dietary supplements under study, two revealed delta (13)C V-PDB and delta (2)H V-SMOW values in areas as found for synthetic references, and the other three had values near those of biotechnological beta-carotene produced by D. salina. The delta (13)C V-PDB and delta (2)H V-SMOW values recorded for natural lycopene ( n = 4) and lutein ( n = 5) ranged from -31.1 per thousand to -31.8 per thousand and from -180 to -201 per thousand, as well as from -28.8 per thousand to -32.2 per thousand and from -186 per thousand to -245 per thousand, respectively. Synthetic canthaxanthin ( n = 3) exhibited delta (13)C V-PDB and delta (2)H V-SMOW values ranging from -25.0 per thousand to -28.6 per thousand and from -133 per thousand to -153 per thousand, respectively. The EA-C/P-IRMS application of this study showed that the natural stable isotopic composition of carotenoids is a powerful tool for determining their origin.     

Improved detection of sugar addition to maple syrup using malic acid as internal standard and in 13C isotope ratio mass spectrometry (IRMS)

Stable carbon isotope ratio mass spectrometry (delta13C IRMS) was used to detect maple syrup adulteration by exogenous sugar addition (beet and cane sugar). Malic acid present in maple syrup is proposed as an isotopic internal standard to improve actual adulteration detection levels. A lead precipitation method has been modified to isolate quantitatively malic acid from maple syrup using preparative reversed-phase liquid chromatography. The stable carbon isotopic ratio of malic acid isolated from this procedure shows an excellent accuracy and repeatability of 0.01 and 0.1 per thousand respectively, confirming that the modified lead precipitation method is an isotopic fractionation-free process. A new approach is proposed to detect adulteration based on the correlation existing between the delta13Cmalic acid and the delta13Csugars-delta13Cmalic acid (r = 0.704). This technique has been tested on a set of 56 authentic maple syrup samples. Additionally, authentic samples were spiked with exogeneous sugars. The mean theoretical detection level was statistically lowered using this technique in comparison with the usual two-standard deviation approach, especially when maple syrup is adulterated with beet sugar : 24 +/- 12% of adulteration detection versus 48 +/- 20% (t-test, p = 7.3 x 10-15). The method was also applied to published data for pineapple juices and honey with the same improvement.     

Evaluation of solid-phase microextraction for the isotopic analysis of volatile compounds produced during fermentation by lactic acid bacteria

The use of solid-phase microextraction (SPME) coupled with isotope ratio mass spectrometry (IRMS) for the analysis of flavor compounds produced by lactic acid bacteria has been evaluated using both liquid and headspace sampling modes. Initially, it was necessary to optimize the conditions for the SPME extraction of flavors-diacetyl and acetoin-in standard aqueous solutions. The effects of salt, headspace versus liquid sampling, and coating phase were tested. Second, the suitability of the coupling of SPME and gas chromatography-combustion interface-IRMS (GC-C-IRMS) for the determination of delta(13)C values was assessed. It is shown that neither the analyte concentration nor the period of fiber exposure has an effect on the delta(13)C values. Finally, having verified that there are no matrix effects from the fermentation medium, it is reported for the first time that flavor compounds can be extracted directly from culture supernatant by SPME and their delta(13)C values can be obtained by GC-C-IRMS.     

