Similarity analyses of chromatographic fingerprints as tools for identification and quality control of green tea.

Similarity assessment of complex chromatographic profiles of herbal medicinal products is important as a potential tool for their identification. Mathematical similarity parameters have the advantage to be more reliable than visual similarity evaluations of often subtle differences between the fingerprint profiles. In this paper, different similarity analysis (SA) parameters are applied on green-tea chromatographic fingerprint profiles in order to test their ability to identify (dis)similar tea samples. These parameters are either based on correlation or distance measurements. They are visualised in colour maps and evaluation plots. Correlation (r) and congruence (c) coefficients are shown to provide the same information about the similarity of samples. The standardised Euclidean distance (ds) reveals less information than the Euclidean distance (de), while Mahalanobis distances (dm) are unsuitable for the similarity assessment of chromatographic fingerprints. The adapted similarity score (ss*) combines the advantages of r (or c) and de. Similarity analysis based on correlation is useful if concentration differences between samples are not important, whereas SA based on distances also detects concentration differences well. The evaluation plots including statistical confidence limits for the plotted parameter are found suitable for the evaluation of new suspected samples during quality assurance. The ss* colour maps and evaluation plots are found to be the best tools (in comparison to the other studied parameters) for the distinction between deviating and genuine fingerprints. For all studied data sets it is confirmed that adequate data pre-treatment, such as aligning the chromatograms, prior to the similarity assessment, is essential. Furthermore, green-tea samples chromatographed on two dissimilar High-Performance Liquid Chromatography (HPLC) columns provided the same similarity assessment. Combining these complementary fingerprints did not improve the similarity analysis of the studied data set.

Pressurized capillary electrochromatography in a screening for possible antioxidant molecules in Mallotus fingerprints: challenges, potentials and prospects.

Because of its eminent high resolution potential and minimal solvent consumption, pressurized capillary electrochromatography (pCEC) may offer an interesting alternative to HPLC for screening applications that need to resolve complex samples. In this paper, its potential was assessed in a screening of plant extracts from Mallotus species to indicate compounds with possible antioxidant activities by means of a PLS model built from their pCEC fingerprints. The main aim of this research was to find out whether pCEC can have an added value for this application. To get a complete overview of the techniques potential for this application, it was also assessed whether the technique can meet the requirements in terms of precision, sensitivity and column robustness. Encountered benefits and downsides were reported. Fingerprints with satisfactory sensitivity and precision could be obtained by concentrating the sample 5-fold and using optimized rinsing procedures, respectively. From the generated pCEC fingerprints of 39 Mallotus samples and their respective DPPH radical scavenging activity test results, a three-component PLS model was being built. The model proved good predictive abilities and easily allowed the indication of possible antioxidant compounds in the fingerprints. Despite its much higher peak capacity, the performance of pCEC to fingerprint the majority of the Mallotus extracts did not surpass that of a custom HPLC method. This was also reflected in its comparable power to indicate possible antioxidant compounds in the fingerprints after modeling. Because of its low detection sensitivity and modest column robustness, the benefit of the lower solvent consumption was partly paid-off by the current need for more system maintenance, also limiting the sample throughput. For the considered screening application, pCEC may suit as a viable but no preferred alternative technique.

Exploratory analysis of chromatographic fingerprints to distinguish rhizoma Chuanxiong and rhizoma Ligustici.

Identification and quality control of products of natural origin, used for preventive and therapeutical goals, is required by regulating authorities, as the World Health Organization. This study focuses on the identification and distinction of the rhizomes from two Chinese herbs, rhizoma Chuanxiong (from Ligusticum chuanxiong Hort.) and rhizoma Ligustici (from Ligusticum jeholense Nakai et Kitag), by chromatographic fingerprints. A second goal is using the fingerprints to assay ferulic acid, as its concentration provides an additional differentiation feature. Several extraction methods were tested, to obtain the highest number of peaks in the fingerprints. The best results were found using 76:19:5 (v/v/v) methanol/water/formic acid as solvent and extracting the pulverized material on a shaking bath for 15 min. Then fingerprint optimization was done. Most information about the herbs, i.e. the highest number of peaks, was observed on a Hypersil ODS column (250 mm × 4.6 mm ID, 5 µm), 1.0% acetic acid in the mobile phase and employing within 50 min linear gradient elution from 5:95 (v/v) to 95:5 (v/v) acetonitrile/water. The final fingerprints were able to distinguish rhizoma Chuanxiong and Ligustici, based on correlation coefficients combined with exploratory data analysis. The distinction was visualized using Principal Component Analysis, Projection Pursuit and Hierarchical Clustering Analysis techniques. Quantification of ferulic acid was possible in the fingerprints of both rhizomes. The time-different intermediate precisions of the fingerprints and of the ferulic acid quantification were shown to be acceptable.