Nitrogen isotope composition of organically and conventionally grown crops

Authentic samples of commercially produced organic and conventionally grown tomatoes, lettuces, and carrots were collected and analyzed for their delta15N composition in order to assemble datasets to establish if there are any systematic differences in nitrogen isotope composition due to the method of production. The tomato and lettuce datasets suggest that the different types of fertilizer commonly used in organic and conventional systems result in differences in the nitrogen isotope composition of these crops. A mean delta15N value of 8.1 per thousand was found for the organically grown tomatoes compared with a mean value of -0.1 per thousand for those grown conventionally. The organically grown lettuces had a mean value of 7.6 per thousand compared with a mean value of 2.9 per thousand for the conventionally grown lettuces. The mean value for organic carrots was not significantly different from the mean value for those grown conventionally. Overlap between the delta15N values of the organic and conventional datasets (for both tomatoes and lettuces) means that it is necessary to employ a statistical methodology to try and classify a randomly analyzed "off the shelf" sample as organic/conventional, and such an approach is demonstrated. Overall, the study suggests that nitrogen isotope analysis could be used to provide useful "intelligence" to help detect the substitution of certain organic crop types with their conventional counterparts. However, delta15N analysis of a "test sample" will not provide unequivocal evidence as to whether synthetic fertilizers have been used on the crop but could, for example, in a situation when there is suspicion that mislabeling of conventionally grown crops as "organic" is occurring, be used to provide supporting evidence.     

Geography and vintage predicted by a novel GIS model of wine delta18O

Wine hydrogen and oxygen stable isotopes record the climatic conditions experienced by the grape vine and the isotopic composition of the vine's source water during berry development. As such, stable isotopes have been explored extensively for use in detecting wine adulteration or for independently verifying claims of origin. We present the results of a study designed to evaluate the relationships between wine water delta18O and spatial climate and precipitation delta18O patterns across the winegrape-growing regions of Washington, Oregon, and California. Retail wines produced from typically small vineyards across these regions were obtained from the 2002 vintage, and the delta18O of wine water was analyzed using a CO2 equilibration method. Significant correlations were observed between the measured wine water delta18O from 2002 and the long-term average precipitation delta18O and late season 2002 climate, based on a spatial join with continuous geographic information system (GIS) maps of these drivers. We then developed a regression model that was implemented spatially in a GIS. The GIS model is the first of its kind and allows spatially explicit predictions of wine delta18O across the region. Because high spatial resolution monthly climate layers are now available for many years, wine delta18O could be modeled for previous years. We therefore tested the model by executing it for specific years and comparing the model predictions with previously published results for wine delta18O from seven vintages from Napa and Livermore Valleys, California. With the exception of one year, an anomaly potentially related to the effects of El Ni?o on precipitation isotopic composition, the model predicted well the wine delta18O for both locations for all vintages and generally reflected the consistent enrichment of wine from Napa relative to Livermore. Our results suggest that wine water delta18O records both source water delta18O and climate during the late stages of winegrape ripening and that GIS models of wine water delta18O are useful tools for independently verifying claims of regional origin and vintage.     

Comprehensive authentication of (E)-alpha(beta)-ionone from raspberries, using constant flow MDGC-C/P-IRMS and enantio-MDGC-MS

A new coupling system of GC-GC, connected via a Multi Column Switching Device MCS2 for measuring isotope ratios, is introduced. By means of several standard substances the precise and accurate measurement of isotopic values is proved. First applications concerning the authentication of raspberry aroma compounds are established. Consequently, the combination of constant flow multidimensional gas chromatography-combustion/pyrolysis-isotope ratio mass spectrometry (MDGC-C/P-IRMS) is applied to the authenticity assessment of (E)-alpha(beta)-ionone from six different raspberry cultivars. Furthermore, 12 commercially available raspberry products and samples of (E)-alpha(beta)-ionone, some declared to be natural, are investigated. delta(2)Eta(V)(-)(SMOW) and delta(13)C(V)(-)(PDB) values of (E)-alpha(beta)-ionone are determined, and characteristic authenticity ranges were concluded from raspberries by correlation of both delta(2)Eta(V)(-)(SMOW) and delta(13)C( V)(-)(PDB) values. The results are correlated with the determination of enantiomeric purities of (E)-alpha-ionone, using stir bar sorptive extraction enantio-multidimensional gas chromatography mass spectrometry (SBSE-enantio-MDGC-MS).     

Wetland criteria and birds in a changing delta

An assessment of the changes in the ornithological value of the delta area in the southwestern part of The Netherlands was made, based on the criteria and standards of Szijj, by comparing data derived from bird counts made before the implementation of the delta project with those made after the closure of two estuaries and with the estimated numbers of birds for three possible future infrastructural models.It appears that all the sites examined are, and will remain, of international ornithological importance.Owing to their different environmental character each individual basin of the delta area can be considered as an internationally important wetland.As a result of the delta works, different types of habitat and management of the basins will have to be chosen so that a species of a group of species may be given priority.To justify the choice, fixed target numbers of the populations and a sound knowledge of the availability of suitable habitats is needed. A number of questions arose about the selection of sites and the possibility of conserving wetlands such as those in the delta area. Further development of the criteria and standards of Szijj and more uniform application is advocated.     

基于GIS的黄河三角洲土壤肥力质量自动化评价

土壤盐碱加重、质量退化是黄河三角洲土地开发利用中面临的重要问题,定量客观评价土壤质量对该区土地资源合理利用与保护有重要意义。本文运用相关分析法筛选土壤质量评价指标,确定其权重,通过G IS叠加分析划分评价单元,以隶属度模型和指数和法计算土壤质量综合指标值,进而评价土壤质量。结果显示:黄河三角洲土壤总体质量较差,适宜种植业的Ⅰ、Ⅱ、Ⅲ等地仅占土地总面积的18.62%,质量最差的Ⅷ等地(光板地)占19.56%,质量中等Ⅳ、Ⅴ、Ⅵ等地占总面积56.78%;评价结果与实际作物产量高度相关。在此基础上,研究提出了该区农业生产和土地资源合理配置的措施建议。     

ICP-AES法测定土壤及肥料中的硼含量

采用岛津 ICP- 10 0 0 型真空单道扫描发射光谱仪测定了土壤及肥料中的硼含量 ,方法经标准土壤样品验证 ,并与肥料测定的国家标准方法相比较 ,结果均十分符合。同时给出方法的精密度、检出限等参数 ,说明该方法准确度、灵敏度高 ,操作简便快速     

黄河三角洲盐碱地造林绿化关键技术

[目的]解决黄河三角洲地区盐碱地改良造林绿化的难点。[方法]分析黄河三角洲目前的盐碱地资源和特点,阐述盐碱地改良与造林绿化现状。在此基础上,依据前人的技术和研究成果,结合作者多年来盐碱地生态改良的研究与实践。[结果]提出了适宜黄河三角洲盐碱地造林绿化的关键技术:(1)利用传统方法造林绿化改良盐碱地;(2)重视新技术和新成果的应用。[结论]利用盐碱地造林绿化关键技术,实现黄河三角形洲滨海盐碱地改良是切实可行的。     

Flavor authentication studies of alpha-ionone, beta-ionone, and alpha-ionol from various sources

In addition to the already available information on the authenticity of alpha- (1) and beta-ionone (2) from plant tissues, there is an interest in the stable isotope data of 1 and 2 available by synthesis from citral and acetone, as European Union regulations, in contrast to the United States and other countries, do not allow a product to be declared as 'natural' that has been chemically synthesized (e.g., by using a natural catalyst) from natural educts. Analyses performed by on-line capillary gas chromatography-isotope ratio mass spectrometry in the combustion and pyrolysis modes (HRGC-C/P-IRMS) as well as by elemental analyzers (EA-C/P-IRMS) measuring delta(13)C(V)-PDB and delta(2)H(V)-SMOW values provide for the first time isotope data of such 'natural' 1 and 2 as well as of synthetic and 'ex plant' alpha-ionol (3). The isotope data recorded for synthesized 1 and 2 reflected the influence of the origin of the used citral, whereas that of acetone was less remarkable. For instance, 'natural' 1 ex citral from lemongrass showed, as expected for a C4 plant, an enriched delta(13)C(V)-PDB value of -18.5 per thousand. In addition, the use of synthetic citral resulted in an enriched delta(2)H(V)-SMOW value of -43 per thousand, whereas with citral ex Litsea cubeba and ex lemongrass values of -242 and -232 per thousand, respectively, were recorded. IRMS analyses of 'natural' 2 revealed delta(13)C(V)-PDB and delta(2)H(V)-SMOW values that were nearly identical to that recorded for 'natural' 1. As to both 1 and 2, variations of synthesis conditions led to distinct changes in the delta(13)C(V)-PDB but not the delta(2)H(V)-SMOW values. Synthetic 3 showed delta(13)C(V)-PDB and delta(2)H(V)-SMOW values of -24.5 and -184 per thousand, respectively. These data differed from those found in raspberry fruit under study (n = 8), that is, ranging from -33.6 to -36.6 per thousand for delta(13)C(V)-PDB and from -200 to -225 per thousand for delta(2)H(V)-SMOW. The values determined additionally for 1 and 2 in raspberry fruit samples ranged from -30.3 to -35.1 per thousand and from -176 to -221 per thousand for delta(13)C(V)-PDB and delta(2)H(V)-SMOW, respectively, and thus corresponded to the already known literature information.     