Viability of increasing the tariff of freshwater for irrigation as a tool to stimulate wastewater reuse in the MENA region.

Despite water scarcity and high agricultural water demand in the Middle East and North Africa region, substantial proportions of treated wastewater are discharged into the environment and seas without proper utilization. All countries of the region, low pricing of reclaimed wastewater is a common tool to make reuse attractive. However, low pricing of reclaimed wastewater is ineffectual due to farmers' access to freshwater for irrigation at low tariff. Therefore, increasing the prices of freshwater in such a way that does not jeopardize feasibility of agriculture would promote irrigation with reclaimed wastewater even at increased prices. On one hand, it increases the gap between the price of freshwater and that of reclaimed wastewater, making the later more attractive. On the other hand, it would be used as a financial resource for funding the investment costs of the infrastructure needed for conveyance and distribution of reclaimed wastewater. This paper studies the viability of increasing the prices of freshwater and reclaimed wastewater. The results show that irrigation with reclaimed wastewater even for restricted irrigation can be as profitable as, and sometimes better than, freshwater irrigation. Some of the permitted crops such as fruit trees can be more profitable than vegetables. Thus, it appears that the level of knowledge farmers and others on the benefits of reclaimed wastewater is still limited.

Chromatographic fingerprint development for herbal extracts: a screening and optimization methodology on monolithic columns.

Herbs are used worldwide for preventive and therapeutic purposes. Therefore, identification and quality control of products of vegetal origin is required. Fingerprint chromatography is accepted by the World Health Organization as an identification and quality evaluation technique for medicinal herbs. In fingerprint development, the first step is to create general conditions maximizing the peak capacity. Four herbs, Liquorice, Cascara, Curcuma and Artichoke, were examined using different experimental conditions in order to propose a methodology to develop fingerprint chromatograms in high-performance liquid chromatography (HPLC) with ultra-violet (UV) and evaporative light scattering (ELS) detection. The methodology comprised a screening and an optimization phase. Monolithic C18 columns were used as stationary phases. Several organic modifiers were tested to define a gradient elution system with an optimal selectivity. From the screening phase, linear gradients of 5-60%, 5-54%, 5-95% and 5-95% acetonitrile for Liquorice, Cascara, Curcuma and Artichoke, respectively, were selected. The ELS detection did not provide additional information to the UV detection. The optimization phase selected the best experimental conditions for wavelength, column length, flow rate and slope of the gradient for the best modifier determined at the end of the screening. For the four examined herbs 254 nm as detection wavelength, 300 mm column length, 2 ml/min flow rate and a gradient time of 50 min were defined as the best conditions. If these latter unique conditions are confirmed for other case studies, the actual strategy even might be simplified by reducing the optimization stage.

Treatment of fish processing wastewater in a one- or two-step upflow anaerobic sludge blanket (UASB) reactor.

The performance of one-step UASB reactors treating fish processing wastewater of different lipid levels was determined using artificially generated influent simulating that of the canning of sardines and tuna. The organic loading rates (OLR) and the hydraulic retention times (HRT) were 5-8 g COD.l(-1).d(-1) and 11-12 hours, respectively. In treating a wastewater that contains 3-4 g.l(-1) total COD of which 5-9% was lipids, the COD removal and conversion to methane were ca.78% and 61%, respectively. In treating a wastewater with a higher lipid content (ca. 47% of the total COD), the total COD removed and converted to methane were 92% and 47%, respectively. A considerable part of the influent total COD was removed via adsorption on reactor surfaces and sludge particles. The adsorption of lipids on sludge particles threatens the stability of the UASB operation. Thus, the performance of a first-step UASB reactor in removing suspended solids (SS) from a "high-lipid" wastewater was also determined in this study.