Sediment management options for the lower Ebro River and its delta

Background, Aim and Scope  Past and present management of the Ebro catchment have altered water, sediment and nutrient fluxes of the lower Ebro River and its delta. The construction of the Mequinensa and Riba-Roja dams during the 1960s disrupted the sediment transport continuity. As a result, the lower Ebro River and its delta are facing a reduction in sediment delivery which is estimated to be up to 99% of its original yield (about 3 × 10⁷ t/yr). Consequently, about 45% of the emerged delta will be under the mean sea level by 2100 due to subsidence and sea level rise, whereas the delta coast is retreating at a rate of several meters per year in the mouth area. This paper aims to establish the basis for a sediment management plan directed to offset the effects of the sediment delivery deficit of the Ebro delta. Main Features  A new management plan named ‘Integrated Plan for the Protection of the Ebro Delta’ (PIPDE) is being presently elaborated in order to develop sustainable management of the Ebro River and delta through an integrated management of water, sediment and habitats, in order to achieve European Union (EU) Water Framework Directive (WFD) requirements. Among other aspects, the plan aims to restore the sediment flux of the lower Ebro River by means of both the removal of the sediment trapped behind the dams and the transport of the sediment downstream of the reservoirs to the river mouth and delta plain. Results  Preliminary studies show that the ‘flushing flood’ method has lower costs and is the most adapted method to transfer the sediments retained into the Riba-Roja dam. The required sediment load to stop coastal retreat in the mouth area and to compensate relative sea level rise represents 10 times the present suspended load (0.021 g/l), but is 10 times lower than the total volume of sediment delivered to the sea under natural conditions. Sediment delivery to the delta plain can be accomplished through the rice irrigation system, a method used prior to dam construction. Discussion  Problems of achieving a sustainable management of water and sediment are mostly linked to reservoir management. Technical problems associated with by-passing sediments through the reservoirs can be solved through operational and structural changes. Benefits of sediment flow recovery are multiple, including maintenance of the reservoir capacity, possible decline of invasive species, reduction of elevation loss and coastal retreat in the delta. Conclusions  The partial restoration of sediment fluxes in the lower Ebro River and its delta is technically feasible and environmentally desirable, but further detailed studies need to be carried out before the plan can be implemented. Perspectives  Overall, the sustainability of the lower Ebro River and delta can only be guaranteed by the implementation of a new reservoir management concept where the ecological and morphological values, as well as the economical and social values, have to be taken into consideration.     

Liquid chromatographic determination of carbamazepine in tablets

A simple and rapid liquid chromatographic method is described for the qualitative and quantitative determination of carbamazepine in tablet composites and individual tablets, using the internal standard technique. Analyses were performed on a C-18 reverse-phase column with tetrahydrofuran-methanol-water (8 + 37 + 55) as the mobile phase. A linear relationship was obtained between detector responses at 254 nm and amounts of carbamazepine injected ranging from 0.2 to 1.7 micrograms. The coefficient of variation for 10 consecutive injections of a standard preparation was 0.4%. Recoveries of carbamazepine from 100 and 200 mg tablets averaged 101.4 and 99.7%, respectively. Assay results for commercial tablets analyzed by the proposed method agreed favorably with those obtained by the method of USP XXI. The assay results for individual tablets indicated that deviations from the average value and the range of individual values are much wider with the compendial method than with the proposed method.     

Authenticity assessment of gamma- and delta-decalactone from prunus fruits by gas chromatography combustion/pyrolysis isotope ratio mass spectrometry (GC-C/P-IRMS)

Authenticity assessment of gamma-decalactone (1) and delta-decalactone (2) from peach (Prunus persica var. persica), apricot (Prunus armeniaca), and nectarine (Prunus persica var. nectarina) was performed using gas chromatography-isotope ratio mass spectrometry (GC-IRMS) in the combustion (C) and pyrolysis (P) mode. In addition, commercially available synthetic (nature-identical) 1 and 2 as well as biotechnologically produced samples (declared to be "natural") were characterized by their delta(2)H(V)(-)(SMOW) and delta(13)C(V)(-)(PDB) values. For the Prunus fruits under study, rather narrow ranges of delta(13)C(V)(-)(PDB) and delta(2)H(V)(-)(SMOW) data of 1, varying from - 34.6 per thousand to - 38.4 per thousand and -160 per thousand to -206 per thousand, respectively, were obtained. Synthetic references of 1 showed delta(13)C(V)(-)(PDB) and delta(2)H(V)(-)(SMOW) data ranging from -27.4 per thousand to -28.3 per thousand and -151 per thousand to -184 per thousand, respectively. Samples of 1 declared to be "natural" exhibited ranges from -28.1 per thousand to -29.2 per thousand and -192 per thousand to -286 per thousand for delta(13)C(V)(-)(PDB) and delta(2)H(V)(-)(SMOW), respectively. For 2 from peach, apricot, and nectarine, delta(13)C(V)(-)(PDB) values ranging from -34.0 per thousand to -37.9 per thousand were determined; the delta(2)H(V)(-)(SMOW) values ranged from -171 per thousand to -228 per thousand. The delta(13)C(V)(-)(PDB) and delta(2)H(V)(-)(SMOW) data for synthetic 2 were -28.2 per thousand and -171 per thousand, respectively, that is, similar to those of 2 from "natural" origin, ranging from -27.7 per thousand to -30.1 per thousand and -185 per thousand to -230 per thousand for delta(13)C(V)(-)(PDB) and delta(2)H(V)(-)(SMOW), respectively. GC-C/P-IRMS allowed clear-cut analytical differentiation of the synthetic and "ex-plant" origin of 1 and 2, whereas narrow ranges of delta(13)C(V)(-)(PDB) and delta(2)H(V)(-)(SMOW) data were found for samples of synthetic and "natural" origin.     

Oxidation and fate of chromium in soils

Abstract

The ammonia electrode method was used to characterize soil organic nitrogen. Amide-N, α-amino-N and hexosamine-N were estimated by measuring the ammonium-N derived from each organic-N with an ammonia electrode after hydrolysis of standard compounds followed by certain treatments. Each organic-N was recovered quantitatively from each standard compound in the presence and absence of soil. Twenty soil samples were analyzed for the above forms of organic nitrogen by both the distillation and electrode methods. The results obtained by the ammonia electrode method for each form of organic nitrogen agreed closely with those obtained by the distillation method. The electrode method was preferred for subsequent soil studies since it is simple and sensitive.     

啤酒感官质量的计算机模糊综合评判

在啤酒GB4927—91质量标准基础上,建立了啤酒感官质量标准的一级模糊综合评判模型,提出并设计出适合计算机模糊综合评判的数值算法,用此算法设计的一级模糊综合评判FOR—TRAN语言处理程序,经过FACOMM34OS计算机上的实际运行,与实际评判结果具有很好的一致性,而且使得评判结果更为准确。